JP2014149370A - Toner, developer, image forming apparatus, process cartridge, and fixation image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming apparatus which ensures low-temperature fixability, hot-offset resistance having a trade-off relationship therewith, and heat-resistant preservability, while improving fold fixing strength.SOLUTION: In toner including at least binder resin, a colorant, and a mold-releasing agent satisfies 8≤F/L≤12, a gradient F/L of a curve to a separation point P, which indicates a relationship between a sensor output F and a scratch distance L in a micro-scratch test of the toner with respect to a fixation image satisfies 8≤F/L≤12.

Description

  The present invention relates to a toner used for electrophotographic image formation such as a copying machine, electrostatic printing, facsimile, printer, electrostatic recording, and the like, and a developer, an image forming apparatus, a process cartridge, and a fixed image using the toner. .

In recent years, heat-fixing image forming apparatuses require a large amount of power in the process of fusing toner and fixing it on a recording medium such as paper. Is one of the important characteristics.
In order to improve the low-temperature fixability of the toner, it is necessary to control the thermal characteristics of the binder resin that occupies most of the toner.

  For example, in Patent Document 1, in a toner having a crystalline resin as a main component of a binder resin, it is possible to satisfy both low-temperature fixability and heat-resistant storage stability by defining the composition and thermal characteristics of the crystalline resin. Proposed. Further, in Patent Document 2, a toner containing two types of crystalline resins having different molecular weights as a binder resin (in particular, a statement that a crystalline polyester resin is preferable) is used under specific fixing conditions, so that low temperature fixability is achieved. It has been proposed that the cracking of the fixed image can be suppressed while improving.

  Patent Document 3 proposes that both low-temperature fixability and pressure storage stability can be achieved by including two types of crystalline polyester resins having different storage elastic moduli at 160 ° C. as the binder resin. Yes. Further, Patent Document 4 proposes that the binder resin contains at least a crystalline polyester, and that the crystal structure exists in a toner state, so that both low-temperature fixability and heat-resistant storage stability can be achieved. .

  On the other hand, image forming apparatuses are increasingly used not only as office machines but also as production machines for bookbinding and folding booklets as color, speed, and image quality increase. Accordingly, it has become important that the toner does not peel off at the fold when the image after fixing is folded by a post-processing process.

For example, in order to solve this problem, Patent Document 5 proposes that both bending strength and friction resistance can be achieved by blending urethane particles in a binder resin for toner. Patent Document 6 proposes that both low-temperature fixability, high-temperature offset resistance, and crease-fixing strength can be achieved by dissolving polyurethane at a molecular level in a binder resin mainly composed of styrene acrylic resin. Yes.
However, none of these techniques has sufficiently solved the above problems.

  The present invention has been made in view of the above problems. Its purpose is to achieve both low-temperature fixability to achieve energy savings and hot-offset resistance and heat-storability that are trade-offs, and the toner can be peeled off even when the image support is folded. An object of the present invention is to provide a toner capable of forming an image having excellent crease fixing strength.

  The above-described problem is that a curve indicating the relationship between the scratch distance L and the sensor output F in the micro-scratch test on the fixed image of the toner in the toner composed of at least the binder resin, the colorant, and the release agent of the present invention. The toner is characterized in that the gradient F / L up to the peeling point P satisfies the relationship of 8 ≦ F / L ≦ 12. ”

  The toner of the present invention can achieve both low-temperature fixability for achieving energy saving and hot offset resistance and heat-resistant storage stability that are in a trade-off relationship with the low-temperature fixability. Furthermore, the toner of the present invention enables image formation with excellent crease fixing strength that does not cause separation of the toner at the fold even if the image support after fixing is folded in the post-processing step.

It is a figure which shows an example of the graph after fitting at the time of crystallinity calculation of the toner of this invention. 1 is a schematic view for explaining an electrophotographic process and an image forming apparatus of the present invention. 1 is a schematic view for explaining a tandem-type full-color electrophotographic apparatus of the present invention. FIG. It is the schematic for demonstrating the process cartridge of this invention.

  The toner of the present invention will be described. It is easy for those skilled in the art to change or modify the present invention within the scope of the claims to form other embodiments, and these changes and modifications are included in the scope of the claims. The following description is an example of the best mode of the present invention, and does not limit the scope of the claims.

Hereinafter, characteristics of the toner used in the image forming apparatus according to the present embodiment will be described.
In the toner of the present invention, the gradient F / L up to the peeling point P of the curve indicating the relationship between the scratch distance L and the sensor output F by the micro scratch test on the fixed image of the toner is in the range of 8 ≦ F / L ≦ 12. It is characterized by being.
When the curve slope F / L satisfies the above relationship, the toner layer of the image after fixing is in a sufficiently melted state with no particle interface, and the toner layer itself is elastic with moderate softness. To have. As a result, even when a support such as paper is bent, the toner layer is not easily broken at the crease, and the adhesive surface with the paper (support) can be maintained without being peeled off. For this reason, an image having excellent fixing strength at the fold can be obtained.
On the other hand, when the gradient F / L is less than 8, the toner layer of the image after fixing has a particle interface, or the toner layer itself is very hard even if it does not exist. For this reason, when the paper (support) is bent, the toner layer is broken at the fold, and the adhesive surface with the paper (support) is also peeled off and easily peeled off. On the other hand, when the gradient F / L is larger than 12, the toner layer itself of the image after fixing is very soft, so that the pressure tends to be easily deformed. For this reason, traces due to rollers or claws during conveyance are likely to be attached to the toner layer, leading to a reduction in the quality of the fixed image.

  Here, in the micro scratch test for the fixed image after fixing, an ultra-thin scratch tester (Model CSR-2000, manufactured by Reska Co., Ltd.) is used to examine the gradient to the inflection point of the scratch distance-sensor output curve. This is done by a simple method.

Hereinafter, the fixed image used for evaluation and its evaluation method will be described in detail.
The fixed image was formed as a solid image having an adhesion amount of 0.85 ± 0.10 mg / cm ² , fixed at 140 ° C., stored in a room temperature and normal humidity (25 ° C., 60% RH) environment for 1 day, and then fixed. Secure to the sample table of the scratch testing machine.

  The micro-scratch test is one of the thin film adhesion tests, which can give a stronger mechanical stimulus than the tape test and the peeling method using an adhesive, and has a relatively strong adhesion with a film thickness of about 1 μm or less. It is used for the evaluation of adhesion.

  In the measurement of the micro scratch test, a hemispherical diamond having a radius of curvature (stylus diameter) of 5 μm to 100 μm attached to the tip of a small cantilever is used as a measuring needle. Attach it to the cartridge similar to the pickup for the record player and increase the load of the needle while pulling it sideways (scratch) while pressing the needle against the surface of the fixed image while vibrating with the amplitude of 5-100 μm parallel to the surface of the fixed image. To go. Then, solid friction acts on the needle tip and relative movement occurs between the cartridge body and a voltage signal is generated in the sensor in proportion to the friction force.

  Specifically, the fixed image is attached to a horizontal sample table, and the sample table is moved laterally at a driving speed of 0 to 30 μm / sec while pressing the needle at the tip of the cantilever on the surface of the fixed image. The needle is pushed up by the movement of the sample stage, and a load W of 1 mN to 1 N is gradually applied to the needle tip due to positional distortion between the cantilever and the high sensitivity sensor. Simultaneously with this lateral movement, the cartridge body is forcibly vibrated in parallel with the fixed image surface with an excitation amplitude of 5 to 100 μm. A voltage signal generated in proportion to the friction force applied to the needle tip is detected by a high sensitivity sensor.

  By detecting this voltage signal in real time, a frictional force proportional to the load is generated before the fixed image is damaged (toner peeling at the support interface), and when the critical load is reached, the vibration caused by the breakdown is reached. And irregularities on the damaged surface can be observed as scratch noise. Then, by obtaining a mechanical characteristic curve indicating the relationship between the scratch distance L and the sensor output F, that is, a scratch distance-sensor output characteristic curve, the adhesion and wear resistance characteristics of the fixed image are evaluated from the result. The peeling point P indicates the inflection point of the sensor output F when the critical load at which the fixed image is damaged is reached.

  If the fixed image does not break and the sensor output F becomes sufficiently large to exceed the maximum force acting from the cartridge side (maximum elastic restoring force of the cantilever), the output signal is saturated. .

  In the present invention, the scratch test is performed under the conditions that the stylus diameter of the measuring needle is 5 μm (spring constant 100 g / mm), the amplitude is 100 μm, the driving speed is 20 μm / sec, the load is 20 mN, and the scratch time is 30 sec.

  In order to form a fixed image in which the slope F / L of the curve falls within the range of the present invention, it is difficult with a conventionally marketed toner, and it is established for the first time with the toner of the present invention. The configuration of the toner will be described below.

With the toner of the present invention, it is possible to form an image with excellent crease fixing strength that does not cause toner separation at the crease even when the support of the image after fixing is folded in the post-processing step. Further, by using the toner of the present invention, not only image formation using an office machine but also image formation using a production machine can be performed.
Furthermore, the toner of the present invention can achieve both low-temperature fixability for achieving energy saving and hot offset resistance and heat-resistant storage stability that are in a trade-off relationship with the low-temperature fixability.

Hereinafter, the toner of the present invention will be described in detail.
<Toner>
The toner of the present invention is a toner containing at least a binder resin, a colorant, and a release agent.
The binder resin preferably contains a crystalline resin. The crystalline resin is a crystalline resin having a urethane bond and / or a urea bond, and the crystalline resin (A) (low molecular weight body) and the crystalline resin (B) (high molecular weight body) having different average molecular weights. It is preferable to contain these two types of crystalline resins.

(Binder resin)
The binder resin in the present invention is a resin containing a crystalline resin having a urethane bond and / or a urea bond in the main chain.
The crystalline resin in the present invention is a resin having a portion having a crystal structure, and has a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The property of the crystalline resin is the ratio of the softening temperature measured with the Kaohsiung flow tester to the maximum peak temperature of the melting heat measured with a differential scanning calorimeter (DSC) (softening temperature / maximum peak temperature of the melting heat). ) Is preferably 0.8 to 1.6, and preferably exhibits a property of being rapidly softened by heat.

  The non-crystalline resin in the present invention is a resin having no crystal structure, and does not have a diffraction peak derived from the crystal structure in a diffraction spectrum obtained by an X-ray diffractometer. The property of the non-crystalline resin is such that the ratio between the softening temperature and the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is greater than 1.6, indicating that it is softened gently by heat. preferable.

  The softening temperature of the resin can be measured using a Koka flow tester (for example, CFT-500D (manufactured by Shimadzu Corporation)). While heating 1 g of resin as a sample at a temperature rising rate of 3 ° C./min, a load of 2.94 MPa is applied by a plunger and extruded from a nozzle having a diameter of 0.5 mm and a length of 1 mm. Then, the amount of plunger drop of the flow tester against the temperature was plotted, and the temperature at which half of the sample flowed out was defined as the softening temperature.

The maximum peak temperature of the heat of fusion of the resin can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). As a pretreatment, a sample to be used for measurement of the maximum peak temperature of heat of fusion is melted at 130 ° C., then lowered from 130 ° C. to 70 ° C. at a rate of 1.0 ° C./minute, and then from 70 ° C. to 10 ° C. The temperature is lowered at a rate of 0.5 ° C./min. Here, by DSC, the temperature is increased at a rate of temperature increase of 10 ° C./min to measure the endothermic change, and a graph of “endothermic amount” and “temperature” is drawn. The endothermic peak temperature at 100 ° C. is defined as “Ta ^* ”. When there are a plurality of endothermic peaks, the temperature of the peak with the largest endothermic amount is Ta ^* . Thereafter, the sample is stored at (Ta ^* −10) ° C. for 6 hours, and further stored at (Ta ^* −15) ° C. for 6 hours. Next, the sample was cooled to 0 ° C. by DSC at a temperature decrease rate of 10 ° C./min, and then the temperature was increased at a temperature increase rate of 10 ° C./min to measure the endothermic change. The temperature corresponding to the maximum peak of heat quantity was defined as the maximum peak temperature of heat of fusion.

  The content of the crystalline resin with respect to the binder resin is preferably 50% by mass or more from the viewpoint of maximizing the compatibility of excellent low-temperature fixability and heat-resistant storage stability with the crystalline resin. Further, the content of the crystalline resin is more preferably 65% by mass or more, further preferably 80% by mass or more, and particularly preferably 95% by mass or more. When the content of the crystalline resin is 50% by mass or more, the thermal steepness of the binder resin can be expressed well on the viscoelastic properties of the toner, and both low-temperature fixability and heat-resistant storage stability can be achieved. .

  In the diffraction spectrum obtained by the X-ray diffractometer for the toner, the ratio (C) is the integral intensity of the spectrum derived from the crystal structure, and (A) is the integral intensity of the spectrum derived from the amorphous structure ( C) / ((C) + (A)) is preferably 0.15 or more from the viewpoint of achieving both fixability and heat-resistant storage stability. The ratio (C) / ((C) + (A)) is more preferably 0.20 or more, further preferably 0.30 or more, and particularly preferably 0.45 or more.

  The ratio (C) / ((C) + (A)) is an index indicating the amount of crystallization sites in the binder resin, and is mainly derived from the crystal structure in the diffraction spectrum obtained by X-ray diffraction measurement. It is the area ratio of the diffraction peak to the halo. The X-ray diffraction measurement in the present invention was performed using a two-dimensional detector-mounted X-ray diffraction apparatus (D8 DISCOVER with GADDS / Bruker).

The capillary used for the measurement was a mark tube (Lindenman glass) having a diameter of 0.70 mm. The sample was packed up to the top of the capillary tube and measured. Further, tapping was performed when filling the sample, and the number of tapping was 100 times.
Detailed measurement conditions are shown below.

Tube current: 40 mA
Tube voltage: 40 kV
Goniometer 2θ axis: 20.000 °
Goniometer Ω axis: 0.0000 °
Goniometer φ axis: 0.0000 °
Detector distance: 15cm (wide angle measurement)
Measurement range: 3.2 ≦ 2θ (°) ≦ 37.2
Measurement time: 600 sec

  For the incident optical system, a collimator having a pinhole of φ1 mm was used. The obtained two-dimensional data was integrated with the attached software (chi axis is 3.2 ° to 37.2 °) and converted into one-dimensional data of diffraction intensity and 2θ. A method for calculating the ratio (C) / ((C) + (A)) based on the obtained X-ray diffraction measurement result will be described below.

Examples of diffraction spectra obtained by X-ray diffraction measurement are shown in FIGS. 1 (A) and 1 (B). The horizontal axis is 2θ, the vertical axis is the X-ray diffraction intensity, and both are linear axes. In the X-ray diffraction spectrum in FIG. 1A, there are main peaks (P1, P2) at 2θ = 21.3 ° and 24.2 °, and a halo (h) is observed in a wide range including these two peaks. . Here, the main peak is derived from the crystal structure, and the halo is derived from the amorphous structure.
These two main peaks and halos are Gaussian functions,
f _p1 (2θ) = a _p1 exp {− (2θ−b _p1 ) ² / (2c _p1 ² )} (Formula A (1))
f _p2 (2θ) = a _p2 exp {− (2θ−b _p2 ) ² / (2c _p2 ² )} (Formula A (2))
f _h (2θ) = a _h exp {− (2θ−b _h ) ² / (2c _h ² )} (Formula A (3))
(In the above formula, f _p1 (2θ), f _p2 (2θ), and f _h (2θ) are functions corresponding to the main peaks P1, P2, and halo, respectively.)
And the sum of these three functions: f (2θ) = f _p1 (2θ) + f _p2 (2θ) + f _h (2θ) (formula A (4))
Was the fitting function of the entire X-ray diffraction spectrum (shown in FIG. 1B), and fitting by the least square method was performed.

There are nine fitting variables, a _p1 , b _p1 , c _p1 , a _p2 , b _p2 , c _p2 , a _h , b _h , and c _h . As initial values of the fitting of each variable, b _p1 , b _p2 , and b _h are X-ray diffraction peak positions (b _p1 = 21.3, b _p2 = 24.2, b _h = 22 in the example of FIG. 1). .5) is appropriately input for other variables, and values obtained by matching the two main peaks and the halo with the X-ray diffraction spectrum as much as possible are set. The fitting can be performed using, for example, a Microsoft Excel 2003 solver.

The integrated area (Sp1) for each of the Gaussian functions f _p1 (2θ), f _p2 (2θ) corresponding to the two main peaks (P1, P2) after fitting, and the Gaussian function f _h (2θ) corresponding to the halo. , Sp2, Sh) where (S _p1 + S _p2 ) is (C) and (S _p1 + S _p2 + S _h ) is (A), the ratio (C) / (which is an index indicating the amount of crystallization sites A) can be calculated.

  The maximum peak temperature of the heat of fusion of the crystalline resin is preferably 50 ° C. to 70 ° C., more preferably 55 ° C. to 68 ° C., and 60 ° C. to 65 ° C. from the viewpoint of achieving both low temperature fixability and heat resistant storage stability. Particularly preferred. When the maximum peak temperature is 50 ° C. or higher, the heat resistant storage stability is improved. Further, when the maximum peak temperature is 70 ° C. or lower, the low-temperature fixability is improved.

  The ratio of the softening temperature of the crystalline resin to the maximum peak temperature of the heat of fusion (softening temperature / maximum peak temperature of the heat of fusion) is 0.8 to 1.6, preferably 0.8 to 1.5. 0.8 to 1.4 is more preferable, and 0.8 to 1.3 is particularly preferable. The smaller the ratio, the more rapidly the resin softens, which is superior from the viewpoint of both low-temperature fixability and heat-resistant storage stability.

  The weight average molecular weight (Mw) of the crystalline resin is preferably from 2,000 to 100,000, more preferably from 5,000 to 60,000, particularly preferably from 8,000 to 30,000, from the viewpoint of fixability. preferable. When the weight average molecular weight of the binder resin is 2,000 or more, the hot offset resistance is improved. Further, when the weight average molecular weight is 100,000 or less, the low-temperature fixability is improved.

