JP2009122653A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having high offset resistance and preferable charging property, even though the toner is a capsule type toner that is superior in low-temperature fixability, and further, is capable of giving high-quality images with fine black characters, lines and dots, and having a spherical form, a small particle diameter and sharp particle size distribution. <P>SOLUTION: The toner comprises capsule-type toner particles, having a surface layer (B) on the surface of a toner base particle (A) containing at least a binder resin (a) essentially comprising polyester, a magnetic material and wax. The surface layer (B) contains a resin (b), and the resin (b) comprises a resin selected from polyester resin (b1), vinyl resin (b2) and urethane resin (b3). The glass transition temperature Tg(a) of the binder resin and the glass transition temperature Tg(b) of the resin (b) satisfy the relation Tg(a)<Tg(b). The magnetization of the toner in an external magnetic field of 79.6 kA/m is in the range of 12 Am<SP>2</SP>/kg to 30 Am<SP>2</SP>/kg. If the temperature at which the loss modulus of the toner is maximum is represented by Tt(°C), 40°C≤Tt≤60°C is satisfied. If the loss moduli of the toner at a temperature (Tt+5)°C and at a temperature (Tt+25)°C are represented by G"t(Tt+5) and G"t(Tt+25), respectively, G"t(Tt+5)/G"t(Tt+25) is larger than 40. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

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

In recent years, energy saving has been considered as a major technical problem in electrophotographic apparatuses, and a great reduction in the amount of heat applied to a fixing apparatus has been cited. Accordingly, there is a growing need for so-called “low-temperature fixability” that can fix toner with lower energy.
Conventionally, in order to enable low-temperature fixing, a method of sharp melting toner is known.
Patent Document 1 proposes a capsule toner in which the ratio (G ′ (60) / G ′ (80)) between the storage elastic modulus of toner at 60 ° C. and the storage elastic modulus of toner at 80 ° C. is 10 or more and 40 or less. ing. However, when used in a high-speed machine, the sharp melt property is weak and the low-temperature fixability may be insufficient.

On the other hand, for the purpose of high resolution and high definition, the toner has been made smaller in particle size and sharpened in its particle size distribution, and spherical toner has been suitably used for the purpose of improving transfer efficiency and fluidity. It is coming. A solution suspension method is known as a method for efficiently preparing spherical toner particles having a small particle diameter.
In Patent Document 2, toner base particles are prepared in the presence of resin fine particles including any of vinyl resins, polyurethane resins, epoxy resins, polyester resins, or a combination thereof, and toner particles whose toner surfaces are coated with the fine particles are disclosed. An adjustment method has been proposed.
Patent Document 3 proposes toner particles by a dissolution suspension method using urethane-modified polyester resin fine particles as a dispersant.
Patent Document 4 discloses a core-shell type composed of one or more film-like shell layers (P) made of polyurethane resin (a) and one core layer (Q) made of resin (b). Toner particles have been proposed.
The core / shell type toner particles have a structure in which the core portion has a low viscosity and the heat resistance storage stability of the shell portion compensates for the inferior heat resistance storage stability. In this case, since the shell portion uses a thermally hard resin, it is necessary to devise highly cross-linking or high molecular weight, so that low temperature fixability may be hindered.

For monochrome printers, there is a strong demand for miniaturization. In response to this requirement, a one-component development system that facilitates downsizing of the apparatus is preferably used. The one-component development method includes a magnetic one-component development method in which magnetic particles are contained in toner and the developer is carried and conveyed by the action of magnetic force, and the developer is caused by the action of triboelectric charge of the developer without using magnetic particles. There is a non-magnetic one-component developing method in which the toner is carried on a developer carrying member (developing sleeve). In the magnetic one-component development system, a colorant such as carbon black is not used, and a magnetic material can also be used as a colorant.

Various toners have been proposed so far for magnetic toners used in the magnetic one-component development system. Patent Document 5 proposes a toner of a solution suspension method using polyester. However, the toner charge amount tends to decrease, and it is easy to cause development failure and transfer failure. A toner that exhibits both excellent low-temperature fixability and heat-resistant storage stability and exhibits good developability has not been provided so far.
JP 2006-293273 A JP 2004-271919 A Japanese Patent No. 3455523 WO2005 / 073287 JP-A-8-286423

The present invention has been made in view of the above problems, and an object thereof is to provide a toner having a high offset resistance and a good charging property while being a capsule-type toner excellent in low-temperature fixability. Furthermore, black characters, lines, and dots are fine, and a high-quality image is obtained. It is another object of the present invention to provide a spherical toner having a small particle size and a sharp particle size distribution.

The toner of the present invention comprises capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a binder resin (a) containing polyester as a main component, a magnetic material and wax. A toner containing,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the binder resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less,
When the temperature indicating the maximum loss elastic modulus of the toner is Tt (° C.), 40 ° C. ≦ Tt ≦ 60 ° C.
When the loss elastic moduli of the toner at temperature (Tt + 5) ° C. and temperature (Tt + 25) ° C. are G ″ t (Tt + 5) and G ″ t (Tt + 25), respectively, G ″ t (Tt + 5) / G ″ t ( Tt + 25) is greater than 40.

According to a preferred embodiment of the present invention, the toner is a toner having capsule-type toner particles having toner base particles (A) and a surface layer (B). Then, the toner base particles (A) are provided with functions such as low viscosity, releasability, coloring power, and magnetism, and the surface layer (B) is provided with functions such as heat resistance and chargeability related to developability. This function separation structure provides excellent performance. According to a preferred embodiment of the present invention, it is possible to provide a magnetic toner that exhibits sufficient heat storage stability and exhibits excellent low-temperature fixability and excellent offset resistance, chargeability, and developability.

The toner of the present invention comprises capsule-type toner particles having a surface layer (B) on the surface of toner base particles (A) containing at least a binder resin (a) containing polyester as a main component, a magnetic material and wax. A toner containing,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the binder resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 A
m ² / kg or less,
When the temperature indicating the maximum loss elastic modulus of the toner is Tt (° C.), 40 ° C. ≦ Tt ≦ 60 ° C.
When the loss elastic moduli of the toner at temperature (Tt + 5) ° C. and temperature (Tt + 25) ° C. are G ″ t (Tt + 5) and G ″ t (Tt + 25), respectively, G ″ t (Tt + 5) / G ″ t ( Tt + 25) is greater than 40.

The toner of the present invention is a capsule type (capsule structure) having a surface layer (B) on the surface of toner base particles (A) containing a binder resin (a) mainly composed of polyester, a magnetic material and wax. Contains toner particles.
In order to solve the above problems, the toner of the present invention is required to have a capsule structure.
The capsule structure (encapsulation) means that the surface of the toner base particles (A) is shielded by the surface layer (B), and the toner base particles (A) are not exposed on the surface of the toner particles. That is, the capsule structure can prevent the magnetic substance and wax from being exposed, and can exhibit excellent developability and durability stability.

The surface layer (B) used in the present invention contains a resin (b), and the resin (b) contains a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3). Resin.
Further, the glass transition temperature Tg (a) of the binder resin (a) mainly composed of polyester used in the present invention and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1). Fulfill. Tg (a) <Tg (b) (1)

That is, by making Tg (b) of the capsule-type toner larger than Tg (a), it is possible to maintain heat resistance and storage stability while realizing low viscosity at low temperature. Further, the resin (b) forming the surface layer (B) is difficult to melt at normal storage temperature, but preferably has a property of melting immediately upon heating, and exhibits excellent heat resistance and low temperature fixability. . Furthermore, desired toner viscoelasticity can be obtained by using the binder resin (a) whose main component is a polyester resin for the toner base particles (A).

In the dynamic viscoelasticity measurement at a constant temperature increase rate of the toner, the following is observed when the temperature change of the loss elastic modulus is observed. That is, when the temperature showing the maximum value of the loss elastic modulus of the toner is Tt (° C.), the toner maintains a glass state in a temperature range lower than the temperature Tt (° C.) and causes a phase transition at the temperature Tt (° C.). When the temperature is higher than the temperature Tt (° C.), the viscosity decreases as the temperature increases. The toner is preferably not easily deformed at a temperature lower than the temperature Tt (° C.), and exhibits good heat-resistant storage stability. On the other hand, the viscosity of the toner is preferably lowered rapidly in the temperature range higher than the temperature Tt (° C.), and exhibits excellent low-temperature fixability.

In the present invention, when the temperature indicating the maximum loss elastic modulus of the toner is Tt (° C.), 40 ° C. ≦ Tt ≦ 60 ° C. When the temperature Tt (° C.) is within this range, material design for achieving both heat-resistant storage stability and low-temperature fixability can be performed. The temperature Tt (° C.) is preferably controlled within the above range by appropriately selecting the main component of the toner particles, that is, the binder resin (a) mainly composed of polyester.
When temperature Tt (degreeC) is less than 40 degreeC, heat-resistant storage stability may fall. On the other hand, when the temperature Tt (° C.) exceeds 60 ° C., the low temperature fixability may be inferior. Furthermore, the temperature Tt (° C.) is preferably 45 ° C. or higher and 55 ° C. or lower.
FIG. 1 shows an example of a diagram showing a change in the loss elastic modulus of toner with temperature.

In the toner of the present invention, when the loss elastic moduli of the toner at the temperature (Tt + 5) ° C. and the temperature (Tt + 25) ° C. are G ″ t (Tt + 5) and G ″ t (Tt + 25), respectively, “T (Tt + 5) / G” t (Tt + 25) is larger than 40.
G ″ t (Tt + 5) / G ″ t (Tt + 25) means the sharp melt property of the toner in a temperature region higher than the temperature Tt (° C.). The sharp melt property represents the degree of change in loss elastic modulus with respect to temperature change in a temperature region higher than the temperature Tt (° C.). That is, the larger G ″ t (Tt + 5) / G ″ t (Tt + 25), the stronger the sharp melt property of the toner. If the sharp melt property of the toner is strong, the sensitivity to heat is high and low temperature fixing is possible.
When G ″ t (Tt + 5) / G ″ t (Tt + 25) is 40 or less, the low-temperature fixability may be inferior. Of the low-temperature fixability, in particular, the adhesion to paper tends to decrease. Further, G ″ t (Tt + 5) / G ″ t (Tt + 25) is preferably 50 or more, more preferably G ″ t (Tt + 5) / G ″ t (Tt + 25) is 60 or more. On the other hand, the above value is preferably smaller than 200. When the above value is 200 or more, high temperature offset may occur.

In the present invention, the magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less. The magnetization is preferably 15 Am ² / kg or more and 28 Am ² / kg or less. When the magnetization is less than 12 Am ² / kg, the holding ability of the toner carrier is reduced, which is likely to cause toner scattering and fogging on paper. On the other hand, when the magnetization exceeds 30 Am ² / kg, the magnetic substance is excessive. When the amount of the magnetic material is excessive, it is easy to cause poor dispersion of the magnetic material and a decrease in fixing property due to a decrease in the resin component, and G ″ t (Tt + 5) / G ″ t (Tt + 25) tends to be smaller than 40.

In order to make G ″ t (Tt + 5) / G ″ t (Tt + 25) larger than 40, the following measures can be preferably exemplified.
The binder resin (a) containing the polyester as a main component (hereinafter also simply referred to as a binder resin (a)) contains at least a resin (a1) and a resin (a2) having different softening points, and the resin (a1 ) Is preferably 40 ° C. or higher and 100 ° C. or lower, and the softening point of the resin (a2) is preferably 120 ° C. or higher and 200 ° C. or lower. More preferably, the softening point of the resin (a1) is 50 ° C. or higher and 90 ° C. or lower, and the softening point of the resin (a2) is 130 ° C. or higher and 180 ° C. or lower.

In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin (a1), the weight average molecular weight (Mw) is preferably 2,000 or more and 20,000 or less. More preferably, it is 3,000 or more and 15,000 or less. On the other hand, in the molecular weight distribution measured by GPC of the THF soluble content of the resin (a2), the weight average molecular weight (Mw) is preferably 30,000 to 150,000. More preferably, it is 50,000 or more and 120,000 or less.
When the weight average molecular weight of the THF-soluble component of the resin (a1) is less than 3,000, the heat resistant storage stability may be deteriorated and the toner particle size distribution may be broadened. On the other hand, when the weight average molecular weight of the THF soluble part of the resin (a1) exceeds 10,000, G ″ t (Tt + 5) / G ″ t (Tt + 25) may be smaller than 40.
When the weight average molecular weight of the THF soluble part of the resin (a2) is less than 30,000, high temperature offset tends to occur. On the other hand, when the weight average molecular weight of the THF soluble part of the resin (a2) exceeds 150,000, the viscosity of the resin solution tends to be high and the particle size distribution of the toner tends to be broad.

In the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin (a1), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw) / Mn) is preferably 1.0 or more and 8.0 or less. More preferably, it is 1.2 or more and 6.0 or less. When the THF soluble content (Mw / Mn) of the resin (a1) exceeds 8.0, the sharp melt property of the resin (a1) decreases, and G ″ t (Tt + 5) / G ″ t (Tt + 25) It becomes difficult to take a value larger than 40.

In the present invention, the proportion of the resin (a1) in the binder resin (a) is preferably 50% by mass or more and 90% by mass or less. More preferably, it is 55 mass% or more and 85 mass% or less. When the ratio of the resin (a1) to the binder resin (a) is less than 50% by mass, G ″ t (Tt + 5) / G ″ t (Tt + 25) may be smaller than 40. On the other hand, when the ratio exceeds 90% by mass, high temperature offset is likely to occur.

In the present invention, the surface layer (B) contains the resin (b), and the sharp melt property of the resin (b) also affects the sharp melt property of the toner. The temperature showing the maximum value of the loss elastic modulus of the resin (b) is Tb (° C.). ) And G ″ b (Tb + 25), it is preferable that G ″ b (Tb + 5) / G ″ b (Tb + 25) is greater than 10 and 200 or less. More preferably, it is 20 or more and 100 or less. When G ″ b (Tb + 5) / G ″ b (Tb + 25) is 10 or less, that is, when the sharp melt property of the resin (b) is weak, G ″ t (Tt + 5) / G ″ t (Tt + 25) is 40 or less. There is a case.
The adjustment of G ″ b (Tb + 5) / G ″ b (Tb + 25) is carried out under conditions where the polymerization product tends to be uniform during the preparation of the resin (b), for example, ester exchange reaction or acid anhydride if it is an ester bond. It is possible to use it. If a urethane bond is generated, it is possible to satisfy the above range by using a raw material having a uniform composition for diol and diisocyanate, for example, monomer diol.

