JP2017009982A - Toner, developer, image forming apparatus, and toner storage unit - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner that has excellent low-temperature fixability and prevents the occurrence of a phenomenon in which output sheets are adhered to each other with a fixing image therebetween (paper ejection blocking).SOLUTION: There is provided a toner that is fixed to an image carrier by heat, the toner having a storage elastic modulus measured by a rheometer satisfying the following conditions. The storage elastic modulus at 100°C during an increase in temperature is 1×10to 1×10Pa; the storage elastic modulus at 100°C during a decrease in temperature is 1×10to 1×10Pa and the value of the storage elastic modulus at 100°C during a decrease in temperature is larger than that during an increase in temperature.SELECTED DRAWING: None

Description

The present invention relates to a toner, a developer, an image forming apparatus, and a toner storage unit.

Various image forming apparatuses using an electrophotographic system have been devised as image forming apparatuses such as copying machines and printers, and are well known in the art.
In the image forming process, an electrostatic latent image is formed on the surface of the photosensitive drum as an image carrier, and the electrostatic latent image on the photosensitive drum is developed with a toner as a developer to be visualized and developed. This process is established by a process in which the transferred image is transferred onto a recording paper by a transfer device to carry the image, and the toner image on the recording paper is fixed by a fixing device using pressure or heat.

In this fixing device, a fixing member and a pressure member constituted by opposing rollers or belts or a combination thereof are arranged so as to contact each other to form a nip portion, and a recording sheet is sandwiched in the nip portion, Heat and pressure are applied to fix the toner image on the recording paper.
For these fixing devices, studies are being made to significantly improve heat conduction efficiency, reduce energy consumption, and at the same time realize miniaturization. In addition, a device has been proposed that has advantages such as a short waiting time from power-on of the image forming apparatus to an image forming executable state (quick start property) and significantly low power consumption during standby (power saving). (See Patent Documents 1 to 7).

In this fixing process, since a large amount of electric power is required to heat and melt the toner, low temperature fixability is one of the important characteristics of the toner from the viewpoint of energy saving.
In order to improve the low-temperature fixability of the toner, in recent years, a toner containing a crystalline resin as a binder resin has been used (see, for example, Patent Documents 8 and 9).

With the downsizing of the fixing device, quick start system, and power saving, the toner is required to have a low temperature fixing property. For this reason, a toner that is easily softened at a low temperature is used.
When a large amount of paper that has a large image area on both sides is accumulated in the paper discharge unit, the toner on the fixed image is fixed to the output paper that is overlaid, and the output paper is bonded to each other through the fixed image. Phenomenon (paper discharge blocking) tends to occur. This is a phenomenon that occurs because the image portion of another output sheet overlaps where the toner is not cooled sufficiently after being melt-fixed and remains softened.
Since the low-temperature fixability of toner and prevention of paper discharge blocking are in a trade-off relationship, no technology has been found to achieve both.
An object of the present invention is to provide a toner that is excellent in low-temperature fixability and does not cause a phenomenon in which output sheets are bonded to each other via a fixed image (discharge blocking).

As a result of intensive studies by the present inventors, it has been found that the above problem can be solved by the toner described in the following (1).
(1) A toner that is fixed to an image bearing member by heat and has a storage elastic modulus measured by a rheometer of the toner that satisfies the following condition.
The storage elastic modulus G ′ at 100 ° C. at the time of temperature rise is 1 × 10 ³ to 1 × 10 ⁶ Pa
-Storage elastic modulus G 'at 100 ° C during temperature drop is 1 x 10 ³ to 1 x 10 ⁶ Pa
In addition, the value of the storage elastic modulus G ′ at 100 ° C. is higher when the temperature is lowered than when the temperature is raised.

  According to the present invention, it is possible to provide a toner that is excellent in low-temperature fixability and does not cause a phenomenon in which output papers adhere to each other through a fixed image (discharge blocking).

1 is a schematic diagram illustrating an example of an image forming apparatus. FIG. 3 is a cross-sectional view illustrating a configuration of a process cartridge that is an aspect of a toner storage unit according to the present invention. It is a figure which shows the method of determining the peak half value width by X-ray-diffraction measurement of crystalline polyester.

(Conventional technology)
As a technique for preventing paper discharge blocking, there is a method of cooling the stacked paper discharge portions by blowing cooling air with a fan or the like to prevent the image and the image support, paper, and the images from adhering to each other. is there. However, this method requires a dedicated additional device and cannot be installed on a low-cost machine. Further, even if the toner is provided with a low-temperature fixing property in order to reduce power consumption, the stacking temperature of the paper discharge is not lowered as much as the fixing temperature and the fixing energy, and blocking cannot be prevented.

(Resin improvement)
On the other hand, in order to reduce the adhesiveness of the paper discharge portion of the image, the heat melting characteristics of the toner can be made difficult to flow. For this purpose, the molecular weight of the resin constituting the resin is increased, the melting point or the glass transition point (Tg) of the resin is increased, or the resin has a crosslinked structure.
However, these methods increase the fixing temperature and sacrifice energy saving. In addition, it is difficult to obtain an image with high gloss after fixing, which is not suitable for a high-definition image system or a system with clear colors.

(Give release properties)
On the other hand, there is an attempt to increase the releasability of the image surface and prevent the adhesion between output images. This is intended to bleed a lot of wax as a release agent on the image surface. However, in order to bleed a lot of wax, it is necessary to increase the amount of wax used or to dispose the wax on the toner surface so that the wax can be easily separated from the toner. These tend to deteriorate the fluidity and chargeability of the toner, and in order to achieve low-temperature fixing, a wax having a lower melting point must be selected, which promotes the above-mentioned difficulties.

(Features of the present invention)
Therefore, in the present invention, in the elastic modulus of the molten toner that can exhibit low-temperature fixability,
-Storage elastic modulus at 100 ° C. during temperature rise is 1 × 10 ³ to 1 × 10 ⁶ Pa
-Storage elastic modulus at 100 ° C. during temperature drop is 1 × 10 ³ to 1 × 10 ⁶ Pa
In addition, it has been found that by allowing the storage elastic modulus at 100 ° C. to be higher when the temperature is lowered than when the temperature is raised, paper discharge blocking can be prevented even in a toner that can be fixed at a low temperature. It came to.

In order to adjust the storage elastic modulus at 100 ° C. at the time of temperature rise to a desired region, a resin composition having a low Tg is selected, and the molecular weight and molecular weight distribution are adjusted. In that case, the storage elastic modulus at the time of a fusion | melting can be further adjusted by mix | blending crystalline resin, a plasticizer, etc.
In addition, in order to adjust the storage elastic modulus at 100 ° C. when the temperature is lowered to a desired region, the addition amount, particle size, dispersion state, and the like of a salicylic acid derivative metal salt, which is an additive added to the resin described later, are prepared.

In the toner of the present invention, the elastic modulus of the toner changes depending on the heat energy at the time of fixing.
For example, a hydrogen bond, a covalent bond, an ionic bond, or a coordinate bond can be used to induce an interaction between polymer polymers. More preferably, the use of ionic bonds is effective because changes are likely to occur at low temperatures.
As a result, a polymer component is generated, and the molecular weight of the toner after heating increases. In order to improve the blocking characteristics, the change rate of the weight average molecular weight due to heating of the toner is preferably 10% or more and 140% or less. When it is 140% or less, the fixing property is improved and it is easy to adhere to paper or the like. A change rate of preferably 30% or more and 80% or less can satisfactorily satisfy both the fixing property and the blocking property.

  Conventionally, there has been a technique for preventing hot offset by increasing the elastic modulus when the toner is heated at a high temperature by utilizing such bond generation. In the present invention, even when heated at a low temperature of 100 ° C., the interaction between the polymers is generated, and the effect of preventing blocking appears.

In the embodiment of the present invention, ion or coordination bond generation by heating a salicylic acid derivative metal salt and a polar group of a resin is utilized.
As the resin, a resin having a carboxyl group is preferable. A polyester resin having a carboxyl group at the terminal is particularly suitable. The acid value is preferably 10 to 50 mgKOH / g, more preferably 20 to 40 mgKOH / g.

When a plurality of resins are used, a low molecular weight, low Tg resin may be mixed as one component in order to place importance on low-temperature fixability. At this time, if the acid value of the low molecular weight, low Tg resin component is made high, the crosslinking reaction preferentially occurs with the low molecular weight, low Tg resin component, so that the blocking effect of the low-temperature fixing toner becomes higher.
The inclusion of a hydroxyl group is also important for enhancing the bonding property between polymers. Those having a hydroxyl value of 5 to 40 mgKOH / g are preferred, and those having 10 to 30 mgKOH / g are more preferred.

式中、Ｒ₁〜Ｒ_４は、水素原子、炭素数１〜１２のアルキル基、炭素数２〜１２のアルケニル基、−ＯＨ，−ＮＨ₂，−ＮＨ（ＣＨ₃），−Ｎ（ＣＨ₃）₂，−ＯＣＨ₃，−Ｏ（Ｃ₂Ｈ₅），−ＣＯＯＨ及び−ＣＯＮＨ₂から選ばれる同一又は異なる基を示す。
また、金属塩を形成する金属は、Ｚｎ²⁺，Ａｌ³⁺，Ｃｒ³⁺，Ｆｅ³⁺，Ｚｒ⁴⁺ のいずれかである。 As the salicylic acid derivative metal salt, those represented by the following general formula (1) are preferable.

In the formula, R _{1 to} R ₄ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —OCH ₃ , —O (C ₂ H ₅ ), —COOH and —CONH ₂ are the same or different groups.
The metal forming the metal salt is any one of Zn ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Zr ⁴⁺ .

Among those represented by the general formula (1), a metal having a valence of 3 or more is preferable as a material that efficiently causes interaction.
In particular, a zirconium compound represented by the following formula (2) is preferable.

式中、ｍは１〜２０の整数、ｎは０〜２０の整数、ｓは０〜２０の整数、ｒは１〜２０の整数であり、ｔ-Ｂｕはターシャリーブチル基を示す。

In the formula, m is an integer of 1 to 20, n is an integer of 0 to 20, s is an integer of 0 to 20, r is an integer of 1 to 20, and t-Bu represents a tertiary butyl group.

-Molecular weight change The toner of the present invention increases in molecular weight by heating. By heating at 100 ° C., the polymer component is increased and the weight average molecular weight is increased. The top molecular weight is characterized by little change. Therefore, it is considered that a cross-linking reaction has occurred in some polymer components.
When the weight average molecular weight of the toner before temperature increase is Mw1 and the weight average molecular weight of the toner after temperature decrease is Mw2, the change rate R _M (%) calculated by the following formula (1) is 10% or more and 140%. Or less, more preferably 30% or more and 80% or less.

・ Reduction of acid value
The acid value of the toner decreases with the reaction. The rate of decrease is considered to depend on the acid value of the toner before heating and the presence state of the salicylic acid derivative metal salt. The change rate R _AV (%) calculated by the following formula (2) is preferably 20% or more and 80% or less.

The acidic group reacts with the salicylic acid metal salt to increase the storage elastic modulus of the resin, so that the change rate of the acid value is preferably large from the viewpoint of preventing blocking. On the other hand, since the presence of acidic groups improves the fixability, the change rate of the acid value should not be too large from the viewpoint of fixability (adhesion with paper).
Therefore, the change rate is preferably 20 to 80% from the viewpoint of improving the fixing property and the blocking property.

Conventionally, a salicylic acid derivative metal salt is added to a resin as a charge control agent. For example, in a pulverized toner, a salicylic acid derivative metal salt is added to a resin and melt kneaded and pulverized. However, when such a melt-kneading and pulverizing step is performed, the toner is heated at the stage of obtaining the toner, so that the elastic modulus of the toner after the temperature rise becomes larger than the elastic modulus of the toner before the temperature rise. There is no.
Conventionally, the salicylic acid derivative metal salt added as a charge control agent may be present on the surface of the toner and does not need to be uniformly dispersed in the toner.