  In the present invention, the weight average molecular weight (Mw) of the resin can be measured using a gel permeation chromatography (GPC) measuring device (for example, GPC-8220 GPC (manufactured by Tosoh Corporation)). As a column, TSKgel SuperHZM-H 15 cm triple (made by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C. In measuring the molecular weight of the sample, it was calculated from the relationship between the logarithmic value of the calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. Examples of the standard polystyrene sample include Showdex STANDARD Std. No S-7300, S-210, S-390, S-875, S-1980, S-10.9, S-629, S-3.0, S-0.580, and toluene were used. An RI (refractive index) detector was used as the detector.

(Crystalline resin)
The crystalline resin used in the present invention is preferably composed mainly of a resin having a crystalline polyester unit because it is easy to design a melting point suitable as a toner and has excellent binding properties to paper. Specifically, the resin having a crystalline polyester unit is 50% by mass or more, preferably 60% by mass or more, more preferably 75% by mass, and still more preferably 90% by mass or more of the entire binder resin. This is because the more the resin having a crystalline polyester unit, the better the low-temperature fixability of the toner.

  The resin having a crystalline polyester unit includes a resin composed only of a crystalline polyester unit (also simply referred to as a crystalline polyester resin), a resin in which a crystalline polyester unit is linked, and a crystalline polyester unit and another polymer bonded together. Resin (so-called block polymer, graft polymer). A resin composed only of a crystalline polyester unit has a portion having a crystal structure, but may be easily deformed by an external force. The reason for this is that it is difficult to crystallize all the parts of the crystalline polyester, and it is easy to deform due to the high degree of freedom of the molecular chain of the non-crystallized part (non-crystalline part). It is done. In addition, regarding the portion having a crystal structure, the higher-order structure is usually a so-called lamellar structure in which molecular surfaces are folded while overlapping, but a so-called lamellar structure is formed, but a large bonding force does not work between the lamellar layers. For this reason, it is possible that the lamellar layer is easily displaced. As a binder resin for toner, if it is easily deformed by an external force, it is deformed and aggregated in the image forming apparatus, adheres to or adheres to a member, and an image that is finally output is easily damaged. May cause problems. For this reason, the binder resin must be capable of withstanding deformation to some extent against external forces and must have toughness.

  From the viewpoint of imparting toughness of the resin, a resin in which a crystalline polyester unit having a urethane cohesive site having a large cohesive energy, a urea bonding site, or a phenylene site, or a crystalline polyester unit and another polymer are bonded. Resins (so-called block polymers and graft polymers) are preferred. Among these, in particular, the urethane bond site and the urea bond site are considered to be able to form a pseudo-crosslinking point due to a large intermolecular force between the non-crystalline site and the lamella layer by being present in the molecular chain. Furthermore, these portions are preferable because they can easily wet the paper even after fixing to the paper and can increase the fixing strength.

<Crystalline polyester unit>
Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

-Polyol-
Examples of the polyol include diols, trivalent to octavalent or higher polyols (hereinafter also referred to as low molecular weight polyols), and the like. A polymer having a hydroxyl group at the terminal or side chain (hereinafter referred to as a high molecular weight polyol) may be used.
There is no restriction | limiting in particular as said diol, According to the objective, it can select suitably, For example, aliphatic diols, such as a linear aliphatic diol and a branched aliphatic diol; 36 alkylene ether glycol; alicyclic diol having 4 to 36 carbon atoms; alkylene oxide of the alicyclic diol (hereinafter abbreviated as AO); AO adduct of bisphenols; polylactone diol; polybutadiene diol; carboxyl group Diols having sulfonic acid groups or sulfamic acid groups, and diols having other functional groups such as salts thereof. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together.

The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between the low-temperature fixability and the heat-resistant storage stability is good, and the resin hardness tends to be improved.
The linear aliphatic diol is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 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, Examples include 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, 1,20-eicosanediol. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.
The branched aliphatic diol having 2 to 36 chain carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,2-propylene glycol, butanediol, hexanediol, octanediol, Examples include decanediol, dodecanediol, tetradecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.

The alkylene ether glycol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. For example, diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether And glycols.
The alicyclic diol having 4 to 36 carbon atoms is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include 1,4-cyclohexanedimethanol and hydrogenated bisphenol A.

There is no restriction | limiting in particular as alkylene oxide (henceforth AO) of the said alicyclic diol, According to the objective, it can select suitably, For example, ethylene oxide (henceforth EO), propylene oxide ( Hereinafter, adducts (number of added moles of 1 to 30) such as butylene oxide (hereinafter abbreviated as BO) and the like can be mentioned.
There is no restriction | limiting in particular as said bisphenol, It can select suitably according to the objective, For example, AO (EO, PO, BO, etc.) addition products (addition mole number 2-such as bisphenol A, bisphenol F, bisphenol S). 30).
There is no restriction | limiting in particular as said polylactone diol, According to the objective, it can select suitably, For example, poly-epsilon-caprolactone diol etc. are mentioned.

There is no restriction | limiting in particular as said diol which has a carboxyl group, According to the objective, it can select suitably, For example, 2, 2- dimethylol propionic acid (DMPA), 2, 2- dimethylol butanoic acid, 2, 2 -Dialkylol alkanoic acids having 6 to 24 carbon atoms such as dimethylol heptanoic acid and 2,2-dimethylol octanoic acid.
The diol having the sulfonic acid group or the sulfamic acid group is not particularly limited and may be appropriately selected depending on the intended purpose. For example, N, N-bis (2-hydroxyethyl) sulfamic acid and N, N- Sulfamic acid diols such as bis (2-hydroxyethyl) sulfamic acid PO2 molar adduct, [N, N-bis (2-hydroxyalkyl) sulfamic acid (C1-6 of alkyl group) and AO adduct (AO) As EO or PO, AO addition mole number 1 to 6); bis (2-hydroxyethyl) phosphate and the like can be mentioned.

There is no restriction | limiting in particular as a neutralization base of the diol which has these neutralization bases, According to the objective, it can select suitably, For example, the said C3-C30 tertiary amine (triethylamine etc.), an alkali metal ( Sodium salt).
Among these, alkylene glycols having 2 to 12 carbon atoms, diols having a carboxyl group, AO adducts of bisphenols, and combinations thereof are preferable.

  Moreover, there is no restriction | limiting in particular as said trivalent-8 valence or more polyol used as needed, According to the objective, it can select suitably, For example, alkane polyol and its intramolecular or intermolecular dehydration thing (E.g., glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, etc.), saccharides and derivatives thereof (e.g., sucrose, methylglucoside, etc.), etc. Octahydric or higher polyhydric aliphatic alcohols; AO adducts of trisphenols (trisphenol PA, etc.) (addition moles 2-30); AO adducts of novolac resins (phenol novolac, cresol novolac, etc.) (addition) Mole number 2-30); hydroxyethyl (meth) acrylate and other vinyl And acrylic polyols such as a copolymer of monomers. Among these, trivalent to octavalent or higher polyhydric aliphatic alcohols and novolak resin AO adducts are preferred, and novolak resin AO adducts are more preferred.

Examples of the method for producing the high molecular weight polyol include the following methods.
(1) A method of obtaining a polyurethane having a hydroxyl group at a terminal by reacting a low molecular weight polyisocyanate and a low molecular weight polyol with an excess amount of hydroxyl groups.
(2) A method of obtaining a polyester having a hydroxyl group at the terminal by reacting a polycarboxylic acid and a low molecular weight polyol compound with an excess amount of hydroxyl group.

In order to adjust the polyurethane or polyester having a hydroxyl group at the terminal, the ratio [OH] / [NCO] of the low molecular weight polyol and the low molecular weight polyisocyanate, or the ratio [OH] / [COOH] of the low molecular weight polyol and the polycarboxylic acid. Is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1, and more preferably 1.3 / 1 to 1.02 / 1.
When the molar ratio of the hydroxyl groups is 2 or less, the polymerization reaction proceeds well, and a desired high molecular weight polyol can be obtained. Moreover, when the molar ratio of the hydroxyl groups is 1.02 or more, the degree of polymerization can be moderately suppressed, and the molecular weight of the high molecular weight polyol can be suppressed from becoming too large. Thereby, in manufacturing a toner, it can be mixed well with other materials. Moreover, it can suppress that the elasticity modulus in a molten state becomes high too much, and can make fixing property favorable.

-Polycarboxylic acid-
Examples of the polycarboxylic acid include dicarboxylic acids, trivalent to hexavalent or higher polycarboxylic acids.
The dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic dicarboxylic acids such as linear aliphatic dicarboxylic acids and branched aliphatic dicarboxylic acids; aromatic dicarboxylic acids and the like. Are preferable. Among these, linear aliphatic dicarboxylic acid is more preferable.

  The aliphatic dicarboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose.For example, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, octadecanedicarboxylic acid, decylsuccinic acid, etc. Alkane dicarboxylic acids having 4 to 36 carbon atoms; alkenedicarboxylic acids having 4 to 36 carbon atoms such as alkenyl succinic acids such as dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid, maleic acid, fumaric acid and citraconic acid Preferable examples include acids; alicyclic dicarboxylic acids having 6 to 40 carbon atoms such as dimer acid (dimerized linoleic 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, t-butylisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4 Preferred examples include aromatic dicarboxylic acids having 8 to 36 carbon atoms such as 4,4'-biphenyldicarboxylic acid.
Examples of the trivalent to hexavalent or higher polycarboxylic acid used as necessary include C9-20 aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid.
As the dicarboxylic acid or the trivalent to hexavalent or higher polycarboxylic acid, the above acid anhydrides or lower alkyl esters having 1 to 4 carbon atoms (methyl ester, ethyl ester, isopropyl ester, etc.) are used. It may be used.

  Among the dicarboxylic acids, it is particularly preferable to use the aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

-Lactone ring-opening polymer-
The lactone ring-opening polymer is not particularly limited and may be appropriately selected depending on the purpose. For example, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc. A lactone ring-opening polymer obtained by ring-opening polymerization of lactones such as 12 monolactones (one ester group in the ring) using a metal oxide, an organometallic compound or the like; glycol ( Examples thereof include a lactone ring-opening polymer having a hydroxyl group at the terminal, obtained by ring-opening polymerization of the monolactone having 3 to 12 carbon atoms using ethylene glycol, diethylene glycol, or the like.
There is no restriction | limiting in particular as said C3-C12 monolactone, Although it can select suitably according to the objective, (epsilon) -caprolactone is preferable from a crystalline viewpoint.
In addition, as the lactone ring-opening polymer, a commercially available product may be used. Examples of the commercially available product include highly crystalline polycaprolactones such as H1P, H4, H5, and H7 of the PLACEL series manufactured by Daicel Corporation. Can be mentioned.

-Polyhydroxycarboxylic acid-
The method for preparing the polyhydroxycarboxylic acid is not particularly limited and may be appropriately selected depending on the purpose. Dehydration condensation method: cyclic ester having 4 to 12 carbon atoms corresponding to dehydration condensate between two or three molecules of hydroxycarboxylic acid such as glycolide, lactide (L-form, D-form, racemate, etc.) Examples of the method include ring-opening polymerization of 2 to 3 ester groups using a catalyst such as a metal oxide or an organometallic compound. The method of ring-opening polymerization is preferable from the viewpoint of adjusting the molecular weight.
Among the cyclic esters, L-lactide and D-lactide are preferable from the viewpoint of crystallinity. These polyhydroxycarboxylic acids may be modified so that the terminal is a hydroxyl group or a carboxyl group.

<Resin connected with crystalline polyester unit>
Examples of a method for obtaining a resin in which a crystalline polyester unit is linked include a method in which a crystalline polyester unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and linked with polyisocyanate. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.

  Examples of the polyisocyanate include diisocyanate, trivalent or higher polyisocyanate, and the like.

  There is no restriction | limiting in particular as said diisocyanate, According to the objective, it can select suitably, For example, aromatic diisocyanate, aliphatic diisocyanate, alicyclic diisocyanate, araliphatic diisocyanate etc. are mentioned. Among these, the carbon number except carbon in the NCO group is 6-20 aromatic diisocyanate, 2-18 aliphatic diisocyanate, 4-15 alicyclic diisocyanate, 8-15 araliphatic diisocyanate, these Preferred is a modified product of diisocyanate (urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanurate group, oxazolidone group-containing modified product), and a mixture of two or more of these. . If necessary, trivalent or higher isocyanates may be used in combination.

  The aromatic diisocyanates are not particularly limited and may be appropriately selected depending on the intended purpose. For example, 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6- Tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane diisocyanate (MDI), crude MDI [crude diaminophenylmethane [formaldehyde and aromatic amine (aniline) or a mixture thereof] Condensation product: phosgenation product of polyaminopolyisocyanate (PAPI)], 1,5-naphthylene diisocyanate, 4,4, a mixture of diaminodiphenylmethane and a small amount (for example, 5 to 20% by mass) of a trifunctional or higher polyamine ', 4' '-triphenylmethane triisocyanate, m- and p-i Such cyanatophenyl sulfonyl isocyanate.

  There is no restriction | limiting in particular as said aliphatic diisocyanate, According to the objective, it can select suitably, For example, ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 1,6,11-undecane Triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2- And isocyanatoethyl-2,6-diisocyanatohexanoate.

  The alicyclic diisocyanates are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), and cyclohexylene diisocyanate. , Methylcyclohexylene diisocyanate (hydrogenated TDI), bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and 2,6-norbornane diisocyanate.

  There is no restriction | limiting in particular as said araliphatic diisocyanate, According to the objective, it can select suitably, For example, m- and p-xylylene diisocyanate (XDI), (alpha), (alpha), (alpha) ', (alpha)'-tetramethyl And xylylene diisocyanate (TMXDI).

  The modified diisocyanate is not particularly limited and may be appropriately selected depending on the intended purpose. For example, urethane group, carbodiimide group, allophanate group, urea group, burette group, uretdione group, uretoimine group, isocyanate Examples thereof include modified products containing a nurate group and an oxazolidone group. Specifically, modified MDI such as urethane-modified MDI, carbodiimide-modified MDI, trihydrocarbyl phosphate-modified MDI, and modified diisocyanates such as urethane-modified TDI such as isocyanate-containing prepolymers; a mixture of two or more of these modified diisocyanates (For example, combined use of modified MDI and urethane-modified TDI).

  Among these diisocyanates, aromatic diisocyanates having 6 to 15 carbon atoms excluding carbon in the NCO group, 4 to 12 aliphatic diisocyanates, and 4 to 15 alicyclic diisocyanates are preferable, and TDI, MDI, HDI, Hydrogenated MDI and IPDI are particularly preferred.

<Resin combining crystalline polyester unit and other polymer>
Examples of a method for obtaining a resin in which a crystalline polyester unit and another polymer are bonded include the following methods (A) to (C).
(A) A method in which a crystalline polyester unit and another polymer unit are separately prepared and bonded together.
(B) A method in which one of a crystalline polyester unit and another polymer unit is produced in advance, and then the other polymer is polymerized in the presence of the produced unit.
(C) Or a method obtained by polymerizing a crystalline polyester unit and another polymer unit simultaneously or sequentially in the same reaction field.
Among the above methods, the method (A) or (B) is preferable in that the reaction can be easily controlled as designed.

  As the method of (A), a method in which a unit having an active hydrogen such as a hydroxyl group at the terminal is prepared in advance and connected with polyisocyanate, as in the method for obtaining the resin in which the crystalline polyester unit is connected, is mentioned. It is done. As the polyisocyanate, those described above can be used, and it can also be obtained by introducing an isocyanate group at the terminal of one unit and reacting with the active hydrogen of the other unit. When this means is used, a urethane bond site can be introduced into the resin skeleton, so that the toughness of the resin can be increased.

  As the method of (B), when the crystalline polyester unit is prepared first, if the polymer unit to be prepared next is an amorphous polyester unit, polyurethane unit, polyurea unit, etc., the hydroxyl group at the end of the crystalline polyester unit By reacting a group or a carboxyl group with a monomer for obtaining another polymer unit, a resin in which the crystalline polyester unit and another polymer are bonded can be obtained.

<Amorphous polyester unit>
As an amorphous polyester unit, the polycondensation polyester unit synthesize | combined from a polyol and polycarboxylic acid is mentioned, for example.
For the polyol and polycarboxylic acid, those exemplified in the above-mentioned crystalline polyester unit can be used. However, in order to design the polymer so as not to have crystallinity, the polymer skeleton should be provided with many bending points and branch points. That's fine. In order to give an inflection point, for example, bisphenol such as bisphenol A, bisphenol F, bisphenol S, etc. (EO, PO, BO, etc.) adducts (addition mole number 2 to 30), etc. As the carboxylic acid, phthalic acid, isophthalic acid, or t-butylisophthalic acid may be used. In addition, a trivalent or higher polyol or polycarboxylic acid may be used to introduce the branch point.

<Polyurethane unit>
Examples of the polyurethane unit include a polyurethane unit synthesized from a polyol such as a diol, a trivalent to octavalent or higher polyol, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate. Among these, a polyurethane unit synthesized from the diol and the diisocyanate is preferable.
Examples of the diol and the trivalent to octavalent or higher polyol include those similar to the diol and the trivalent to octavalent or higher polyol cited in the polyester resin.
Examples of the diisocyanate and the trivalent or higher polyisocyanate include the same diisocyanates and trivalent or higher polyisocyanates.

<Polyurea unit>
Examples of the polyurea unit include a polyurea unit synthesized from a polyamine such as a diamine or a trivalent or higher polyamine, and a polyisocyanate such as a diisocyanate or a trivalent or higher polyisocyanate.
There is no restriction | limiting in particular as said diamine, According to the objective, it can select suitably, For example, aliphatic diamines and aromatic diamines are mentioned. Among these, C2-C18 aliphatic diamines and C6-C20 aromatic diamines are preferable. Further, if necessary, the above trivalent or higher amines may be used.