A value (Tb−Tt) obtained by subtracting the temperature Tt (° C.) from the temperature Tb (° C.) is preferably 5 ° C. or more and 20 ° C. or less. More preferably, they are 5 degreeC or more and 15 degrees C or less.
When the above (Tb−Tt) is less than 5 ° C., the heat resistant storage stability may be deteriorated. When (Tb−Tt) exceeds 20 ° C., G ″ t (Tt + 5) / G ″ t (Tt + 25) may be 40 or less.

In the present invention, the storage elastic modulus (G′t (120)) at 120 ° C. of the toner is preferably 5.0 × 10 ² Pa or more and 5.0 × 10 ⁴ Pa or less. More preferably, it is 8.0 × 10 ² Pa or more and 3.0 × 10 ⁴ Pa or less.
When G′t (120) is 5.0 × 10 ² Pa or more and 5.0 × 10 ⁴ Pa or less, good offset resistance can be exhibited.
When G′t (120) is less than 5.0 × 10 ² Pa, the toner does not exhibit sufficient elasticity, and offset tends to occur. On the other hand, when G′t (120) exceeds 5.0 × 10 ⁴ Pa, the low-temperature fixability tends to be hindered.
G′t (120) satisfies the above range by adjusting the elasticity of the binder resin (a) at 120 ° C., the ratio of the resin (a2) to the binder resin (a), the amount of magnetic material, and the like. Is possible.

In the present invention, the toner particles preferably contain 3 mass% or more and 10 mass% or less of tetrahydrofuran (THF) insoluble matter excluding the magnetic material. More preferably, it is 4 mass% or more and 8 mass% or less. When the THF-insoluble matter excluding the magnetic material is less than 3% by mass, the offset resistance tends to be lowered. On the other hand, when the THF-insoluble content excluding the magnetic substance exceeds 10% by mass, G ″ t (Tt + 5) / G ″ t (Tt + 25) hardly takes a value greater than 40.

In the present invention, the surface layer (B) is preferably 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles (A). More preferably, the surface layer (B) is 2.0% by mass or more and 10.0% by mass or less with respect to the toner base particles (A).
When the ratio of the surface layer (B) to the toner base particles (A) is less than 1.0% by mass, the encapsulation is insufficient and the toner base particles (A) are easily exposed. As a result, the developability is lowered due to the exposure of the magnetic substance and wax, the heat resistant storage stability is lowered, and the particle size distribution is broadened due to the coalescence of the toner. On the other hand, when the ratio of the surface layer (B) to the toner base particles (A) exceeds 15.0% by mass, the particle size of the toner tends to be small and particle size control may be difficult.

In the present invention, in order to encapsulate the toner particles, it is preferable that the resin (b) is not compatible with the binder resin (a) and easily adheres to the binder resin (a). For the above reasons, the resin (b) is preferably a urethane resin (b3).

Conventionally, when a magnetic toner using a polyester resin is prepared by a dissolution suspension method, a poor dispersion of the magnetic material is likely to occur. In addition, the addition of a magnetic material has made it difficult to stably produce toner particles, and it has been easy for white dust to occur, precipitation of the magnetic material on the toner surface, and hence particle size variation due to poor granulation. In order to solve the above problems, in the present application, it is possible to provide a toner that can cope with high image quality by using the following methods (1) to (3).
(1) The binder resin (a) containing a polyester resin as a main component and the magnetic material are sufficiently premixed to increase the dispersibility of the magnetic material.
(2) The polarity of the resin (b) used for the surface layer (B) is increased, and the magnetic substance is sealed in the toner base particles (A).
(3) Hydrophobizing the magnetic material to reduce the affinity for the aqueous phase.

Hereinafter, (1) a method of sufficiently preliminarily mixing the binder resin (a) containing polyester as a main component and a magnetic material to improve the dispersibility of the magnetic material will be described.
In order to improve the dispersibility of the magnetic material, it is preferable to implement the following method in the present invention.
1) Wet dispersion (media dispersion)
2) Dry kneading Further, in order to increase the dispersibility of the magnetic material, the following method is preferred.
3) Wet dispersion of dry kneaded product 4) Addition of solvent at the time of dry kneading preparation 5) Addition of wax at the time of dry kneading preparation These methods can be performed alone or in combination.
In addition, after the preliminary dispersion of various materials, the dispersion process tends to be insufficient in the mixing process during the preparation of the oil phase. In particular, in the present invention, poor dispersion of the magnetic material tends to be noticeable in performance degradation. In the present invention, the dispersion of the magnetic substance into the toner particles can be improved by adding not only the dispersion with a normal mechanical stirring blade but also the fine dispersion process using ultrasonic waves or the media dispersion of the oil phase mixture. .

In order to increase the polarity of the resin (b) used in the above (2), that is, the surface layer (B), and to seal the magnetic substance in the toner base particles (A), the following method is preferably used.
It is preferable to introduce a highly polar functional group into the resin (b) used for the surface layer (B). For example, the resin (b) preferably has at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a carboxylate, and a sulfonate in the side chain. Specifically, at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a carboxylate, and a sulfonate is introduced into the resin (b). Furthermore, it is also effective to introduce a functional group using a resin having a urethane bond in the main chain.

The above (3), that is, reducing the affinity for the aqueous phase by hydrophobizing the magnetic material is effective for reducing the free magnetic material that has come out of the toner base particles (A). When increasing the amount of processing of the magnetic material or using a highly hydrophobic processing agent for the magnetic material, care should be taken because the magnetic material tends to aggregate in the toner base particles (A).

The toner base particles (A) used in the present invention are described in detail below.
The toner base particles (A) used in the present invention contain at least a binder resin (a) containing polyester as a main component, a magnetic material and a wax. Therefore, in addition to the above, other additives may be included as necessary.

As described above, the binder resin (a) containing polyester as a main component contains at least the resin (a1) and the resin (a2) having different softening points. Moreover, the said binder resin (a) used for this invention contains polyester as a main component. Here, “main component” means that the polyester occupies 50% by mass or more based on the total amount of the binder resin (a). For the polyester (including the polyester contained in the resin (a1) and the resin (a2)), a polyester using an aliphatic diol as a main component as an alcohol component and / or an aromatic diol as a main component. It is preferable to use the polyester used.

The aliphatic diol preferably has 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms.
Examples of the aliphatic diol having 2 to 8 carbon atoms include the following.
Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol, 1 , 7-heptanediol, diols such as 1,8-octanediol, trihydric or higher polyhydric alcohols such as glycerin, pentaerythritol and trimethylolpropane. Among these, α, ω-linear alkanediol is preferable, and 1,4-butanediol and 1,6-hexanediol are more preferable. Furthermore, from the viewpoint of durability, the content of the aliphatic diol is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, in the alcohol component constituting the polyester.

Examples of the aromatic diol include the following.
Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane.

Examples of the carboxylic acid component constituting the polyester include the following.
Aromatic polyvalent carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid and pyromellitic acid, fumaric acid, maleic acid, adipic acid, succinic acid, dodecenyl succinic acid and octenyl succinic acid. Aliphatic polycarboxylic acids such as succinic acid substituted with alkyl groups or alkenyl groups having 2 to 20 carbon atoms, anhydrides of these acids and alkyl (1 to 8 carbon atoms) esters of these acids.

From the viewpoint of chargeability, the carboxylic acid preferably contains an aromatic polyvalent carboxylic acid compound, and the content thereof is preferably 30 to 100 mol% in the carboxylic acid component constituting the polyester, 50-100 mol% is more preferable.
In addition, the raw material monomer may contain a trivalent or higher polyvalent monomer, that is, a trivalent or higher polyhydric alcohol and / or a trivalent or higher polyvalent carboxylic acid compound from the viewpoint of fixability.

The manufacturing method of the said polyester is not specifically limited, What is necessary is just to follow a well-known method. For example, a production method in which an alcohol component and a carboxylic acid component are subjected to polycondensation at a temperature of 180 to 250 ° C. in an inert gas atmosphere using an esterification catalyst as necessary.

The binder resin (a) preferably contains as a main component a polyester using the aliphatic diol as an alcohol component. On the other hand, even when the binder resin (a) contains a polyester using a bisphenol monomer as an alcohol component, there is no significant difference in the melting characteristics of the binder resin (a). However, in order to affect the granulation property in relation to the resin (b), it is effective to select an appropriate polyester as appropriate.

The binder resin (a) is a resin other than a polyester using a specific amount of aliphatic diol or aromatic diol as an alcohol component, for example, a polyester resin in which the amount of the aliphatic diol is outside the above range, styrene-acrylic A resin, a mixed resin of polyester and styrene acrylic, an epoxy resin, or the like may be contained. In that case, the content of the polyester using the specific amount of the aliphatic diol as an alcohol component is preferably 50% by mass or more, and more preferably 70% by mass or more based on the total amount of the binder resin (a).

Further, in the present invention, in the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble part of the binder resin (a), the peak molecular weight (Mp) is preferably 8000 or less, more preferably It is less than 5500. Furthermore, the proportion of the molecular weight of 100,000 or more is preferably 5.0% or less, more preferably 1.0% or less.

If the peak molecular weight exceeds 8000 or the ratio of the molecular weight of 100,000 or more exceeds 5.0%, the fixability may be impaired depending on the type and amount of the surface layer resin.

In the present invention, the ratio of the binder resin (a) having a molecular weight of 1000 or less is preferably 10.0% or less, more preferably less than 7.0%.
When the ratio of the molecular weight of 1000 or less is more than 10.0%, a low molecular weight component that is relatively thermally unstable may contaminate the member.

In the present invention, the following preparation method can be preferably used in order to make the ratio of the molecular weight of 1000 or less particularly 10.0% or less.

In order to reduce the ratio of the molecular weight of 1000 or less, the ratio of the molecular weight of 1000 or less can be effectively reduced by dissolving the binder resin in a solvent and leaving the solution in contact with water. That is, by such an operation, the low molecular weight component having a molecular weight of 1000 or less is eluted in water and can be effectively removed from the resin solution.

For the above reasons, for example, the above-described dissolution suspension method is preferably used as a toner production method. A low molecular weight component is efficiently obtained by using a method in which a solution in which a binder resin (a), a magnetic material and a wax are dissolved or dispersed is left in contact with an aqueous medium before being suspended in the aqueous medium. Can be removed.

In the present invention, it is one of preferred embodiments that the binder resin (a) contains a crystalline polyester. By containing the crystalline polyester, the sharp melt property of the binder resin (a) can be further enhanced. As a result, G ″ t (Tt + 5) / G ″ t (Tt + 25) can be further increased. As the crystalline polyester, a resin obtained by polycondensation of an alcohol component mainly containing an aliphatic diol and a carboxylic acid component mainly containing an aliphatic dicarboxylic acid compound is preferable.
The crystalline polyester is obtained using a monomer containing an alcohol component composed of a polyhydric alcohol having a valence of 2 or more and a carboxylic acid component composed of a polycarboxylic acid compound having a valence of 2 or more. Among them, an alcohol component containing 60 mol% or more of an aliphatic diol having 2 to 6 carbon atoms, preferably 4 to 6 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 8 carbon atoms, preferably 4 to 6 carbon atoms, more preferably 4 carbon atoms. A resin obtained by condensation polymerization of a carboxylic acid component containing 60 mol% or more of an acid compound is preferred.

The following are mentioned as said C2-C6 aliphatic diol which comprises the said crystalline polyester.
Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-butenediol. Among these, 1,4-butanediol and 1,6-hexanediol are preferable.

The alcohol component constituting the crystalline polyester may contain a polyhydric alcohol component other than the aliphatic diol. Examples of the polyhydric alcohol component include the following. Alkylene of bisphenol A such as polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane ( C2-C3) Divalent aromatic alcohols such as oxides (average addition mole number 1-10) adducts, and tri- or higher alcohols such as glycerin, pentaerythritol, and trimethylolpropane.

The following are mentioned as a C2-C8 aliphatic dicarboxylic acid compound which comprises the said crystalline polyester. Oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and anhydrides, alkyl (C1 to C3) esters of these acids. Of these, fumaric acid and adipic acid are preferred, and fumaric acid is more preferred.

The carboxylic acid component constituting the crystalline polyester may contain a polyvalent carboxylic acid component other than the aliphatic dicarboxylic acid compound. Examples of the polyvalent carboxylic acid component include the following. Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Aliphatic dicarboxylic acids such as sebacic acid, azelaic acid, n-dodecyl succinic acid and n-dodecenyl succinic acid; Alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; Trimerit Acids, trivalent or higher polyvalent carboxylic acids such as pyromellitic acid; and anhydrides and alkyl (carbon number 1 to 3) esters of these acids.

The alcohol component and the carboxylic acid component constituting the crystalline polyester can be subjected to polycondensation by reacting at a temperature of 150 to 250 ° C. in an inert gas atmosphere, if necessary, using an esterification catalyst or the like. it can.

In the binder resin (a), a known resin can be used in addition to the polyester. Such resins include, but are not limited to, the following:
Polystyrene; polymer of styrene derivatives such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester Copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene- Styrene copolymer such as isoprene copolymer, styrene-acrylonitrile-indene copolymer; polyvinyl chloride; phenol resin; modified phenol resin; male resin; acrylic resin; methacrylic resin; Polyure Down resin; polyamide resin, polyvinyl butyral, terpene resins, coumarone-indene resins; petroleum resins.

In the present invention, the toner particles contain a wax. Examples of the wax used in the present invention include the following.
Low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight olefin copolymer, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax; fat Waxes based on fatty acid esters such as aromatic hydrocarbon-based ester waxes; and partially or fully deoxidized fatty acid esters such as deoxidized carnauba wax; partial esters of fatty acids and polyhydric alcohols such as behenic acid monoglyceride A methyl ester compound having a hydroxyl group obtained by hydrogenating vegetable oils and the like.
The wax particularly preferably used in the present invention is, in the dissolution suspension method, easy preparation of the wax dispersion, easy incorporation into the prepared toner, seepage from the toner during fixing, releasability Therefore, ester wax is preferable. Furthermore, ester wax is also preferable in terms of increasing G ″ t (Tt + 5) / G ″ t (Tt + 25).