On the other hand, in the present invention, the salicylic acid derivative metal salt does not react in the toner before the temperature rise, and the salicylic acid derivative metal salt needs to react with the resin at the time of the temperature rise.
Therefore, it is important not to provide a heating process at a high temperature so as not to cause a reaction during the toner manufacturing process, and the manufacturing process does not include a heating process in which the temperature of the toner obtained in the toner manufacturing process is Tg + 20 ° C. or higher. It is preferred to select a method. If heating to Tg + 20 ° C. or higher is performed in the toner manufacturing process, the crosslinking of the toner resin is promoted, and the elastic modulus of the toner is increased and the low-temperature fixability is impaired.
It is also important that the salicylic acid derivative metal salt is dissolved in the form of molecules or dispersed in the toner as fine particles or crystals in order to effectively carry out the reaction between the salicylic acid derivative metal salt and the resin by heating at a low temperature. is there. For this purpose, it is necessary to devise such as forming a salt in the toner during the toner manufacturing process and providing a fine dispersion process.

For the toner, in order to achieve low-temperature fixing, the storage elastic modulus G ′ at 100 ° C. at the time of temperature rise is desirably 1 × 10 ³ to 1 × 10 ⁶ Pa. More preferably, the storage elastic modulus G ′ at 100 ° C. at the time of temperature increase is preferably 1 × 10 ^{4 to} 3 × 10 ⁵ Pa. The storage elastic modulus G ′ at the time of the temperature increase at 100 ° C. is 1 × 10 ⁶ Pa or less. If present, the toner itself is excellent in thermoplasticity, which means that the toner is fixed at a low temperature. Further, when the storage elastic modulus at the time of temperature rise is less than 1 × 10 ³ Pa, it is difficult to ensure the storage stability of the toner.

In order to prevent paper discharge blocking, it is preferable that the storage elastic modulus G ′ at 100 ° C. when the temperature is lowered is 1 × 10 ³ to 1 × 10 ⁶ Pa, and the value at 100 ° C. is higher when the temperature is lower than the temperature rise. . More preferably, the storage elastic modulus G ′ at 100 ° C. when the temperature is lowered is 1 × 10 ^{4 to} 3 × 10 ⁵ Pa, and the value at 100 ° C. is higher when the temperature is lowered than when the temperature is raised. Under these conditions, the image (printing) portion at the paper discharge temperature is sufficiently hard, the images are not fused together, and paper discharge blocking can be prevented. When the storage elastic modulus G ′ at the time of temperature rise exceeds 1 × 10 ⁶ Pa, the elasticity of the toner becomes high at the time of fixing, and the glossiness of the image becomes insufficient.

  Furthermore, it has been found that when the elastic modulus at the time of temperature rise and temperature drop is within the above range and the elastic modulus after the temperature rise is higher than that at the time of temperature rise, the storage stability of the output image is improved. In other words, when the image is stored not only at the time of paper discharge but also at high temperature and high humidity, a so-called document offset phenomenon occurs in which the image and paper, and the image and the image adhere to each other. It became clear that it became difficult to receive the change by heat or moisture by increasing.

A chemical toner manufacturing method is suitable as a method for causing the salicylic acid derivative compound to be finely present in the toner. Specifically, it is as follows.
1) In the suspension polymerization and dissolution suspension method, a step of finely dispersing in the oil phase by a mechanical method is provided.
2) In the suspension polymerization and dissolution suspension methods, a method for producing fine crystals and particles in the oil phase (polymerizable monomer and resin solvent solution) includes in-situ in the oil phase and a salicylic acid derivative compound. There is a method to synthesize. For example, when a 1,3-di-t-butylsalicylic acid aqueous solution and a zirconium oxychloride aqueous solution are put in the oil phase, a fine zirconium compound can be produced in the toner raw material by reaction. In order to allow the reaction to proceed smoothly, water or a polar solvent such as alcohol or ether may coexist in the oil phase.
3) In the emulsion aggregation method, a step of finely dispersing in the aqueous phase by mechanical means is provided. Thereafter, the toner is aggregated and formed into particles with other toner materials such as a resin latex to obtain a toner.
4) In the emulsion aggregation method, as a method for producing fine crystals and particles in the aqueous phase, there is a method of synthesizing a salicylic acid derivative compound in the aqueous phase. For example, when a 1,3-di-t-butylsalicylic acid aqueous solution and a zirconium oxychloride aqueous solution are placed in the aqueous phase, they react to form a fine zirconium compound, which can be produced in the aqueous phase. Thereafter, the toner is agglomerated and particled with a toner material such as a resin latex to obtain a toner. However, in order not to cause a crosslinking reaction inside the toner, it is preferable to perform the fusion process of the fine particles at as low a temperature as possible. For example, it is also effective to use a resin emulsion using an organic solvent for the binder resin material.

  In the present invention, the salicylic acid derivative compound is considered to have a crosslinked structure with the polyester resin in the toner when the temperature rises, and increases the storage viscoelasticity of the toner. In order to incorporate the above-exemplified zirconium compound into the toner, it is necessary to add the heating temperature preferably at a temperature in the production process of Tg + 20 ° C. or less, more preferably Tg or less of the resin. When the temperature is Tg + 20 ° C. or higher, the crosslinking reaction with the toner proceeds, and the storage elasticity of the toner at the time of temperature increase increases, which may impair the low-temperature fixability.

The amount of the salicylic acid derivative compound is preferably 0.01 to 10% by mass and more preferably 0.1 to 2% by mass with respect to the toner. When the amount of the salicylic acid derivative compound is 0.01% by mass or more, the storage elastic modulus at the time of cooling can be increased, and when it is 10% by mass or less, the fixing property of the toner is inhibited by the zirconium compound in the toner. It will not be done.
In the toner of the present invention, it is effective to use a crystalline polyester resin or a polyester resin having a low glass transition temperature in order to achieve low-temperature fixing.

<Measurement of storage elastic modulus G '>
The storage elastic modulus (G′100) at 100 ° C. at the time of temperature increase and temperature decrease in the present invention is measured by the following method.
As a measuring apparatus, a rotating plate type rheometer “ARES” (manufactured by TA INSTRUMENTS) is used. As a measurement sample, a sample obtained by press molding a toner into a disk shape having a diameter of 8.0 mm ± 0.3 mm and a thickness of 1.0 mm ± 0.3 mm using a tablet molding machine in an environment of 25 ° C. Use.
The sample was mounted on a parallel plate having a diameter of 8.0 mm and stabilized at 40 ° C., and the frequency was set to 10 Hz (6.28 rad / s) and the strain amount was set to 0.1% (strain amount control mode). The temperature is raised to 120 ° C. at 0 ° C./min, and then lowered to 40 ° C. at 2.0 ° C./min.
At this time, it is important to set the sample so that the initial normal force becomes zero. Further, as described below, in the subsequent measurement, the effect of normal force can be canceled by performing automatic tension adjustment (Auto Tension Adjustment ON).

The detailed setting of the apparatus for measuring the storage elastic modulus G ′ is as follows.
(1) Use a parallel plate with a diameter of 8.0 mm.
(2) The frequency (Frequency) is 10 Hz (6.28 rad / s).
(3) The applied strain initial value (Strain) is set to 0.1%.
(4) Measure between 40 ° C and 200 ° C at a ramp rate of 2.0 ° C / min. In the measurement, the following automatic adjustment mode setting conditions are used. Measurement is performed in an automatic strain adjustment mode (Auto Strain).
(5) Maximum strain (Max Applied Strain) is set to 200%.
(6) The maximum torque (Max Allowed Torque) is set to 500 g · cm, and the minimum torque (Min Allowed Torque) is set to 500 g · cm.
(7) Set distortion adjustment (Strain Adjustment) as 15% of Current Strain. In the measurement, an automatic tension adjustment mode (Auto Tension) is adopted.
(8) The automatic tension direction (Auto Tension Direction) is set as the compression (Compression).
(9) The initial static force (Initial Static Force) is set to 10.0 g, and the automatic tension sensitivity (Auto Tension Sensitivity) is set to 300 g.
(10) The operating condition of the automatic tension is that the sample modulus is 10 (Pa) or more.
The value of the storage elastic modulus G ′ at 100 ° C. at the time of temperature rise when measuring the storage elastic modulus G ′ from a temperature of 40 ° C. to 120 ° C. by the above method was defined as G ′ ↑ 100.
Thereafter, the temperature was lowered under the same conditions, and the value of the storage elastic modulus G ′ at 100 ° C. when the storage elastic modulus G ′ from 120 ° C. to 40 ° C. was measured was defined as G ′ ↓ 100.

<Amorphous polyester resin>
Details of the constituent components of the amorphous polyester resin will be described below.
--- Diol ---
The diol is not particularly limited as long as it contains 50 mol% or more of an aliphatic diol having 3 to 10 carbon atoms, and can be appropriately selected according to the purpose. For example, ethylene glycol, 1,2-propylene glycol 1,3-propylene glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1,12 -Aliphatic diols such as dodecanediol; Diols having an oxyalkylene group such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol; 1,4-cyclohexanedimethanol, hydrogenated bisphenol A Alicyclic ring Diols: Alicyclic diols added with alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide; Bisphenols such as bisphenol A, bisphenol F and bisphenol S; Bisphenols such as ethylene oxide, propylene oxide and butylene oxide Examples include alkylene oxide adducts of bisphenols such as those having an alkylene oxide added thereto. Among these, aliphatic diols having 4 to 12 carbon atoms are preferable. These diols may be used alone or in combination of two or more.

--- Dicarboxylic acid ---
There is no restriction | limiting in particular as said dicarboxylic acid, According to the objective, it can select suitably, For example, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, etc. are mentioned. Moreover, these water substances may be used, a lower (C1-C3) alkyl esterified substance may be used, and a halide may be used.

  The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include succinic acid, adipic acid, sebacic acid, dodecanedioic acid, maleic acid, and fumaric acid.

The aromatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc. Among these, carbon number of 4 or more Twelve or less aliphatic dicarboxylic acids are preferred.
These dicarboxylic acids may be used alone or in combination of two or more.

--Trivalent or higher aliphatic alcohol ---
The trihydric or higher aliphatic alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, dipentaerythritol and the like. It is done.
Among these, 3-4 aliphatic alcohols are preferable. These trivalent or higher aliphatic alcohols may be used alone or in combination of two or more.

  The acid value of the amorphous polyester resin is not particularly limited and can be appropriately selected according to the purpose. However, in order to achieve desired low-temperature fixability from the viewpoint of the affinity between paper and resin. 10 mgKOH / g or more is preferable, and 20 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 50 mgKOH / g or less is preferable.

  The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, in order to achieve a desired low-temperature fixability and a good blocking property, 5 mg KOH / G-40 mgKOH / g is preferable, and 10 mgKOH / g-30 mgKOH / g is more preferable.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) Weigh accurately 0.5 to 2.0 g of toner and let the weight of the polymer component be Wg.
(2) A sample is put into a 300 ml beaker, and 150 ml of a mixed solution of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is B (ml), and the following formula (C) is used. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W Formula (C)

  Further, the viscoelasticity of the toner can be adjusted by a hydrogen bonding force using a polyester resin containing a urethane bond and a urea bond.

--Polyester resin containing urethane bond and urea bond--
There is no restriction | limiting in particular as a polyester resin containing the said urethane bond and a urea bond, According to the objective, it can select suitably, For example, the reaction product of the polyester resin and polyisocyanate which have an active hydrogen group, etc. are mentioned. It is done.

--- Polyisocyanate ---
There is no restriction | limiting in particular as said polyisocyanate, According to the objective, it can select suitably, For example, diisocyanate, trivalent or more isocyanate etc. are mentioned.
Examples of the diisocyanate include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, araliphatic diisocyanates, isocyanurates, and those blocked with phenol derivatives, oximes, caprolactams, and the like.