  There is no restriction | limiting in particular as said C2-C18 aliphatic diamine, According to the objective, it can select suitably, For example, carbon, such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, etc. Alkylene diamine having 2 to 6 carbon atoms; polyalkylene diamine having 4 to 18 carbon atoms such as diethylenetriamine, iminobispropylamine, bis (hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine; dialkylaminopropylamine , Alkylene diamines such as trimethylhexamethylenediamine, aminoethylethanolamine, 2,5-dimethyl-2,5-hexamethylenediamine, methyliminobispropylamine, and the polyal C1-C4 alkyl or C2-C4 hydroxyalkyl substituted range amine; 1,3-diaminocyclohexane, isophoronediamine, mensendiamine, 4,4'-methylenedicyclohexanediamine (hydrogenated methylenedi C 4-15 alicyclic diamine such as aniline); piperazine, N-aminoethylpiperazine, 1,4-diaminoethylpiperazine, 1,4-bis (2-amino-2-methylpropyl) piperazine, 3, C4-C15 heterocyclic diamine such as 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane; xylylenediamine, tetrachloro-p-xylylenediamine And aromatic ring-containing aliphatic amines having 8 to 15 carbon atoms such as amines.

  There is no restriction | limiting in particular as said C6-C20 aromatic diamine, According to the objective, it can select suitably, For example, 1, 2-, 1, 3- and 1, 4- phenylene diamine, 2, 4'- and 4,4'-diphenylmethanediamine, crude diphenylmethanediamine (polyphenylpolymethylenepolyamine), diaminodiphenylsulfone, benzidine, thiodianiline, bis (3,4-diaminophenyl) sulfone, 2,6-diaminopyridine, m -Unsubstituted aromatic diamines such as aminobenzylamine, triphenylmethane-4,4 ', 4 "-triamine, naphthylenediamine; 2,4- and 2,6-tolylenediamine, crude tolylenediamine, diethyl Tolylenediamine, 4,4′-diamino-3,3′-dimethyldiphenylmethane, , 4'-bis (o-toluidine), dianisidine, diaminoditolyl sulfone, 1,3-dimethyl-2,4-diaminobenzene, 1,3-dimethyl-2,6-diaminobenzene, 1,4-diisopropyl- 2,5-diaminobenzene, 2,4-diaminomesitylene, 1-methyl-3,5-diethyl-2,4-diaminobenzene, 2,3-dimethyl-1,4-diaminonaphthalene, 2,6-dimethyl- 1,5-diaminonaphthalene, 3,3 ′, 5,5′-tetramethylbenzidine, 3,3 ′, 5,5′-tetramethyl-4,4′-diaminodiphenylmethane, 3,5-diethyl-3 ′ -Methyl-2 ', 4-diaminodiphenylmethane, 3,3'-diethyl-2,2'-diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldi Phenylmethane, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminobenzophenone, 3,3 ′, 5,5′-tetraethyl-4,4′-diaminodiphenyl ether, 3,3 ′, 5,5 An aromatic diamine having a C1-C4 nucleus-substituted alkyl group such as' -tetraisopropyl-4,4'-diaminodiphenylsulfone; the unsubstituted aromatic diamine to the C1-C4 nucleus-substituted alkyl group; Mixtures of various proportions of isomers of aromatic diamines having; methylenebis-o-chloroaniline, 4-chloro-o-phenylenediamine, 2-chloro-1,4-phenylenediamine, 3-amino-4-chloroaniline, 4-bromo-1,3-phenylenediamine, 2,5-dichloro-1,4-phenylenediamine, 5-nitro-1,3-phenylenediamine 3,4-dimethoxy-4-aminoaniline; 4,4′-diamino-3,3′-dimethyl-5,5′-dibromodiphenylmethane, 3,3′-dichlorobenzidine, 3,3′-dimethoxybenzidine, bis (4-amino-3-chlorophenyl) oxide, bis (4-amino-2-chlorophenyl) propane, bis (4-amino-2-chlorophenyl) sulfone, bis (4-amino-3-methoxyphenyl) decane, bis ( 4-aminophenyl) sulfide, bis (4-aminophenyl) telluride, bis (4-aminophenyl) selenide, bis (4-amino-3-methoxyphenyl) disulfide, 4,4′-methylenebis (2-iodoaniline) 4,4′-methylenebis (2-bromoaniline), 4,4′-methylenebis (2-fluoroaniline) ), Aromatic diamines having a nucleus-substituted electron withdrawing group such as 4-aminophenyl-2-chloroaniline (halogens such as Cl, Br, I and F; alkoxy groups such as methoxy and ethoxy; nitro groups and the like); 4 , 4′-di (methylamino) diphenylmethane, 1-methyl-2-methylamino-4-aminobenzene and other aromatic amino diamines [the unsubstituted aromatic diamine, the carbon number of 1-4] Aromatic diamines having a nucleus-substituted alkyl group, mixtures of these isomers in various proportions, and a part or all of the primary amino groups of the aromatic diamine having a nucleus-substituted electron withdrawing group are lower alkyls such as methyl and ethyl In which a secondary amino group is replaced by a group].

In addition to these, as the diamine, a low molecular weight polyamide obtained by condensation of a dicarboxylic acid (such as a dimer acid) and an excess (more than 2 moles per mole of the acid) the polyamine (the alkylene diamine, the polyalkylene polyamine, etc.). Polyamide polyamines such as polyamines; polyether polyamines such as hydrides of cyanoethylated polyether polyols (polyalkylene glycol and the like).
Moreover, you may use what capped the amino group of the amine compound with the ketone compound etc.
Among these, a polyurea unit synthesized from the diamine and the diisocyanate is preferable.
Examples of the diisocyanate and the trivalent or higher polyisocyanate include those similar to the diisocyanate and the trivalent or higher polyisocyanate.

<Vinyl polymer unit>
Examples of other polymers to be bonded to the crystalline polyester unit include polymers containing vinyl polymer units in addition to the above. The vinyl polymer unit is a polymer unit obtained by homopolymerizing or copolymerizing vinyl monomers.

Examples of the vinyl monomer include the following (1) to (10).
(1) Vinyl hydrocarbons:
Aliphatic vinyl hydrocarbons: alkenes such as ethylene, propylene, butene, isobutylene, pentene, heptene, diisobutylene, octene, dodecene, octadecene, α-olefins other than the above, etc .; alkadienes such as butadiene, isoprene, 1,4-pentadiene, 1,6-hexadiene, 1,7-octadiene.
Alicyclic vinyl hydrocarbons: mono- or di-cycloalkenes and alkadienes such as cyclohexene, (di) cyclopentadiene, vinylcyclohexene, ethylidenebicycloheptene, etc .; terpenes such as pinene, limonene, indene and the like.
Aromatic vinyl hydrocarbons: Styrene and its hydrocarbyl (alkyl, cycloalkyl, aralkyl and / or alkenyl) substitutions such as α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, Butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, crotyl benzene, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene, etc .; and vinyl naphthalene.

(2) Carboxyl group-containing vinyl monomers and salts thereof:
C3-C30 unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and its anhydride and its monoalkyl (C1-24) ester, for example, (meth) acrylic acid, (anhydrous) maleic acid, monoalkyl maleate Carboxyl group-containing vinyl monomers such as esters, fumaric acid, fumaric acid monoalkyl esters, crotonic acid, itaconic acid, itaconic acid monoalkyl esters, itaconic acid glycol monoether, citraconic acid, citraconic acid monoalkyl esters, and cinnamic acid.

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

(4) Phosphoric acid group-containing vinyl monomers and salts thereof:
(Meth) acryloyloxyalkyl phosphoric acid monoesters such as 2-hydroxyethyl (meth) acryloyl phosphate, phenyl-2-acryloyloxyethyl phosphate, (meth) acryloyloxyalkyl (C1-24) phosphonic acids, such as 2-acryloyloxyethylphosphonic acid; and salts thereof.
Examples of the salts (2) to (4) include alkali metal salts (sodium salts, potassium salts, etc.), alkaline earth metal salts (calcium salts, magnesium salts, etc.), ammonium salts, amine salts, or quaternary grades. An ammonium salt is mentioned.

(5) Hydroxyl group-containing vinyl monomer:
Hydroxystyrene, N-methylol (meth) acrylamide, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, (meth) allyl alcohol, crotyl alcohol, isocrotyl alcohol, 1- Buten-3-ol, 2-buten-1-ol, 2-butene-1,4-diol, propargyl alcohol, 2-hydroxyethylpropenyl ether, sucrose allyl ether, and the like.

(6) Nitrogen-containing vinyl monomer:
Amino group-containing vinyl monomers: aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, t-butylaminoethyl methacrylate, N-aminoethyl (meth) acrylamide, (meth) allylamine, Morpholinoethyl (meth) acrylate, 4-vinylpyridine, 2-vinylpyridine, crotylamine, N, N-dimethylaminostyrene, methyl-α-acetaminoacrylate, vinylimidazole, N-vinylpyrrole, N-vinylthiopyrrolidone, N-arylphenylenediamine, aminocarbazole, aminothiazole, aminoindole, aminopyrrole, aminoimidazole, aminomercaptothiazole, and salts thereof.
Amide group-containing vinyl monomers; (meth) acrylamide, N-methyl (meth) acrylamide, N-butyl acrylamide, diacetone acrylamide, N-methylol (meth) acrylamide, N, N-methylene-bis (meth) acrylamide, cinnamon Acid amide, N, N-dimethylacrylamide, N, N-dibenzylacrylamide, methacrylformamide, N-methyl-N-vinylacetamide, N-vinylpyrrolidone and the like.
Nitrile group-containing vinyl monomers: (meth) acrylonitrile, cyanostyrene, cyanoacrylate, and the like.
Quaternary ammonium cationic group-containing vinyl monomers: tertiary amine group-containing vinyl monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylamide, diethylaminoethyl (meth) acrylamide and diallylamine Monomer quaternized product (quaternized with a quaternizing agent such as methyl chloride, dimethyl sulfate, benzyl chloride, dimethyl carbonate).
Nitro group-containing vinyl monomers: nitrostyrene and the like.

(7) Epoxy group-containing vinyl monomer:
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, p-vinylphenylphenyl oxide and the like.

(8) Vinyl esters, vinyl (thio) ethers, vinyl ketones, vinyl sulfones:
Vinyl esters such as vinyl acetate, vinyl butyrate, vinyl propionate, vinyl butyrate, diallyl phthalate, diallyl adipate, isopropenyl acetate, vinyl methacrylate, methyl-4-vinylbenzoate, cyclohexyl methacrylate, benzyl methacrylate, phenyl (meth) acrylate, Vinyl methoxyacetate, vinyl benzoate, ethyl-α-ethoxyacrylate, alkyl (meth) acrylate having an alkyl group having 1 to 50 carbon atoms [methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl ( (Meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) ) Acrylate, eicosyl (meth) acrylate, etc.], dialkyl fumarate (two alkyl groups are straight, branched or alicyclic groups having 2 to 8 carbon atoms), dialkyl maleate (2 Each alkyl group is a linear, branched or alicyclic group having 2 to 8 carbon atoms), poly (meth) allyloxyalkanes [diallyloxyethane, triaryloxyethane, tetraaryl. Roxyethane, tetraallyloxypropane, tetraallyloxybutane, tetrametaallyloxyethane, etc.] vinyl monomers having a polyalkylene glycol chain [polyethylene glycol (molecular weight 300) mono (meth) acrylate, polypropylene glycol (molecular weight 500) Monoacrylate, methyl alcohol ethylene oxide 10 mol adduct (meth) ac Lilate, lauryl alcohol ethylene oxide 30-mole adduct (meth) acrylate, etc.], poly (meth) acrylates [poly (meth) acrylate of polyhydric alcohols: ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, polyethylene glycol di (meth) acrylate, etc.].
Vinyl (thio) ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, hinyl butyl ether, vinyl-2-ethylhexyl ether, vinyl phenyl ether, vinyl-2-methoxyethyl ether, methoxybutadiene, vinyl-2-butoxy Ethyl ether, 3,4-dibutyro-1,2-pyran, 2-butoxy-2′-vinyloxydiethyl ether, vinyl-2-ethylmercaptoethyl ether, acetoxystyrene, phenoxystyrene and the like.
Vinyl ketones, such as vinyl methyl ketone, vinyl ethyl ketone, vinyl phenyl ketone, etc.
Vinyl sulfones such as divinyl sulfide, p-vinyl diphenyl sulfide, vinyl ethyl sulfide, vinyl ethyl sulfone, divinyl sulfone, divinyl sulfoxide and the like.

(9) Other vinyl monomers:
Isocyanate ethyl (meth) acrylate, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.

(10) Fluorine atom element-containing vinyl monomer:
4-fluorostyrene, 2,3,5,6-tetrafluorostyrene, pentafluorophenyl (meth) acrylate, pentafluorobenzyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, perfluorocyclohexylmethyl (meth) acrylate, 2, 2,2-trifluoroethyl (meth) acrylate 2,2,3,3-tetrafluoropropyl (meth) acrylate, 1H, 1H, 4H-hexafluorobutyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (Meth) acrylate, 1H, 1H, 7H-dodecafluoroheptyl (meth) acrylate, perfluorooctyl (meth) acrylate, 2-perfluorooctylethyl (meth) acrylate, heptadecafluorodecyl ( Acrylate), trihydroperfluoroundecyl (meth) acrylate, perfluoronorbornylmethyl (meth) acrylate, 1H-perfluoroisobornyl (meth) acrylate 2- (N-butylperfluorooctanesulfonamido) ethyl (meth) acrylate, 2- (N-ethylperfluorooctanesulfonamido) ethyl (meth) acrylate and the corresponding compounds derived from α-fluoroacrylic acid, bis-hexafluoroisopropyl itaconate, bis-hexafluoroisopropyl maleate, bis-perfluoro Octyl itaconate, bis-perfluorooctyl maleate, bis-trifluoroethyl itaconate and bis-trifluoroethyl maleate, vinyl heptafluorobutyrate, Vinyl perfluoroheptanoate, vinyl perfluorononanoate, vinyl perfluorooctanoate and the like.

<Crystalline resin having urea bond in main chain>
The binder resin preferably includes a crystalline resin having a urea bond in the main chain.
According to Solubility Parameter Values (Polymer handbook 4th Ed), the cohesive energy of urea bonds is 50,230 [J / mol], which is about twice the cohesive energy of urethane bonds (26,370 [J / mol]]). Therefore, even if the amount is small, it is possible to expect the toughness of the toner and the effect of improving the offset resistance at the time of fixing.

  In order to obtain a resin having a urea bond in the main chain, a polyisocyanate compound and a polyamine compound are reacted, or a polyisocyanate compound and water are reacted to react an amino group generated by hydrolysis of the isocyanate with the remaining isocyanate group. There is a way to make it. In addition, in obtaining a resin having a urea bond in the main chain, in addition to the above-mentioned compounds, a polyol compound can be reacted at the same time to increase the degree of freedom in resin design.

  In order for the obtained resin to have crystallinity, a polymer unit having crystallinity may be introduced into the main chain. Examples of the crystalline polymer unit having a melting point suitable as a binder resin for toner include a crystalline polyester unit and a long-chain alkyl ester unit of polyacrylic acid or polymethacrylic acid. Among these, a crystalline polyester unit is preferable because a terminal alcohol can be easily produced and can be easily introduced into a resin having a urea bond as the polyol compound.

  Examples of the crystalline polyester unit include a polycondensation polyester unit synthesized from a polyol and a polycarboxylic acid, a lactone ring-opening polymer, and a polyhydroxycarboxylic acid. Among these, a polycondensation polyester unit of diol and dicarboxylic acid is preferable from the viewpoint of crystallinity.

  As the diol, the diols mentioned in the aforementioned polyols can be used. Among these, an aliphatic diol having 2 to 36 chain carbon atoms is preferable, and a linear aliphatic diol is more preferable. These may be used individually by 1 type and may use 2 or more types together. Among these, ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol are preferable in view of availability.

  The content of the linear aliphatic diol with respect to the entire diol is preferably 80 mol% or more, and more preferably 90 mol% or more. When the content is 80 mol% or more, the crystallinity of the resin is improved, the compatibility between low-temperature fixability and heat-resistant storage stability is good, and the resin hardness tends to be improved.

As dicarboxylic acid, the dicarboxylic acid mentioned in the above-mentioned polycarboxylic acid can be used, Among these, linear aliphatic dicarboxylic acid is more preferable.
Among the dicarboxylic acids, it is particularly preferable to use the aliphatic dicarboxylic acid (preferably adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, isophthalic acid, etc.) alone, but the aromatic dicarboxylic acid and the aromatic Those obtained by copolymerizing an aromatic dicarboxylic acid (preferably terephthalic acid, isophthalic acid, t-butylisophthalic acid, etc .; lower alkyl esters of these aromatic dicarboxylic acids, etc.) are also preferred. The copolymerization amount of the aromatic dicarboxylic acid is preferably 20 mol% or less.

<<< Polyisocyanate >>>
As polyisocyanates, in addition to diisocyanates as described above, trivalent or higher polyisocyanates (hereinafter also referred to as low molecular weight polyisocyanates), polymers having isocyanate groups at the terminals and side chains (hereinafter also referred to as prepolymers). May be used.
Examples of the method for producing the prepolymer include the following methods (1) and (2). (1) A method of obtaining a polyurea prepolymer having an isocyanate group at a terminal by reacting a low molecular weight polyisocyanate with a polyamine compound described later in an excess amount of isocyanate. (2) A method in which a low molecular weight polyisocyanate and a polyol compound are reacted in an excess amount of isocyanate to obtain a prepolymer having an isocyanate group at the terminal. The prepolymers obtained by these methods may be used alone or in combination of two or more types of prepolymers obtained by the same method, or two or more types of prepolymers obtained by the above two methods. I do not care. Further, one kind or a plurality of kinds of prepolymer and low molecular weight polyisocyanate may be used in combination.