In the present invention, the ester wax only needs to have at least one ester bond in one molecule, and either natural ester wax or synthetic ester wax may be used.

Examples of the synthetic ester wax include a monoester wax synthesized from a long-chain linear saturated fatty acid and a long-chain linear saturated alcohol. When representing a long, straight-chain saturated fatty acid with general formula _C n _H 2n + 1 COOH, of about n = 5 to 28 is preferably used. Also when it represents a long-chain linear saturated alcohol _C n _{H 2n +} 1 OH, of about n = 5 to 28 is preferably used.

Examples of the long-chain linear saturated fatty acid include the following.
Capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, pentadecylic acid, heptadecanoic acid, tetradecanoic acid, stearic acid, nonadecanoic acid, aramonic acid, behenic acid, lignoceric acid, serotic acid, heptacosanoic acid, montanic acid And melicic acid.

On the other hand, examples of the long-chain linear saturated alcohol include the following.
Amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol , Nonadecyl alcohol, eicosyl alcohol, seryl alcohol and heptadecanool.

Examples of the ester wax having two or more ester bonds per molecule include the following.
Trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol-bis-stearate, polyalkanol ester (tristearyl trimellitic acid , Distearyl maleate).

Moreover, as a natural ester wax, the following are mentioned.
Candelilla wax, carnauba wax, rice wax, wax, jojoba oil, beeswax, lanolin, castor wax, montan wax and derivatives thereof.

Other modified waxes include the following.
Polyalkanoic acid amides (ethylenediamine dibehenyl amide); polyalkylamides (trimellitic acid tristearyl amide); and dialkyl ketones (distearyl ketone).

The wax may be partially saponified.
Among the above, more preferable waxes are synthetic ester waxes composed of long-chain linear saturated fatty acids and long-chain linear saturated aliphatic alcohols, or natural waxes based on the above esters.

The reason for this is not clear, but it is thought that the mobility in the molten state is increased due to the wax having a linear structure. In other words, it is necessary for the wax to permeate into the toner surface layer through a relatively high-polarity substance such as polyester as a binder resin or a resin containing a reaction product of diol and diisocyanate in the surface layer at the time of fixing. Therefore, it seems that it is advantageous that the wax has a linear structure as much as possible in order to pass between such highly polar substances.
Furthermore, it is considered that the ester wax acts as a dispersion aid for the magnetic substance in the toner and works advantageously for reducing aggregates and free substances.

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

In the present invention, it is also one of preferred modes to use a hydrocarbon wax other than the ester wax as needed.

Examples of hydrocarbon waxes other than the ester wax include the following. Natural waxes such as paraffin wax, microcrystalline wax, petroleum-based natural waxes such as petrolatum and derivatives thereof, synthetic hydrocarbons such as Fischer-Tropsch wax, polyolefin waxes and derivatives thereof (polyethylene wax, polypropylene wax), ozokerite, ceresin.

In the present invention, the content of the wax in the toner is preferably 5.0 to 20.0 parts by mass, more preferably 5.0 to 15.0 parts by mass, per 100 parts by mass of the binder resin. When the amount is less than 5.0 parts by mass, the releasability of the toner cannot be maintained, and when the amount is more than 20.0 parts by mass, the wax is likely to be exposed on the toner surface, which may cause deterioration in heat resistant storage stability.

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

Next, the magnetic material used in the present invention will be described. An example of the structure and manufacturing method of the magnetic material used in the present invention will be described.

Examples of the magnetic material used in the present invention include magnetite, iron oxide such as ferrite, iron, cobalt, nickel and the like, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, Examples thereof include alloys with metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

The magnetic material used in the present invention is produced, for example, by the following method. After adding the ferrous salt aqueous solution and silicate, an alkali such as sodium hydroxide is added in an equivalent amount or more to the iron component to prepare an aqueous solution containing ferrous hydroxide. Air is blown in while maintaining the pH of the prepared aqueous solution at pH 7 or higher (preferably pH 8 to 10), and iron oxide is oxidized while heating the aqueous solution to 70 ° C. or higher, which becomes the core of the magnetic body. First, seed crystals are formed.

Next, an aqueous solution containing an equivalent amount of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. Thereafter, while maintaining the pH of the liquid at 6 to 10, the reaction of ferrous hydroxide is promoted while blowing air, and the magnetic iron oxide particles are grown with the seed crystal as the core. Magnetic iron oxide characterized by maintaining a constant composition ratio of elements on the outermost surface of the body is characterized by advancing the oxidation reaction step by step in combination with pH adjustment. For example, the oxidation reaction is allowed to proceed stepwise depending on the pH, such that the pH is 9-10 at the beginning of the reaction, the pH is 8-9 during the middle of the reaction, and the pH is 6-8 during the latter half of the reaction. Thus, the composition ratio of the outermost surface of magnetic iron oxide can be controlled more easily. Further, the pH of the liquid shifts to the acidic side as the oxidation reaction proceeds, but it is preferable that the pH of the liquid not be less than 6.

As the iron salt used for the addition, sulfate, nitrate and chloride can be used. Examples of the silicate that can be used for addition include sodium silicate and potassium silicate.

As the ferrous salt, iron sulfate generally produced as a by-product in the production of sulfuric acid titanium, iron sulfate produced as a by-product with the surface cleaning of the copper plate can be used, and iron chloride can also be used.

In the method for producing a magnetic substance by the aqueous solution method, generally, an iron concentration of 0.5 to 2 mol / liter is used from the viewpoint of preventing an increase in viscosity during the reaction and the solubility of iron sulfate. Generally, the lower the iron sulfate concentration, the finer the particle size of the product. In the reaction, the larger the amount of air and the lower the reaction temperature, the easier the atomization.

In the present invention, as the magnetic material, spherical particles, octahedral particles, hexahedral particles and mixtures thereof can be used as observed by transmission electron micrographs.

In the present invention, the magnetic substance has a bulk density based on a measurement method described later, preferably 0.3 to 2.0 g / cm ³ , more preferably 0.5 to 1.3 g / cm ³ . When the bulk density is less than 0.3 g / cm ³ , the physical mixing properties of the toner with other constituent materials at the time of toner production are adversely affected, and the dispersibility in the toner may deteriorate.

In the present invention, the magnetic substance has a BET specific surface area based on a measurement method described later, preferably 15.0 m ² / g or less, more preferably 12.0 m ² / g or less. Moreover, Preferably it is 3.0 m < ² > / g or more, More preferably, it is 5.0 m < ² > / g or more. If the BET specific surface area of the magnetic material is within the above range, the moisture adsorption property of the magnetic material can be suppressed, and the charging property of the magnetic toner can be maintained better.

In the present invention, the magnetic properties of the magnetic material used in the present invention are such that the magnetization under a magnetic field of 79.6 kA / m is preferably 10 to 200 Am ² / kg, more preferably 50 to 100 Am ² / kg. The residual magnetization is preferably 1 to 100 Am ² / kg, more preferably ^{2 to 20} Am ² / kg. Furthermore, the coercive force is preferably 1 to 30 kA / m, more preferably 2 to 15 kA / m. By having such magnetic characteristics, it is possible to obtain good developability in which the magnetic toner has a balance between image density and fog.

In the present invention, the magnetic material preferably has a number average particle diameter based on a measurement method described later of from 0.10 μm to 0.30 μm. More preferably, it is 0.15 μm or more and 0.25 μm or less. By satisfying the above range, the dispersibility of the magnetic substance in the binder resin (a), the uniformity of toner charging, the coloring power of the toner, and the color tone are improved. Further, the magnetic material used in the present invention preferably has a number-based variation coefficient of particle size of 50% or less. By adjusting the coefficient of variation to the above range, it is possible to improve the dispersibility of the magnetic material and obtain a toner with excellent color.

The magnetic material is preferably contained in an amount of 30% by mass to 120% by mass with respect to the binder resin (a) containing polyester as a main component. More preferably, it is 40 mass% or more and 110 mass% or less. When the content of the magnetic material is small, the coloring power is insufficient and the magnetization of the toner is low, so that the binding force on the toner carrier is low, and problems such as scattering and fogging are likely to occur. On the other hand, when the content of the magnetic substance is large, it is difficult to control the dispersion of the magnetic substance in the toner particles. In addition, the toner dissolution characteristics change, the fixability at low temperatures deteriorates, and problems such as low temperature offset and insufficient gloss are likely to occur.

The toner in the present invention contains a magnetic material and exhibits a black color. However, it can be used in combination with other black colorants. Moreover, it is also possible to use together with another coloring agent as color adjustment.

As other black colorants, organic pigments such as carbon black and aniline black, and metal oxides such as composite oxides having nonmagnetic black can be used in combination. Examples of carbon black include the following. Carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black.
In particular, when a reddish magnetic material is used, it is effective to add a blue or cyan colorant.

As the cyan colorant, a pigment or a dye can be used. Specific examples include the following. C. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 16, 17, 60, 62, 66; I. Bat Blue 6, C.I. I. Acid Blue 45. Examples of the dye include the following. C. I. Solvent Blue 25, 36, 60, 70, 93, 95. These may be used alone or in combination of two or more.

In the present invention, it is not preferable to use a dye or pigment having extremely high solubility in water as the colorant. When the above-mentioned dyes / pigments are used, they may dissolve in water during the production process, and granulation may be disturbed or desired coloration may not be obtained.

In the present invention, a charge control agent can be used as necessary. The charge control agent may be contained in the toner base particles (A) containing at least the binder resin (a), the magnetic substance and the wax, or may be contained in the surface layer (B).

Examples of the charge control agent include the following.
Nigrosine dyes, triphenylmethane dyes, metal-containing azo complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, simple substances of phosphorus Or a compound, a simple substance or compound of tungsten, a fluorine-based activator, a metal salt of salicylic acid, and a metal salt of a salicylic acid derivative.

Specific examples include the following.
Bontron N-03, a nigrosine dye, Bontron P-51, a quaternary ammonium salt,
Metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenolic condensate E-89 (above, manufactured by Orient Chemical Industries), No. 4 TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, quaternary ammonium salt Copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA
-901, LR-147 (made by Nippon Carlit Co., Ltd.) which is a boron complex, copper phthalocyanine, perylene, quinacridone, azo pigments, and other polymer systems having functional groups such as sulfonic acid groups, carboxyl groups and quaternary ammonium salts Compound.

Next, the surface layer (B) used in the present invention will be described.
The surface layer (B) contains the resin (b). The resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3). As the resin (b), two or more of the above resins may be used in combination.
In order to lower the melt viscosity of the surface layer (B), polyester resin (b1) and urethane resin (b3) having polyester as a constituent element are preferable. In addition, the resin (b) contains a urethane resin (b3) which is a compound formed by a urethane bond because it exhibits a moderate affinity for the solvent, water dispersibility, viscosity adjustment, and ease of particle size alignment. It is particularly preferred.
Furthermore, in this invention, it is preferable that resin (b) has at least 1 chosen from the group which consists of a carboxyl group, a sulfonic acid group, carboxylate, and a sulfonate in a side chain.

The glass transition temperature Tg (b) of the resin (b) is higher than the glass transition temperature Tg (a) of the binder resin (a). Therefore, in order to set the glass transition temperature Tg (b) of the resin (b) to a predetermined value, it is preferable to control the monomer type, molecular weight, and branched structure. Tg (b) is preferably 45 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 75 ° C. or lower. As a result, it is possible to obtain a toner that is excellent in low-temperature fixability while satisfying heat-resistant storage stability.

In the present invention, the polyester resin (b1) can be produced by the same method using the same raw materials as the binder resin (a).
However, when the same composition as that of the binder resin (a) is used, it is easy to dissolve in the solvent to be used, and it becomes difficult to maintain the toner particles during the granulation step or the shell configuration. Therefore, it is preferable to introduce a highly polar functional group such as a sulfonic acid group, a carboxyl group, or a salt thereof into the side chain with respect to the binder resin (a).

The vinyl resin (b2) is a polymer obtained by homopolymerizing or copolymerizing vinyl monomers. Examples of the vinyl monomer used include the following monomers.
(1) Vinyl hydrocarbons:
(1-1) Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene , Isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
(1-2) Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene and the like; terpenes such as pinene, limonene, Inden.
(1-3) Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutes such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethyl Styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, and the like; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and their metal salts:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-C24) ester, such as (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

(3) Sulfonic group-containing vinyl monomers, vinyl sulfate monoesters and their salts:
Alkene sulfonic acids having 2 to 14 carbon atoms such as vinyl sulfonic acid, (meth) allyl sulfonic acid, methyl vinyl sulfonic acid, styrene sulfonic acid; and alkyl derivatives having 2 to 24 carbon atoms such as α-methyl styrene sulfonic acid Sulfo (hydroxy) alkyl- (meth) acrylate or (meth) acrylamide, such as sulfopropyl (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropylsulfonic acid, 2- (meth) acryloylamino-2 , 2-dimethylethanesulfonic acid, 2- (meth) acryloyloxyethanesulfonic acid, 3- (meth) acryloyloxy-2-hydroxypropanesulfonic acid, 2- (meth) acrylamido-2-methylpropanesulfonic acid, 3- (Meth) acrylamide-2- Droxypropanesulfonic acid, alkyl (C3-18) allylsulfosuccinic acid, poly (n = 2-30) oxyalkylene (ethylene, propylene, butylene: single, random or block) mono (meth) acrylate sulfuric acid Esters [poly (n = 5 to 15) oxypropylene monomethacrylate sulfate, etc.], polyoxyethylene polycyclic phenyl ether sulfate, and sulfates represented by the following general formulas (1-1) to (1-3) Sulfonic acid group-containing monomers; and their salts.

（上記式（１−１）〜（１−３）中、Ｒは炭素数１〜１５のアルキル基、Ａは炭素数２〜４のアルキレン基を示し、ｎが複数の場合同一でも異なっていてもよく、異なる場合はランダムでもブロックでもよい。Ａｒはベンゼン環を示し、ｎは１〜５０の整数を示し、Ｒ’はフッ素原子で置換されていてもよい炭素数１〜１５のアルキル基を示す。）

(In the above formulas (1-1) to (1-3), R represents an alkyl group having 1 to 15 carbon atoms, A represents an alkylene group having 2 to 4 carbon atoms, and when n is plural, they may be the same or different. If different, they may be random or block, Ar represents a benzene ring, n represents an integer of 1 to 50, and R ′ represents an alkyl group having 1 to 15 carbon atoms which may be substituted with a fluorine atom. Show.)