  The aliphatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, methyl 2,6-diisocyanatocaproate, octamethylene diisocyanate, decametin Examples thereof include diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and tetramethylhexane diisocyanate.

  The alicyclic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate and cyclohexylmethane diisocyanate.

  The aromatic diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, tolylene diisocyanate, diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4′-diisocyanato Examples include diphenyl, 4,4′-diisocyanato-3,3′-dimethyldiphenyl, 4,4′-diisocyanato-3-methyldiphenylmethane, 4,4′-diisocyanato-diphenyl ether, and the like.

  There is no restriction | limiting in particular as said araliphatic diisocyanate, According to the objective, it can select suitably, For example, (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl xylylene diisocyanate etc. are mentioned.

There is no restriction | limiting in particular as said isocyanurates, According to the objective, it can select suitably, For example, a tris (isocyanatoalkyl) isocyanurate, a tris (isocyanatocycloalkyl) isocyanurate, etc. are mentioned.
These polyisocyanates may be used alone or in combination of two or more. Further, it is preferably used as a reaction precursor (hereinafter also referred to as “prepolymer”) to be reacted with a curing agent described later.

-Curing agent-
The curing agent is not particularly limited as long as it reacts with the prepolymer, and can be appropriately selected according to the purpose. Examples thereof include an active hydrogen group-containing compound.

-Active hydrogen group-containing compound-
There is no restriction | limiting in particular as an active hydrogen group in the said active hydrogen group containing compound, According to the objective, it can select suitably, For example, a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group Etc. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as said active hydrogen group containing compound, Although it can select suitably according to the objective, Amines are preferable at the point which can form a urea bond.

The amines are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diamines, trivalent or higher valent amines, amino alcohols, amino mercaptans, amino acids, and those obtained by blocking these amino groups. Can be mentioned. These may be used individually by 1 type and may use 2 or more types together.
Among these, diamine and a mixture of a diamine and a small amount of a trivalent or higher amine are preferable.

There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aromatic diamine, alicyclic diamine, aliphatic diamine etc. are mentioned.
There is no restriction | limiting in particular as said aromatic diamine, According to the objective, it can select suitably, For example, phenylenediamine, diethyltoluenediamine, 4,4'- diaminodiphenylmethane etc. are mentioned.
The alicyclic diamine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diaminocyclohexane and isophorone diamine. It is done.
There is no restriction | limiting in particular as said aliphatic diamine, According to the objective, it can select suitably, For example, ethylenediamine, tetramethylenediamine, hexamethylenediamine etc. are mentioned.

The trivalent or higher amine is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diethylenetriamine and triethylenetetramine.
The amino alcohol is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethanolamine and hydroxyethylaniline.
The amino mercaptan is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminoethyl mercaptan and aminopropyl mercaptan.

The amino acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aminopropionic acid and aminocaproic acid.
There is no restriction | limiting in particular as what blocked the said amino group, According to the objective, it can select suitably, For example, it is obtained by blocking an amino group with ketones, such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Examples include ketimine compounds and oxazoline compounds.

The molecular structure of the amorphous polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc., in addition to NMR measurement by solution or solid. As a simple example, there is a method of detecting, as an amorphous polyester resin, an infrared absorption spectrum having no absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ and 990 ± 10 cm ^−1. .

  There is no restriction | limiting in particular as content of the amorphous polyester resin used as said prepolymer, Although it can select suitably according to the objective, 5 mass parts-25 mass parts with respect to 100 mass parts of said toners Is preferable, and 10 to 20 parts by mass is more preferable. When the content is less than 5 parts by mass, the low-temperature fixability and the high-temperature offset resistance may be deteriorated. When the content is more than 25 parts by mass, the heat-resistant storage stability is deteriorated, and the glossiness of the image obtained after fixing is obtained. The degree may decrease. When the content is within the more preferable range, it is advantageous in that it is excellent in all of low-temperature fixability, high-temperature offset resistance, and heat-resistant storage stability.

<Crystalline polyester resin>
Since the crystalline polyester resin has crystallinity, it may be used together with the non-crystalline polyester resin in order to exhibit a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. By using the crystalline polyester resin having such characteristics together with the amorphous polyester resin, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, the crystalline polyester resin rapidly melts due to melting. Therefore, a toner having both good heat storage stability and low-temperature fixability can be obtained. Also, good results are shown for the release width (difference between the fixing lower limit temperature and the high temperature resistant offset occurrence temperature).
The crystalline polyester resin is obtained using a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, or a polyvalent carboxylic acid ester, or a derivative thereof.

  In the present invention, as described above, the crystalline polyester resin uses a polyhydric alcohol and a polyvalent carboxylic acid such as a polyvalent carboxylic acid, a polyvalent carboxylic acid anhydride, a polyvalent carboxylic acid ester, or a derivative thereof. A polyester resin modified, for example, the prepolymer and a resin obtained by crosslinking and / or elongation reaction of the prepolymer do not belong to the crystalline polyester resin.

  In the crystalline polyester resin used in the present invention, the half width of the peak in the X-ray diffraction of the crystalline polyester resin is preferably less than 1.0 ° / 2θ, and more preferably less than 0.6 ° / 2θ. preferable. When the peak width at half maximum of the crystalline polyester is less than 1.0 ° / 2θ, the crystallinity of the crystalline polyester is low, so that the sharp melt property is inferior and sufficient low-temperature fixability cannot be obtained.

  In addition, when the crystalline polyester is dissolved and recrystallized in an organic solvent, the half width of the peak in X-ray diffraction is preferably less than 1.0, and more preferably less than 0.6. . If the half width of the peak after dissolution and recrystallization of the crystalline polyester is less than 1.0, the crystallinity of the crystalline polyester present in the toner is low, and a part of the crystalline polyester is an amorphous polyester. Since it is in a compatible state, the low-temperature fixability and heat-resistant storage stability are deteriorated, and the crystalline polyester is easily filmed in the developing machine, causing the developing unit to be contaminated and the image to be deteriorated.

(Peak half-width measurement by X-ray diffraction measurement)
X-ray diffraction measurement of crystalline polyester can be confirmed by a crystal analysis X-ray diffractometer (X'Pert MRDX'Pert MRD Philips). The measurement method is described below. First, a target sample is ground with a mortar to prepare a sample powder, and the obtained sample powder is uniformly applied to a sample holder. Thereafter, a sample holder is set in the diffractometer and measurement is performed to obtain a diffraction spectrum.
Peaks obtained in the range of 20 ° <2θ <25 ° from the obtained diffraction peaks are defined as P1, P2,... In descending order of peak intensity.
The peak half width (FWHM) is defined as the difference x2−x1 between the points x1 and x2, which is half the maximum peak intensity, as shown in FIG.

The measurement conditions for X-ray diffraction are described below.
Tension kV: 45kV
Current: 40A
MPSS
Upper
Gonio
Scanmode: continuos
Start angle: 3 °
End angle: 35 °
Angle Step: 0.02 °
Lucident beam optics
Divergence slit: Div slit 1/2
Difflection beam optics
Anti scatter slit: As Fixed 1/2
Receiving slit: Prog rec slit

(Method of dissolving and recrystallizing crystalline polyester in organic solvent)
The method for dissolving and recrystallizing the crystalline polyester in an organic solvent is as follows.
-Stir 10 g of crystalline polyester and 90 g of organic solvent at 70 ° C for 1 hour.
-The solution after stirring is cooled at 20 ° C for 12 hours to recrystallize the crystalline polyester.
-The crystalline polyester organic solvent dispersion after the recrystallization was applied to Kiriyama funnel (manufactured by Kiriyama Seisakusho) and filter paper No. 1 for Kiriyama funnel. 4 (manufactured by Kiriyama Seisakusho) is set and suction filtered with an aspirator to separate the organic solvent and the crystalline polyester.
The crystalline polyester obtained by separation is dried at 35 ° C. for 48 hours to obtain a recrystallized product of the crystalline polyester.

Details of the constituent components of the crystalline polyester resin will be described below.
-Polyhydric alcohol-
There is no restriction | limiting in particular as said polyhydric alcohol, According to the objective, it can select suitably, For example, diol and trihydric or more alcohol are mentioned.
Examples of the diol include saturated aliphatic diol. Examples of the saturated aliphatic diol include linear saturated aliphatic diols and branched saturated aliphatic diols. Among these, linear saturated aliphatic diols are preferable, and linear saturated fats having 2 to 12 carbon atoms are preferred. Group diols are more preferred. When the saturated aliphatic diol is branched, the crystallinity of the crystalline polyester resin C may be lowered, and the melting point may be lowered. Further, when the saturated aliphatic diol has more than 12 carbon atoms, it is difficult to obtain a practical material. The number of carbon atoms is more preferably 12 or less.

  Examples of the saturated aliphatic diol include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1, 8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1, Examples thereof include 18-octadecanediol and 1,14-eicosandecanediol. Among these, the crystalline polyester resin C has high crystallinity and is excellent in sharp melt properties, so that ethylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1, 10-decanediol and 1,12-dodecanediol are preferred. Examples of the trihydric or higher alcohol include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. These may be used individually by 1 type and may use 2 or more types together.

-Multivalent carboxylic acid-
There is no restriction | limiting in particular as said polyvalent carboxylic acid, According to the objective, it can select suitably, For example, bivalent carboxylic acid and trivalent or more carboxylic acid are mentioned.
Examples of the divalent carboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, peric acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1, Saturated aliphatic dicarboxylic acids such as 12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid; phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, malonic acid, Aromatic dicarboxylic acids such as dibasic acids such as mesaconic acid; and the like, and anhydrides and lower (C1 to C3) alkyl esters thereof.

Examples of the trivalent or higher carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, and the like, and anhydrides thereof. Lower (carbon number 1 to 3) alkyl ester and the like.
In addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, the polyvalent carboxylic acid may include a dicarboxylic acid having a sulfonic acid group. Furthermore, in addition to the saturated aliphatic dicarboxylic acid and aromatic dicarboxylic acid, a dicarboxylic acid having a double bond may be contained. These may be used individually by 1 type and may use 2 or more types together.

  The crystalline polyester resin is preferably composed of a linear saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a linear saturated aliphatic diol having 2 to 12 carbon atoms. That is, the crystalline polyester resin preferably has a structural unit derived from a saturated aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a structural unit derived from a saturated aliphatic diol having 2 to 12 carbon atoms. . By doing so, since crystallinity is high and it is excellent in sharp melt property, it is preferable at the point which can exhibit the outstanding low-temperature fixability.

  There is no restriction | limiting in particular as melting | fusing point of the said crystalline polyester resin, Although it can select suitably according to the objective, It is preferable that it is 60 to 80 degreeC. When the melting point is less than 60 ° C., the crystalline polyester resin is likely to melt at a low temperature and the heat-resistant storage stability of the toner may be reduced. When the melting point exceeds 80 ° C., the crystalline polyester resin is heated by heat at the time of fixing. Insufficient melting may reduce the low-temperature fixability.

  The molecular weight of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, those having a sharp molecular weight distribution and a low molecular weight are excellent in low-temperature fixability, and many components have a low molecular weight. From the viewpoint that heat-resistant storage stability is lowered, the soluble content of orthodichlorobenzene of the crystalline polyester resin is determined by GPC measurement in terms of weight average molecular weight (Mw) 3,000 to 30,000, number average molecular weight (Mn). It is preferably 1,000 to 10,000 and Mw / Mn 1.0 to 10. Furthermore, it is preferable that they are weight average molecular weight (Mw) 5,000-15,000, number average molecular weight (Mn) 2,000-10,000, and Mw / Mn 1.0-5.0.

  The acid value of the crystalline polyester resin is not particularly limited and can be appropriately selected according to the purpose. From the viewpoint of the affinity between paper and resin, in order to achieve desired low-temperature fixability, 5 mgKOH / g or more is preferable and 10 mgKOH / g or more is more preferable. On the other hand, in order to improve the high temperature offset resistance, 45 mgKOH / g or less is preferable.