The ratio of polyisocyanate used is equivalent ratio [NCO] / [NH ₂ ] of isocyanate group [NCO] and amino group [NH ₂ ] of polyamine, or equivalent ratio [NCO] / [ OH] is usually 5/1 to 1.01 / 1, preferably 4/1 to 1.2 / 1, and more preferably 2.5 / 1 to 1.5 / 1.
When the molar ratio of [NCO] is 5 or less, the number of urethane bonds and urea bonds becomes appropriate. That is, when the finally obtained resin is used as a binder resin for toner, the elastic modulus in the molten state is suppressed from becoming too high, and the fixability is improved. Moreover, when the molar ratio of [NCO] is 1.01 or more, the degree of polymerization is appropriate and the molecular weight of the prepolymer can be prevented from becoming too large. As a result, when the toner is manufactured, mixing with other materials becomes good. Further, it is possible to suppress the elastic modulus in the molten state from becoming too high, and to improve the fixability.

<<< Polyamine >>>
Examples of the polyamine include diamines as described above, trivalent or higher polyamines, and the like.

<<< Introduction of crystalline resin having urea bond in main chain into toner >>>
A resin in which a urea bond is formed in advance as a binder resin is used, and a toner can be obtained by mixing with a toner constituent material other than the binder resin such as a colorant, a release agent, and a charge control agent to form particles. . Further, a urea bond is formed by mixing a polyisocyanate compound, a polyamine compound and / or water with a toner constituent material other than a binder resin such as a colorant, a release agent, and a charge control agent as necessary. May be. In particular, by using a prepolymer as the polyisocyanate compound, a crystalline resin having a high molecular weight urea bond can be uniformly introduced into the toner, so that the toner has uniform heat characteristics and chargeability and is fixable. It is preferable because it can easily balance the stress resistance of the toner with the toner. Furthermore, as the prepolymer, a prepolymer obtained by reacting a low molecular weight polyisocyanate and a polyol compound in an excess amount of isocyanate is preferable because viscoelasticity is suppressed. As the polyol compound, a polyester having a hydroxyl group at the terminal by reacting a polycarboxylic acid and a low molecular weight polyol compound with an excess amount of hydroxyl group is preferable because thermal characteristics suitable for the toner can be easily obtained. Furthermore, when the polyester is composed of a crystalline polyester unit, it is preferable because a high molecular weight component in the toner becomes a sharp melt and a toner having excellent low-temperature fixability can be obtained.
Further, when the toner of the present invention is obtained by granulating in an aqueous medium, the urea bond can be formed under mild conditions by the water of the dispersion medium reacting with the polyisocyanate compound.

The said binder resin in this invention may be used individually by 1 type, and may use 2 or more types together. In addition, binder resins having different weight average molecular weights may be used in combination. In this case, at least the first crystalline resin and the second crystalline resin having a weight average molecular weight Mw larger than that of the first crystalline resin satisfy both excellent low-temperature fixability and hot offset resistance. It is preferable in that it can be performed.
The second crystalline resin is obtained by extending the resin by reacting with a compound having an active hydrogen group using the binder resin precursor which is a modified crystalline resin having an isocyanate group. It is preferable that In this case, the reaction between the binder resin precursor and the compound having an active hydrogen group is more preferably performed in the toner production process, and a crystalline resin having a large weight average molecular weight can be uniformly dispersed in the toner. In addition, variation in characteristics among toner particles can be suppressed.

Further, the first crystalline resin is a crystalline resin having a urethane bond and / or a urea group bond in the main chain, and the second crystalline resin is a modification of the first crystalline resin. It is preferable that the binder resin precursor is reacted with a compound having an active hydrogen group and elongated. By bringing the composition structures of the first crystalline resin and the second crystalline resin close to each other, the two types of binder resins are more easily dispersed in the toner, and the variation in characteristics between toner particles is further increased. Can be suppressed.
The crystalline resin may be a combination of the crystalline resin and the amorphous resin, and the main component of the binder resin is preferably the crystalline resin.

(Release agent)
There is no restriction | limiting in particular as said mold release agent, According to the objective, it can select suitably from well-known things, For example, waxes, such as carbonyl group containing wax, polyolefin wax, and long-chain hydrocarbon, are mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, a carbonyl group-containing wax is preferable.
Examples of the carbonyl group-containing wax include polyalkanoic acid esters, polyalkanol esters, polyalkanoic acid amides, polyalkylamides, and dialkyl ketones.

  Examples of the polyalkanoic acid ester include carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, and 1,18-octadecane. Examples thereof include diol distearate. Examples of the polyalkanol ester include tristearyl trimellitic acid and distearyl maleate. Examples of the polyalkanoic acid amide include dibehenyl amide. Examples of the polyalkylamide include trimellitic acid tristearylamide. Examples of the dialkyl ketone include distearyl ketone. Of these carbonyl group-containing waxes, polyalkanoic acid esters are particularly preferred.

Examples of the polyolefin wax include polyethylene wax and polypropylene wax.
Examples of the long chain hydrocarbon include paraffin wax and sazol wax.
There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 50 to 100 degreeC is preferable and 60 to 90 degreeC is more preferable. When the melting point is 50 ° C. or higher, the heat resistant storage stability is improved. Further, when the melting point is 100 ° C. or less, it is difficult to cause cold offset even when fixing at a low temperature.

  The melting point of the release agent can be measured using, for example, a differential scanning calorimeter (TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of the mold release agent is put into an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. From the obtained DSC curve, using the analysis program in the DSC-60 system, the maximum peak temperature of the heat of fusion at the second temperature rise can be obtained as the melting point.

  The melt viscosity of the release agent is preferably 5 mPa · sec to 100 mPa · sec, more preferably 5 mPa · sec to 50 mPa · sec, and particularly preferably 5 mPa · sec to 20 mPa · sec as a measured value at 100 ° C. When the melt viscosity is 5 mPa · sec or more, the releasability is improved. Further, when the melt viscosity is 100 mPa · sec or less, the hot offset resistance and the release property at a low temperature are improved.

  There is no restriction | limiting in particular as content in the said toner of the said mold release agent, Although it can select suitably according to the objective, 1 mass%-20 mass% are preferable, and 3 mass%-10 mass% are more preferable. . When the content of the release agent is 1% by mass or more, the hot offset resistance is improved. Further, when the content of the release agent is 20% by mass or less, heat resistant storage stability, chargeability, transferability, and stress resistance are improved.

(Coloring agent)
There is no restriction | limiting in particular as a coloring agent used for the toner of this invention, According to the objective, it can select suitably from a well-known coloring agent.
The color of the colorant of the toner is not particularly limited and can be appropriately selected according to the purpose, and can be at least one selected from black toner, cyan toner, magenta toner, and yellow toner, Each color toner can be obtained by appropriately selecting the type of colorant, but is preferably a color toner.

  Examples of black products include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black, copper, iron (CI pigment black 11), titanium oxide, and the like. And organic pigments such as aniline black (CI Pigment Black 1).

  Examples of the magenta color pigment include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 39, 40, 41, 48, 48: 1, 49, 50, 51, 52, 53, 53: 1, 54, 55, 57, 57: 1, 58, 60, 63, 64, 68, 81, 83, 87, 88, 89, 90, 112, 114, 122, 123, 150, 163, 177, 179, 184, 202, 206, 207, 209, 211, 269; I. Pigment violet 19; C.I. I. Bat red 1, 2, 10, 13, 15, 23, 29, 35, etc. are mentioned.

  Examples of the color pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 60; I. Bat Blue 6; C.I. I. Acid Blue 45 and copper phthalocyanine pigments having 1 to 5 phthalimidomethyl groups substituted on the phthalocyanine skeleton, Green 7, Green 36, and the like.

  Examples of the color pigment for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 10, 11, 12, 13, 14, 15, 16, 17, 23, 55, 65, 73, 74, 83, 97, 110, 139, 151, 154, 155, 180, 185; I. Bat yellow 1, 3, 20, orange 36 and the like.

  The content of the colorant in the toner is preferably 1% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content of the colorant is 1% by mass or more, the coloring power of the toner is sufficiently exhibited. Further, when the content of the colorant is 15% by mass or less, the dispersibility of the pigment in the toner is good, and the coloring power and the electric characteristics of the toner are good.

  The colorant may be used as a master batch combined with a resin. Such a resin is not particularly limited, but from the viewpoint of compatibility with the binder resin in the present invention, the binder resin of the present invention or a resin having a structure similar to the binder resin of the present invention should be used. Is preferred.

  The masterbatch can be produced by applying a high shear force and mixing or kneading the resin and the colorant. At this time, it is preferable to add an organic solvent in order to enhance the interaction between the colorant and the resin. Also, the so-called flushing method is preferable in that the wet cake of the colorant can be used as it is, and there is no need to dry it. The flushing method is a method in which an aqueous paste containing water of a colorant is mixed or kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove water and the organic solvent. For mixing or kneading, for example, a high shear dispersion device such as a three-roll mill can be used.

(Charge control agent)
Further, in order to impart an appropriate charging ability to the toner, a charge control agent can be contained in the toner as necessary.
Any known charge control agent can be used as the charge control agent. Since the color tone may change when a colored material is used, a colorless or nearly white material is preferable. Modified quaternary ammonium salts), alkylamides, phosphorus alone or compounds thereof, tungsten alone or compounds thereof, fluorine-based activators, metal salts of salicylic acid, metal salts of salicylic acid derivatives, and the like. These may be used individually by 1 type and may use 2 or more types together.

  The content of the charge control agent is determined by the toner production method including the type of the binder resin and the dispersion method, and is not uniquely limited. 01 mass%-5 mass% are preferable, and 0.02 mass%-2 mass% are more preferable. When the addition amount of the charge control agent is 5% by mass or less, the charging property of the toner can be suppressed and the effect of the charge control agent can be sufficiently exerted, The suction force is moderated, and the developer fluidity and image density are improved. Moreover, when the addition amount of the charge control agent is 0.01% by mass or more, the charge rising property and the charge amount become sufficient.

(External additive)
Various external additives can be added to the toner for purposes such as fluidity modification, charge amount adjustment, and electrical property adjustment. The external additive is not particularly limited and may be appropriately selected from known ones according to the purpose. For example, silica fine particles, hydrophobized silica fine particles, fatty acid metal salts (for example, zinc stearate, stearin) Metal oxides (for example, titania, alumina, tin oxide, antimony oxide, etc.) or their hydrophobized products, fluoropolymers, and the like. Among these, hydrophobized silica fine particles, titania particles, and hydrophobized titania fine particles are preferable.

  Examples of the hydrophobized silica fine particles include HDK H2000, HDK H2000 / 4, HDK H2050EP, HVK21, HDK H1303 (all manufactured by Hoechst); R972, R974, RX200, RY200, R202, R805, R812 (all Also manufactured by Nippon Aerosil Co., Ltd.). Examples of the titania fine particles include P-25 (manufactured by Nippon Aerosil Co., Ltd.); STT-30, STT-65C-S (both manufactured by Titanium Industry Co., Ltd.); TAF-140 (manufactured by Fuji Titanium Industry Co., Ltd.); Examples include MT-150W, MT-500B, MT-600B, MT-150A (all manufactured by Teika Corporation). Examples of the hydrophobized titanium oxide fine particles include T-805 (manufactured by Nippon Aerosil Co., Ltd.); STT-30A, STT-65S-S (both manufactured by Titanium Industry Co., Ltd.); TAF-500T, TAF-1500T. (Both manufactured by Fuji Titanium Industry Co., Ltd.); MT-100S, MT-100T (both manufactured by Teika Co., Ltd.); IT-S (produced by Ishihara Sangyo Co., Ltd.) and the like.

  Hydrophobized silica fine particles, hydrophobized titania fine particles, and hydrophobized alumina fine particles are obtained by treating hydrophilic fine particles with a silane coupling agent such as methyltrimethoxysilane, methyltriethoxysilane, or octyltrimethoxysilane. Can be obtained. Examples of the hydrophobizing agent include silane coupling agents such as dialkyl dihalogenated silanes, trialkyl halogenated silanes, alkyl trihalogenated silanes, and hexaalkyldisilazanes, silylating agents, and silane couplings having a fluorinated alkyl group. Agents, organic titanate coupling agents, aluminum coupling agents, silicone oils, silicone varnishes and the like.

  1-100 nm is preferable and, as for the average particle diameter of the primary particle of the said inorganic fine particle, 3-70 nm is more preferable. When the average particle size of the primary particles of the inorganic fine particles is 1 nm or more, the inorganic fine particles are prevented from being buried in the toner, and the function is effectively exhibited. Further, when the average particle size is 100 nm or less, it is possible to suppress the surface of the electrostatic latent image carrier from being damaged.

As the external additive, inorganic fine particles or hydrophobized inorganic particles can be used in combination, but the hydrophobized primary particles have an average particle size of at least two types of inorganic fine particles of 20 nm or less, and 30 nm or more. More preferably, it contains at least one kind of inorganic fine particles.
Moreover, it is preferable that the specific surface area by BET method of the said inorganic fine particle is 20-500 m < ² > / g.

The amount of the external additive added is preferably 0.1 to 5% by mass and more preferably 0.3 to 3% by mass with respect to the toner.
Resin fine particles can also be added as the external additive. For example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, or dispersion polymerization; copolymer of methacrylic acid ester, acrylic acid ester; polycondensation system such as silicone, benzoguanamine, nylon; polymer particles made of thermosetting resin It is done. By using such resin fine particles in combination, the chargeability of the toner can be enhanced, the reversely charged toner can be reduced, and the background stain can be reduced. The addition amount of the resin fine particles is preferably 0.01 to 5% by mass, and more preferably 0.1 to 2% by mass with respect to the toner.

(Toner production method)
The toner production method and materials in the present invention can be any known ones as long as they satisfy the conditions, and are not particularly limited. There is a so-called chemical method of granulating.

  Examples of the chemical method include a suspension polymerization method, an emulsion polymerization method, a seed polymerization method, a dispersion polymerization method, etc., in which a monomer is used as a starting material; a resin or a resin precursor is dissolved in an organic solvent and the like in an aqueous medium. Dispersing or emulsifying dissolution suspension method; in the dissolution suspension method, an oil phase composition containing a resin precursor (reactive group-containing prepolymer) having a functional group capable of reacting with an active hydrogen group is contained in resin fine particles. A method of emulsifying or dispersing in an aqueous medium and reacting the active hydrogen group-containing compound and the reactive group-containing prepolymer in the aqueous medium (production method (I)); Phase inversion emulsification method in which water is added to a solution composed of an emulsifier; the resin particles obtained by these methods are aggregated in a state of being dispersed in an aqueous medium and granulated into particles of a desired size by heating and melting. Aggregation And the like. Among these, the toner obtained by the dissolution suspension method, the production method (I), and the aggregation method is preferable from the viewpoint of granulation properties (particle size distribution control, particle shape control, etc.) by the crystalline resin, and the production method described above. The toner obtained in (I) is more preferable.

In the following, a detailed description of these production methods will be given.
The kneading and pulverizing method is, for example, a method of producing the toner base particles by pulverizing and classifying a toner material having at least a colorant, a binder resin, and a release agent melted and kneaded.

  In the melt kneading, the toner materials are mixed, and the mixture is charged into a melt kneader and melt kneaded. As the melt kneader, for example, a uniaxial or biaxial continuous kneader or a batch kneader using a roll mill can be used. For example, a KTK type twin screw extruder manufactured by Kobe Steel, a TEM type extruder manufactured by Toshiba Machine Co., Ltd., a twin screw extruder manufactured by Casey Kay, a PCM type twin screw extruder manufactured by Ikegai Iron Works, and a Kneader manufactured by Buss Co., Ltd. are suitable. Used. This melt-kneading is preferably performed under appropriate conditions so as not to cause the molecular chains of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin. If the temperature is higher than the softening point, cutting is severe, and if the temperature is too low, dispersion may not proceed.

  In the pulverization, the kneaded product obtained by the kneading is pulverized. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.

In the classification, the pulverized product obtained by the pulverization is classified and adjusted to particles having a predetermined particle diameter. The classification can be performed, for example, by removing the fine particle portion with a cyclone, a decanter, a centrifuge, or the like.
After the pulverization and classification are completed, the pulverized product is classified into an air stream by centrifugal force or the like, and toner base particles having a predetermined particle diameter can be produced.

In the dissolution suspension method, for example, an oil phase composition in which a toner composition containing at least a binder resin or a resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is used. This is a method for producing toner base particles by dispersing or emulsifying in a medium.
The organic solvent used for dissolving or dispersing the toner composition is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal of the solvent later.
Examples of the organic solvent include ester solvents such as ethyl acetate, butyl acetate, methoxybutyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, and propylene glycol monomethyl. Ether solvents such as ether, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, cyclohexanone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2 -Alcohol solvents, such as ethyl hexyl alcohol and benzyl alcohol, and these 2 or more types of mixed solvents are mentioned.

  In the dissolution suspension method, when the oil phase composition is dispersed or emulsified in an aqueous medium, an emulsifier or a dispersant may be used as necessary. As the emulsifier or dispersant, known surfactants, water-soluble polymers and the like can be used. The surfactant is not particularly limited, and is an anionic surfactant (alkyl benzene sulfonic acid, phosphate ester, etc.), a cationic surfactant (quaternary ammonium salt type, amine salt type, etc.), an amphoteric surfactant (carbon carboxyl). Acid salt type, sulfate ester type, sulfonate salt type, phosphate ester salt type, etc.), nonionic surfactants (AO addition type, polyhydric alcohol type, etc.) and the like. One surfactant may be used alone, or two or more surfactants may be used in combination.

Examples of the water-soluble polymer include cellulose compounds (for example, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, hydroxypropyl cellulose and saponified products thereof), gelatin, starch, dextrin, gum arabic, chitin, chitosan. , Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene glycol, polyethyleneimine, polyacrylamide, acrylic acid (salt) -containing polymer (sodium polyacrylate, potassium polyacrylate, ammonium polyacrylate, sodium hydroxide partially neutralized polyacrylic acid) , Sodium acrylate-acrylic acid ester copolymer), sodium hydroxide of styrene-maleic anhydride copolymer ( Min) neutralized product water-soluble polyurethane (polyethylene glycol, reaction products of polycaprolactone diol with polyisocyanate and the like) and the like.
Moreover, said organic solvent, a plasticizer, etc. can also be used together as an auxiliary | assistant of emulsification or dispersion | distribution.