In the present invention, the resin (b) is preferably a resin containing a urethane resin (b3). Moreover, it is preferable that this urethane resin (b3) is resin containing the reaction material of alcohol and isocyanate. Furthermore, the alcohol is preferably one having two hydroxyl groups in one molecule (diol), and the isocyanate is preferably one having two isocyanate groups in one molecule (diisocyanate). That is, the urethane resin (b3) is preferably a resin containing a reaction product of a diol component and a diisocyanate component.
In order to increase the reactivity of the alcohol with the isocyanate, a primary alcohol is more preferable. An alcohol having three or more hydroxyl groups in one molecule and an isocyanate having three or more isocyanate groups in one molecule are not preferred. A cross-linking reaction is likely to occur, and viscoelasticity control may be difficult.

When preparing the urethane resin (b3) from the diol component and the diisocyanate component, when the number of moles of the diol component is represented as [OH] and the number of moles of the diisocyanate component is represented as [NCO], the ratio of [NCO] to [OH]. [NCO] / [OH] is preferably 1.0 or less. Furthermore, [NCO] / [OH] is more preferably 0.5 or more and 0.9 or less.
When [NCO] / [OH] exceeds 1.0, a cross-linking reaction between diisocyanate components may occur. In this case, the temperature Tb may be higher than 85 ° C. As a result, G ″ t (Tt + 5) / G ″ t (Tt + 25) may be smaller than 40.
On the other hand, when [NCO] / [OH] is less than 0.5, the toner particle size distribution may be broad.

The following are mentioned as said diisocyanate component.
Carbon number (excluding carbon in NCO group, the same shall apply hereinafter) 6 to 20 aromatic diisocyanate, C2 to C18 aliphatic diisocyanate, C4 to C15 alicyclic diisocyanate, C8 to C15 aroma Group hydrocarbon diisocyanates and modified products of these diisocyanates (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, uretdione groups, uretoimine groups, isocyanurate groups, oxazolidone group-containing modified products, etc.) Also a mixture of two or more thereof.

Examples of the aromatic diisocyanate include the following.
1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate (TDI), 2,4′-diphenylmethane diisocyanate, 4 , 4'-diphenylmethane diisocyanate (MDI).

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

Examples of the alicyclic diisocyanate include the following. Isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1, 2-dicarboxylate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate.

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

Examples of the modified diisocyanate include the following.
Modified MDI (urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, etc.), modified isocyanates such as urethane-modified TDI, and mixtures of two or more thereof (for example, modified MDI and urethane-modified TDI (isocyanate-containing prepolymer)) Together with].
Of these, preferred are aromatic diisocyanates having 6 to 15 carbon atoms, aliphatic diisocyanates having 4 to 12 carbon atoms, and alicyclic diisocyanates having 4 to 15 carbon atoms, and particularly preferred are HDI, XDI, and IPDI. is there.

In addition to the above-mentioned diisocyanate component, the resin (b) can also use a tri- or higher functional isocyanate compound as the urethane resin (b3). Examples of the trifunctional or higher functional isocyanate compound include polyallyl polyisocyanate (PAPI), 4,4 ′, 4 ″ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, and p-isocyanatophenylsulfonyl isocyanate. Is mentioned.

Moreover, the following are mentioned as a diol component which can be used for the said urethane resin (b3).
Alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, etc.);
Alkylene ether glycols (diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.);
Alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S);
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol;
Alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adducts of the above bisphenols;
In addition, polylactone diol (such as poly ε-caprolactone diol), polybutadiene diol.
The alkyl part of the above-described alkylene ether glycol may be linear or branched. In the present invention, alkylene glycol having a branched structure can also be preferably used.

Among these, an alkyl structure is preferable in view of solubility (affinity) in ethyl acetate, and an alkylene glycol having 2 to 12 carbon atoms is preferably used.

In the urethane resin, in addition to the diol component described above, a polyester oligomer having a terminal hydroxyl group (terminal diol polyester oligomer) can also be used as a suitable diol component.

At this time, the molecular weight (number average molecular weight) of the terminal diol polyester oligomer is preferably 3000 or less, more preferably 800 or more and 2000 or less.

When the molecular weight of the terminal diol polyester oligomer is larger than the above, the reactivity with the isocyanate-terminated compound tends to decrease.

Further, the content of the terminal diol polyester oligomer described above is preferably 1 mol% or more and 10 mol% or less, more preferably 3 mol% or more and 6 mol%, in the monomer constituting the reaction product of the diol component and the diisocyanate component. It is as follows.

When the terminal diol polyester oligomer is contained in an amount exceeding 10 mol%, the reaction product of the diol component and the diisocyanate component may be soluble in ethyl acetate.

On the other hand, if the amount of terminal diol polyester oligomer is less than 1 mol%, the reaction product of the diol component and the diisocyanate component becomes too hard to inhibit fixing or the affinity with the binder resin (a) is lowered. As a result, it may be difficult to form the surface layer.

The polyester skeleton of the terminal diol polyester oligomer and the polyester skeleton of the binder resin (a) are preferably the same in order to form capsule-type toner particles. This relates to the affinity between the reaction product of the diol component and the diisocyanate component of the surface layer (B) and the binder resin (a).

Moreover, the terminal diol polyester oligomer mentioned above may have an ether bond modified with ethylene oxide, propylene oxide or the like.

In the urethane resin (b3), the reaction product of at least the diisocyanate component and the diol component described above is at least one selected from the group consisting of a carboxyl group, a sulfonic acid group, a carboxylate, and a sulfonate. It is preferable to have in the chain. These can be easily produced by introducing a carboxyl group, a sulfonic acid group, a carboxylate or a sulfonate into the side chain of the diol component or diisocyanate component.

For example, diol components having a carboxyl group or carboxylate introduced in the side chain include dimethylolacetic acid, dimethylolpropionic acid (DMPA), dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolpentanoic acid, and the like. And metal salts thereof.

A monomer having a sulfonic acid group or a sulfonate introduced in the side chain can easily form an aqueous dispersion, and is effective for stably forming a capsule structure without dissolving in an oil phase solvent. Examples of the diol compound in which a sulfonic acid group or a sulfonate is introduced into the side chain include 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid, sulfoisophthalic acid, N, N-bis (2-hydroxy). And ethyl) -2-aminoethanesulfonic acid and metal salts thereof.

In the present invention, it is more preferable to use a carboxyl group-containing diol component and a sulfonic acid group-containing diol component in combination. The reason for this is not clear, but according to the study by the inventors, in order to maintain dispersibility in water, insolubility in ethyl acetate, and proper affinity of the toner base particles (A) to the polyester resin, The combined use resulted in favorable results.
In the carboxyl group-containing diol component and the sulfonic acid group-containing diol component, it is preferable to mainly use the carboxyl group-containing diol component.
The carboxyl group-containing diol component and / or the sulfonic acid group-containing diol component is 10 mol% or more and 50 mol% or less, more preferably 20 mol%, based on all monomers forming a reaction product of the diol component and the diisocyanate component. More than 40 mol% is preferable.
When the diol component is less than 10 mol%, the dispersibility of resin fine particles, which will be described later, tends to deteriorate, and the granulation property may be impaired. On the other hand, when it is more than 50 mol%, the reaction product of the diol component and the diisocyanate component may be dissolved in the aqueous medium, and the function as a dispersant may not be achieved.
In addition, the presence of a polar group called a carboxyl group in the side chain of the reaction product of the diol component and the diisocyanate component also has the effect of lowering the solubility in ethyl acetate. When the carboxyl group-containing diol component is less than the above, it may be dissolved in ethyl acetate depending on the molecular weight and composition of the reaction product of the diol component and the diisocyanate component.

The surface layer (B) is preferably formed using resin fine particles containing the resin (b).
The method for preparing the resin fine particles is not particularly limited, and is an emulsion polymerization method or a method in which the resin is dissolved or melted in a solvent to be liquefied and granulated by suspending it in an aqueous medium. Can be used.

For the preparation of the resin fine particles, a known surfactant or dispersant can be used, or the resin constituting the resin fine particles can be made self-emulsifying.

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

Moreover, when preparing the said resin fine particle, the manufacturing method using the resin fine particle containing the reaction material of a diol component and a diisocyanate component as a dispersing agent is one of the preferable forms. In this production method, a prepolymer having a diisocyanate component is produced, which is rapidly dispersed in water, followed by the addition of a diol component, thereby extending or crosslinking the chain.

That is, a prepolymer having a diisocyanate component and other necessary components as necessary are dissolved or dispersed in a solvent having high solubility in water such as acetone or alcohol among the above solvents. By throwing this into water, the prepolymer having a diisocyanate component is rapidly dispersed. And it is the method of adding the said diol component continuously and preparing the reaction material of the diol component and diisocyanate component with a desired physical property.

The resin fine particles preferably have a number average particle size of 30 nm or more and 100 nm or less in order for the toner particles to form a capsule structure.

That is, when the number average particle diameter is smaller than 30 nm, the granulation stability and the like tend to be reduced as in the case where the coating amount of the resin fine particles is small. As a result, formation of the capsule structure becomes difficult, and the heat resistant storage stability tends to deteriorate.

On the other hand, when the number average particle diameter is larger than 100 nm, the dispersibility in the aqueous phase is lowered, as in the case where the coating amount of the resin fine particles is large, and the particles are coalesced or irregularly shaped. It tends to produce particles.

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

In the method for preparing the oil phase, the following can be exemplified as the organic medium for dissolving the binder resin (a) and the like.
Hydrocarbon solvents such as ethyl acetate, xylene and hexane, halogenated hydrocarbon solvents such as methylene chloride, chloroform and dichloroethane, ester solvents such as methyl acetate, ethyl acetate, butyl acetate and isopropyl acetate, ethers such as diethyl ether Ketone solvents such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexane.

The binder resin (a) is preferably used in the form of a resin dispersion dissolved in the organic medium. In this case, although it differs depending on the viscosity and solubility of the resin, the binder resin (a) is blended in the range of 40% by mass to 60% by mass as a resin component in the organic solvent in consideration of ease of production in the next step. It is preferable to do. In addition, heating at the melting point or lower of the organic medium at the time of dissolution is preferable because the solubility of the resin increases.

The wax and magnetic material are also preferably dispersed in the organic medium. That is, it is preferable to disperse the wax and magnetic material, which have been wet or dry mechanically ground in advance, in an organic medium to prepare a wax dispersion and a magnetic material dispersion, respectively.

The dispersibility of the wax and the magnetic material can also be improved by adding a dispersant and a resin that match each of them. Since these differ depending on the wax, magnetic substance, resin, and organic solvent used, they can be selected and used as appropriate. In particular, the magnetic material is preferably used after being previously dispersed in an organic medium together with the binder resin (a).

The oil phase can be prepared by blending a desired amount of the resin dispersion, wax dispersion, magnetic dispersion, and organic medium, and dispersing each of the components in the organic medium.

Hereinafter, the method for preparing the magnetic dispersion liquid will be further described with examples.
In the present invention, the following method was used in order to increase the dispersibility of the magnetic material beyond normal.
(1) Wet dispersion (media dispersion)
In this method, a magnetic material is dispersed in a solvent in the presence of a dispersing medium. For example, a magnetic material, resin, other additives and the organic solvent are mixed, and the mixture is dispersed using a disperser in the presence of a dispersion medium. The used dispersion medium is collected to obtain a magnetic dispersion. As the dispersing machine, for example, an attritor (Mitsui Miike Koki Co., Ltd.) is used. Examples of the dispersing medium include alumina, zirconia, glass and iron beads, but zirconia beads with very little media contamination are preferred. In this case, the bead diameter is preferably 2 mm to 5 mm because of excellent dispersibility.
(2) Dry kneaded resin, magnetic material, and other additives are melt kneaded with a kneader or roll type disperser (dry type), and the melt kneaded product of the obtained resin and magnetic material is pulverized and dissolved in the organic solvent. By doing so, a magnetic dispersion liquid is obtained.

Furthermore, the following method is effective for increasing the dispersibility of the magnetic material.
(3) Wet dispersion of dry melt-kneaded product A magnetic dispersion prepared by using a melt-kneaded product of resin and magnetic material obtained by the above dry process is further wet-dispersed using the above-mentioned dispersion media and disperser. .
(4) Solvent addition at the time of preparing the dry melt-kneaded product A solvent is added at the time of preparing the dry melt-kneaded product. The temperature during melt kneading is preferably not less than the glass transition temperature (Tg) of the resin and not more than the boiling point of the solvent. The solvent to be used is preferably a solvent capable of dissolving the resin, and a solvent used in the oil phase is preferable.
(5) Addition of wax during preparation of dry melt-kneaded product A wax is added during preparation of the dry melt-kneaded product. The temperature during melt kneading is preferably not less than the glass transition temperature (Tg) of the resin and not more than the boiling point of the solvent. As the wax to be used, a wax that dissolves in the oil phase may be used, but other relatively high melting point wax may be used.
(6) A resin having high affinity with the magnetic material is used as the resin.
A resin having a high affinity with the magnetic material is used as the resin used for the production of the dry melt kneaded product. For example, at least two types of resins (a1) and (a2) having different softening points are used for the binder resin (a) containing polyester as a main component, and the magnetic material is dispersed in one resin (a2).
Here, it is preferable that a resin synthesized from at least an aliphatic diol is used for the resin (a1), and a crystalline polyester or a resin synthesized from at least an aromatic diol is used for the resin (a2). One.

Furthermore, after mixing each dispersion liquid, a fine dispersion process using ultrasonic waves is effective. In this case, the aggregates of the magnetic substance in the dispersion after the oil phase preparation is loosened and further fine dispersion is possible.

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

In the present invention, it is preferable to use the resin fine particles containing the resin (b) dispersed in an aqueous medium. The resin fine particles containing the resin (b) are used in a desired amount according to the stability of the oil phase in the next step and the encapsulation of the toner base particles. In the present invention, when resin fine particles are used for forming the surface layer (B), the amount of the resin fine particles used is 1.0% by mass or more and 15.0% by mass or less based on the toner base particles (A). It is preferable that

In the aqueous medium, a known surfactant, dispersant, dispersion stabilizer, water-soluble polymer, or viscosity modifier may be added.