  The hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected according to the purpose. However, in order to achieve a desired temperature fixability and good charging characteristics, 0 mgKOH / G to 50 mgKOH / g are preferable, and 5 mgKOH / g to 50 mgKOH / g are more preferable.

The molecular structure of the crystalline polyester resin can be confirmed by X-ray diffraction, GC / MS, LC / MS, IR measurement, etc. in addition to NMR measurement by solution or solid. As a simple example, there is a method of detecting, as a crystalline polyester resin, an infrared absorption spectrum having an absorption based on δCH (out-of-plane variable vibration) of olefin at 965 ± 10 cm ⁻¹ or 990 ± 10 cm ⁻¹ .

  There is no restriction | limiting in particular as content of the said crystalline polyester resin, Although it can select suitably according to the objective, 3 mass parts-20 mass parts are preferable with respect to 100 mass parts of the said toner, and 5 mass parts. -15 mass parts is more preferable. When the content is less than 3 parts by mass, the low-temperature fixability may be inferior because sharp melting by the crystalline polyester resin is insufficient, and when it exceeds 20 parts by mass, the heat-resistant storage stability is reduced. In addition, image fogging may occur easily. When the content is within the more preferable range, it is advantageous in that it is excellent in all of high image quality and low temperature fixability.

<Other toner components>
Examples of other components include a release agent, a colorant, a charge control agent, an external additive, a fluidity improver, a cleaning property improver, and a magnetic material.

-Release agent-
There is no restriction | limiting in particular as a mold release agent, It can select suitably from well-known things. Examples of mold release agents for waxes and waxes include plant waxes such as carnauba wax, cotton wax, and wood wax rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin And natural waxes such as petroleum waxes such as microcrystalline and petrolatum.

In addition to these natural waxes, synthetic hydrocarbon waxes such as Fischer-Tropsch wax, polyethylene, and polypropylene; synthetic waxes such as esters, ketones, and ethers;
Furthermore, fatty acid amide compounds such as 12-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbon; low molecular weight crystalline polymer resin, poly-n-stearyl methacrylate, poly-n -Polyacrylate homopolymer or copolymer such as lauryl methacrylate (eg, n-stearyl acrylate-ethyl methacrylate copolymer); crystalline polymer having a long alkyl group in the side chain, etc. Good.
Among these, hydrocarbon waxes such as paraffin wax, microcrystalline wax, Fischer-Tropsch wax, polyethylene wax, and polypropylene wax are preferable.

  There is no restriction | limiting in particular as melting | fusing point of a mold release agent, Although it can select suitably according to the objective, 60 degreeC or more and 80 degrees C or less are preferable. When the melting point is less than 60 ° C., the release agent is likely to melt at a low temperature, and the heat resistant storage stability may be inferior. When the melting point exceeds 80 ° C., even when the resin is melted and is in the fixing temperature range, the release agent may not be sufficiently melted, resulting in fixing offset and image loss.

  There is no restriction | limiting in particular as content of a mold release agent, Although it can select suitably according to the objective, 2 mass parts-10 mass parts are preferable with respect to 100 mass parts of said toner, 3 mass parts-8 Part by mass is more preferable. When the content is less than 2 parts by mass, the high-temperature offset resistance during fixing and the low-temperature fixability may be inferior. When the content exceeds 10 parts by mass, the heat-resistant storage stability is deteriorated, and image fogging occurs. Etc. may occur easily. When the content is within the more preferable range, it is advantageous in terms of improving image quality and improving fixing stability.

-Colorant-
There is no restriction | limiting in particular as a coloring agent, According to the objective, it can select suitably, For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow Iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phi Sared, Paracro Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyra Ron Red, Polyazo Red, Chrome Vermillion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green Examples include lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, and lithobon.

  There is no restriction | limiting in particular as content of a coloring agent, Although it can select suitably according to the objective, 1 mass part-15 mass parts are preferable with respect to 100 mass parts of said toners, and 3 mass parts-10 masses. Part is more preferred.

  The colorant can also be used as a master batch combined with a resin. Examples of the resin to be kneaded together with the production of the master batch or the master batch include, in addition to the amorphous polyester resin, a polymer of styrene such as polystyrene, poly p-chlorostyrene, polyvinyl toluene, or a substituted product thereof; styrene-p -Chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene- Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethacrylic acid Methyl copolymer, styrene-acrylo Tolyl copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester Styrene copolymers such as copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid Examples thereof include resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, and paraffin waxes. These may be used individually by 1 type and may use 2 or more types together.

  The master batch can be obtained by mixing a resin for a master batch and a colorant under high shearing force and kneading to obtain a master batch. In this case, an organic solvent can be used in order to enhance the interaction between the colorant and the resin. In addition, a so-called flushing method, which is a wet method of colorant, is a method of mixing and kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, transferring the colorant to the resin side, and removing moisture and organic solvent components. Since the cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shear dispersion device such as a three-roll mill is preferably used.

-Charge control agent-
The charge control agent is not particularly limited and may be appropriately selected depending on the purpose. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy Amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, metal salts of salicylic acid derivatives, etc. Can be mentioned. Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of phenol-based condensate (above, manufactured by Orient Chemical Co., Ltd.), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), LRA- 901, boron complex LR-147 (manufactured by Nippon Carlit Co., Ltd.), copper phthalocyanine, perylene, quinacridone, azo pigment, other polymer compounds having functional groups such as sulfonic acid group, carboxyl group, quaternary ammonium salt Is mentioned.

  There is no restriction | limiting in particular as content of a charge control agent, According to the objective, it can select suitably, However, 0.1 mass part-10 mass parts are preferable with respect to 100 mass parts of said toners, 0.2 Mass parts to 5 parts by mass are more preferable. When the content exceeds 10 parts by mass, the chargeability of the toner is too large, the effect of the main charge control agent is reduced, the electrostatic attraction force with the developing roller is increased, and the flowability of the developer is reduced. The image density may be reduced. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or of course, may be added when directly dissolving or dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. May be.

-External additive-
The external additive is not particularly limited and may be appropriately selected depending on the intended purpose. Particularly suitable additives include hydrophobized silica, titania, titanium oxide, and alumina fine particles. Hydrophobized fine particles can be obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane.

Examples of the hydrophobized silica fine particles include R972, R974, RX200, RY200, R202, R805, and R812 (all manufactured by Nippon Aerosil Co., Ltd.).
Examples of the titania fine particles subjected to hydrophobic treatment include P-25 (manufactured by Nippon Aerosil Co., Ltd.), STT-30, STT-65C-S (all manufactured by Titanium Industry Co., Ltd.), TAF-140 (Fuji Titanium Industry Co. Co., Ltd.), MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Co., Ltd.) and the like.
The content of the external additive is not particularly limited and may be appropriately selected depending on the intended purpose. More preferred is 3 parts by mass.

-Cleaning improver-
The cleaning property improving agent is not particularly limited as long as it is added to the toner in order to remove the transferred developer remaining on the photoreceptor or the primary transfer medium, and may be appropriately selected according to the purpose. And polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution, and those having a volume average particle size of 0.01 μm to 1 μm are suitable.

-Magnetic material-
There is no restriction | limiting in particular as a magnetic material in the case of making the toner of this invention a magnetic toner, According to the objective, it can select suitably, For example, iron powder, a magnetite, a ferrite etc. are mentioned. Among these, white is preferable in terms of color tone.

When the Tg1st is less than 20 ° C., the heat resistant storage stability is lowered, blocking in the developing machine, and filming on the photoreceptor occurs, and when it exceeds 50 ° C., the low temperature fixability of the toner is deteriorated. When the Tg2nd is less than 0 ° C., the blocking resistance of the fixed image (printed material) is lowered, and when it is 30 ° C. or more, sufficient low-temperature fixability and glossiness may not be obtained.
The volume average particle diameter of the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 3 μm or more and 7 μm or less. The ratio of the volume average particle diameter to the number average particle diameter is preferably 1.2 or less. Further, it is preferable to contain 1% by number or more and 10% by number or less of a component having a volume average particle diameter of 2 μm or less.

<Calculation method and analysis method of various characteristics of toner and toner component>
The Tg, acid value, hydroxyl value, molecular weight, and melting point of the amorphous polyester resin, the crystalline polyester resin, and the release agent may be measured on their own, but they may be measured by gel penetration from an actual toner. It is possible to calculate the SP value, Tg, molecular weight, melting point, and mass ratio of the constituent components by performing separation by chromatography (GPC) or the like, and taking the analysis method described later for the separated components.

For the weight average molecular weight Mw of the toner and the resin, the THF-soluble content of the resin was measured by a GPC measuring apparatus GPC-150C (manufactured by Waters). KF801-807 (manufactured by Shodex) is used for the column, and RI (refractive index) detector is used for the detector.
A sample for GPC measurement was prepared as follows.
1 g of toner is put into 100 mL of THF to obtain a solution in which soluble components are dissolved while stirring for 30 minutes at 25 ° C. This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner. Next, this is diluted with THF to obtain a sample for GPC measurement.
The material obtained above is injected into the GPC used for measuring the molecular weight of the toner.
Separation of each component by GPC can be performed, for example, by the following method.
In GPC measurement using THF (tetrahydrofuran) as a mobile phase, the eluate is fractionated by a fraction collector or the like, and fractions corresponding to a desired molecular weight portion of the entire surface of the elution curve are collected.

After concentrating and drying the collected eluate with an evaporator or the like, the solid content is dissolved in a heavy solvent such as deuterated chloroform or deuterated THF, and ¹ H-NMR measurement is performed. The constituent monomer ratio of is calculated.
As another method, after concentrating the eluate, it is hydrolyzed with sodium hydroxide or the like, and the decomposition product is subjected to qualitative quantitative analysis by high performance liquid chromatography (HPLC) to calculate the constituent monomer ratio.

  In the case where the toner manufacturing method forms toner base particles while generating amorphous polyester resin A by an extension reaction and / or a cross-linking reaction between the nonlinear reactive precursor and the curing agent. May be obtained by separating the actual toner by GPC or the like, and obtaining the Tg of the amorphous polyester resin, or separately, the elongation reaction between the non-linear reactive precursor and the curing agent, and An amorphous polyester resin may be synthesized by a cross-linking reaction, and Tg and the like may be measured from the synthesized amorphous polyester resin.

<< Toner component separation means >>
An example of the separation means for each component when analyzing the toner will be described in detail.
First, 1 g of toner is put into 100 mL of THF, and a solution in which the soluble components are dissolved is obtained while stirring for 30 minutes at 25 ° C.
This is filtered through a membrane filter having an opening of 0.2 μm to obtain a THF soluble component in the toner.
Subsequently, this is melt | dissolved in THF, it is set as the sample for GPC measurement, and it inject | pours into GPC used for the molecular weight measurement of each above-mentioned resin.
On the other hand, a fraction collector is placed at the eluate discharge port of GPC, and the eluate is collected every predetermined count, and the eluate is eluted every 5% in area ratio from the elution curve elution start (curve rise). Get.
Next, for each elution, 30 mg of sample is dissolved in 1 mL of deuterated chloroform, and 0.05% by volume of tetramethylsilane (TMS) is added as a reference substance.
The solution is filled in a 5 mm diameter glass tube for NMR measurement, and a spectrum is obtained by performing integration 128 times at a temperature of 23 ° C. to 25 ° C. using a nuclear magnetic resonance apparatus (JNM-AL400 manufactured by JEOL Ltd.). .