  The toner of the present invention comprises at least a binder resin, a binder resin precursor having a functional group capable of reacting with an active hydrogen group (reactive group-containing prepolymer), a colorant, and a release agent in a dissolution suspension method. The oil phase composition is dispersed or emulsified in an aqueous medium containing resin fine particles, the active hydrogen group-containing compound contained in the oil phase composition and / or the aqueous medium, and the reactive group-containing prepolymer, It is preferable to obtain the toner base particles by a method of reacting the toner (production method (I)).

  The resin fine particles can be formed using a known polymerization method, but is preferably obtained as an aqueous dispersion of resin fine particles. Examples of the method for preparing an aqueous dispersion of resin fine particles include the methods shown in the following (a) to (h).

(A) A method in which an aqueous dispersion of resin fine particles is directly prepared from a vinyl monomer as a starting material by any one of a suspension polymerization method, an emulsion polymerization method, a seed polymerization method and a dispersion polymerization method. (B) After dispersing a precursor of polyaddition or condensation resin such as polyester resin, polyurethane resin, epoxy resin (monomer, oligomer, etc.) or a solvent solution thereof in an aqueous medium in an aqueous medium, A method of preparing an aqueous dispersion of resin fine particles by heating or adding a curing agent to cure.

(C) Polyaddition or condensation resin precursors (monomers, oligomers, etc.) such as polyester resins, polyurethane resins, and epoxy resins, or solvent solutions thereof (preferably liquids, which may be liquefied by heating). A method for preparing an aqueous dispersion of resin fine particles by dissolving a suitable emulsifier in the mixture and then adding water to effect phase inversion emulsification.
(D) A resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is pulverized and classified using a mechanical rotary type or jet type fine pulverizer. A method of preparing an aqueous dispersion of resin fine particles by obtaining resin fine particles and then dispersing in water in the presence of an appropriate dispersant.

(E) Fine resin particles are formed by spraying a resin solution in which a resin synthesized in advance by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) is dissolved in a solvent. Then, resin fine particles are dispersed in water in the presence of a suitable dispersant to prepare an aqueous dispersion of resin fine particles.
(F) A poor solvent is added to a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, or heated to a solvent in advance. By cooling the dissolved resin solution, the resin fine particles are precipitated, the solvent is removed to form the resin fine particles, and then the resin fine particles are dispersed in water in the presence of an appropriate dispersant to disperse the resin fine particles in water. A method for preparing a liquid.

(G) A resin solution obtained by dissolving a resin previously synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent in the presence of an appropriate dispersant. A method of preparing an aqueous dispersion of resin fine particles by dispersing in a solvent and then removing the solvent by heating, decompression or the like.
(H) A suitable emulsifier is dissolved in a resin solution prepared by previously dissolving a resin synthesized by a polymerization reaction (for example, addition polymerization, ring-opening polymerization, polyaddition, addition condensation, condensation polymerization, etc.) in a solvent, and then water To prepare an aqueous dispersion of resin fine particles by phase inversion emulsification.

  The volume average particle diameter of the resin fine particles is preferably 20 nm or more and 90 nm or less, and more preferably 30 nm or more and 80 nm or less. When the volume average particle diameter of the resin fine particles is 20 nm or more, the entire toner layer can be appropriately hardened, and deformation with respect to pressure can be made difficult to occur. Thereby, it can suppress that peeling and a mark are attached by the roller and nail | claw in conveyance. Moreover, adhesiveness can be made favorable and peeling at the paper interface can also be suppressed. Furthermore, the particle size distribution of the toner can be improved. When the volume average particle diameter of the resin fine particles is 90 nm or less, the toner particles are sufficiently melted and fixed, so that the interface of the toner particles can be prevented and cracking at the interface can be suppressed. it can. Further, even when the paper is folded, the toner layer can be prevented from breaking at the fold. Furthermore, the particle size distribution of the toner can be improved.

  The solid content concentration of the oil phase is preferably about 40 to 80% by mass. When the solid content concentration is 40% by mass or more, the productivity of the toner can be improved. In addition, when the solid content concentration is 80% by mass or less, dissolution or dispersion can be performed satisfactorily and the viscosity is appropriate, so that the handleability is improved.

  The toner composition other than the binder resin such as the colorant and the release agent, and the masterbatch thereof are individually dissolved or dispersed in an organic solvent, and then mixed with the binder resin solution or dispersion. May be.

  As the aqueous medium, water alone may be used, but a solvent miscible with water may be used in combination. Examples of miscible solvents include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The dispersion or emulsification method in the aqueous medium is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied. Among these, the high-speed shearing method is preferable from the viewpoint of reducing the particle size of the particles. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 20 to 80 ° C.

  In order to remove the organic solvent from the obtained emulsified dispersion, there is no particular limitation, and a known method can be used. For example, the whole system is gradually raised while stirring the whole system under normal pressure or reduced pressure. A method of warming and completely evaporating and removing the organic solvent in the droplets can be employed.

  As a method of washing and drying the toner base particles dispersed in the aqueous medium, a known technique is used. That is, after solid-liquid separation with a centrifuge, a filter press or the like, the obtained toner cake is redispersed in ion-exchanged water at room temperature to about 40 ° C., and the pH is adjusted with acid or alkali as necessary. The toner powder is then removed by repeating the process of solid-liquid separation again several times to remove impurities, surfactants, etc., and then dried with an air dryer, circulating dryer, vacuum dryer, vibration fluid dryer, etc. Get. At this time, the fine particle component of the toner may be removed by centrifugation or the like, and a desired particle size distribution can be obtained using a known classifier after drying, if necessary.

  In the agglomeration method, for example, a toner base particle is produced by mixing and aggregating a resin fine particle dispersion comprising at least a binder resin, a colorant particle dispersion, and a release agent particle dispersion as necessary. is there. The resin fine particle dispersion is obtained by a known method such as emulsion polymerization, seed polymerization, phase inversion emulsification, and the like. The colorant particle dispersion and the release agent particle dispersion are obtained by a known wet dispersion method. It can be obtained by dispersing a colorant or a release agent in an aqueous medium.

For the control of the aggregation state, methods such as applying heat, adding a metal salt, and adjusting pH are preferably used.
There is no restriction | limiting in particular as said metal salt, The monovalent metal which comprises salts, such as sodium and potassium; The bivalent metal which comprises salts, such as calcium and magnesium; The trivalent metal which comprises salts, such as aluminum, etc. Is mentioned.

Examples of the anion constituting the salt include chloride ion, bromide ion, iodide ion, carbonate ion, and sulfate ion. Among these, magnesium chloride, aluminum chloride, and complexes and multimers thereof are preferable. .
In addition, heating between the agglomeration and after completion of the agglomeration can promote fusion of the resin fine particles, which is preferable from the viewpoint of toner uniformity. Furthermore, the shape of the toner can be controlled by heating. Normally, the toner becomes more spherical when heated further.

As the method for washing and drying the toner base particles dispersed in the aqueous medium, the above-described method and the like can be used.
Further, in order to improve the fluidity, storage stability, developability and transferability of the toner, inorganic fine particles such as hydrophobic silica fine powder may be further added to and mixed with the toner base particles produced as described above.

  For mixing the additives, a general powder mixer is used, but it is preferable to equip a jacket or the like to adjust the internal temperature. In order to change the load history applied to the additive, the additive may be added midway or gradually. In this case, you may change the rotation speed, rolling speed, time, temperature, etc. of a mixer. Alternatively, a strong load may be applied first, then a relatively weak load, or vice versa. Examples of the mixing equipment that can be used include a V-type mixer, a rocking mixer, a Ladige mixer, a Nauter mixer, and a Henschel mixer. Next, the toner is obtained by passing through a sieve of 250 mesh or more to remove coarse particles and aggregated particles.

  The shape, size, etc. of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The average circularity, volume average particle diameter, volume average particle diameter as follows. And the ratio of the number average particle diameter (volume average particle diameter / number average particle diameter).

  The average circularity is a value obtained by dividing the circumference of an equivalent circle having the same projected shape as the shape of the toner by the circumference of the actual particles. For example, 0.950 to 0.980 is preferable, and 0.960 to 0 is preferable. .975 is more preferred. The particles having an average circularity of less than 0.950 are preferably 15% or less.

  When the average circularity is 0.950 or more, satisfactory transferability and high-quality images free from dust can be obtained. Further, when the average circularity is 0.980 or less, the cleaning property can be improved, and a high-quality image can be obtained. That is, in an image forming system that employs blade cleaning or the like, the cleaning performance on the photoreceptor and the transfer belt is improved. Then, in the case of image formation with a high image area ratio such as a photographic image, such as a photographic image, an image in which toner that has formed an untransferred image due to poor paper feed or the like is accumulated as a transfer image on the photoreceptor. It is possible to suppress the occurrence of soil contamination. Further, it is possible to suppress contamination of a charging roller that contacts and charges the photosensitive member, and to fully exhibit the original charging ability.

  The average circularity was measured using a flow type particle image analyzer (“FPIA-2100”, manufactured by Sysmex Corporation), and analyzed using analysis software (FPIA-2100 Data Processing Program for FPIA version 00-10). Specifically, 0.1 to 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml glass beaker, and each toner 0 is added. 0.1 to 0.5 g was added, and the mixture was mixed with a micropartel, and then 80 mL of ion-exchanged water was added. The obtained dispersion was subjected to a dispersion treatment for 3 minutes with an ultrasonic disperser (manufactured by Honda Electronics Co., Ltd.). Using the FPIA-2100, the dispersion was measured for toner shape and distribution until a concentration of 5,000 to 15,000 / μL was obtained. In this measurement method, it is important that the concentration of the dispersion is 5,000 to 15,000 / μL from the viewpoint of measurement reproducibility of average circularity. In order to obtain the concentration of the dispersion, it is necessary to change the conditions of the dispersion, that is, the amount of surfactant to be added and the amount of toner. The amount of the surfactant varies depending on the hydrophobicity of the toner as in the measurement of the toner particle diameter described above. If it is added in a large amount, noise due to bubbles is generated, and if it is too small, the toner cannot be sufficiently wetted. It will be enough. Further, the amount of toner added varies depending on the particle size, and it is necessary to decrease the small particle size and increase the large particle size. When the toner particle size is 3 μm to 10 μm, the dispersion concentration can be adjusted to 5,000 / μl to 15,000 / μl by adding 0.1 g to 0.5 g of the toner amount.

  There is no restriction | limiting in particular as a volume average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 3 micrometers-10 micrometers are preferable, and 4 micrometers-7 micrometers are more preferable. When the volume average particle size is 3 μm or more, even in a two-component developer, the toner is prevented from fusing to the surface of the carrier due to long-term stirring in the developing device, so that the charging ability of the carrier is not lowered. can do. Further, when the volume average particle size is 10 μm or less, a high-resolution and high-quality image can be obtained. Further, when the balance of the toner in the developer is performed, the fluctuation of the toner particle size can be reduced.

The ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.25, and more preferably 1.00 to 1.15.
The volume average particle diameter and the ratio of the volume average particle diameter to the number average particle diameter (volume average particle diameter / number average particle diameter) are measured using a particle size measuring device (“Multisizer III”, manufactured by Beckman Coulter, Inc.). The measurement was performed with an aperture diameter of 100 μm, and the analysis was performed with analysis software (Beckman Coulter Mutlisizer 3 Version 3.51). Specifically, 0.5 ml of 10% by weight surfactant (alkylbenzene sulfonate, Neogen SC-A, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is added to a 100 ml beaker made of glass, and 0.5 g of each toner is added. The mixture was stirred with a micropartel, and then 80 ml of ion exchange water was added. The obtained dispersion was subjected to a dispersion treatment for 10 minutes with an ultrasonic disperser (W-113MK-II, manufactured by Honda Electronics Co., Ltd.). The dispersion was measured using the Multisizer III and Isoton III (manufactured by Beckman Coulter, Inc.) as the measurement solution. In the measurement, the toner sample dispersion was dropped so that the concentration indicated by the apparatus was 8 ± 2%. In this measurement method, it is important that the concentration is 8 ± 2% from the viewpoint of the reproducibility of the particle size. Within this concentration range, no error occurs in the particle size.

In order to suppress the occurrence of image conveyance flaws, the maximum endothermic peak temperature of the first temperature increase in the range of 0 ° C. to 100 ° C. of the toner measured by a differential scanning calorimeter (DSC) under the following conditions is T1 (° C. ), When the maximum exothermic peak temperature during temperature drop is T2 (° C.), the following relational expression (1) is preferably satisfied.
T1-T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 100 ° C. in the first temperature increase is 10 ° C./min, and the rate of temperature decrease from 100 ° C. to 0 ° C. is 10 ° C./min.)

<Measurement method and conditions for maximum heat absorption and heat generation peak of toner>
The maximum endothermic peak of the toner was measured using DSC system Q-200 (manufactured by TA Instruments). Specifically, first, about 5.0 mg of resin was put in an aluminum sample container, and the sample container was placed on a holder unit and set in an electric furnace. Next, after raising the temperature from 0 ° C. to 100 ° C. at 10 ° C./min in a nitrogen atmosphere, the temperature was lowered from 100 ° C. to 0 ° C. at 10 ° C./min. Using an analysis program in DSC system Q-200 (manufactured by TA Instruments), a DSC curve at the first temperature rise was selected, and the maximum endothermic peak temperature T1 of the toner was measured. Similarly, the maximum heat generation peak temperature T2 of the toner when the temperature was lowered was measured.

  T1 of the toner is preferably 50 ° C to 70 ° C, more preferably 53 ° C to 65 ° C, and particularly preferably 58 ° C to 62 ° C. When the T1 is 50 ° C. to 70 ° C., the minimum heat-resistant storage stability required for the toner can be ensured, and a toner having excellent low-temperature fixability that is not conventionally obtained can be obtained. When the T1 is 50 ° C. or higher, the heat resistant storage stability is improved. Further, when T1 is 70 ° C. or lower, the low-temperature fixability is improved.

  The T2 is preferably 30 ° C to 55 ° C, more preferably 35 ° C to 55 ° C, and particularly preferably 40 to 55 ° C. When T2 is 30 ° C. or higher, the speed at which the fixed image is cooled to solidified can be increased, and blocking of toner images (printed matter) and conveyance flaws can be suppressed. The T2 is desirably as high as possible. However, since T2 is a crystallization temperature, it is impossible to take a temperature higher than the melting point T1. That is, it is desirable that the difference between T1 and T2 (T1−T2) is within a certain range in order to suppress toner image blocking and conveyance flaws while maintaining excellent heat-resistant storage stability and low-temperature fixability. T1-T2 is preferably 30 ° C. or lower, more preferably 25 ° C. or lower, and particularly preferably 20 ° C. or lower. When T1-T2 is 30 ° C. or less, the difference between the fixing temperature and the temperature at which the toner image is solidified is small, and the effect of suppressing blocking of toner images and conveyance flaws is enhanced.

  An output image of a toner containing a crystalline polyester resin having a urethane bond and / or a urea bond as a binder resin is likely to cause conveyance scratches. This is due to the low recrystallization rate when the crystalline polyester resin having a urethane bond and / or a urea bond is cooled to a melting point or lower from a melted state.

  A method of reducing the amount of urethane bonds and / or urea bonds can be considered as a means for adjusting the physical cross-linking points and the heterogeneity of the molecular structure, which are the main factors for reducing the recrystallization rate. However, with this method, the strength of the image decreases with a decrease in the elastic modulus, so that the conveyance scratches tend to deteriorate, and the hot offset resistance also deteriorates. Similarly, a method of adjusting the molecular weight is also conceivable. However, even in this method, it is impossible to suppress the occurrence of transport flaws, and it is impossible to simultaneously improve the two contradictory characteristics of image recrystallization speed and elastic modulus.

  Thus, as a result of intensive studies, the authors have improved the recrystallization speed while maintaining the elastic modulus by combining a crystalline polyester resin having a urethane bond and / or a urea bond with an unmodified crystalline polyester. Found that is possible.

  The effect of improving the crystallization speed is obtained by the unmodified crystalline polyester resin. Due to this effect, even when a crystalline polyester resin having a urethane bond and / or a urea bond is used as the binder resin, the elastic modulus and strength of the image can be greatly improved before contacting the conveying member. Therefore, the occurrence of transport flaws can be suppressed. In addition, at this time, the presence of the crystalline polyester resin having a urethane bond and / or a urea bond maintains the hot offset resistance, and the unmodified crystalline polyester resin has an effect of favoring low-temperature fixability. give.

  By including a crystalline polyester resin having at least a urethane bond and / or a urea bond as a binder resin and an unmodified crystalline polyester resin, both low-temperature fixing and heat-resistant storage stability are achieved at a high level, and The occurrence of conveyance flaws and insufficient strength of the output image can be resolved. This is a combination of a non-modified crystalline polyester resin and a crystalline polyester having a urethane bond and / or urea bond with high cohesive energy that can improve the strength of hot offset resistance, heat resistant storage, and output image. This is because the recrystallization speed of the image after heat fixing is improved, and the hardness of the output image can be improved before the image reaches the conveyance member causing the conveyance flaw.

  The unmodified crystalline polyester resin and the crystalline polyester resin having a urethane bond and / or a urea bond are preferably in a state where both are uniformly mixed in the image. Therefore, it is preferable that both are uniformly mixed or uniformly distributed in the toner. From the viewpoint of uniform mixing and dispersibility in the toner, the crystalline polyester portion of the unmodified crystalline polyester resin and the crystalline polyester resin having a urethane bond and / or a urea bond may have a similar skeleton. preferable.