Examples of the surfactant include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. These can be arbitrarily selected according to the polarity at the time of toner particle formation.

Specifically, anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates, phosphate esters; alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and alkyltrimethyl Ammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, pyridinium salt, alkylisoquinolinium salt, quaternary ammonium salt type cationic surfactants such as benzethonium chloride; fatty acid amide derivatives, polyhydric alcohol derivatives, etc. Nonionic surfactants; amphoteric surfactants such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl-N, N-dimethylammonium betaine.

The following are mentioned as said dispersing agent.
Acids such as acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride;
Β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-acrylate Hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide, etc. (Meth) acrylic monomers containing the hydroxyl groups of
Ethers with vinyl alcohol or vinyl alcohol such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether;
Esters of vinyl alcohol and compounds containing a carboxyl group, such as vinyl acetate, vinyl propionate and vinyl butyrate;
Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; Homopolymer or copolymer;
Polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl Polyoxyethylenes such as phenyl ester, polyoxyethylene nonylphenyl ester;
Celluloses such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose.

When a dispersant is used, the dispersant can remain on the surface of the toner particles. However, it is preferable to dissolve and remove it from the charged surface of the toner.

In the present invention, a solid dispersion stabilizer may be used to maintain a more preferable dispersion state.
In the present invention, it is preferable to use a dispersion stabilizer. The reason is as follows. The organic medium in which the binder resin (a) that is the main component of the toner is dissolved has a high viscosity. Therefore, the dispersion stabilizer surrounds the oil droplets formed by finely dispersing the organic medium with high shearing force, preventing the oil droplets from reaggregating and stabilizing.

As the above dispersion stabilizer, inorganic dispersion stabilizers and organic dispersion stabilizers can be used. In the case of inorganic dispersion stabilizers, toner particles are granulated in a state of adhering to the particle surface after dispersion. Those that can be removed by non-acidic acids such as hydrochloric acid are preferred. For example, calcium carbonate, calcium chloride, sodium hydrocarbon, potassium hydrocarbon, sodium hydroxide, potassium hydroxide, hydroxyapatite, and calcium triphosphate can be used.

The dispersion method used when preparing the toner particles is not particularly limited, and general-purpose devices such as a low-speed shearing method, a high-speed shearing method, a friction method, a high-pressure jet method, and an ultrasonic wave can be used. In order to achieve the degree, a high-speed shearing type is preferable.

If it is a stirrer which has a rotary blade, there will be no restriction | limiting in particular, If it is a general thing as an emulsifier and a disperser, it can be used for the said dispersion | distribution method.
For example, the following are mentioned. Ultra Thalax (manufactured by IKA), Polytron (manufactured by Kinematica), TK auto homomixer (manufactured by Special Mechanized Industry Co., Ltd.), Ebara Milder (manufactured by Ebara Corporation), TK homomic line flow (special Kika Kogyo Co., Ltd.), colloid mill (Shinko Pantech Co., Ltd.), slasher, trigonal wet milling machine (Mitsui Miike Kako Co., Ltd.), Cavitron (Eurotech Co., Ltd.), Fine Flow Mill (Pacific Ocean) Continuous type emulsifiers such as Kiko (manufactured by Kiko Co., Ltd.), batch-type emulsifiers such as Claremix (made by M Technique Co., Ltd.) and Fillmix (made by Tokushu Kika Kogyo Co., Ltd.).

When a high-speed shearing disperser is used for the dispersion method, the rotation speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 3000 to 20000 rpm.

In the case of a batch method, the dispersion time in the dispersion method is usually 0.1 to 5 minutes. The temperature during dispersion is usually 10 to 150 ° C. (under pressure), preferably 10 to 100 ° C.

In order to remove the organic solvent from the obtained dispersion, it is possible to gradually elevate the temperature of the entire system and completely evaporate and remove the organic solvent in the droplets.

Alternatively, the dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner particles, and at the same time, the water in the dispersion can be removed by evaporation.

In that case, as the dry atmosphere in which the dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, etc., especially various air currents heated to a temperature higher than the boiling point of the highest boiling solvent used is generally used. It is done. Even in a short time using a spray dryer, belt dryer or rotary kiln, the desired quality can be obtained sufficiently.

When the dispersion obtained by the above dispersion method has a wide particle size distribution, and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.

The dispersant used in the dispersion method is preferably removed from the obtained dispersion as much as possible, but more preferably it is performed simultaneously with the classification operation.

In the production method, it is also possible to provide a heating step after removing the organic solvent. By providing the heating step, the toner particle surface can be smoothed or the sphericity of the toner particle surface can be adjusted.

In the classification operation, the fine particles can be removed in the liquid by a cyclone, a decanter, a centrifugal separator or the like. Of course, the classification operation may be performed after obtaining the powder after drying, but it is preferable in the liquid to perform the classification operation.

Unnecessary fine particles or coarse particles obtained by the classification operation can be returned to the dissolving step and used for forming particles. At that time, fine particles or coarse particles may be wet.

In the toner of the present invention, inorganic fine particles can be used as an external additive for assisting the fluidity, developability and chargeability of the toner.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm, and more preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method of an inorganic fine particle is 20-500 m < ² > / g.

The use ratio of the inorganic fine particles is preferably 0.01 parts by mass to 5 parts by mass, and more preferably 0.01 parts by mass to 2.0 parts by mass with respect to 100 parts by mass of the toner particles.

The inorganic fine particles may be used alone or in combination of a plurality of types.

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

The inorganic fine particles are preferably increased in hydrophobicity by using a surface treatment agent in order to prevent deterioration of toner flow characteristics and charging characteristics even under high humidity.

The following are mentioned as a preferable surface treating agent.
Silane coupling agent, silylating agent, silane coupling agent having a fluoroalkyl group, organic titanate coupling agent, aluminum coupling agent, silicone oil, modified silicone oil.

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

In the present invention, the weight average particle diameter (D4) of the toner is preferably 4.0 μm or more and 9.0 μm or less, and more preferably 4.5 μm or more and 7.0 μm or less.
When the weight average particle diameter of the toner is within the above range, the occurrence of toner charge-up can be satisfactorily suppressed even after a long period of use, and the decrease in image density can be suppressed. In addition, even when a line image or the like is output, occurrence of scattering and dropout can be satisfactorily suppressed.
Further, the weight average particle diameter (D4) of the toner can be adjusted to the above range by controlling the addition amount of the resin (b) and the blending amount of the oil phase and the dispersion liquid.

The average circularity of the toner of the present invention is preferably 0.960 or more and 1.000 or less. When the average circularity of the toner is less than 0.960, the transfer efficiency tends to be lowered. More preferably, the average circularity of the toner is 0.965 or more and 0.990 or less. The average circularity can be achieved, for example, by preparing a toner using a dissolution suspension method, or by spheroidizing the slurry in the process.

A method for measuring various physical properties of the toner of the present invention will be described below.
<Measuring method of glass transition temperature (Tg) of resin>
The glass transition temperature (Tg) of the resin was measured in accordance with ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
For the temperature correction of the device detection unit, the melting points of indium and zinc were used, and for the correction of the heat amount, the heat of fusion of indium was used.
Specifically, about 2 mg of a sample is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference, held at 20 ° C. for 1 minute, and the rate of temperature increase from 20 ° C. to 180 ° C. Measurement was performed at 10 ° C./min. Subsequently, it hold | maintained at 180 degreeC for 10 minute (s), and cooled to 10 degreeC at 10 degreeC / min. Furthermore, the measurement was performed from 10 ° C. to 180 ° C. at a temperature rising rate of 10 ° C./min. In the second temperature raising process, a specific heat change was obtained in the temperature range of 30 ° C to 100 ° C. At this time, the point of intersection between the line of the midpoint of the baseline before and after the change in specific heat and the differential heat curve was defined as the glass transition temperature (Tg) of the sample.

<Measurement method of softening point (Tm) of resin>
The softening point (Tm) of the resin was measured under the following conditions using an elevated flow tester CFT500C (manufactured by Shimadzu Corporation), which is a constant load extrusion type capillary rheometer, according to the operation manual of the device. The flow tester curve based on the obtained data was in a state as shown in FIGS. 2A and 2B, and each temperature was read therefrom. The melting temperature in the 1/2 method in FIG. 2 (b) was taken as the softening point (Tm). Ts is a softening temperature and Tfb is an outflow start temperature.
(Measurement condition)
Load: 10 kgf / cm ² (9.807 × 10 ⁵ Pa) Temperature increase rate: 4.0 ° C./min
Die diameter: 1.0mm
Die length: 1.0mm

<Measurement method of molecular weight distribution and molecular weight of resin>
The molecular weight distribution, weight average molecular weight, number average molecular weight, and peak molecular weight measured by gel permeation chromatography (GPC) of the resin in tetrahydrofuran (THF) were measured as follows.
First, a sample is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is prepared so that the concentration of components soluble in THF is about 0.8% by mass. Using this sample solution, measurement was performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Shodex KF-801, 802, 803, 804, 805,
7 series of 806, 807 (made by Showa Denko)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) were used.

<Method for measuring acid value of resin>
The acid value is the number of mg of potassium hydroxide necessary to neutralize the acid contained in 1 g of the sample. The acid value of the resin is measured according to JIS K 0070-1966, and specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchange water is added to make 100 ml to obtain a “phenolphthalein solution”.
Dissolve 7 g of special grade potassium hydroxide in 5 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. Place in an alkali-resistant container so as not to touch carbon dioxide gas, leave it for 3 days, and filter to obtain a “potassium hydroxide solution”. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The orientation is performed according to JIS K 0070-1996.
(2) Operation (A) 2.0 g of the pulverized sample in this test is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titrated with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Titration similar to the above operation is performed except that no blank test sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(BC) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

<Measurement method of magnetization>
The strength of magnetization of the magnetic material and the toner was determined from the magnetic properties and the mass. The magnetic properties of the magnetic material and the toner were measured using a “vibration data type magnetometer VSM-3S-15” (manufactured by Toei Industry Co., Ltd.). As a measuring method, a cylindrical plastic container is filled with a magnetic substance or toner so as to be sufficiently dense, while an external magnetic field of 1.00 kilo Oersted (79.6 kA / m) is created, and in this state, the container The magnetization moment of the magnetic material or toner filled in was measured. Next, the actual mass of the magnetic material or toner filled in the container was measured to determine the magnetization intensity (Am ² / kg) of the magnetic material or toner.
Further, the residual magnetization (σr) was obtained by drawing a hysteresis loop when the maximum applied magnetic field was set to 1.00 kilo Oersted (79.6 kA / m).

<Method for measuring BET specific surface area of magnetic substance>
The BET specific surface area of the magnetic material of the present invention was measured as follows.
The BET specific surface area was obtained by a BET multipoint method using a fully automatic gas adsorption amount measuring device (Autosoap 1) manufactured by Yuasa Ionics Co., Ltd., using nitrogen as the adsorption gas. As a sample pretreatment, deaeration was performed at 50 ° C. for 10 hours.

<Method for Measuring Particle Diameter of Wax Particles in Resin Fine Particles and Wax Dispersion>
The particle size of the resin fine particles and the wax particles in the wax dispersion is measured using a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.) with a range setting of 0.001 μm or more and less than 10 μm. The number average particle diameter was measured.

<Measurement method of solid content ratio of resin fine particles and wax>
Using a moisture meter FD240 (manufactured by Kett Science Laboratory Co., Ltd.), set the temperature to 120 ° C., and evaporating the water until no change in weight is observed for 1 minute. Was measured.

<Method for Measuring Loss Elastic Modulus (G ″) and Storage Elastic Modulus (G ′)>
Measurement was performed using a viscoelasticity measuring device (rheometer) ARES (manufactured by Rheometrics Scientific). The outline of the measurement is described in ARES operation manuals 902-30004 (August 1997 version) and 902-00153 (July 1993 version) published by Rheometrics Scientific, Inc., and is as follows.
・ Measurement jig: Use a 7.9mm diameter, serrated parallel plate ・ Measurement sample: Use a pressure molding machine to maintain 15kN for 1 minute at room temperature, a circle of about 8mm in diameter and about 2mm in height A columnar sample is prepared. As the pressure molding machine, a 100 kN press NT-100H (manufactured by NPa System) was used.
The temperature of the serrated parallel plate is adjusted to 90 ° C., the cylindrical sample is heated and melted to bite the saw blade, and a vertical load is applied so that the axial force does not exceed 30 (g weight). It was made to adhere to the parallel plate. At this time, a steel belt may be used so that the diameter of the sample is the same as the diameter of the parallel plate. The serrated parallel plate and the columnar sample were gradually cooled to a measurement start temperature of 30.00 ° C. over 1 hour.
Measurement frequency: 6.28 radians / second Measurement strain setting: Initial value set to 0.1%, measurement in automatic measurement mode Sample extension correction: adjustment in automatic measurement mode Measurement temperature: 30 Temperature rise / measurement interval from ℃ to 180 ℃ at a rate of 2 ℃ per minute: Viscoelasticity data is measured every 30 seconds, that is, every 1 ℃

RSI Orchestrator VER. Running on Microsoft Windows 2000. Data was transferred through the interface to 6.5.6 (control, data collection and analysis software) (Rheometrics Scientific).
RSI Orchestrator VER. In 6.5.6, [Peak and Valleys] was selected from [Tools], and a temperature indicating the maximum value was obtained using [AutoFind Peaks].