The monomer composition and the composition ratio of the amorphous polyester resin and the crystalline polyester resin contained in the toner can be obtained from the peak integration ratio of the obtained spectrum.
For example, peak assignment is performed as follows, and the component ratio of the constituent monomer is determined from each integral ratio.
The attribution of the peak is, for example,
Near 8.25 ppm: derived from benzene ring of trimellitic acid (for one hydrogen)
8.07 ppm to around 8.10 ppm: derived from benzene ring of terephthalic acid (for 4 hydrogens)
7.1 ppm to 7.25 ppm vicinity: derived from benzene ring of bisphenol A (for 4 hydrogens)
Around 6.8 ppm: derived from benzene ring of bisphenol A (for 4 hydrogens) and from double bond of fumaric acid (for 2 hydrogens)
5.2 ppm to around 5.4 ppm: methine derived from bisphenol A propylene oxide adduct (one hydrogen)
3.7 ppm to around 4.7 ppm: bisphenol A propylene oxide adduct derived from methylene (for 2 hydrogens) and bisphenol A ethylene oxide adduct derived from methylene (for 4 hydrogens)
Around 1.6 ppm: derived from methyl group of bisphenol A (for 6 hydrogens)
It can be.

From these results, for example, the extract recovered in the fraction in which the amorphous polyester resin accounts for 90% or more can be treated as the amorphous polyester resin.
Similarly, the extract recovered in the fraction in which the crystalline polyester resin accounts for 90% or more can be treated as the crystalline polyester resin.

<< Measurement Method of Melting Point and Glass Transition Temperature (Tg) >>
The melting point and glass transition temperature (Tg) in the present invention can be measured using, for example, a DSC system (differential scanning calorimeter) (“Q-200”, manufactured by TA Instruments).
Specifically, the melting point and glass transition temperature of the target sample can be measured by the following procedure.
First, about 5.0 mg of a target sample is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, heating is performed from −80 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere (first temperature increase). Thereafter, the temperature is decreased from 150 ° C. to −80 ° C. at a temperature decrease rate of 10 ° C./min, and further heated to 150 ° C. at a temperature increase rate of 10 ° C./min (second temperature increase). In each of the first temperature increase and the second temperature increase, the DSC curve is measured using a differential scanning calorimeter (“Q-200”, manufactured by TA Instruments).

  From the obtained DSC curve, the DSC curve at the first temperature rise can be selected using the analysis program in the Q-200 system, and the glass transition temperature at the first temperature rise of the target sample can be obtained. Similarly, the DSC curve at the second temperature increase can be selected, and the glass transition temperature at the second temperature increase of the target sample can be obtained.

Further, from the obtained DSC curve, using the analysis program in the Q-200 system, the DSC curve at the first temperature rise is selected, and the endothermic peak top temperature at the first temperature rise of the target sample is obtained as the melting point. Can do. Similarly, the DSC curve at the second temperature rise is selected, and the endothermic peak top temperature at the second temperature rise of the target sample is obtained as the melting point. In this specification, the first time when the toner is used as the target sample. The glass transition temperature at the time of temperature rise is Tg1st, and the glass transition temperature at the second temperature rise is Tg2nd.
Further, in the present specification, the glass transition temperature and melting point of the non-crystalline polyester resin, the crystalline polyester resin, and other components such as the release agent are not particularly specified. The endothermic peak top temperature and Tg at the time are defined as the melting point and Tg of each target sample.

<Toner production method>
The method for producing the toner is not particularly limited and may be appropriately selected depending on the purpose such as a polymerization method, a pulverization method, etc., but the toner includes the amorphous polyester resin and the crystalline polyester resin. Further, if necessary, it is preferably granulated by dispersing an oil phase containing the release agent, the colorant and the like in an aqueous medium.
The toner further includes a polyester resin that is a prepolymer containing a urethane bond and a urea bond as the amorphous polyester resin, a polyester resin that does not contain a urethane bond and a urea bond, and the crystalline polyester resin. Accordingly, it is more preferable to perform granulation by dispersing an oil phase containing the curing agent, the release agent, the colorant and the like in an aqueous medium.
An example of such a method for producing the toner is a known dissolution suspension method. As an example of the method for producing the toner, a method for forming toner base particles while stretching an amorphous polyester resin by an elongation reaction and / or a crosslinking reaction between the prepolymer and the curing agent will be described below. In such a method, the aqueous medium is prepared, the oil phase containing the toner material is prepared, the toner material is emulsified or dispersed, and the organic solvent is removed.
Each step will be described below.

-Preparation of aqueous medium (aqueous phase)-
The aqueous medium can be prepared, for example, by dispersing resin particles in an aqueous medium. The amount of the resin particles added to the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.5 parts by mass to 10 parts by mass with respect to 100 parts by mass of the aqueous medium. .
There is no restriction | limiting in particular as said aqueous medium, According to the objective, it can select suitably, For example, water, the solvent miscible with water, these mixtures etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, water is preferable.
The solvent miscible with water is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, dimethylformamide, tetrahydrofuran, cellosolves, and lower ketones. There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, isopropanol, ethylene glycol etc. are mentioned. There is no restriction | limiting in particular as said lower ketone, According to the objective, it can select suitably, For example, acetone, methyl ethyl ketone, etc. are mentioned.

-Preparation of oil phase-
The oil phase containing the toner material is prepared by the amorphous polyester resin being a prepolymer containing a urethane bond and a urea bond, the polyester resin not containing a urethane bond and a urea bond, and the crystalline polyester resin. And a toner material containing at least the curing agent, the mold release agent, the colorant, and the like, if necessary, may be dissolved or dispersed in an organic solvent.
There is no restriction | limiting in particular as said organic solvent, Although it can select suitably according to the objective, The organic solvent whose boiling point is less than 150 degreeC is preferable at the point which is easy to remove.
The organic solvent having a boiling point of less than 150 ° C. is not particularly limited and may be appropriately selected depending on the intended purpose. For example, toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1 1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, methyl ethyl ketone, methyl isobutyl ketone, and the like. These may be used individually by 1 type and may use 2 or more types together.
Among these, ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, carbon tetrachloride and the like are preferable, and ethyl acetate is more preferable.

-Preparation of fine dispersion of salicylic acid derivative salt-
As a method of finely dispersing the salicylic acid derivative compound in the toner, it is finely dispersed by a mechanical method in an oil phase, and in the emulsion aggregation method, in a water phase. The raw salicylic acid derivative compound is made into fine particles in the oil phase using a bead mill, a high-pressure homogenizer, or the like. It is necessary to disperse to a particle size of preferably 1 μm or less, more preferably 0.5 μm or less.
Moreover, as a method for producing fine crystals and particles in the oil phase and the aqueous phase, there is a method of synthesizing a salicylic acid derivative compound in the oil phase. For example, by adding an alkyl-substituted salicylic acid derivative aqueous solution and a metal salt aqueous solution to the oil phase, a fine zirconium compound can be produced in the toner oil phase by causing a salt and complex formation reaction. In order to allow the reaction to proceed smoothly, water or a polar solvent such as alcohol or ether may coexist in the oil phase.

-Emulsification or dispersion-
The emulsification or dispersion of the toner material can be performed by dispersing the oil phase containing the toner material in the aqueous medium. When the toner material is emulsified or dispersed, the curing agent and the prepolymer can be subjected to an extension reaction and / or a crosslinking reaction.
The reaction conditions (reaction time, reaction temperature) for producing the prepolymer are not particularly limited and may be appropriately selected depending on the combination of the curing agent and the prepolymer.
There is no restriction | limiting in particular as said reaction time, Although it can select suitably according to the objective, 10 minutes-40 hours are preferable, and 2 hours-24 hours are more preferable.
There is no restriction | limiting in particular as said reaction temperature, Although it can select suitably according to the objective, 0 to 150 degreeC is preferable and 30 to 50 degreeC is more preferable.

A method for stably forming the dispersion in the aqueous medium is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a toner material is dissolved or dispersed in a solvent in an aqueous medium phase. For example, a method of adding an oil phase prepared in such a manner and dispersing it by shearing force may be used.
The disperser for the dispersion is not particularly limited and can be appropriately selected according to the purpose. For example, a low-speed shear disperser, a high-speed shear disperser, a friction disperser, and a high-pressure jet disperser. And an ultrasonic disperser.
Among these, a high-speed shearing disperser is preferable in that the particle diameter of the dispersion (oil droplets) can be controlled to 2 μm to 20 μm.
When the high-speed shearing disperser is used, conditions such as the number of rotations, the dispersion time, and the dispersion temperature can be appropriately selected according to the purpose.
There is no restriction | limiting in particular as said rotation speed, Although it can select suitably according to the objective, 1,000 rpm-30,000 rpm are preferable, and 5,000 rpm-20,000 rpm are more preferable.

There is no restriction | limiting in particular as said dispersion | distribution time, Although it can select suitably according to the objective, In the case of a batch system, 0.1 minute-5 minutes are preferable.
There is no restriction | limiting in particular as said dispersion | distribution temperature, Although it can select suitably according to the objective, 0 to 50 degreeC is preferable under pressure, and 30 to 45 degreeC is more preferable. In general, dispersion is easier when the dispersion temperature is higher.

The amount of the aqueous medium used when emulsifying or dispersing the toner material is not particularly limited and may be appropriately selected depending on the intended purpose. It is 50 to 2 parts by mass with respect to 100 parts by mass of the toner material. 1,000 parts by mass is preferable, and 100 parts by mass to 1,000 parts by mass is more preferable.
When the amount of the aqueous medium used is less than 50 parts by mass, the dispersion state of the toner material is deteriorated, and toner base particles having a predetermined particle diameter may not be obtained, and the amount exceeds 2,000 parts by mass. The production cost may increase.

When emulsifying or dispersing the oil phase containing the toner material, it is preferable to use a dispersant from the viewpoint of stabilizing the dispersion such as oil droplets to obtain a desired shape and sharpening the particle size distribution. .
There is no restriction | limiting in particular as said dispersing agent, According to the objective, it can select suitably, For example, surfactant, a slightly water-soluble inorganic compound dispersing agent, a polymeric protective colloid, etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, surfactants are preferable.

There is no restriction | limiting in particular as said surfactant, According to the objective, it can select suitably, For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant etc. are used. be able to.
There is no restriction | limiting in particular as said anionic surfactant, According to the objective, it can select suitably, For example, alkylbenzene sulfonate, (alpha) -olefin sulfonate, phosphate ester etc. are mentioned. Among these, those having a fluoroalkyl group are preferable.

-Removal of organic solvent-
The method for removing the organic solvent from the dispersion such as the emulsified slurry is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the temperature of the entire reaction system is gradually raised, Examples include a method of evaporating the organic solvent, and a method of removing the organic solvent in the oil droplets by spraying the dispersion into a dry atmosphere.

  When the organic solvent is removed, toner base particles are formed. The toner base particles can be washed, dried, etc., and further classified. The classification may be performed by removing fine particle portions in a liquid by a cyclone, a decanter, centrifugation, or the like, or may be performed after drying.

The obtained toner base particles may be mixed with particles such as the external additive and the charge control agent. At this time, by applying a mechanical impact force, it is possible to prevent the particles such as the external additive from detaching from the surface of the toner base particles.
The method for applying the mechanical impact force is not particularly limited and can be appropriately selected depending on the purpose. For example, a method for applying the impact force to the mixture using blades rotating at high speed, For example, a method may be used in which the mixture is charged and accelerated to cause the particles or particles to collide with an appropriate collision plate.
The apparatus used in the above method is not particularly limited and can be appropriately selected depending on the purpose. For example, an ang mill (manufactured by Hosokawa Micron), an I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) and a pulverization air pressure are modified. And a hybridization system (manufactured by Nara Machinery Co., Ltd.), a kryptron system (manufactured by Kawasaki Heavy Industries, Ltd.), and an automatic mortar.

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

<Career>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.

−Core material−
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 50 emu / g to 90 emu / g manganese-strontium material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.
These may be used individually by 1 type and may use 2 or more types together.

There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause scattering of the carrier. In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.
When the toner is used for a two-component developer, it may be used by mixing with the carrier.