For toners whose main component is a crystalline resin as a binder resin, the property of sharply decreasing viscoelasticity above the melting point that was previously considered effective for low-temperature fixability (sharp melt properties) can be fixed depending on the paper type. It is considered that the temperature range is greatly different. Accordingly, the binder resin used in the conventional toner having excellent low-temperature fixability contains a certain amount or more of a higher component, and further, the weight average molecular weight is within a certain range. It was found that it can be fixed at a constant temperature and at a constant speed regardless of the species.
Specifically, the ratio of the molecular weight in terms of polystyrene of 100,000 or more in gel diffusion chromatography (GPC) soluble in tetrahydrofuran (THF) of the toner is 5% or more, and the weight average molecular weight (Mw) is 20 It is preferable that it is 7,000 or more and 70,000 or less.

  As described above, the toner preferably has 5% or more of a component having a molecular weight of 100,000 or more, more preferably 7% or more, and still more preferably 9% or more. When the component having a molecular weight of 100,000 or more has 5% or more, the temperature dependency of the fluidity and viscoelasticity of the toner after melting becomes small. For this reason, even if it is a thin paper that easily transfers heat during fixing, even if it is a thick paper that does not easily transfer heat to the toner, there is no significant difference in toner fluidity and elastic modulus, and the fixing device has a constant temperature and a constant speed. It becomes possible to fix.

The reason why the effect of the present invention can be obtained is considered as follows.
That is, the crystalline resin has a sharp melt property as described above, but the internal cohesive force and viscoelasticity of the toner in the molten state vary greatly depending on the molecular weight and structure of the resin. For example, when it has a urethane bond or a urea bond, which is a linking group having a large cohesive energy, it behaves like an elastic body such as rubber at a relatively low temperature even when melted. However, as the temperature increases, the thermal kinetic energy of the polymer chain increases, so that the aggregation between the bonds gradually dissolves and approaches the viscous body.

  When such a resin is used as a binder resin for toner, even if the fixing can be performed without problems when the fixing temperature is low, a problem occurs when the fixing temperature is high. That is, since the internal cohesive force at the time of melting the toner is small, a so-called hot offset phenomenon that the upper side of the toner image adheres to the fixing member at the time of fixing may occur, and the image quality is remarkably impaired. Increasing the number of urethane bond or urea bond sites to avoid hot offset can be performed without problems in fixing at high temperatures, but causes problems when fixing at low temperatures. That is, the gloss of the image is low, the melt impregnation into the paper is insufficient, and the image is easily detached from the paper. In particular, when fixing on paper having a large thickness and unevenness on the surface, the heat transfer efficiency to the toner at the time of fixing is low, and the fixing state is further deteriorated. In addition, since the pressure is not sufficiently applied to the toner by the fixing member in the concave portion, the fixing state of the toner which is particularly in an elastic state is remarkably deteriorated.

  When the molecular weight is considered as a means for controlling the viscoelasticity after melting, as a matter of course, the larger the molecular weight, the more obstacles to the movement of the molecular chain, so the viscoelasticity increases. Further, when the molecular weight is large, entanglement occurs, and the elastic behavior is exhibited. Considering the fixability to paper, a smaller molecular weight is preferable because the viscosity at the time of melting is lower. On the other hand, if there is no elasticity, hot offset occurs. However, if the molecular weight is increased as a whole, the fixability is impaired, and particularly in the case of thick paper, the heat transfer efficiency to the toner at the time of fixing is low, and the fixing state is further deteriorated. Therefore, the viscoelasticity after melting can be suitably controlled by including a high molecular weight crystalline component while preventing the molecular weight of the binder resin from being too large as a whole. Regardless of this, a toner that can be fixed at a constant temperature and at a constant speed can be obtained.

  The range of the weight average molecular weight is preferably 20,000 or more and 70,000 or less, more preferably 30,000 or more and 60,000 or less, and particularly preferably 35,000 or more and 50,000 or less. When the weight average molecular weight is 70,000 or less, since the entire binder resin does not become too high in molecular weight, the fixing property is good, the gloss is high, and the image after fixing is stabilized against external stress. Therefore, it is preferable. A weight average molecular weight of 20,000 or more is preferable because the high molecular weight component increases internal cohesion when the toner is melted, and can suppress hot offset and paper wrapping around the fixing member.

  As a method of obtaining a toner having a binder resin having a molecular weight distribution as described above, there is a method of using a resin having a controlled molecular weight distribution during polymerization, using two or more resins having different molecular weight distributions in combination. .

  When two or more kinds of resins having different molecular weight distributions are used in combination, at least two kinds of relatively high molecular weight resins and low molecular weight resins are used. As the high molecular weight resin, a resin having a large molecular weight may be used in advance, or a modified resin having an isocyanate group at the terminal may be elongated in the production process of the toner to form a high molecular weight body. In the latter method, the high molecular weight body can be uniformly present in the toner, and in the production method in which the binder resin is dissolved in the organic solvent, the high molecular weight resin is first dissolved than the high molecular weight resin. Is preferable because it is easy.

  The ratio of the high molecular weight resin (including a modified resin having an isocyanate group) and the low molecular weight resin as the binder resin is such that the ratio of the high molecular weight resin / low molecular weight resin is 5 / It is preferable that it is 95-60 / 40. The ratio is more preferably 8/92 to 50/50, still more preferably 12/88 to 35/65, and particularly preferably 15/85 to 25/75. When the ratio is 5/95 to 60/40, it becomes easy to obtain a toner having a binder resin having the above molecular weight distribution.

  In the case of using a resin whose molecular weight distribution is controlled at the time of polymerization, examples of a method for obtaining such a resin include the following methods. That is, for example, in the case of a polymerization form such as polycondensation, polyaddition, and addition condensation, the molecular weight distribution can be broadened by adding a small amount of a monomer having a different number of functional groups in addition to a bifunctional monomer. Monomers with different numbers of functional groups include tri- or higher-functional monomers and mono-functional monomers. However, when tri- or higher-functional monomers are used, a branched structure is generated. May be difficult to form. If a monofunctional monomer is used, the polymerization reaction is stopped by the monofunctional monomer, so that the low molecular weight resin in the case of using two or more types of resins is purified, and a part of the polymerization reaction proceeds to increase the high molecular weight component. It becomes.

  In the present invention, the tetrahydrofuran-soluble content of the toner and the molecular weight distribution and weight average molecular weight (Mw) of the resin are measured using a gel permeation chromatography (GPC) measuring device (for example, HLC-8220 GPC (manufactured by Tosoh Corporation)). It can be measured. As the column, TSKgel SuperHZM-H 15 cm triplet (manufactured by Tosoh Corporation) was used. The resin to be measured was made into a 0.15 mass% solution in tetrahydrofuran (THF) (containing a stabilizer, manufactured by Wako Pure Chemical Industries), filtered through a 0.2 μm filter, and the filtrate was used as a sample. 100 μl of the THF sample solution was injected into a measuring apparatus, and measurement was performed at a flow rate of 0.35 ml / min in an environment at a temperature of 40 ° C.

  The molecular weight was calculated using a calibration curve prepared with a monodisperse polystyrene standard sample. As the standard polystyrene sample, Showdex STANDARD series manufactured by Showa Denko KK and toluene were used. The following three types of monodisperse polystyrene standard sample THF solutions were prepared and measured under the above conditions, and a calibration curve was prepared using the peak top retention time as the light scattering molecular weight of the monodisperse polystyrene standard sample.

Solution A: S-7450 2.5mg, S-678 2.5mg, S-46.5 2.5mg, S-2.90 2.5mg, THF 50ml
Solution B: S-3730 2.5mg, S-257 2.5mg, S-19.8 2.5mg, S-0.580 2.5mg, THF 50ml
Solution C: S-1470 2.5mg, S-112 2.5mg, S-6.93 2.5mg, Toluene 2.5mg, THF 50ml
An RI (refractive index) detector was used as the detector.

  The ratio of the component having a molecular weight of 100,000 or more and the ratio of the component having a molecular weight of 250,000 or more can be examined from the intersection of the molecular weight of 100,000 and the molecular weight of 250,000 in the integral molecular weight distribution curve.

The high molecular weight component needs to have a resin structure close to that of the entire binder resin. If the binder resin has crystallinity, the high molecular weight component also needs to have crystallinity. When the high molecular weight component is significantly different in structure from the other resin components, the polymer is easily phase-separated and becomes a sea-island state, so that it cannot be expected to contribute to improvement of viscoelasticity and cohesive force on the whole toner.
As a comparison of the content of the crystalline structure between the high molecular weight component and the entire binder resin, for example, it is preferable to satisfy the following relationship. That is, the endothermic amount (ΔH (H)) in the differential scanning calorimeter (DSC) of the toner with respect to the mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by mass ratio) of the toner, The ratio (ΔH (H) / ΔH (T)) to the endothermic amount (ΔH (T)) in DSC is preferably in the range of 0.2 to 1.25. The ratio (ΔH (H) / ΔH (T)) is more preferably in the range of 0.3 to 1.0, and particularly preferably in the range of 0.4 to 0.8.

  As a specific test method for obtaining an insoluble content in a mixed solvent of tetrahydrofuran (THF) and ethyl acetate (mixing ratio is 50:50 by mass ratio), toner 0. After adding 4 g and shaking and mixing for 20 minutes, a solution obtained by precipitating the insoluble component and removing the supernatant by a centrifugal separator can be obtained by vacuum drying.

<Developer>
The developer of the present invention contains at least the toner of the present invention, and other components such as a carrier selected as appropriate. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

In the case of the one-component developer using the toner of the present invention, fluctuations in the particle diameter of the toner can be reduced even if the toner is balanced. In addition, there is no filming of the toner on the developing roller as the developer carrying member, and the toner is not fused to the layer thickness regulating member such as a blade for thinning the toner. ), Good and stable developability and images can be obtained.
In the case of the two-component developer using the toner of the present invention, the toner particle diameter in the developer is little changed even if the toner balance is maintained over a long period of time. Stable developability is obtained.

<Career>
Next, the carrier used for the developer of the present invention will be described. First, the important point (weight average particle diameter) of the carrier used in the developer of the present invention will be described, and the constituent material of the carrier and the production method will be described later.

(Carrier characteristics evaluation method)
<Weight average particle size>
The weight average particle diameter Dw of the carrier is calculated based on the particle diameter distribution (relationship between the number frequency and the particle diameter) of the particles measured on the basis of the number. The weight average particle diameter Dw in this case is represented by the formula (3).
Dw = {1 / Σ (nD3)} × {Σ (nD4)} Expression (3)

  In formula (3), D represents the representative particle size (μm) of the particles present in each channel, and n represents the total number of particles present in each channel. The channel indicates a length for equally dividing the particle size range in the particle size distribution diagram, and 2 μm is adopted in the present invention. In addition, as the representative particle size of the particles present in each channel, the lower limit value of the particle size of the particles stored in each channel was adopted.

Further, the number average particle diameter Dp of the carrier and the core material particles of the carrier is calculated based on the particle diameter distribution of the particles measured on the basis of the number. The number average particle diameter Dp in this case is represented by the formula (4).
Dp = (1 / ΣN) × (ΣnD) (4)
In Equation (4), N represents the total number of particles measured, n represents the total number of particles present in each channel, and D represents the lower limit of the particle size of the particles stored in each channel (2 μm). Show.

In the present invention, a microtrack particle size analyzer model HRA9320-X100 (Honewell) can be used as a particle size analyzer for measuring the particle size distribution. The measurement conditions are as follows.
[1] Particle size range: 8 to 100 μm
[2] Channel length (channel width): 2 μm
[3] Number of channels: 46
[4] Refractive index: 2.42

(Constituent materials and manufacturing method of carriers)
As the carrier in the present invention, conventionally known carriers such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 15 to 45 μm can be used. Examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Polyvinyl and polyvinylidene resins such as acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and styrene acrylic copolymer resins, Halogenated olefin resins such as vinyl, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, polyhexafluoropropylene resins , Copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinyl fluoride Fluoro such as terpolymers of isopropylidene and a non-fluorinated monomer, and silicone resins. Moreover, you may contain electrically conductive powder etc. in coating resin as needed. As the conductive powder, metal powder, carbon black, titanium oxide, tin oxide, zinc oxide or the like can be used. These conductive powders preferably have an average particle diameter of 1 μm or less. When the average particle diameter of the conductive powder is 1 μm or less, the electric resistance can be easily controlled.

<Image forming apparatus>
An image forming apparatus according to the present invention includes an image carrier, charging means for charging the image carrier, latent image forming means for forming an electrostatic latent image on the image carrier, and the image carrier. In an image forming apparatus including a developing unit that develops an electrostatic latent image with toner, the toner of the present invention is used as the toner replenished to the developing unit. The image forming apparatus of the present invention preferably includes a plurality of image carriers, and the toner images formed on the image carriers are sequentially transferred to a transfer medium.

Hereinafter, the image forming apparatus of the present invention will be described in detail with reference to the drawings.
FIG. 2 is a schematic diagram for explaining the electrophotographic process and the image forming apparatus of the present invention, and the following examples also belong to the category of the present invention.
The photosensitive member (10) rotates in the direction of the arrow in FIG. ), A cleaning member (17), a charge removal member (18), and the like are disposed. The cleaning member (17) and the charge removal member (18) may be omitted.

  The operation of the image forming apparatus is basically as follows. The charging member (11) charges the surface of the photoreceptor (10) almost uniformly. Subsequently, image light writing corresponding to the input signal is performed by the image exposure member (12) to form an electrostatic latent image. Next, the electrostatic latent image is developed by the developing member (13), and a toner image is formed on the surface of the photoreceptor. The formed toner image is transferred onto the transfer paper (15) sent to the transfer site by the transport roller (14) by the transfer member. This toner image is fixed on the transfer paper by a fixing device (not shown). Part of the toner that has not been transferred to the transfer paper is cleaned by the cleaning member (17). Subsequently, the charge remaining on the photoreceptor is neutralized by the neutralizing member (18), and the process proceeds to the next cycle.

  As shown in FIG. 2, the photoconductor (10) has a drum shape, but may have a sheet shape or an endless belt shape. As the charging member (11) and the transfer member (16), in addition to corotron, scorotron, solid state charger (solid state charger), a roller-shaped charging member or a brush-shaped charging member is used. Are all usable.

  On the other hand, light sources such as the image exposure member (12) and the charge removal member (18) include fluorescent lamps, tungsten lamps, halogen lamps, mercury lamps, sodium lamps, light emitting diodes (LEDs), semiconductor lasers (LD), and electroluminescence (EL). ) And other luminescent materials can be used. Among these, a semiconductor laser (LD) and a light emitting diode (LED) are mainly used.

  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 light source or the like irradiates the photoconductor (10) with light by providing a transfer process, a static elimination process, a cleaning process, or a pre-exposure process using light irradiation together. However, the exposure of the photoconductor (10) in the static elimination process has a large influence of fatigue on the photoconductor (10), and may cause a decrease in charge and an increase in residual potential.
Therefore, there is a case where it is possible to eliminate static electricity by applying a reverse bias in the charging process or cleaning process instead of static elimination by exposure, which may be effective from the viewpoint of enhancing the durability of the photoreceptor.

When the electrophotographic photosensitive member (10) is positively (negatively) charged and image exposure is performed, a positive (negative) electrostatic latent image is formed on the surface of the photosensitive member. A positive image can be obtained by developing this with negative (positive) toner (electrodetection fine particles), and a negative image can be obtained by developing with positive (negative) toner.
A known method is applied to the developing unit, and a known method is also used for the charge eliminating unit.

  Among contaminants adhering to the surface of the photoconductor, discharge substances generated by charging, external additives contained in the toner, etc. easily pick up the influence of humidity and cause abnormal images. Paper dust is one of the causative substances of such abnormal images, and when they adhere to the photoconductor, not only abnormal images are likely to be generated, but also the wear resistance is reduced or biased. There is a tendency to cause wear. Therefore, it is more preferable from the viewpoint of high image quality that the photoconductor and the paper are not in direct contact for the above reason.

The toner developed on the photoreceptor (10) by the developing member (13) is transferred to the transfer paper (15), but not all is transferred, and the toner remaining on the photoreceptor (10). Also occurs. Such toner is removed from the photoreceptor (10) by the cleaning member (17).
As the cleaning member, a known member such as a cleaning blade or a cleaning brush is used. Moreover, both may be used together.

  The photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. Therefore, as an image forming apparatus or method for using the above photoreceptor more effectively, each developing unit corresponding to a plurality of colors of toner is provided with a plurality of corresponding photoreceptors, thereby performing parallel processing. It is very effectively used in a so-called tandem image forming apparatus. The tandem image forming apparatus includes at least four color toners of yellow (C), magenta (M), cyan (C), and black (K) required for full-color printing and a developing unit that holds them. Further, by providing at least four photoconductors corresponding to them, full-color printing can be performed at a very high speed as compared with a conventional image forming apparatus capable of full-color printing.

FIG. 3 is a schematic view for explaining the tandem-type full-color electrophotographic apparatus of the present invention, and modifications as described below also belong to the category of the present invention.
In FIG. 3, photoconductors (10C (cyan)), (10M (magenta)), (10Y (yellow)), and (10K (black)) are drum-like photoconductors (10), and these photoconductors. (10C, 10M, 10Y, 10K) rotate in the direction of the arrow in the figure, around which at least the charging members (11C, 11M, 11Y, 11K), the developing members (13C, 13M, 13Y, 13K), Cleaning members (17C, 17M, 17Y, 17K) are arranged.
From the back side of the photoreceptor (10) between the charging member (11C, 11M, 11Y, 11K) and the developing member (13C, 13M, 13Y, 13K), laser light (12C, 12M, 12Y, 12K) is irradiated, and electrostatic latent images are formed on the photoconductors (10C, 10M, 10Y, 10K).