<Measurement Method of Toner Weight Average Particle Size (D4) and Number Average Particle Size (D1)>
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner are measured with a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman 2) Effective measurement channel number 25,000 using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) and attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” for measurement condition setting and measurement data analysis Measurement was performed on the channel, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter) can be used.
Prior to measurement and analysis, dedicated software was set up as follows.
In the “Standard measurement method (SOM) change screen” of the dedicated software, set the total count in the control mode to 50000 particles, the number of measurements is 1 and the Kd value is “standard particles 10.0 μm” (Beckman Coulter, Inc.) The value obtained using the above was set. The threshold and noise level were automatically set by pressing the threshold / noise level measurement button. Further, the current was set to 1600 μA, the gain was set to 2, the electrolyte was set to ISOTON II, and the aperture tube flash after the measurement was checked.
In the “Pulse to Particle Size Conversion Setting Screen” of the dedicated software, the bin interval was set to logarithmic particle size, the particle size bin to 256 particle size bin, and the particle size range from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution was placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod was stirred counterclockwise at 24 rotations / second. The dirt and bubbles in the aperture tube were removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 mL flat bottom beaker, and “Contaminone N” (a nonionic surfactant, an anionic surfactant, and an organic builder consisting of an organic builder is measured accurately as a dispersant. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (manufactured by Wako Pure Chemical Industries, Ltd.) with ion exchange water 3 times by mass was added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and placed in a water tank of an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water was added, and about 2 ml of the above-mentioned Contaminone N was added to this water tank.
(4) The beaker of (2) was set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser was operated. Then, the height position of the beaker was adjusted so that the resonance state of the liquid surface of the electrolytic aqueous solution in the beaker was maximized.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) was irradiated with ultrasonic waves, about 10 mg of toner was added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion treatment was further continued for 60 seconds. In the ultrasonic dispersion, the water temperature in the water tank was appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker (1) installed in the sample stand, the electrolyte aqueous solution (5) in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. . The measurement was performed until the number of measured particles reached 50,000.
(7) The measurement data was analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) were calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

<Measurement of THF-insoluble content excluding magnetic material>
The THF-insoluble content of the resin component, excluding the magnetic material in the toner, was measured as follows. About 1.0 g of toner is weighed (W1 (g)), put in a pre-weighed cylindrical filter paper (for example, trade name No. 86R (size 28 mm × 100 mm), manufactured by Advantech Toyo Co., Ltd.), and set in a Soxhlet extractor. Extraction is performed for 16 hours using 200 mL of tetrahydrofuran (THF) as a solvent. At this time, extraction was performed at a reflux rate such that the solvent extraction cycle was about once every 5 minutes.
After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40 ° C. for 8 hours. The mass of the cylindrical filter paper including the extraction residue is weighed, and the mass of the extraction residue is subtracted from the mass of the cylindrical filter paper ( W2 (g)) was calculated.
Then, the THF-insoluble content can be obtained by subtracting the content (W3 (g)) of the magnetic material as shown in the following formula (1).
THF insoluble matter (mass%) = {(W2-W3) / (W1-W3)} × 100 (1) The content of the magnetic substance can be measured by a known analysis means, If it is difficult, the THF-insoluble content can be obtained by estimating the content of the magnetic substance (incineration residual ash content (W3 ′ (g))) in the toner and subtracting the content as follows. .
The incineration residual ash content in the toner was determined by the following procedure. About 2 g of toner was weighed (Wa (g)) into a 30 ml magnetic crucible weighed in advance. Put the crucible in an electric furnace, heat at about 900 ° C for about 3 hours, let cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, and crucible Incineration residual ash content (Wb (g)) was calculated by subtracting the mass of. And the mass (W3 ′) of the incineration residual ash in the sample W1 (g) according to the following formula (2)
(G)) was calculated.
W3 ′ = W1 × (Wb / Wa) (2)
In this case, the THF-insoluble matter was determined by the following formula (3).
THF-insoluble matter (mass%) = {(W2-W3 ′) / (W1-W3 ′)} × 100 (3)

<Measurement of bulk density of magnetic material>
For the bulk density of the magnetic material, a powder tester PT-R (manufactured by Hosokawa Micron) is used.
Measurement was performed according to the operation manual of the instrument.
Using a sieve with a mesh opening of 500 μm, while vibrating with an amplitude of 1 mm, replenishing the magnetic material to just 10 ml, tapping the metallic cup up and down 180 times with an amplitude of 18 mm, and the amount of magnetic material after tapping From the above, the bulk density (g / cm ³ ) was calculated.

<Measuring method of number average particle diameter D1 of magnetic substance and coefficient of variation of particle diameter of magnetic substance>
The number average particle diameter D1 and standard deviation σ of the magnetic material were calculated by measuring particle images (arbitrarily 350 particles) taken with an electron microscope using a statistical analysis (Digitizer KD4620 manufactured by Graphtec Corporation).
Further, the coefficient of variation of the particle diameter of the magnetic material was calculated according to the following formula from the number average diameter D1 (μm) and the standard deviation σ (μm). The smaller the value of the particle size distribution, the better the particle size distribution.
(Formula) Coefficient of variation (%) of particle size of magnetic material = (σ / D1) × 100

<Measurement method of toner charge amount>
A method for measuring the triboelectric charge amount of the toner will be described below.
First, a predetermined carrier (spherical carrier N-01, which is a standard carrier of the Japan Imaging Society, ferrite core surface-treated) and toner are put in a plastic bottle with a lid, and a shaker (YS-L
D, manufactured by Yayoi Co., Ltd.), and shaken for 1 minute at a speed of 4 reciprocations per second to charge the developer composed of toner and carrier. Next, the triboelectric charge amount is measured in the apparatus for measuring the triboelectric charge amount shown in FIG. In FIG. 4, about 0.5 to 1.5 g of the developer described above is placed in a metal measuring container 2 having a 500 mesh screen 3 at the bottom, and a metal lid 4 is formed. The total mass of the measurement container 2 at this time is weighed and is defined as W1 (g). Next, in the suction machine 1 (at least the part in contact with the measurement container 2) is sucked from the suction port 7 and the air volume control valve 6 is adjusted so that the pressure of the vacuum gauge 5 is 250 mmAq. In this state, suction is performed for 2 minutes to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor, and the capacity is C (mF). Moreover, the mass of the whole measurement container after suction is weighed and is defined as W2 (g). The triboelectric charge amount (mC / kg) of this sample is calculated as follows.
(Expression) Frictional charge of sample (mC / kg) = C × V / (W1−W2)

<Measuring method of average circularity of toner>
The average circularity of the toner was measured using a flow particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during calibration work.
As a specific measurement method, an appropriate amount of a surfactant as a dispersant, preferably sodium dodecylbenzenesulfonate, is added to 20 ml of ion-exchanged water, 0.02 g of a measurement sample is added, an oscillation frequency of 50 kHz, electrical output Dispersion treatment was performed for 2 minutes using a 150 W tabletop type ultrasonic cleaner / disperser (for example, “VS-150” (manufactured by Vervo Creer)) to obtain a dispersion for measurement. In that case, it cooled suitably so that the temperature of a dispersion liquid might be 10 degreeC or more and 40 degrees C or less.
The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, 3000 toner particles are measured in the total count mode in the HPF measurement mode, and the binarization threshold at the time of particle analysis is 85%. The analysis particle diameter was limited to a circle equivalent diameter of 2.00 μm or more and 200.00 μm or less, and the average circularity of the toner particles was determined.
In the measurement, before starting the measurement, standard latex particles (for example, Duke Scientific)
automatic focusing is performed using “5100A” manufactured by ific Co., Ltd.). Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In this embodiment, a flow type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, has an analysis particle diameter of 2.00 μm. The measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that it was limited to 200.00 μm or less.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not restrict | limited at all to this. In addition, the number of parts in the following composition is part by mass unless otherwise specified.
First, a method for preparing a toner material will be described. Next, a toner preparation method will be described.

<Preparation of resin (a1) -1>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-Propylene glycol 800 parts by mass-Terephthalic acid dimethyl ester 760 parts by mass-Adipic acid 300 parts by mass-Tetrabutoxy titanate (condensation catalyst) 3 parts by mass Reacting for 8 hours while distilling off the generated methanol at 180 ° C It was. Then, while gradually raising the temperature to 230 ° C., the mixture is reacted for 4 hours while distilling off generated water and the like, and further reacted under a reduced pressure of 20 mmHg. When the softening point reaches 90 ° C. I took it out. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a resin (a1) -1, which is a linear polyester resin using an aliphatic diol. The physical properties are shown in Table 1.

<Preparation of resin (a1) -2>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-1,4-pentanediol 1200 parts by weight-terephthalic acid dimethyl ester 950 parts by weight-adipic acid 250 parts by weight-tetrabutoxy titanate (condensation catalyst) 3 parts by weight In the same manner as the preparation of resin (a1) -1, aliphatic Resin (a1) -2 which was a linear polyester resin was obtained. The physical properties are shown in Table 1.

・テレフタル酸ジメチルエステル ３５０質量部
・アジピン酸 １８０質量部
・テトラブトキシチタネート（縮合触媒） ３質量部
樹脂（ａ１）−１の調製と同様にして、芳香族線形ポリエステル樹脂である樹脂（ａ１）−３を得た。物性を表１に示す。 <Preparation of resin (a1) -3>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
A bisphenol derivative represented by the following formula (A) (R: ethylene group x + y = 2)
1600 parts by mass

-350 parts by weight of dimethyl terephthalate-180 parts by weight of adipic acid-3 parts by weight of tetrabutoxy titanate (condensation catalyst) Resin (a1)-which is an aromatic linear polyester resin in the same manner as the preparation of resin (a1) -1 3 was obtained. The physical properties are shown in Table 1.

<Preparation of resin (a1) -4>
Resin (a1), which is an aromatic linear polyester resin, was prepared in the same manner as in the preparation of Resin (a1) -3 except that tetrabutoxytitanate (condensation catalyst) was changed to 2 parts by mass and the temperature was raised to 210 ° C. ) -4 was obtained. The physical properties are shown in Table 1.

<Preparation of resin (a1) -5>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-Bisphenol derivative represented by the above formula (A) (R: ethylene group x + y = 2)
1300 parts by mass, dimethyl terephthalate 500 parts by mass, 250 parts by mass of adipic acid, tetrabutoxy titanate (condensation catalyst) 3 parts by mass Resin which is an aromatic linear polyester resin (a1) -1 a1) -5 was obtained. The physical properties are shown in Table 1.

<Preparation of resin (a1) -6>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-320 parts by mass of styrene-146 parts by mass of n-butyl acrylate-11 parts by mass of methacrylic acid Further, 8 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added as a polymerization initiator, and at 60 ° C Polymerization was performed for 8 hours, and the temperature was raised to 150 ° C. and taken out from the reaction vessel. After cooling to room temperature, the mixture was pulverized and granulated to obtain a linear vinyl resin (a1) -6. The physical properties are shown in Table 1.

<Preparation of resin (a2) -1>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
Propylene glycol 800 parts by mass Terephthalic acid dimethyl ester 815 parts by mass Adipic acid 263 parts by mass Tetrabutoxy titanate (condensation catalyst) 3 parts by mass Reacting for 8 hours while distilling off the generated methanol at 180 ° C It was. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off generated water and the like in a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 180 ° C., 173 parts by mass of trimellitic anhydride was added, reacted for 2 hours under sealed at normal pressure, reacted at 220 ° C. normal pressure, and taken out when the softening point reached 180 ° C. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a resin (a2) -1 which is a nonlinear polyester resin. The physical properties are shown in Table 1.

<Preparation of resin (a2) -2>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-928 parts by mass of 1,4-butanediol-776 parts by mass of dimethyl terephthalate-292 parts by mass of adipic acid-3 parts by mass of tetrabutoxy titanate (condensation catalyst) The reaction was allowed for 8 hours. Next, while gradually raising the temperature to 230 ° C., the reaction was performed for 4 hours while distilling off generated water and the like in a nitrogen stream, and the reaction was further performed for 1 hour under a reduced pressure of 20 mmHg. Next, the mixture was cooled to 180 ° C., 115 parts by mass of trimellitic anhydride was added, reacted for 2 hours under sealed at normal pressure, reacted at 220 ° C. normal pressure, and taken out when the softening point reached 180 ° C. The taken-out resin was cooled to room temperature and then pulverized and granulated to obtain a resin (a2) -2 which is a nonlinear polyester resin. The physical properties are shown in Table 1.

<Preparation of resin (a2) -3>
(Production Example 1 of aromatic carboxylic acid titanium compound)
After dissolving 19.6 parts by mass of terephthalic acid in 100 parts by mass of pyridine, 80.4 parts by mass of tetra-n-butoxytitanium was added dropwise to this solution, and the mixture was maintained at 40 ° C. for 2 hours in a nitrogen atmosphere. n-Butoxytitanium and terephthalic acid were reacted. Thereafter, pyridine and butanol as a reaction product were distilled by distillation under reduced pressure to obtain an aromatic carboxylate titanium compound 1.

これらに、触媒として上記芳香族カルボン酸チタン化合物１を４質量部添加し、２３０℃で１０時間縮合重合した。ここで、無水トリメリット酸３０質量部、シュウ酸チタニルカリウム２質量部を追加触媒として添加し、さらに縮合重合を進め、架橋芳香族ポリエステル樹脂である樹脂（ａ２）−３を得た。 -Bisphenol derivative represented by the following formula (A) (R: ethylene group x + y = 2)
200 parts by mass-bisphenol derivative represented by the following formula (A) (R: propylene group x + y = 3)
200 parts by mass / 180 parts by mass of terephthalic acid

4 parts by mass of the above aromatic carboxylic acid titanium compound 1 was added thereto as a catalyst, and condensation polymerization was performed at 230 ° C. for 10 hours. Here, 30 parts by mass of trimellitic anhydride and 2 parts by mass of potassium titanyl oxalate were added as an additional catalyst, and the condensation polymerization was further performed to obtain a resin (a2) -3 which is a crosslinked aromatic polyester resin.

<Preparation of resin (a2) -4>
The following was put into a reaction vessel equipped with a cooling tube, a nitrogen introducing tube and a stirrer.
-Styrene 320 parts by mass-n-butyl acrylate 146 parts by mass-Methacrylic acid 11 parts by mass-Divinylbenzene 5.5 parts by mass Further, 2,2'-azobis (2,4-dimethylvaleronitrile) 8 parts by mass as a polymerization initiator The polymerization was carried out at 60 ° C. for 8 hours, and the temperature was raised to 150 ° C. and taken out from the reaction vessel. After cooling to room temperature, it was pulverized and granulated to obtain a linear vinyl resin (a2) -4. The physical properties are shown in Table 1.

The resins (a1) -1 to -6 and resins (a2) -1 to -4 were mixed at the ratios shown in Table 2 to obtain binder resins (a) -1 to binder resins (a) -18. .