(Image forming apparatus and image forming method)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, and a developing unit, and further includes other units as necessary.
The image forming method according to the present invention includes at least an electrostatic latent image forming step and a developing step, and further includes other steps as necessary.

<Electrostatic latent image carrier>
The material, structure, and size of the electrostatic latent image carrier are not particularly limited and may be appropriately selected from known materials. Examples of the material include inorganic photoreceptors such as amorphous silicon and selenium. And organic photoreceptors such as polysilane and phthalopolymethine. Among these, amorphous silicon is preferable in terms of long life.

<Electrostatic latent image forming means and electrostatic latent image forming step>
The electrostatic latent image forming means is not particularly limited as long as it is a means for forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. Examples thereof include at least a charging member that charges the surface of the electrostatic latent image carrier and an exposure member that exposes the surface of the electrostatic latent image carrier imagewise.
The electrostatic latent image forming step is not particularly limited as long as it is a step of forming an electrostatic latent image on the electrostatic latent image carrier, and can be appropriately selected according to the purpose. After the surface of the electrostatic latent image carrier is charged, the imagewise exposure can be performed, and the electrostatic latent image forming unit can be used.

<< Charging member and charging >>
The charging member is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charger including a conductive or semiconductive roller, brush, film, rubber blade, etc. And non-contact chargers utilizing corona discharge such as corotron and scorotron.
The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charging member.
The shape of the charging member may take any form such as a magnetic brush or a fur brush in addition to a roller, and can be selected according to the specifications and form of the image forming apparatus.
The charging member is not limited to the contact-type charging member, but it is preferable to use a contact-type charging member because an image forming apparatus in which ozone generated from the charging member is reduced can be obtained.

<< Exposure member and exposure >>
The exposure member is not particularly limited and may be appropriately selected depending on the purpose, as long as the surface of the electrostatic latent image carrier charged by the charging member can be exposed like an image to be formed. Examples thereof include various exposure members such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
There is no restriction | limiting in particular as a light source used for the said exposure member, According to the objective, it can select suitably, For example, a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light emitting diode (LED), a semiconductor laser General light emitting materials such as (LD) and electroluminescence (EL).
In addition, various types of filters such as a sharp cut filter, a band pass filter, a near infrared cut filter, a dichroic filter, an interference filter, and a color temperature conversion filter can be used to irradiate only light in a desired wavelength range.
The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure member.
In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

<Developing means and development process>
The developing unit is not particularly limited as long as it is a developing unit including toner that develops the electrostatic latent image formed on the electrostatic latent image carrier to form a visible toner image. Can be appropriately selected according to the purpose.
The developing step is not particularly limited as long as it is a step of developing the electrostatic latent image formed on the electrostatic latent image carrier using toner to form a visible toner image. Depending on the purpose, it can be selected as appropriate. For example, it can be carried out by the developing means.
The developing means includes a stirrer for charging the toner by frictional stirring and a magnetic field generating means fixed inside, and a developer carrying that can carry and rotate the developer containing the toner on the surface. A developing device having a body is preferred.

<< Developer >>
The developer of the present invention contains at least the toner and, if necessary, other components such as a carrier as appropriate.
A two-component developer composed of toner and carrier is preferable when used in a high-speed printer or the like corresponding to the recent improvement in information processing speed because the life is improved.

<<< Career >>>>
There is no restriction | limiting in particular as said carrier, Although it can select suitably according to the objective, What has a core material and the resin layer which coat | covers a core material is preferable.
The material for the core material is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 50 emu / g to 90 emu / g manganese-strontium material, 50 emu / g to 90 emu / g manganese- Examples include magnesium-based materials. In order to ensure the image density, it is preferable to use a highly magnetized material such as iron powder of 100 emu / g or more and magnetite of 75 emu / g to 120 emu / g. In addition, since the impact of the developer in the standing state on the photoconductor can be alleviated and it is advantageous for high image quality, a low-magnetization material such as a copper-zinc system of 30 emu / g to 80 emu / g should be used. Is preferred.

  There is no restriction | limiting in particular as a volume average particle diameter of the said core material, Although it can select suitably according to the objective, 10 micrometers-150 micrometers are preferable, and 40 micrometers-100 micrometers are more preferable. When the volume average particle diameter is less than 10 μm, fine powder is increased in the carrier, and magnetization per particle may be reduced to cause carrier scattering. When the volume average particle diameter is more than 150 μm, the specific surface area is decreased, and the toner In the case of a full color with many solid portions, reproduction of the solid portions may be deteriorated.

  When the toner is used for a two-component developer, it may be used by mixing with the carrier. The content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. It is 90 to 98 parts by mass with respect to 100 parts by mass of the two-component developer. Part is preferable, and 93 parts by mass to 97 parts by mass is more preferable.

The developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.
In the developing means, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state, thereby forming a magnetic brush. . The magnet roller is disposed in the vicinity of the electrostatic latent image carrier. Therefore, a part of the toner constituting the magnetic brush formed on the surface of the magnet roller moves to the surface of the electrostatic latent image carrier by an electric attractive force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier.

<Other means and other processes>
Examples of the other means include a transfer means, a fixing means, a cleaning means, a static elimination means, a recycling means, and a control means.
Examples of the other processes include a transfer process, a fixing process, a cleaning process, a static elimination process, a recycling process, and a control process.

<< Transfer means and transfer process >>
The transfer means is not particularly limited as long as it is a means for transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, the visible image is transferred onto an intermediate transfer member and combined. An embodiment having a primary transfer unit for forming a transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The transfer step is not particularly limited as long as it is a step of transferring a visible image to a recording medium, and can be appropriately selected according to the purpose. However, an intermediate transfer member is used, and the transfer step can be performed on the intermediate transfer member. It is preferable that the visual image is firstly transferred and then the visible image is secondarily transferred onto the recording medium.
The transfer step can be performed by, for example, charging the visible image using a transfer charger and the transfer unit.

Here, when the image to be secondarily transferred onto the recording medium is a color image composed of a plurality of colors of toner, the toner of each color is sequentially superimposed on the intermediate transfer member by the transfer means. An image can be formed on the body, and the image on the intermediate transfer body can be collectively transferred onto the recording medium by the intermediate transfer unit.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

The transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer unit that peels and charges the visible image formed on the photoconductor toward the recording medium. Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is typically plain paper, but is not particularly limited as long as it can transfer an unfixed image after development, and can be appropriately selected according to the purpose. A PET base or the like can also be used.

<< Fixing means and fixing process >>
The fixing unit is not particularly limited as long as it is a unit that fixes the transferred image transferred to the recording medium, and can be appropriately selected according to the purpose. However, a known heating and pressing member is preferable. Examples of the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
The fixing step is not particularly limited as long as it is a step of fixing the visible image transferred to the recording medium, and can be appropriately selected according to the purpose. For example, the recording medium for each color toner May be performed each time the toner is transferred to the toner image, or may be performed simultaneously at the same time in a state in which the toner of each color is laminated.

The fixing step can be performed by the fixing unit.
The heating in the heating and pressing member is usually preferably 80 ° C to 200 ° C.
In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing unit depending on the purpose.
The surface pressure in the fixing step is not particularly limited and may be appropriately selected depending on the intended ^purpose, is preferably ^{10N / cm 2 ~80N / cm 2} .

<< Cleaning means and cleaning process >>
The cleaning means is not particularly limited as long as it can remove the toner remaining on the photoconductor, and can be appropriately selected according to the purpose. For example, a magnetic brush cleaner, an electrostatic brush cleaner, Examples thereof include a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
The cleaning step is not particularly limited as long as it can remove the toner remaining on the photoreceptor, and can be appropriately selected according to the purpose. For example, the cleaning step can be performed by the cleaning unit.

<< Static elimination means and static elimination process >>
The neutralizing means is not particularly limited as long as it is a means for neutralizing by applying a neutralizing bias to the photosensitive member, and can be appropriately selected according to the purpose. Examples thereof include a neutralizing lamp.
The neutralization step is not particularly limited as long as it is a step of neutralizing by applying a neutralization bias to the photoconductor, and can be appropriately selected according to the purpose. For example, it can be performed by the neutralization unit. .

<< Recycling means and recycling process >>
The recycling unit is not particularly limited as long as it is a unit that recycles the toner removed in the cleaning step to the developing device, and can be appropriately selected according to the purpose. Can be mentioned.
The recycling process is not particularly limited as long as it is a process for recycling the toner removed in the cleaning process to the developing device, and can be appropriately selected according to the purpose. For example, the recycling unit performs the recycling process. Can do.

Next, one mode for carrying out the method of forming an image by the image forming apparatus of the present invention will be described with reference to FIG.
The image forming apparatus 1 is a printer, but the image forming apparatus is not particularly limited as long as the image forming apparatus can form an image using toner of a copying machine, a facsimile machine, a multifunction machine, or the like.
The image forming apparatus 1 includes a paper feeding unit 210, a conveyance unit 220, an image forming unit 230, a transfer unit 240, and a fixing device 250.
The paper feed unit 210 includes a paper feed cassette 211 on which paper P to be fed is loaded, and a paper feed roller 212 that feeds the paper P loaded on the paper feed cassette 211 one by one.

The transport unit 220 waits between a roller 221 that transports the paper P fed by the paper feed roller 212 in the direction of the transfer unit 240 and a leading end of the paper P transported by the roller 221, and waits for a predetermined paper. A pair of timing rollers 222 that are sent to the transfer unit 240 at a timing and a paper discharge roller 223 that discharges the paper P on which the color toner image has been fixed to a paper discharge tray 224 are provided.
The image forming unit 230 includes an image forming unit Y for forming an image using a developer having yellow toner and cyan toner in order from left to right in the figure at a predetermined interval. The image forming unit C using the developer, the image forming unit M using the developer having magenta toner, the image forming unit K using the developer having black toner, and the exposure device 233 are provided.

In addition, when showing arbitrary image formation units among image formation units (Y, C, M, K), it is called an image formation unit.
The developer includes toner and a carrier.
The four image forming units (Y, C, M, and K) have substantially the same mechanical configuration except that the developers used are different.
The transfer unit 240 has a driving roller 241 and a driven roller 242, and an intermediate transfer belt 243 that can rotate counterclockwise in the drawing as the driving roller 241 is driven. The secondary transfer roller (244Y, 244C, 244M, 244K) provided opposite to the body drum 231 and the secondary transfer roller provided opposite to the intermediate transfer belt 243 at the transfer position of the toner image onto the paper. 245 and a secondary transfer roller 246.
The fixing device 250 is provided with a heater, and includes a pressure roller 252 that forms a nip by rotatably pressing the fixing belt 251 that heats the paper P against the fixing belt 251. . As a result, heat and pressure are applied to the color toner image on the paper P, and the color toner image is fixed. The paper P on which the color toner image has been fixed is discharged to a discharge tray 224 by a discharge roller 223, and a series of image forming processes is completed.

(Toner storage unit)
The toner storage unit in the present invention refers to a unit in which toner is stored in a unit having a function of storing toner. Here, examples of the toner storage unit include a toner storage container, a developing device, and a process cartridge.
The toner container is a container that contains toner.
The developing device is a unit having a means for containing and developing toner.
The process cartridge is a cartridge in which at least the image carrier and the developing unit are integrated, accommodates toner, and is detachable from the image forming apparatus. The process cartridge may further include at least one selected from a charging unit, an exposure unit, and a cleaning unit.

  By mounting the toner storage unit of the present invention on an image forming apparatus to form an image, the durability of the present invention, low-temperature fixability, pulverization during toner production, copy blocking resistance, and filming resistance are excellent. In addition, since image formation is performed with low-cost toner, a high-quality image can be obtained at low cost.