Then, four image forming elements (20C, 20M, 20Y, 20K) centering on such a photoreceptor (10C, 10M, 10Y, 10K) are along a transfer conveyance belt (25) which is a transfer material conveyance unit. Are juxtaposed.
The transfer / conveying belt (19) is disposed between the developing member (13C, 13M, 13Y, 13K) of each image forming unit (20C, 20M, 20Y, 20K) and the cleaning member (17C, 17M, 17Y, 17K). A transfer member (16C) for applying a transfer bias to the surface (rear surface) which is in contact with the photoconductor (10C, 10M, 10Y, 10K) and contacts the back side of the photoconductor (10) side of the transfer conveyance belt (19). , 16M, 16Y, 16K). Each of the image forming elements (20C, 20M, 20Y, 20K) is different in toner color inside the developing device, and the other components have the same configuration.

  In the color electrophotographic apparatus having the configuration shown in FIG. 3, the image forming operation is performed as follows. First, in each of the image forming elements (20C, 20M, 20Y, and 20K), the charging member (11C, 11M, 11Y, and 11K) in which the photosensitive member (10C, 10M, 10Y, and 10K) rotates along with the photosensitive member 10 is rotated. ), And then an electrostatic image corresponding to the image of each color to be created by laser light (12C, 12M, 12Y, 12K) by an exposure unit (not shown) arranged outside the photoconductor (10). A latent image is formed.

  Next, the latent image is developed by a developing member (13C, 13M, 13Y, 13K) to form a toner image. The developing members (13C, 13M, 13Y, and 13K) are developing members that perform development with toners of C (cyan), M (magenta), Y (yellow), and K (black), respectively. 10M, 10Y, and 10K) are overlaid on the transfer belt (19).

  The transfer paper (15) is sent out from the tray by the paper supply roller (21), temporarily stopped by the pair of registration rollers (22), and sent to the transfer member (23) in synchronization with the image formation on the photosensitive member. It is done. The toner image held on the transfer belt (19) is transferred onto the transfer paper (15) by an electric field formed by a potential difference between the transfer bias applied to the transfer member (23) and the transfer belt (19). . The toner image transferred onto the transfer paper is conveyed, the toner is fixed onto the transfer paper by the fixing member (24), and is discharged to a paper discharge unit (not shown). Further, residual toner that is not transferred by the transfer unit and remains on the photosensitive members (10C, 10M, 10Y, and 10K) is collected by cleaning members (17C, 17M, 17Y, and 17K) provided in the respective units. The

The intermediate transfer system as shown in FIG. 3 is particularly effective for an image forming apparatus capable of full-color printing. By forming a plurality of toner images once on an intermediate transfer body and transferring them to paper at once, It is easy to control the color shift and is effective for high image quality.
The intermediate transfer member includes various materials or shapes such as a drum shape and a belt shape. In the present invention, any conventionally known intermediate transfer member can be used. It is effective and useful for achieving high quality or high image quality.

  In the example of FIG. 3, the image forming elements are arranged in the order of C (cyan), M (magenta), Y (yellow), and K (black) from the upstream side to the downstream side in the transfer paper conveyance direction. However, it is not limited to this order, and the color order is arbitrarily set. Further, when a black-only document is created, it is particularly effective to use the present invention to provide a mechanism that stops the image forming elements (20C, 20M, 20Y) other than black.

  The image forming means as described above may be fixedly incorporated in a copying apparatus, a facsimile, or a printer, but may be incorporated in these apparatuses in the form of a process cartridge.

<Process cartridge>
The process cartridge according to the present invention comprises an image carrier, a charging unit for charging the image carrier, a developing unit for developing a latent image on the image carrier, and a transfer residual toner remaining on the image carrier. Used in an image forming apparatus provided with a cleaning means for cleaning, and at least one selected from the image carrier, the charging means, and the cleaning means and the developing means can be integrally attached to and detached from the image forming apparatus main body. And the image forming apparatus is the image forming apparatus of the present invention.

As shown in FIG. 4, the process cartridge includes a photoconductor (10), a charging member (11), an image exposure member (12), a developing member (13), a transfer member (16), a cleaning member. It is one apparatus (part) including the member (17) and the charge removal member.
The above-described tandem image forming apparatus can transfer a plurality of toner images at a time, so that high-speed full-color printing is realized.

However, since at least four photoconductors are required, an increase in the size of the apparatus is unavoidable, and depending on the amount of toner used, there is a difference in the wear amount of each photoconductor, thereby reproducing the color. There are many problems such as a decrease in performance and occurrence of abnormal images.
On the other hand, the photoconductor according to the present invention can be applied to a small-diameter photoconductor because high photosensitivity and high stability are realized. In addition, since the effects of residual potential rise and sensitivity degradation have been reduced, even if the usage amount of the four photoconductors is different, the difference in residual potential and sensitivity over time is small, and it can be used repeatedly for a long time. It is also possible to obtain a full color image with excellent color reproducibility.

<Fixed image>
In the fixed image according to the present invention, the gradient F / L to the peeling point P of the curve indicating the relationship between the scratch distance L and the sensor output F in the micro scratch test satisfies the relationship of 8 ≦ F / L ≦ 12. Features.
Such a fixed image can be formed by using the toner of the present invention. The conditions of the micro scratch test are as described above.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to a following example. In addition, "part" used in an Example represents all parts.
First, tests and measurement methods related to the present invention will be described.

<Folding fixing strength>
The prepared developer is set in an image forming apparatus (RICOH Pro C751EX manufactured by Ricoh Co., Ltd.), and in a normal temperature and normal humidity (25 ° C., 60% RH) environment, Ricoh type 6000 <70 W> paper (A4, T-th) ), A solid pattern having a toner adhesion amount of 0.85 ± 0.10 mg / cm ² was output. The fixing temperature was 140 ° C.

The output image is bent 180 ° so that the image surface is on the inside, and the crease is rubbed once with a nail and then opened.
The rubbed part of the image and the white cotton cloth were visually evaluated according to the following criteria.
[Evaluation criteria]
◎: The white cotton cloth is not dirty at all. ○: The paper is not exposed at the crease part, but the white cotton cloth is dirty. △: The toner at the crease part is partially peeled off and the paper is exposed. The toner on the entire surface is peeled off and the paper is completely exposed. “◎” and “◯” are good ranges (acceptance criteria).

<Fixability (fixing lower limit temperature)>
Using an evaluation machine improved from an image forming apparatus (RICOH Pro C751EX manufactured by Ricoh Co., Ltd.), the amount of toner adhered after transfer onto transfer paper (manufactured by Ricoh Business Expert Co., Ltd., copy printing paper <70>) A solid image (image size 3 cm × 8 cm) of 0.85 ± 0.10 mg / cm ^{2 is formed} , fixing is performed by changing the temperature of the fixing belt, and the surface of the obtained fixed image is drawn on the drawing tester AD. -401 (manufactured by Ueshima Seisakusho) is used to draw with a ruby needle (tip radius 260 μmR to 320 μmR, tip angle 60 degrees), a load of 50 g, and rub the drawing surface with fibers (Hanicot # 440, manufactured by Hanilon) 5 times. The fixing belt temperature at which image shaving is almost eliminated is defined as the minimum fixing temperature. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The lower the fixing minimum temperature, the better the low-temperature fixability.

<Fixability (Hot offset resistance / fixing width)>
Using an evaluation machine with an improved image forming apparatus (RICOH Pro C751EX manufactured by Ricoh Co., Ltd.), the toner adhesion amount after transfer on the transfer paper (type 6200 manufactured by Ricoh Co., Ltd.) is 0.85 ± 0.10 mg. / Cm ² solid paper image (image size 3 cm × 8 cm), fixing by changing the temperature of the fixing belt, visually evaluating the presence or absence of hot offset, an upper limit temperature at which hot offset does not occur, The difference from the minimum fixing temperature was defined as the fixing width. Further, the solid image was created on the transfer paper at a position of 3.0 cm from the front end in the paper passing direction. The speed of passing through the nip portion of the fixing device is 280 mm / s. The wider the fixing width, the better the hot offset resistance, and about 50 ° C. is an average temperature range of the conventional full-color toner.

<Heat resistant storage stability (Penetration)>
Each toner was filled in a 50 mL glass container and left in a constant temperature bath at 50 ° C. for 24 hours. The toner was cooled to 24 ° C., and the penetration (mm) was measured by a penetration test (JIS K2235-1991) and evaluated based on the following criteria. In addition, it shows that heat resistance preservability is excellent, so that the value of penetration is large, and in the case of less than 5 mm, there is a high possibility of problems in use.
In the present invention, the penetration is expressed by the penetration depth (mm).

〔Evaluation criteria〕
◎: Needle penetration of 25 mm or more ○: Needle penetration of 15 mm or more and less than 25 mm △: Needle penetration of 5 mm or more and less than 15 mm ×: Needle penetration of less than 5 mm Note that “◎” and “◯” are in a good range (acceptance criteria) is there.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.
In the following, “part” represents part, and “%” represents “mass%”.
(Toner base 1)
<Production of urethane-modified crystalline polyester resin A-1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 202 parts (1.00 mol) of sebacic acid, 15 parts (0.10 mol) of adipic acid, 177 parts (1.50 mol) of 1,6-hexanediol And 0.5 part of tetrabutoxy titanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the water produced under a nitrogen stream. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, it reacted until Mw reached about 12,000 under reduced pressure of 5-20 mmHg, and [Crystalline polyester resin A′-1] was obtained. The obtained [Crystalline Polyester Resin A′-1] was Mw 12,000.

  Subsequently, the obtained [crystalline polyester resin A′-1] was transferred into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 350 parts of ethyl acetate, 4,4′-diphenylmethane diisocyanate (MDI). ) 30 parts (0.12 mol) was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin A-1]. The obtained [urethane-modified crystalline polyester resin A-1] had an Mw of 22,000 and a melting point of 62 ° C.

<Production of crystalline resin precursor B′-1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 202 parts (1.00 mol) of sebacic acid, 122 parts (1.03 mol) of 1,6-hexanediol, and titanium dihydroxybis (tri Ethanol aminate) 0.5 part was put, and it was made to react for 8 hours, distilling off the water to produce | generate at 180 degreeC under nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 25 under reduced pressure of 5 to 20 mmHg. The reaction was carried out until reaching 1,000.

  The obtained [crystalline resin] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introducing tube, 300 parts of ethyl acetate and 27 parts (0.16 mol) of hexamethylene diisocyanate (HDI) were added, and nitrogen was added. The reaction was carried out at 80 ° C. for 5 hours under an air stream to obtain a 50% ethyl acetate solution of [crystalline resin precursor B′-1] having an isocyanate group at the terminal. 10 parts of the obtained [crystalline resin precursor B′-1] in ethyl acetate was mixed with 10 parts of tetrahydrofuran (THF), and 1 part of dibutylamine was added thereto, followed by stirring for 2 hours. As a result of GPC measurement using the obtained solution as a sample, Mw of [crystalline resin precursor B′-1] was 54,000. Moreover, as a result of performing DSC measurement about the sample obtained by removing a solvent from the said solution, melting | fusing point of [crystalline resin precursor B'-1] was 57 degreeC.

<Production of Amorphous Resin C-1>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen insertion tube, 222 parts of bisphenol A EO 2 mol adduct, 129 parts of bisphenol A PO 2 mol adduct, 166 parts of isophthalic acid, and 0.5 part of tetrabutoxy titanate are placed, and nitrogen is added. The reaction was carried out for 8 hours while distilling off the water produced at 230 ° C. and normal pressure under an air stream. Next, the reaction was carried out under reduced pressure of 5 to 20 mmHg. When the acid value reached 2, the mixture was cooled to 180 ° C., 35 parts of trimellitic anhydride was added, and the mixture was reacted at normal pressure for 3 hours. C-1] was obtained. The obtained [Amorphous resin C-1] was Mw 8,000 and Tg 62 ° C.

<Preparation of toner base>
-Production of graft polymer-
In a reaction vessel equipped with a stirrer and a thermometer, 480 parts of xylene and 100 parts of low molecular weight polyethylene (Sanwax LEL-400 manufactured by Sanyo Chemical Industries, Ltd .: softening point 128 ° C.) were sufficiently dissolved and purged with nitrogen. , 740 parts of styrene, 100 parts of acrylonitrile, 60 parts of butyl acrylate, 36 parts of di-t-butylperoxyhexahydroterephthalate, and 100 parts of xylene are dropped at 170 ° C. for 3 hours for polymerization, and this temperature is further increased. For 30 minutes. Next, the solvent was removed to synthesize [graft polymer]. The obtained [graft polymer] had Mw of 24,000 and Tg of 67 ° C.

-Preparation of release agent dispersion (1)-
Paraffin wax (Nippon Seiki Co., Ltd., HNP-9, hydrocarbon wax, melting point 75 ° C., SP value 8.8) 50 parts, graft polymer 30 parts, and ethyl acetate in a container equipped with a stir bar and thermometer 420 parts are charged, heated to 80 ° C. with stirring, held at 80 ° C. for 5 hours, cooled to 30 ° C. at 1 hour, and fed using a bead mill (Ultra Visco Mill, manufactured by IMEX). Dispersion was carried out under the conditions of a rate of 1 kg / hr, a disk peripheral speed of 6 m / second, 80% by volume of 0.5 mm zirconia beads, and 3 passes to obtain a release agent dispersion (1).

-Production of master batch (1)-
-Urethane modified crystalline polyester resin A-1 100 parts-Carbon black (Printtex 35, manufactured by Degussa) 100 parts (DBP oil absorption: 42 mL / 100 g, pH: 9.5)
-Ion exchange water 50 parts Said raw material was mixed using the Henschel mixer (made by Mitsui Mining Co., Ltd.). The obtained mixture was kneaded using two rolls. The kneading temperature started kneading from 90 ° C., and then gradually cooled to 50 ° C. The obtained kneaded product was pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation) to prepare [Masterbatch (1)].

-Production of oil phase (1)-
In a vessel equipped with a thermometer and a stirrer, 31.5 parts of [urethane-modified crystalline polyester resin A-1] is added, and ethyl acetate is added in an amount such that the solid content concentration is 50%. Heat well to dissolve. To this was added 100 parts of a 50% ethyl acetate solution of [Amorphous Resin C-1], 60 parts of [Releasing Agent Dispersion (1)] and 12 parts of [Masterbatch (1)] at 50 ° C. The mixture was stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotation speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [oil phase (1)]. The temperature of [Oil phase (1)] was kept at 50 ° C. in the container, and was used within 5 hours from the production so as not to crystallize.

-Production of aqueous dispersion of resin fine particles (1)-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 400 rpm for 20 minutes, a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added and aged at 75 ° C. for 6 hours to obtain [resin fine particle aqueous dispersion (1)]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion (1)] was 80 nm, the weight average molecular weight of the resin was 160,000, and Tg was 74 ° C.

-Preparation of aqueous phase (1)-
990 parts of water, 83 parts of [resin fine particle aqueous dispersion (1)], 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and ethyl acetate 90 Parts were mixed and stirred to obtain [Aqueous phase (1)].

-Production of toner base (1)-
In another container in which a stirrer and a thermometer were set, 520 parts of [Aqueous phase (1)] was placed and heated to 40 ° C. 25 parts of ethyl acetate solution of [crystalline resin precursor B′-1] was added to 235 parts of [oil phase (1)] maintained at 50 ° C., and TK homomixer (manufactured by Tokushu Kika Co., Ltd.) The mixture was stirred at 5,000 rpm and uniformly dissolved and dispersed to prepare [oil phase (1 ′)]. While stirring the above [water phase (1)] kept at 40 to 50 ° C. at 13,000 rpm with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), [oil phase (1 ′)] The resultant was added and emulsified for 1 minute to obtain [Emulsified slurry 1].

  Next, [Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and the solvent was removed at 60 ° C. for 6 hours to obtain [Slurry 1]. The obtained [Slurry 1] was filtered under reduced pressure, and then the following washing treatment was performed.

(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 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 (rotation speed: 6,000 rpm for 10 minutes), 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: 6,000 rpm for 5 minutes), and then filtered.
(4) Add 300 parts of ion-exchanged water to the filter cake of (3) above, mix with a TK homomixer (5 minutes at 6,000 rpm), and then filter twice, then filter cake (1) ] Was obtained.
The obtained [Filter cake (1)] was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, it was sieved with a mesh of 75 μm to prepare (Toner Base 1).

(Toner base 2)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] was changed from 31.5 parts to 39 parts, and the addition amount of 50% ethyl acetate solution of [amorphous resin C-1] was changed. (Toner Base 2) In the same manner as (Toner Base 1), except that the addition amount of the ethyl acetate solution of [Crystalline Resin Precursor B′-1] was changed from 100 to 80 parts from 25 to 30 parts ) Was produced.

(Toner base 3)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] was changed from 31.5 parts to 46.5 parts, and a 50 mass% ethyl acetate solution of [amorphous resin C-1] was added. (Toner Base 1) (Except for changing the addition amount from 100 parts to 60 parts and the addition amount of [crystalline resin precursor B′-1] in ethyl acetate solution from 25 parts to 35 parts) Toner base 3) was prepared.

(Toner base 4)
-Production of oil phase (4)-
In a container equipped with a thermometer and a stirrer, 60 parts of [urethane-modified crystalline polyester resin A-1] and 14 parts of [urethane-modified crystalline polyester resin B-1] are added so that the solid concentration is 50%. Of ethyl acetate was added and heated to above the melting point of the resin and dissolved well. To this, 40 parts of 50% ethyl acetate solution of [Amorphous Resin C-1], 60 parts of [Releasing Agent Dispersion (1)] and 12 parts of [Masterbatch (1)] were added, and at 50 ° C. The mixture was stirred with a TK homomixer (manufactured by Tokushu Kika Co., Ltd.) at a rotational speed of 5,000 rpm, and uniformly dissolved and dispersed to obtain [oil phase (4)]. The temperature of [Oil phase (4)] was kept at 50 ° C. in the container, and was used within 5 hours from the production so as not to crystallize.
In addition, [urethane modified crystalline polyester resin B-1] was produced as follows.