<Preparation of dispersion of resin fine particles 1>
An autoclave equipped with a thermometer and a stirrer was charged with the following and heated at 190 ° C. for 120 minutes to conduct a transesterification reaction.
-116 parts by weight of dimethyl terephthalate-66 parts by weight of dimethyl isophthalate-30 parts by weight of 5-sodium sulfoisophthalate methyl ester-5 parts by weight of trimellitic anhydride-150 parts by weight of propylene glycol-0.1 part by weight of tetrabutoxy titanate The temperature of the system was raised to 220 ° C., and the reaction was continued at a system pressure of 10 mmHg for 50 minutes to obtain a raw material resin 1.
40 parts by weight of the raw material resin 1, 15 parts by weight of methyl ethyl ketone, and 10 parts by weight of tetrahydrofuran were dissolved at 80 ° C., and then 60 parts by weight of 80 ° C. water was added with stirring to obtain an aqueous dispersion of the polyester resin. Obtained. Dilution with ion-exchanged water was performed so that the solid content ratio was 13%, whereby a dispersion of resin fine particles 1 was obtained. Table 3 shows the physical properties.

<Preparation of dispersion of resin fine particles 2>
An autoclave equipped with a thermometer and a stirrer was charged with the following and heated at 190 ° C. for 120 minutes to conduct a transesterification reaction.
-116 parts by weight of dimethyl terephthalate-66 parts by weight of dimethyl isophthalate-30 parts by weight of 5-sodium sulfoisophthalate methyl ester-12 parts by weight of trimellitic anhydride-Polyoxypropylene (2.2) -2,2-bis (4 -Hydroxyphenyl) propane

190 parts by weight / tetrabutoxy titanate 0.1 parts by weight Next, the reaction system was heated to 220 ° C., and the reaction was continued at a system pressure of 10 mmHg for 50 minutes to obtain a raw resin 2.
40 parts by weight of the raw material resin 2, 15 parts by weight of methyl ethyl ketone, and 10 parts by weight of tetrahydrofuran were dissolved at 80 ° C., and then 60 parts by weight of 80 ° C. water was added with stirring to obtain an aqueous dispersion of the polyester resin. Obtained. Dilution with ion-exchanged water was performed so that the solid content ratio was 13%, whereby a dispersion of resin fine particles 2 was obtained. Table 3 shows the physical properties.

<Preparation of dispersion of resin fine particles 3>
-Ion-exchanged water 100 parts by mass-Sodium salt of methacrylic acid ethylene oxide adduct sulfate (Eleminol RS-30, manufactured by Sanyo Chemical Industries) 20 parts by mass While stirring with
-120 parts by mass of styrene-30 parts by mass of sodium styrenesulfonate-3 parts by mass of 1 mol / l sodium hydroxide aqueous solution-10 parts by mass of butyl acrylate A mixture of the above monomers was added dropwise over 1 hour. Further, 400 parts by mass of ion exchange water and 100 g of 2% potassium persulfate aqueous solution were added, and the temperature in the container was raised to 90 ° C. and kept warm for 30 minutes. Next, 540 g of 2% potassium persulfate aqueous solution was filled in the dropping device connected to the reaction vessel, and the reaction vessel was stirred at 100 rpm with stirring blades, and the 2% potassium persulfate aqueous solution was taken over 5 hours. The solution was added dropwise to carry out emulsion polymerization. Stirring was continued for another 30 minutes after completion of the dropping, and then the mixture was cooled to room temperature and diluted with ion-exchanged water so that the solid content ratio was 13%, whereby a dispersion of resin fine particles 3 was obtained. Table 3 shows the physical properties.

<Preparation of dispersion of resin fine particles 4>
265 parts by mass of a polyester resin having a weight average molecular weight of about 1000, obtained by polycondensation of 1,3-propanediol and adipic acid, 100 parts by mass of 1,9-nonanediol, 170 parts by mass of dimethylolpropanoic acid (2,3-dihydroxypropoxy) -1-propanesulfonic acid
10 parts by mass The above material was dissolved in 500 parts by mass of acetone, and then 440 parts by mass of isophorone diisocyanate was added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 130 parts by mass of triethylamine was added to the reaction product and stirred. The acetone solution was added dropwise to 1300 parts by mass of ion-exchanged water with stirring and emulsified. Subsequently, it diluted with ion-exchange water so that solid content ratio might be 13%, and the dispersion liquid of the resin fine particle 4 was obtained. Table 3 shows the physical properties.

<Preparation of dispersion of resin fine particles 5>
Polyester resin having a weight average molecular weight of about 1000, obtained by polycondensation of 1,3-propanediol and adipic acid, 220 parts by mass, neopentyl glycol, 70 parts by mass, dimethylolpropanoic acid, 170 parts by mass, 3- (2, 3-Dihydroxypropoxy) -1-propanesulfonic acid
25 parts by mass The above material was dissolved in 500 parts by mass of acetone, and then 410 parts by mass of isophorone diisocyanate and 120 parts by mass of hexamethylene diisocyanate were added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 130 parts by mass of triethylamine was added to the reaction product and stirred. The acetone solution was added dropwise to 1300 parts by mass of ion-exchanged water with stirring and emulsified. Subsequently, it diluted with ion-exchange water so that solid content ratio might be 13%, and the dispersion liquid of the resin fine particle 5 was obtained. Table 3 shows the physical properties.

・ジメチロールプロパン酸 １４０質量部
・３−（２，３−ジヒドロキシプロポキシ）−１−プロパンスルホン酸
１０質量部
上記材料をアセトン５００質量部に溶解し、ついで
・イソホロンジイソシアネート ４２０質量部
を添加し６０℃で４時間反応させた。上記反応物にジメチロールプロパン酸のカルボキシル基を中和するためトリエチルアミン１０５質量部を投入し攪拌した。上記アセトン溶液をイオン交換水１３００質量部に攪拌しながら滴下し、乳化させた。ついで、固形分比が１３％になるようイオン交換水で希釈し、樹脂微粒子６の分散液を得た。物性を表３に示す。 <Preparation of dispersion of resin fine particles 6>
-Bisphenol derivative represented by the following formula (A) (R: ethylene group x + y = 4) 440 parts by mass

・ 140 parts by mass of dimethylolpropanoic acid ・ 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
10 parts by mass The above material was dissolved in 500 parts by mass of acetone, and then 420 parts by mass of isophorone diisocyanate was added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 105 parts by mass of triethylamine was added to the reaction product and stirred. The acetone solution was added dropwise to 1300 parts by mass of ion-exchanged water with stirring and emulsified. Subsequently, it diluted with ion-exchange water so that solid content ratio might be 13%, and the dispersion liquid of the resin fine particle 6 was obtained. Table 3 shows the physical properties.

・ジメチロールプロパン酸 １２０質量部
・３−（２，３−ジヒドロキシプロポキシ）−１−プロパンスルホン酸
１０質量部
上記材料をアセトン５００質量部に溶解し、ついで
・イソホロンジイソシアネート ４４０質量部
を添加し６０℃で４時間反応させた。上記反応物にジメチロールプロパン酸のカルボキシル基を中和するためトリエチルアミン９１質量部を投入し攪拌した。上記アセトン溶液をイオン交換水１３００質量部に攪拌しながら滴下し、乳化させた。ついで、固形分比が１３％になるようイオン交換水で希釈し、樹脂微粒子７の分散液を得た。物性を表３に示す。 <Preparation of dispersion of resin fine particles 7>
-Bisphenol derivative represented by the following formula (A) (R: ethylene group x + y = 2) 430 parts by mass

・ 120 parts by mass of dimethylolpropanoic acid ・ 3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
10 parts by mass The above material was dissolved in 500 parts by mass of acetone, and then 440 parts by mass of isophorone diisocyanate was added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 91 parts by mass of triethylamine was added to the reaction product and stirred. The acetone solution was added dropwise to 1300 parts by mass of ion-exchanged water with stirring and emulsified. Subsequently, it diluted with ion-exchange water so that solid content ratio might be 13%, and the dispersion liquid of the resin fine particle 7 was obtained. Table 3 shows the physical properties.

・ジメチロールプロパン酸 １００質量部
・３−（２，３−ジヒドロキシプロポキシ）−１−プロパンスルホン酸
１８質量部
上記材料をアセトン５００質量部に溶解し、ついで
・イソホロンジイソシアネート ５２０質量部
を添加し６０℃で４時間反応させた。上記反応物にジメチロールプロパン酸のカルボキシル基を中和するためトリエチルアミン７６質量部を投入し攪拌した。上記アセトン溶液をイオン交換水１３００質量部に攪拌しながら滴下し、乳化させた。ついで水３２０質量部、エチレンジアミン１１質量部、ｎ−ブチルアミン６質量部を加え５０℃で４時間反応し、固形分比が１３％になるようイオン交換水で希釈し、樹脂微粒子８の分散液を得た。物性を表３に示す。 <Preparation of dispersion of resin fine particles 8>
-Bisphenol derivative represented by the following formula (A) (R: ethylene group x + y = 2) 360 parts by mass

-100 parts by mass of dimethylolpropanoic acid-3- (2,3-dihydroxypropoxy) -1-propanesulfonic acid
18 parts by mass The above material was dissolved in 500 parts by mass of acetone, and then 520 parts by mass of isophorone diisocyanate was added and reacted at 60 ° C. for 4 hours. In order to neutralize the carboxyl group of dimethylolpropanoic acid, 76 parts by mass of triethylamine was added to the reaction product and stirred. The acetone solution was added dropwise to 1300 parts by mass of ion-exchanged water with stirring and emulsified. Next, 320 parts by mass of water, 11 parts by mass of ethylenediamine, and 6 parts by mass of n-butylamine were added and reacted at 50 ° C. for 4 hours. Obtained. Table 3 shows the physical properties.

<Preparation of Wax Dispersion-1>
Carnauba wax (melting point 81 ° C.) 20 parts by mass Ethyl acetate 80 parts by mass The above was put into a glass beaker with a stirring blade, and the system was heated to 70 ° C. to dissolve carnauba wax in ethyl acetate.
Next, the system was gradually cooled while gently stirring at 50 rpm, and cooled to 25 ° C. over 3 hours to obtain a milky white liquid.
This solution was put into a heat-resistant container together with 20 parts by mass of 1 mm glass beads and dispersed for 3 hours with a paint shaker (manufactured by Toyo Seiki) to obtain wax dispersion 1 (solid content ratio 20%). When the wax particle size in the wax dispersion 1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.15 μm. The characteristics are shown in Table 4.

<Preparation of wax dispersion-2>
Stearyl stearate (melting point 67 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene / n-butyl acrylate / acrylonitrile = 65/35/10 (mass ratio), peak molecular weight 8500) 4 parts by mass Ethyl acetate 80 The above part by mass was put into a glass beaker with a stirring blade, and the inside of the system was heated to 65 ° C. to dissolve stearyl stearate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion 2 (solid content ratio 20%). When the wax particle size in the wax dispersion 1 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.12 μm. The characteristics are shown in Table 4.

<Preparation of wax dispersion-3>
Trimethylolpropane tribehenate (melting point: 58 ° C.) 16 parts by mass Nitrile group-containing styrene acrylic resin (styrene / n-butyl acrylate / acrylonitrile = 65/35/10 (mass ratio), peak molecular weight 8500) 4 parts by mass -80 parts by mass of ethyl acetate The above was put into a glass beaker with a stirring blade, and the system was heated to 60 ° C to dissolve trimethylolpropane tribehenate in ethyl acetate.
Subsequently, the same operation as wax dispersion-1 was performed to obtain wax dispersion 3 (solid content ratio 20%). When the wax particle size in the wax dispersion 3 was measured with a Microtrac particle size distribution analyzer HRA (X-100) (manufactured by Nikkiso Co., Ltd.), the number average particle size was 0.18 μm. The characteristics are shown in Table 4.

The characteristics of the following magnetic body 1 to magnetic body 3 are shown in Table 5.
<Preparation of magnetic dispersion-1>
-125 parts by mass of ethyl acetate-25 parts by mass of resin (a2) -3-100 parts by mass of magnetic material 1-200 parts by mass of glass beads (1 mm) The above substances are put into a sealed container and a paint shaker (manufactured by Toyo Seiki) Dispersion was performed for 5 hours. Next, the glass beads were removed with a nylon mesh to obtain a magnetic dispersion-1 (solid content ratio 50%).

<Preparation of magnetic dispersions-2 to 8>
Magnetic material dispersions 2 to 8 were obtained in the same manner as in the preparation of the magnetic material dispersion-1, except that the type of the magnetic material dispersion resin and the type of the magnetic material were changed as shown in Table 6. The characteristics of the magnetic bodies 1 to 3 are shown in Table 5.

<Example 1>
50 parts by mass of resin (a1) -3 and 6 parts by mass of resin (a2) -3 were dissolved in ethyl acetate and dried overnight at 40 ° C. under reduced pressure to obtain binder resin (a) -1.
<Preparation of toner particles 1>
Resin (a1) -3 50 parts by mass Resin (a2) -3 6 parts by mass Magnetic substance dispersion-1 (solid content ratio 50%) 75 parts by mass Wax dispersion-1 (solid content ratio 20%) 40 parts by mass, ethyl acetate 89 parts by mass, triethylamine 0.6 part by mass The above was put into a glass beaker and stirred at 2000 rpm for 3 minutes with a disper (manufactured by Tokushu Kika Co., Ltd.) to obtain liquid toner composition . Next, ice water was applied to the ultrasonic disperser UT-305HS (manufactured by Sharp), and ultrasonic waves were applied for 5 minutes at an output of 60% to loosen the wax and the magnetic material.
(Emulsification and solvent removal process)
・ Ion-exchanged water 157 parts by mass-Dispersion of resin fine particles 6 (solid content ratio 13%) 31 parts by mass-50% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries) 24 parts by mass Ethyl 18 parts by mass The above was put into a glass beaker and stirred at 2000 rpm for 1 minute with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) to prepare an aqueous phase 1.
The rotational speed of the TK homomixer was increased to 8000 rpm, 160 parts by mass of the liquid toner composition 1 was added, and stirring was continued for 1 minute to suspend the liquid toner composition 1.
A stirrer blade was set in a beaker, stirred at 100 rpm for 20 minutes, transferred to an eggplant-shaped flask, and rotated using a rotary evaporator, and the solvent was removed at room temperature and normal pressure for 10 hours to obtain an aqueous dispersion 1 of toner particles. .