<Process cartridge>
A process cartridge according to the present invention is detachably formed in various image forming apparatuses, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. And at least developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further include other means as necessary.
The developing means includes at least a developer accommodating portion that accommodates the developer of the present invention and a developer carrier that carries and conveys the developer accommodated in the developer accommodating portion. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.
FIG. 2 shows an example of a process cartridge according to the present invention. The process cartridge 110 includes a photosensitive drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.

Examples of the present invention will be described below, but the present invention is not limited to the following examples. Unless otherwise specified, “part” refers to “part by mass”, and “%” refers to “mass%”.
Each measured value in the following examples was measured by the method described in this specification.

(Production Example 1)
<Synthesis of Amorphous Polyester Resin A1>
In a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 20.3 parts of terephthalic acid, 8.7 parts of isophthalic acid, 40.8 parts of 2.2 mol adduct of bisphenol A ethylene oxide, propylene of bisphenol A 30.2 parts of an oxide 2.2 mol adduct and 0.2 part of dibutyltin oxide were added, reacted at 230 ° C. for 4 hours under normal pressure, and then reacted for 5 hours under reduced pressure of 10 mmHg to 15 mmHg. Resin A1] was obtained.

(Production Example 2)
<Synthesis of Amorphous Polyester Resin A2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen introduction tube, 25.8 parts of terephthalic acid, 27.8 parts of adipic acid, 44.9 parts of 3-methyl-1,5-pentanediol, trimethylolpropane, 1. 5 parts and 0.2 part of dibutyltin oxide were added, reacted at 230 ° C. under normal pressure for 4 hours, and then reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain an amorphous polyester resin intermediate. Furthermore, 2.0 parts of trimellitic acid was added and reacted under reduced pressure of 10 mmHg to 15 mmHg for 5 hours to obtain [Amorphous Polyester Resin A2].

(Production Example 3)
<Synthesis of Amorphous Polyester Resin A3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 90 parts of the amorphous polyester resin intermediate obtained in Production Example A2 and 10 parts of isophorone diisocyanate (IPDI) were added, and 100 parts of ethyl acetate was added. After dilution, the mixture was reacted at 80 ° C. for 5 hours to obtain an amorphous polyester resin A3 as a prepolymer and an ethyl acetate solution having a solid content of 50%.

(Production Example 4)
<Synthesis of crystalline polyester resin B>
In a 5 L four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, and a thermocouple, dodecanedioic acid and ethylene glycol were mixed at a OH / COOH molar ratio of hydroxyl group to carboxyl group of 0.9. Then, after reacting with titanium tetraisopropoxide (500 ppm with respect to the resin component) at 180 ° C. for 10 hours, the temperature was raised to 200 ° C. and reacted for 3 hours, and the pressure was further increased to 8.3 kPa. For 2 hours to obtain [Crystalline Polyester Resin B].

  Table 1 shows the physical properties of the amorphous polyester resins A1, A2, A3 and the crystalline polyester resin B.

<Preparation of master batch (MB)>
Add 600 parts of water, 500 parts of carbon black (Nexex 60 Dexa) and 500 parts of [Amorphous Polyester Resin A1], and mix with a Henschel mixer (Mitsui Mining Co., Ltd.). After kneading for 30 minutes, it was rolled and cooled and pulverized with a pulverizer to obtain [Masterbatch 1].

<Synthesis of organic fine particle emulsion (fine particle dispersion)>
In a reaction vessel equipped with a stirrer and a thermometer, 683 parts of water, 11 parts of sodium salt of ethylene oxide methacrylate adduct sulfate (Eleminol RS-30: manufactured by Sanyo Chemical Industries), 138 parts of styrene, 138 parts of methacrylic acid , And 1 part of ammonium persulfate were added and stirred at 400 rpm for 15 minutes to obtain a white emulsion. The system was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 5 hours, and an aqueous dispersion of a vinyl resin (a copolymer of sodium salt of styrene-methacrylic acid-methacrylic acid ethylene oxide adduct sulfate) [fine particles Dispersion] was obtained.
The volume average particle diameter of the [fine particle dispersion] measured by LA-920 (manufactured by HORIBA) was 0.14 μm.

<Preparation of dispersion of crystalline polyester resin B>
100 parts of crystalline polyester resin B and 400 parts of ethyl acetate are charged in a container equipped with a stir bar and a thermometer, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, and then 20 ° C. for 1 hour. Then, using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), the liquid feeding speed is 1 kg / hr, the disk peripheral speed is 6 m / sec, 80% by volume of 0.5 mm zirconia beads are filled, and dispersed under the conditions of 3 passes. Then, ethyl acetate was added to obtain a [crystalline polyester resin dispersion] adjusted to a solid content of 20%.

<Preparation of WAX dispersion>
A container in which a stir bar and a thermometer are set is charged with 100 parts of ester wax (manufactured by NOF Corporation, WEP-3, melting point 70 ° C., acid value 0.1 mg KOH / g) and 400 parts of ethyl acetate as a release agent. The temperature was raised to 80 ° C., kept at 80 ° C. for 5 hours, cooled to 20 ° C. at 1 hour, and using a bead mill (Ultra Visco Mill, manufactured by IMEX), the liquid feeding speed was 1 kg / hr, the disk Filling with 80% by volume of 0.5 mm zirconia beads at a peripheral speed of 6 m / sec, dispersion was carried out under the conditions of 3 passes, and ethyl acetate was added to obtain [WAX dispersion liquid] adjusted to a solid content of 20%.

<Preparation of salicylic acid derivative zirconium salt dispersion 1>
In a vessel equipped with a stir bar and thermometer ・ 50 parts of 1,3-di-t-butyl salicylate (SZr) ・ 50 parts of amorphous polyester resin A1 ・ 400 parts of ethyl acetate The temperature was raised and held at 30 ° C. for 1 hour to dissolve the resin and obtain a salicylic acid derivative metal salt dispersion. Cooled to 20 ° C. in 1 hour, filled with 80% by volume of 0.5 mm zirconia beads at a feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec using a bead mill (Ultra Visco Mill, manufactured by IMEX), 10 passes Dispersion was carried out under the above conditions to obtain [Zirconium 1,3-di-t-butylsalicylate (SZr) dispersion 1] which was adjusted to a solid content of 20% by adding ethyl acetate. The volume average particle diameter of the obtained dispersion measured with LA-920 (manufactured by HORIBA) was 0.25 μm.

<Preparation of salicylic acid derivative zirconium salt dispersion 2>
In the preparation of the above-mentioned “salicylic acid derivative metal salt dispersion 1”, the solid content was adjusted to 20% in the same manner except that 10 passes in the dispersion condition of the bead mill (Ultraviscomil, manufactured by Imex Corporation) was changed to 3 passes [1. , Zirconium 3-di-t-butylsalicylate (SZr) dispersion 2] was obtained. The volume average particle diameter of the obtained dispersion measured with LA-920 (manufactured by HORIBA) was 1.05 μm.

(Oil-water distribution test)
30 parts of the obtained (SZr) dispersion 1 and (SZr) dispersion 2 and 70 parts of ion-exchanged water were charged in a screw vial and vibrated with a shaker for 1 hour. Then, after standing for 3 hours and observing, a cloudy phase containing zirconium 1,3-di-t-butylsalicylate and a clear water phase were clearly separated and confirmed.
On the other hand, 3 parts of zirconium 1,3-di-t-butylsalicylate and 27 parts of ethyl acetate were charged into a screw vial and mixed with stirring for 1 hour. Then, 70 parts of ion-exchanged water was charged into a screw vial and vibrated with a shaker for 1 hour. Then, after standing for 3 hours and observing, a cloudy water phase containing zirconium 1,3-di-t-butylsalicylate and a transparent ethyl acetate phase were confirmed. Therefore, it was confirmed that the zirconium 1,3-di-t-butylsalicylate did not desorb to the aqueous phase side from the (SZr) dispersion.

<Preparation of salicylic acid derivative aluminum salt dispersion>
Similarly, instead of 50 parts of 1,3-di-t-butylsalicylic acid zirconium salt (SZr), 50 parts of 1,3-di-t-butylsalicylic acid aluminum salt (SAl) was used, and a dispersion having a solid content of 20% [1, 3-Di-t-butylaluminum salicylate (SAl) dispersion]. The volume average particle diameter was 0.29 μm.

<Preparation of salicylic acid derivative aluminum salt dispersion>
Further, instead of 50 parts of 1,3-di-t-butylsalicylic acid zirconium salt (SZr), 50 parts of 1,3-di-t-butylsalicylic acid iron (SFe) was used, and a dispersion [1, 1, 3-di-t-butyl salicylate iron (SFe) dispersion]. The volume average particle diameter was 0.23 μm.

<Preparation of salicylic acid derivative aluminum salt dispersion>
Furthermore, instead of 50 parts of zirconium 1,3-di-t-butylsalicylate (SZr), 50 parts of 1,3-di-t-butylsalicylic acid zinc (SZn) was used, and a dispersion [1, 1, 3-di-t-butylsalicylic acid zinc (SZn) dispersion] was prepared. The volume average particle diameter was 0.31 μm.

  When an oil / water distribution test was performed on the (SAl) dispersion, (SFe) dispersion, and (SZn) dispersion, it was confirmed that the salicylic acid derivative metal salt was not detached from the dispersion toward the aqueous phase.

Example 1
<Preparation of aqueous phase>
312 parts of water, 11 parts of [fine particle dispersion], 11 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Kasei Kogyo Co., Ltd.) and 28 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This was designated as [aqueous phase].

<Preparation of oil phase>
[Ethyl acetate] 89 parts, [WAX dispersion] 25 parts, [Amorphous polyester resin A1] 92 parts, [Amorphous polyester resin A2] 8 parts, [Masterbatch 1] 16 parts, [(SZr) dispersion [Liquid 1] 20 parts were put into a container, and mixed with a TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 60 minutes to obtain [oil phase].

<Emulsification / desolvation>
[Oil phase] was added to a container containing [aqueous phase], and mixed with a TK homomixer at 13,000 rpm for 3 minutes to obtain [emulsified slurry].
[Emulsified slurry] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 30 ° C. for 8 hours to obtain [Dispersed slurry].

<Washing and drying>
[Dispersion Slurry] After 100 parts were filtered under reduced pressure, the following processing operation was performed.
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): The operation of (1) to (5) above, wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. Was performed twice to obtain a filter cake. Further, ion-exchanged water was added to the filter cake so that the solid content was 50%, and the resulting mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) to obtain a toner slurry.
This solution was filtered, dried at 45 ° C. for 48 hours with a circulating dryer, and sieved with a mesh of 75 μm to obtain [toner base H1]. NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd. and HSP-160A manufactured by Fuso Chemical Industries Co., Ltd. Part) was mixed with a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain the toner of Example 1.

(Examples 2 to 13, Comparative Examples 1 to 5)
Toners of Examples 2 to 13 and Comparative Examples 1 to 5 were prepared in the same manner as in Example 1 according to the charging amounts shown in Table 2 below. However, Comparative Examples 3, 4, and 5 did not use the (SZr) dispersion.

(Example 14)
<Preparation of aqueous phase>
312 parts of water, 11 parts of [fine particle dispersion], 11 parts of 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7: Sanyo Kasei Kogyo Co., Ltd.) and 28 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This was designated as [aqueous phase].

<Preparation of oil phase>
[Ethyl acetate] 89 parts, [WAX dispersion] 25 parts, [Amorphous polyester resin A1] 88 parts, [Amorphous polyester resin A2] 12 parts, [Masterbatch 1] 16 parts, The mixture was mixed at 5,000 rpm for 60 minutes with a TK homomixer (made by Tokushu Kika) to obtain WAX and a pigment dispersion in an ethyl acetate resin solution.
(Synthesis in zirconium compound dispersion)
While stirring the obtained ethyl acetate dispersion at 600 rpm with a three-one motor, a solution having 0.39 parts of zirconium oxychloride (octahydrate) dissolved in 5 parts of ion-exchanged water was added. On the other hand, 0.61 part of 1,3-di-t-butylsalicyl is dissolved in 5 parts of 1% sodium hydroxide water. This solution was gradually added over 30 minutes to synthesize a zirconium compound in the oil phase.
The obtained oil phase was emulsified, desolvated, washed, dried and mixed with inorganic fine particles in the same manner as in Example 1 to obtain a toner of Example 14.

(Example 15)
The amount of synthesis of the zirconium compound in the oil phase in the dispersion was twice that of Example 14.
That is, while stirring the ethyl acetate dispersion obtained in Example 14 at 600 rpm with a three-one motor, a solution in which 0.78 parts of zirconium oxychloride (octahydrate) was dissolved in 10 parts of ion-exchanged water was added. . Meanwhile, 1.22 parts of 1,3-di-t-butylsalicyl is dissolved in 10 parts of 1% caustic soda water. This solution was gradually added over 60 minutes to synthesize a zirconium compound in the oil phase.
The obtained oil phase was emulsified, desolvated, washed, dried and mixed with inorganic fine particles in the same manner as in Example 1 to obtain a toner of Example 15.

(Example 16)
The amount of synthesis in the dispersion of the zirconium compound in the oil phase was three times that of Example 14.
That is, a solution prepared by dissolving 1.17 parts of zirconium oxychloride (octahydrate) in 15 parts of ion-exchanged water was added while stirring the ethyl acetate dispersion obtained in Example 14 at 600 rpm with a three-one motor. . On the other hand, 1.83 parts of 1,3-di-t-butylsalicyl is dissolved in 15 parts of 1% caustic soda water. This solution was gradually added over 90 minutes to synthesize a zirconium compound in the oil phase.

<Preparation of oil phase>
[Ethyl acetate] 89 parts, [WAX dispersion] 25 parts, [Amorphous polyester resin A1] 96 parts, [Amorphous polyester resin A2] 4 parts, [Masterbatch 1] 16 parts, [(SZr) dispersion [Liquid] 20 parts were put into a container and mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 60 minutes to obtain [oil phase].
The obtained oil phase was emulsified, desolvated, washed, dried and mixed with inorganic fine particles in the same manner as in Example 1 to obtain a toner of Example 16.

(Example 17)
<Preparation of oil phase>
[Ethyl acetate] 49 parts, [WAX dispersion] 25 parts, [Amorphous polyester resin A1] 78 parts, [Amorphous polyester resin A2] 12 parts, Crystalline polyester resin B dispersion 50 parts, [Masterbatch 1] 16 parts were put into a container and mixed with TK homomixer (manufactured by Special Machine) for 60 minutes at 5,000 rpm to obtain [oil phase].

(Synthesis in zirconium compound dispersion)
While stirring the obtained ethyl acetate dispersion at 600 rpm with a three-one motor, a solution having 0.39 parts of zirconium oxychloride (octahydrate) dissolved in 5 parts of ion-exchanged water was added. On the other hand, 0.61 part of 1,3-di-t-butylsalicyl is dissolved in 5 parts of 1% sodium hydroxide water. This solution was gradually added over 30 minutes to synthesize a zirconium compound in the oil phase.
The obtained oil phase was emulsified, desolvated, washed, dried and mixed with inorganic fine particles in the same manner as in Example 1 to obtain a toner of Example 17.
Table 3 shows the storage elastic modulus of the obtained toner at the time of temperature rise and time of temperature fall.

(Example 18)
A toner of Example 18 was made in the same manner as in Example 2, except that [salicylic acid derivative zirconium salt dispersion liquid 2] was used instead of [salicylic acid derivative zirconium salt dispersion liquid 1].

(Comparative Example 6)
A toner was prepared until after the emulsification step in the same manner as in Example 2. Then, [Emulsified slurry] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 80 ° C. for 2 hours to obtain [Dispersed slurry].
<Washing and drying>
After filtering 100 parts of the obtained [dispersed slurry] under reduced pressure,
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1), mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2), mixed with a TK homomixer (rotation speed: 12,000 rpm for 10 minutes), and then filtered.
(4): The operation of (1) to (5) above, wherein 300 parts of ion-exchanged water is added to the filter cake of (3), mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered. Was performed twice to obtain a filter cake. Further, ion-exchanged water was added to the filter cake so that the solid content was 50%, and the resulting mixture was mixed with a TK homomixer (at 12,000 rpm for 10 minutes) to obtain a toner slurry.
This solution was filtered and dried at 45 ° C. for 48 hours in a circulating dryer, and a sieve toner base was obtained with a mesh opening of 75 μm. NX-90S (1.0 part) manufactured by Nippon Aerosil Co., Ltd., JMT-150IB (1.0 part) manufactured by Teika Co., Ltd., and HSP-160A manufactured by Fuso Chemical Industries Co., Ltd. Part) was mixed using a Henschel mixer manufactured by Mitsui Mining Co., Ltd., and sieved with a mesh of 25 μm to obtain a toner of Comparative Example 6.
The obtained toner had a Tg of 52 ° C. Therefore, in the solvent removal process, a temperature of Tg + 28 ° C. of the toner was applied during the process.

The toners of Examples and Comparative Examples were put in an image forming apparatus and evaluated.
The apparatus used was a Ricoh digital full-color multifunction peripheral MP C6003.

<Evaluation of fixability>
A rectangular solid image of 3 cm × 15 cm is formed on the PPC paper type 6000 <70W> A4 T (made by Ricoh Company) so that the toner adhesion amount is 0.85 mg / cm ² and output. The fixing temperature is adjusted, and the temperature is decreased by 1 ° C. from 160 ° C. to output an image. The reattachment state of the toner in the second round of the image to the paper was judged visually, and the temperature at which cold offset began to occur was measured.

<Evaluation of blocking properties>
A rectangular solid image of 3 cm × 15 cm is formed on a PPC paper type 6000 <70W> A4 Tth (manufactured by Ricoh) so that the toner adhesion amount is 0.85 mg / cm ^2, and 200 sheets are continuously output on one side. . The fixing temperature is controlled to be centered on the cold offset temperature + 20 ° C. The 200 output images are stacked for 1 hour and then the pasting of the images is evaluated.
(Blocking evaluation criteria)
A: There is no sticking between papers.
○: There is a little sticking between the papers, but the papers are easily peeled off and there is no problem with the image when released.
○ △: When there is a little sticking between papers and there is a slight noise when the papers are separated, but there is no problem in image quality.
Δ: There is a little sticking between the sheets, and the gloss of the image changes when the sheets are separated.
×: There is sticking between papers, and the images and paper are damaged when the papers are separated.

<Evaluation of image preservation>
A rectangular solid image of 3 cm × 15 cm is formed on the PPC paper type 6000 <70W> A4 T (manufactured by Ricoh) so that the toner adhesion amount is 0.85 mg / cm ² and is output on one side. The fixing temperature is controlled to be centered on the cold offset temperature + 20 ° C. The obtained image surfaces were overlapped and brought into contact with each other, and a weight corresponding to 8 kPa was placed thereon and left in an environment of 60 ° C. and 50% RH for one week. The two stacked sheets were peeled off after standing, and the state at the time of peeling was observed.
(Evaluation criteria for image preservation)
◎: There is no sticking between papers and there is no image loss or transfer ○: There is a little sticking when peeling (slight peeling sound), but the paper is easily peeled off, and the image when released △: There is sticking between papers, and there is image loss and transition. ×: There is sticking between papers. fall into disrepair.
The evaluation results of the toner with a weight average molecular weight of the change rate R _M and an acid number of the change rate R _AV for each toner are shown in Table 4.

From the results shown in Table 4 above, it can be seen that those having a low Av change rate are inferior in blocking properties because reactions at the time of fixing hardly occur.
The image forming apparatus of the present invention can perform low-temperature fixing, can reduce power consumption, and can output an image excellent in blocking resistance and image storage stability.

DESCRIPTION OF SYMBOLS 1 Image forming apparatus 180 Developing device 221 Roller 222 Timing roller 223 Discharge roller 224 Discharge tray 230 Image forming unit 231 Photosensitive drum 232 Charger 233 Exposure device 233a Light source 233b Polygon mirror 240 Transfer unit 241 Drive roller 242 Driven roller 243 Intermediate Transfer belt 244 Primary transfer roller 245 Secondary counter roller 246 Secondary transfer roller 250 Fixing device 251 Fixing belt 252 Pressure roller P Paper

Japanese Patent Laid-Open No. 11-2982 JP-A-4-44075 JP-A-8-262903 JP-A-10-213984 JP 2007-334205 A JP 2008-154822 A JP 2008-216928 A JP 2010-0777419 A JP 2010-151996 A

Claims (11)

A toner that is fixed to an image bearing member by heat and has a storage elastic modulus G ′ measured by a rheometer of the toner that satisfies the following condition.
The storage elastic modulus G ′ at 100 ° C. at the time of temperature rise is 1 × 10 ³ to 1 × 10 ⁶ Pa
-Storage elastic modulus G 'at 100 ° C during temperature drop is 1 x 10 ³ to 1 x 10 ⁶ Pa
In addition, the value of the storage elastic modulus G ′ at 100 ° C. is higher when the temperature is lowered than when the temperature is raised. The storage elastic modulus G ′ at 100 ° C. at the time of temperature rise is 1 × 10 ^{4 to} 3 × 10 ⁵ Pa,
The toner according to claim 1, wherein a storage elastic modulus G ′ at 100 ° C. during the temperature drop is 1 × 10 ^{4 to} 3 × 10 ⁵ Pa. When the weight average molecular weight of the toner before temperature rise is Mw1, and the weight average molecular weight of the toner after temperature drop is Mw2, the change rate R _M (%) calculated by the following formula (1) is 10% or more and 140%. The toner according to claim 1, wherein the toner is:

The toner according to claim 3, wherein the change rate R _M (%) is 30% or more and 80% or less.   The toner according to claim 1, comprising a crystalline polyester resin. The binder contains a polyester resin having an acid value, and contains a metal complex of salicylic acid represented by the following general formula (1) or a salt thereof, or a metal complex of a hydroxynaphthoic acid derivative or a salt thereof. The toner according to any one of 1 to 5.

In the formula, R _{1 to} R ₄ are each a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, —OH, —NH ₂ , —NH (CH ₃ ), —N (CH ₃ ) ₂ , —OCH ₃ , —O (C ₂ H ₅ ), —COOH and —CONH ₂ are the same or different groups.
The metal forming the metal salt is any one of Zn ²⁺ , Al ³⁺ , Cr ³⁺ , Fe ³⁺ , and Zr ⁴⁺ . When the acid value of the toner before temperature increase is Av1 and the acid value of the toner after temperature decrease is Av2, the change rate R _AV (%) calculated by the following equation (2) is 20% or more and 80% or less. The toner according to claim 1, wherein the toner is present.

A toner manufacturing method according to any one of claims 1 to 7,
A toner is obtained by dissolving or dispersing at least a binder resin in an organic solvent, dispersing or emulsifying the dissolved or dispersed material in an aqueous medium, and removing the solvent from the dispersion obtained by granulation. A toner production method characterized by the above.   A toner containing unit containing the toner according to claim 1. A photoreceptor,
Charging means for charging the photoreceptor;
Exposure means for exposing the charged photoreceptor to form an electrostatic latent image; and
Developing means for developing the electrostatic latent image formed on the photoreceptor using toner to form a toner image;
Transfer means for transferring a toner image formed on the photoreceptor to a recording medium;
Fixing means for fixing the toner image transferred to the recording medium,
An image forming apparatus, wherein the toner is the toner according to claim 1. An electrostatic latent image forming step of forming an electrostatic latent image on the photoreceptor;
A developing step of developing the electrostatic latent image formed on the photoreceptor using toner to form a toner image;
A transfer step of transferring the toner image formed on the photoreceptor to a recording medium;
A fixing step of fixing the toner image transferred to the recording medium,
An image forming method, wherein the toner is the toner according to claim 1.

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