(Washing and drying process)
The toner particle aqueous dispersion 1 was filtered and charged into 500 parts by mass of ion-exchanged water to form a reslurry. Then, the system was stirred and hydrochloric acid was added until the system reached pH 4, followed by stirring for 5 minutes. The slurry was filtered again, and the operation of adding 200 parts by mass of ion exchange water and stirring for 5 minutes was repeated 3 times to remove triethylamine remaining in the slurry, and a filter cake of toner particles was obtained. The filter cake was dried at room temperature for 3 days with a vacuum dryer, and sieved with a mesh having a mesh size of 75 μm, whereby toner particles 1 were obtained.
In the toner particles 1, Tg (a) is a glass transition temperature of a resin obtained by combining the binder resin (a) -1 and the resin (a2) -3 contained in the magnetic dispersion liquid, and is 48 ° C. Met.

(Preparation and evaluation of toner 1)
Next, with respect to 40 parts by mass of the toner particles, 0.40 parts by mass of hydrophobic silica having a number average particle diameter of 20 nm (hydrophobized with 20 parts by mass of hexamethyldisilazane per 100 parts by mass of silica fine particles) 0.60 parts by mass of monodispersed silica (silica fine particles produced by a sol-gel method) having a particle size of 120 nm was mixed and stirred with a miller IFM-600DG (manufactured by Iwatani Corp.) (10 seconds stirring, 1 minute rest as one cycle) 4 cycles were performed), and toner 1 was obtained. Toner 1 was evaluated by the method described below. The evaluation results are shown in Table 8.

<Evaluation of heat-resistant storage stability of toner>
The heat-resistant storage stability of the toner was evaluated by placing 3 g of toner in a 100 ml plastic cup, leaving it in a thermostatic bath at 50 ° C. (within ± 0.5 ° C.) for 3 days, and then touching it visually and with the finger pad.
(Evaluation criteria)
A: No change is observed, and very good heat resistant storage stability is exhibited.
B: Although fluidity | liquidity falls a little, it shows the outstanding heat-resistant storage property.
C: Aggregates are generated, but the heat-resistant storage stability is not a problem in practical use.
D: Aggregates can be pinched and do not collapse easily. Inferior to heat-resistant storage.

<Evaluation of fixing start temperature>
The fixing test of the toner was performed in a fixing device of iR4570F (made by Canon) with the fixing unit modified so that the fixing temperature and paper feeding speed can be manually set. The fixing temperature was measured with a non-contact thermometer temperature hitter 3445 (manufactured by Hioki Electric). The sheet passing speed was calculated from the diameter of the fixing roller and the rotation speed by a digital tachometer HT-5100 (manufactured by Ono Sokki).
The iR4570F is used as an image for evaluating the fixing start temperature, and the toner loading on the paper is 0.4 mg / cm ² on A4 paper EN-100 (manufactured by Canon) in a normal temperature and humidity environment (23 ° C./60%). The development contrast was adjusted so that a solid unfixed image having a tip margin of 10 mm, a width of 200 mm, and a length of 20 mm was produced.
In a normal temperature and humidity environment (23 ° C / 60%), the sheet passing speed is set to 280 mm / sec. Went. 5 cm from the rear edge of the fixed image, while applying a load of 4.9 kPa, rubbing 5 times with soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.), before and after rubbing The image density reduction rate ΔD (%) was calculated by the following equation. The image density was evaluated using a reflection densitometer 500 Series Spectrodensitometer manufactured by X-rite. The temperature at which ΔD (%) was less than 1% was determined as the fixing start temperature.
ΔD (%) = (image density before rubbing−image density after rubbing) × 100 / image density before rubbing (evaluation criteria)
A: Excellent fixability when the fixing start temperature is 90 ° C. to 100 ° C. B: Good fixability when the fixing start temperature is 105 ° C. to 120 ° C. C: Fixing start temperature is 125 ° C. to 140 ° C. Fixability D with no practical problem in some cases: Fixation start temperature is 145 ° C. or higher, and fixability is inferior

<Evaluation method of peeling temperature>
The low temperature fixability was evaluated from a viewpoint different from the fixing start temperature. The ease of adhesion to paper at low temperatures was evaluated by the following method. A solid unfixed image was produced in the same manner as the method for evaluating the fixing start temperature, and a fixed image was obtained in the same manner. Subsequently, the fixed image was folded in a cross shape and rubbed 5 times with a soft thin paper (for example, “Dasper”, manufactured by Ozu Sangyo Co., Ltd.) while applying a load of 4.9 kPa. As shown in FIG. 3, the toner is peeled off at the crossed portion, and a sample in which the background of the paper can be seen is obtained. Next, a cross section of 512 pixels was photographed with a CCD camera at a resolution of 800 pixels / inch. The threshold value was set to 60%, the image was binarized, the part where the toner was peeled off was a white part, and the area ratio of the white part was defined as the peeling rate. The smaller the area ratio of the white portion, the more difficult the toner is to peel off.
The peeling rate was measured for each fixing temperature, the fixing temperature was plotted on the horizontal axis, and the peeling rate was plotted on the vertical axis. After smoothly tying, the temperature at which the peeling rate crossed the 10% line was taken as the peeling temperature.
(Evaluation criteria)
A: When the peeling temperature is 90 ° C. to 110 ° C. and excellent low-temperature fixability B: When the peeling temperature is 115 ° C. to 130 ° C. and good low temperature fixability C: When the peeling temperature is 135 ° C. to 155 ° C. Thus, low-temperature fixability D having no practical problem: when the peeling temperature is 160 ° C. or higher, it is determined that the low-temperature fixability is poor.

<Evaluation method of offset resistance>
With respect to the fixed image obtained in the evaluation of the fixing start temperature, it was evaluated whether or not a high temperature offset (a phenomenon in which the fixed image adhered to the fixing roller from the paper and the fixing roller rotated once and reattached to the paper) occurred.
When the image density of the non-image portion showed a density of 0.03 times or more of the solid image density, an offset was generated. The image density is a reflection densitometer 500 Series Spec manufactured by X-Rite.
Evaluation was carried out using a trodentitemeter.
(Evaluation criteria)
A: High temperature offset did not occur and excellent offset resistance B: High temperature offset occurred at 180 ° C. Good offset resistance C: High temperature offset occurred at 175 ° C. and 170 ° C. No offset resistance D: High temperature offset occurs at 165 ° C or lower, resulting in poor offset resistance

<Measurement method of durability stability>
Durability stability evaluation uses iR4570F with a modified process speed of 320 mm / sec, and prints up to 50,000 images (print area ratio 4%) with a grid pattern with a line width of 3 pixels printed on the entire surface of A4 paper. Judgment was made based on the number of images at the time when the image was stained.
(Evaluation criteria)
A: When 50,000 sheets are printed, no stains are generated and excellent durability is exhibited. B: When 40,000 sheets are printed, stains are generated and good durability is exhibited. C: When 20,000 sheets are printed. Despite the occurrence of smudges, it shows durability that is not a problem for practical use. D: Stain is generated when 5,000 sheets are printed, and the durability is poor.

<Measurement method of fine line reproducibility>
The fine line reproducibility was evaluated from the viewpoint of high image quality. Of the images output in the durability stability evaluation, fine line reproducibility was evaluated for the 5000th image. The output resolution of iR4570F is 600 dpi, and the line width of 3 pixels is theoretically 127 μm. The line width of the image is measured with a microscope VK-8500 (manufactured by Keyence), and when this is d (μm), L is defined below as a fine line reproducibility index.
L (μm) = | 127−d |
L defines the difference between the theoretical line width of 127 μm and the line width d on the output image. Since d may be larger than 127 or smaller than 127, it is defined as the absolute value of the difference. Smaller L indicates better fine line reproducibility.
(Evaluation criteria)
A: L is 0 or more and less than 3 μm.
B: L is 3 or more and less than 10 μm.
C: L is 10 or more and less than 20 μm.
D: L is 20 μm or more.

<Evaluation method of fogging on white background>
Using the above iR4570F, in a normal temperature and normal humidity environment (23 ° C./60%), the toner loading amount is adjusted so that the image area density after fixing is 1.4 mg / cm ² , and the white background area potential is developed. From the bias, the potential on the photosensitive member was adjusted to 150 V in the opposite direction with respect to the image portion. The photoconductor was stopped during image formation, and the toner on the photoconductor before the transfer process was peeled off using Mylar tape and pasted on paper (photoconductor sample). In addition, the Mylar tape was used as it was on the paper as a reference sample.
Regarding the measurement, the reflectivity (%) is measured using DENSOMETER TC-6DS (manufactured by Tokyo Denshoku Technical Center), and the difference (reflectance difference) between the reflectivity of the “photoreceptor sample” and the reflectivity of the reference sample is measured. The fogging value was used.
(Evaluation criteria)
A: Good with a reflectance difference of 0.5% or less.
B: The difference in reflectance is 1.0% or less and cannot be discriminated as an image.
C: Reflectance difference exceeds 1.0% but does not appear as an image, and there is no problem in actual use.
D: The difference in reflectance exceeds 1.0%, and fog is seen on the white background on the image.

<Comparative Examples 1 to 8>
(Preparation of toners 2 to 9)
Toner 2 (Comparative Example 1) to Toner 9 (Comparative Example 8) were obtained in the same manner as in Example 1, except that the composition of the resin, magnetic material, wax and resin fine particles was changed as described in Table 7. Table 7 and Table 8). The obtained toner was evaluated in the same manner as in Example 1. Table 8 shows the evaluation results of the toner.

<Examples 2 to 10>
(Preparation of toners 10 to 18)
In Example 1, Toner 10 (Example 2) to Toner 18 (Example 10) were obtained in the same manner except that the composition of the resin, magnetic material, wax, and resin fine particles was changed as described in Table 7. Table 7 and Table 8). The obtained toner was evaluated in the same manner as in Example 1. Table 8 shows the evaluation results of the toner.

It is a figure showing the change with temperature of the loss elastic modulus of a toner. It is a flow curve figure based on the data from a flow tester. FIG. 6 is a sample diagram in which the toner is peeled off and the paper background can be seen. It is the schematic of the apparatus which measures a triboelectric charge amount.

Explanation of symbols

1 Suction machine (at least the part in contact with the measurement container 2 is an insulator)
2 Metal measuring container 3 500 mesh screen 4 Metal lid 5 Vacuum gauge 6 Air flow control valve 7 Suction port 8 Condenser 9 Electrometer

Claims (16)

A toner containing capsule-type toner particles having a surface layer (B) on the surface of a toner base particle (A) containing at least a binder resin (a) containing polyester as a main component, a magnetic substance and a wax. ,
The surface layer (B) contains a resin (b), and the resin (b) is a resin containing a resin selected from a polyester resin (b1), a vinyl resin (b2), or a urethane resin (b3),
The glass transition temperature Tg (a) of the binder resin (a) and the glass transition temperature Tg (b) of the resin (b) satisfy the relationship of the following formula (1):
Tg (a) <Tg (b) (1)
Magnetization of the toner in an external magnetic field of 79.6 kA / m is 12 Am ² / kg or more and 30 Am ² / kg or less,
When the temperature indicating the maximum loss elastic modulus of the toner is Tt (° C.), 40 ° C. ≦ Tt ≦ 60 ° C.
When the loss elastic moduli of the toner at temperature (Tt + 5) ° C. and temperature (Tt + 25) ° C. are G ″ t (Tt + 5) and G ″ t (Tt + 25), respectively, G ″ t (Tt + 5) / G ″ t ( A toner characterized in that Tt + 25) is greater than 40. The binder resin (a) containing the polyester as a main component contains at least a resin (a1) and a resin (a2) having different softening points, and the softening point of the resin (a1) is 100 ° C. or less. The toner according to claim 1, wherein a softening point of the resin (a2) is 120 ° C. or more. In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin (a1), the weight average molecular weight is 2,000 to 20,000, and the tetrahydrofuran (THF) of the resin (a2) 3. The toner according to claim 2, wherein the weight average molecular weight is 30,000 to 150,000 in a molecular weight distribution measured by gel permeation chromatography (GPC) of a soluble part. In the molecular weight distribution measured by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble matter of the resin (a1), the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) The toner according to claim 2, wherein the toner is 1.0 or more and 8.0 or less. 5. The toner according to claim 2, wherein a ratio of the resin (a1) in the binder resin (a) containing the polyester as a main component is 50% by mass or more and 90% by mass or less. . When the temperature that shows the maximum value of the loss modulus of the resin (b) is Tb (° C.), (Tb−Tt) is 5 ° C. or more and 20 ° C. or less, the temperature (Tb + 5) ° C., and the temperature (Tb + 25). ) When the loss elastic moduli of the resin (b) at 0 ° C. are G ″ b (Tb + 5) and G ″ b (Tb + 25), respectively, G ″ b (Tb + 5) / G ″ b (Tb + 25) is greater than 10. The toner according to claim 1, wherein the toner is a toner. 7. The storage elastic modulus (G′t (120)) at 120 ° C. of the toner is 5.0 × 10 ² Pa or more and 5.0 × 10 ⁴ Pa or less. 7. Toner according to. The toner according to claim 1, wherein the toner particles contain 3% by mass or more and 10% by mass or less of tetrahydrofuran (THF) insoluble matter excluding a magnetic substance. The toner according to claim 1, wherein the surface layer (B) is 1.0% by mass or more and 15.0% by mass or less with respect to the toner base particles (A). The said resin (b) has at least 1 chosen from the group which consists of a carboxyl group, a sulfonic acid group, carboxylate, and a sulfonate in a side chain. The toner described. The toner according to any one of claims 1 to 10, wherein the resin (b) is a resin containing a urethane resin (b3). The toner according to claim 11, wherein the urethane resin (b3) is a resin containing a reaction product of a diol component and a diisocyanate component. The toner according to claim 1, wherein the magnetic substance is contained in an amount of 30% by mass to 120% by mass with respect to the binder resin (a) mainly composed of polyester. The toner according to claim 1, wherein the wax is an ester wax. The toner according to claim 1, wherein the surface layer (B) is formed using resin fine particles containing the resin (b). The toner particles include at least a binder resin (a) mainly composed of the polyester, the magnetic substance, and the wax in an organic medium in an aqueous medium in which resin fine particles containing the resin (b) are dispersed. The toner according to claim 1, wherein the toner is obtained by dispersing a solution or dispersion obtained by dissolving or dispersing, removing the solvent from the obtained dispersion, and drying. .

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