<Production of urethane-modified crystalline polyester resin B-1>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 204 parts (1.01 mol) of sebacic acid, 13 parts (0.09 mol) of adipic acid, 136 parts of 1,6-hexanediol (1.15 mol) And 0.5 part of tetrabutoxy titanate as a condensation catalyst were allowed to react at 180 ° C. for 8 hours while distilling off the water produced under a nitrogen stream. Next, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream, and the Mw was about 20 under a reduced pressure of 5 to 20 mmHg. The reaction was continued until it reached 1,000, and [crystalline polyester resin B′-1] was obtained. The obtained [Crystalline Polyester Resin B′-1] was Mw 20,000.

  Subsequently, the obtained [crystalline polyester resin B′-1] was transferred into a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and 200 parts of ethyl acetate, 4,4′-diphenylmethane diisocyanate (MDI). ) 15 parts (0.06 mol) was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin B-1]. The obtained [urethane-modified crystalline polyester resin B-1] had an Mw of 39,000 and a melting point of 63 ° C.

-Preparation of toner base (4)-
In another container with a stirrer and a thermometer, 520 parts of [Aqueous phase (1)] is placed and heated to 40 ° C., and kept at 40-50 ° C. [Oil Phase (4)] was added while stirring at 13,000 rpm, and emulsified for 1 minute to obtain [Emulsified Slurry 4].

  Next, [Emulsion slurry 4] was put into a container in which a stirrer and a thermometer were set, and the solvent was removed at 60 ° C. for 6 hours to obtain [Slurry 4]. The obtained [Slurry 4] was filtered under reduced pressure, and then the following washing treatment was performed.

(1) 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (5 minutes at a rotation speed of 6,000 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 (rotation speed: 6,000 rpm for 10 minutes), 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: 6,000 rpm for 5 minutes), and then filtered.
(4) Add 300 parts of ion-exchanged water to the filter cake of (3) above, mix with a TK homomixer (5 minutes at 6,000 rpm) and then filter twice, and filter cake (4) ] Was obtained.
[Filter cake (4)] obtained was dried at 45 ° C. for 48 hours in a circulating drier. Thereafter, it was sieved with a mesh of 75 μm to prepare (Toner Base 4).

(Toner base 5)
In (Toner Base 4), the addition amount of [urethane-modified crystalline polyester resin A-1] is changed from 60 parts to 62 parts, and the addition amount of [urethane-modified crystalline polyester resin B-1] is changed from 14 parts to 12 parts. A (toner base 5) was produced in the same manner as (toner base 4) except that each was changed.

(Toner base 6)
In (Toner Base 1), [Resin Fine Particle Aqueous Dispersion (1)] is changed to [Resin Fine Particle Aqueous Dispersion (2)], and [Aqueous Phase (1)] is set to [Aqueous Phase (2)] below. (Toner Base 6) was prepared in the same manner as (Toner Base 1), except for the above.

-Production of aqueous dispersion of resin fine particles (2)-
In a reaction vessel equipped with a stir bar and a thermometer, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 600 rpm for 30 minutes, a white emulsion was obtained. This emulsion was heated to raise the temperature in the system to 75 ° C. and reacted for 6 hours. Further, 30 parts of a 1% aqueous solution of ammonium persulfate was added and aged at 75 ° C. for 6 hours to obtain [resin fine particle aqueous dispersion (2)]. The volume average particle diameter of particles contained in this [resin fine particle aqueous dispersion (2)] was 30 nm, the weight average molecular weight of the resin was 140,000, and Tg was 70 ° C.

-Preparation of aqueous phase (2)-
990 parts of water, 83 parts of [resin fine particle aqueous dispersion (2)], 37 parts of a 48.5% by weight aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and ethyl acetate 90 Parts were mixed and stirred to obtain [Aqueous phase (2)].

(Toner base 7)
In (Toner Base 1), 31.5 parts of [Urethane-Modified Crystalline Polyester Resin A-1] is replaced with 54 parts of [Urethane-Modified Crystalline Polyester Resin A-2], and [Amorphous Resin C-1]. The toner base was changed except that the addition amount of the 50% ethyl acetate solution was changed from 100 parts to 40 parts and the addition amount of the [crystalline resin precursor B′-1] was changed from 25 parts to 40 parts. (Toner base 7) was prepared in the same manner as in 1).
In addition, [urethane modified crystalline polyester resin A-2] was produced as follows.

<Production of urethane-modified crystalline polyester resin A-2>
In a reaction vessel equipped with a condenser, a stirrer and a nitrogen inlet tube, 202 parts (1.00 mol) of sebacic acid, 149 parts (1,26 mol) of 1,6-hexanediol, and tetrabutoxy titanate as a condensation catalyst were added. 5 parts were added and reacted for 8 hours at 180 ° C. while distilling off the water produced under a nitrogen stream. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was carried out under reduced pressure of 5 to 20 mmHg until Mw reached approximately 9,000 to obtain [Crystalline Polyester Resin A′-2]. The obtained [Crystalline Polyester Resin A′-2] was Mw 9,000.

  Subsequently, the obtained [crystalline polyester resin A′-2] was transferred into a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube, and 250 parts of ethyl acetate, 4,4′-diphenylmethane diisocyanate (MDI). ) 28 parts (0.11 mol) was added and reacted at 80 ° C. for 5 hours under a nitrogen stream. Subsequently, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin A-2]. The obtained [urethane-modified crystalline polyester resin A-2] had an Mw of 30,000 and a melting point of 67 ° C.

(Toner base 8)
In (Toner Base 4), 60 parts of [Urethane-Modified Crystalline Polyester Resin A-1] are replaced with 54 parts of [Urethane-Modified Crystalline Polyester Resin A-3] and [Urethane-Modified Crystalline Polyester Resin B-1] 14 (Toner Base 8) was prepared in the same manner as (Toner Base 4) except that the parts were changed to 20 parts of [Urethane-Modified Crystalline Polyester Resin B-2] described below.
In addition, [urethane modified crystalline polyester resin A-3] and [urethane modified crystalline polyester resin B-2] were prepared as follows.

<Production of urethane-modified crystalline polyester resin A-3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 1,4-butanediamine 123 parts (1.40 mol), 1,6-hexanediamine 212 parts (1.82 mol), methyl ethyl ketone (MEK) 100 Then, 336 parts (2.00 mol) of hexamethylene diisocyanate (HDI) was added and reacted at 60 ° C. for 5 hours under a nitrogen stream. Next, MEK was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin A-3]. The obtained [urethane-modified crystalline polyester resin A-3] had an Mw of 23,000 and a melting point of 64 ° C.

<Production of urethane-modified crystalline polyester resin B-2>
In a reaction vessel equipped with a condenser, a stirrer, and a nitrogen inlet tube, 79 parts (0.90 mol) of 1,4-butanediamine, 116 parts (1.00 mol) of 1,6-hexanediamine, 600 of methyl ethyl ketone (MEK) 600 After adding a part and stirring, 475 part (1.90 mol) of 4,4'- diphenylmethane diisocyanate (MDI) was added, and it was made to react at 60 degreeC under nitrogen stream for 5 hours. Next, MEK was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin B-2]. The obtained [urethane-modified crystalline polyester resin B-2] had an Mw of 57,000 and a melting point of 66 ° C.

(Toner base 9)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] was changed from 31.5 parts to 54 parts, and the addition amount of 50% ethyl acetate solution of [amorphous resin C-1] was changed. Toner base 9 is the same as (Toner base 1) except that the amount of [crystalline resin precursor B′-1] in ethyl acetate solution is changed from 100 parts to 40 parts from 25 parts to 40 parts. ) Was produced.

(Toner base 10)
(Toner Base 9) (Toner Base 9) was the same as (Toner Base 9) except that 0.05 part of [Nucleating Agent] (ADEKA STAB NA-11, melting point 400 ° C., manufactured by ADEKA) was added to the oil phase. 10) was produced.

(Toner base 11)
In (Toner Base 4), [Resin Fine Particle Aqueous Dispersion (1)] is changed to [Resin Fine Particle Aqueous Dispersion (3)], and [Aqueous Phase (1)] is changed to [Aqueous Phase (3) below. [Toner Base 11] was prepared in the same manner as (Toner Base 4) except that the above was changed.

-Production of aqueous dispersion of resin fine particles (3)-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 450 rpm for 25 minutes, a white emulsion was obtained. The emulsion was heated to raise the system temperature to 75 ° C. and reacted for 5 hours. Further, 30 parts of a 1% aqueous solution of ammonium persulfate was added and aged at 75 ° C. for 6 hours to obtain [resin fine particle aqueous dispersion (3)]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion (3)] was 60 nm, the weight average molecular weight of the resin was 16,800, and Tg was 78 ° C.

-Preparation of aqueous phase (3)-
990 parts of water, 83 parts of an aqueous dispersion of resin fine particles (3), 37 parts of a 48.5% aqueous solution of sodium dodecyldiphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate Were mixed and stirred to obtain [Aqueous phase (3)].

(Toner base 12)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] was changed from 31.5 parts to 69 parts, and the addition amount of 50% ethyl acetate solution of [amorphous resin C-1] was changed. (Toner Base 12) In the same manner as (Toner Base 1), except that the amount of addition of [crystalline resin precursor B′-1] in ethyl acetate was changed from 100 parts to 0 parts from 25 parts to 50 parts. ) Was produced.

(Toner base 13)
-Production of toner base (13)-
[Urethane-modified crystalline polyester resin A-1] 60 parts, [Urethane-modified crystalline polyester resin B-3] 20 parts, [Amorphous resin C-1] 20 parts, paraffin wax (NNP, HNP) -9, melting point 75 ° C.) 5 parts and [Masterbatch (1)] 12 parts were premixed using a Henschel mixer (FM10B, manufactured by Mitsui Miike Chemical Co., Ltd.). Then, it melted and kneaded at a temperature of 80 ° C. to 120 ° C. with a biaxial kneader (Ikegai, PCM-30).
The obtained kneaded product was cooled to room temperature and then coarsely pulverized to 200 μm to 300 μm with a hammer mill. Next, the mixture was finely pulverized using a supersonic jet pulverizer, Labo Jet (manufactured by Nippon Pneumatic Industry Co., Ltd.) while adjusting the pulverization air pressure as appropriate so that the weight average particle diameter was 6.2 ± 0.3 μm. Thereafter, with a gas classifier (manufactured by Nippon Pneumatic Industry Co., Ltd., MDS-I), the louver opening so that the weight average particle size is 7.0 ± 0.2 μm and the amount of fine powder of 4 μm or less is 10% by number or less. Was classified as appropriate to obtain (Mother toner 13).
In addition, [urethane modified crystalline polyester resin B-3] was produced as follows.

<Production of urethane-modified crystalline polyester resin B-3>
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 113 parts (0.56 mol) of sebacic acid, 109 parts (0.56 mol) of dimethyl terephthalate, 132 parts of 1.6-hexanediol (1.12 mol) ), And 0.5 part of titanium dihydroxybis (triethanolamate) as a condensation catalyst, and reacted for 8 hours at 180 ° C. while distilling off the water and methanol produced under a nitrogen stream. Then, while gradually raising the temperature to 220 ° C., the reaction was carried out for 4 hours while distilling off the water and 1,6-hexanediol produced under a nitrogen stream. Furthermore, the reaction was carried out under reduced pressure of 5 to 20 mmHg until Mw reached approximately 35,000 to obtain [Crystalline Polyester Resin B′-3]. The obtained [Crystalline Polyester Resin B′-3] was Mw 34,000.

  Subsequently, the obtained [crystalline polyester resin B′-3] was transferred into a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introducing tube, and 200 parts of ethyl acetate and 10 parts of hexamethylene diisocyanate (HDI) ( 0.06 mol) was added, and the mixture was reacted at 80 ° C. for 5 hours under a nitrogen stream. Next, ethyl acetate was distilled off under reduced pressure to obtain [urethane-modified crystalline polyester resin B-3]. The obtained [urethane-modified crystalline polyester resin B-3] had an Mw of 63,000 and a melting point of 65 ° C.

(Toner base 14)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] is changed from 31.5 parts to 15 parts, and the addition amount of 50% by weight ethyl acetate solution of [amorphous resin C-1]. Was changed from 100 parts to 124 parts, and 34 parts of 50% ethyl acetate solution of [amorphous resin precursor C′-1] was added, and acetic acid of [crystalline resin precursor B′-1] was added. (Toner Base 14) was prepared in the same manner as (Toner Base 1) except that no ethyl solution was added.
[Amorphous resin precursor C′-1] was prepared as follows.

<Production of Amorphous Resin Precursor C′-1>
720 parts of bisphenol A EO 2 mol adduct, 90 parts of bisphenol A PO 2 mol adduct, 290 parts of terephthalic acid, and 1 part of tetrabutoxy titanate are placed in a reaction vessel equipped with a condenser, a stirrer, and a nitrogen insertion tube. At 230 ° C. and normal pressure for 8 hours while distilling off the water produced. Subsequently, it was made to react under reduced pressure of 10-15 mmHg for 7 hours, and [non-crystalline resin] was obtained.

  Next, 400 parts of the obtained [non-crystalline resin], 95 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen insertion tube. The mixture was reacted at 0 ° C. for 8 hours to obtain a 50% by mass ethyl acetate solution of [amorphous resin precursor C′-1] having an isocyanate group at the terminal.

(Toner base 15)
In (Toner Base 1), the addition amount of [urethane-modified crystalline polyester resin A-1] was changed from 31.5 parts to 74 parts, and the addition amount of 50% ethyl acetate solution of [amorphous resin C-1] was changed. (Toner Base 15) was prepared in the same manner as (Toner Base 1) except that the amount was changed from 100 parts to 40 parts and the ethyl acetate solution of [Crystalline Resin Precursor B′-1] was not added.

(Toner base 16)
In (Toner Base 1), [Resin Fine Particle Aqueous Dispersion (1)] is changed to [Resin Fine Particle Aqueous Dispersion (4)], and [Aqueous Phase (1)] is changed to [Aqueous Phase (4) below. [Toner Base 16] was prepared in the same manner as (Toner Base 1), except for the above.

-Production of aqueous dispersion of resin fine particles (4)-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was charged and stirred at 300 rpm for 15 minutes, a white emulsion was obtained. This emulsion was heated to raise the system temperature to 75 ° C. and reacted for 7 hours. Further, 30 parts of a 1% ammonium persulfate aqueous solution was added, and the mixture was aged at 75 ° C. for 7 hours to obtain [Aqueous dispersion of resin fine particles (4)]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion (4)] was 110 nm, the weight average molecular weight of the resin was 18,200, and Tg was 78 ° C.

-Preparation of aqueous phase (4)-
990 parts of water, 83 parts of an aqueous dispersion of resin fine particles (4), 37 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate Were mixed and stirred to obtain [Aqueous phase (4)].

(Toner base 17)
In (Toner Base 1), [Resin Fine Particle Aqueous Dispersion (1)] is changed to [Resin Fine Particle Aqueous Dispersion (5)], and [Aqueous Phase (1)] is changed to [Aqueous Phase (5) below. [Toner Base 17] was prepared in the same manner as (Toner Base 1), except for the above.

-Production of aqueous dispersion of resin fine particles (5)-
In a reaction vessel in which a stir bar and a thermometer are set, 600 parts of water, 120 parts of styrene, 100 parts of methacrylic acid, 45 parts of butyl acrylate, 10 parts of alkylallylsulfosuccinate sodium salt (Eleminol JS-2, manufactured by Sanyo Chemical Industries) When 1 part of ammonium persulfate was added and stirred at 750 rpm for 30 minutes, a white emulsion was obtained. The emulsion 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 to obtain [Aqueous dispersion of resin fine particles (5)]. The volume average particle diameter of the particles contained in this [resin fine particle aqueous dispersion (5)] was 15 nm, the weight average molecular weight of the resin was 13,800, and Tg was 71 ° C.

-Preparation of aqueous phase (5)-
990 parts of water, 83 parts of [resin fine particle aqueous dispersion (5)], 37 parts of 48.5% aqueous solution of dodecyl diphenyl ether disulfonate (Eleminol MON-7, Sanyo Chemical Industries, Ltd.), and 90 parts of ethyl acetate Were mixed and stirred to obtain [Aqueous phase (5)].

-Production of toners (1) to (17)-
100 parts of the obtained (toner base 1) to (toner base 17), 1.0 part of hydrophobic silica (HDK-2000, manufactured by Wacker Chemie) as an external additive, titanium oxide having an average particle size of 15 nm After 5 cycles of mixing 0.5 parts of fine powder (isobutyltrimethoxysilane treatment) with a Henschel mixer (Mitsui Mining Co., Ltd.) at a peripheral speed of 30 m / sec for 30 seconds and resting for 1 minute, Sieve toner (1) to toner (17) were prepared with a mesh having an opening of 35 μm.
Various physical properties of the obtained toners (1) to (17) were measured. About these measurements, it measured according to the above-mentioned measuring method. The results are shown in Table 1.
In addition, the meaning of the symbol in a table | surface is as follows.
Resin fine particles: Average particle diameter of primary particles of resin fine particles Dv: Volume average particle diameter of toner Dn: Number average particle diameter of toner Tsh2nd / Tsh1st: Sole of maximum endothermic peak at first temperature rise by differential scanning calorimeter of toner
Dash temperature Tsh1st and shoulder temperature of maximum endothermic peak at the second temperature increase
Ratio F / L with Tsh2nd: Gradient up to the peel point P of the curve showing the relationship between the scratch distance L and the sensor output F in the micro scratch test on the fixed image of the toner
(C) / ((C) + (A)): In the diffraction spectrum of the toner obtained by the X-ray diffractometer,
The integrated intensity of the spectrum derived from the crystal structure is (C),
Ratio T1: When the integral intensity of the spectrum derived from the amorphous structure is (A), T1: Maximum endothermic peak T2 in the temperature range of 0 to 150 ° C. in the differential scanning calorimeter of toner T2: Differential scanning calorie of toner Maximum exothermic peak Mn at the time of temperature fall in the range of 0 to 150 ° C .: Number average molecular weight of binder resin Mw: Weight average molecular weight of binder resin Mpt: Peak top molecular weight of binder resin
100,000 or more: For gel diffusion chromatography measurement of toner's tetrahydrofuran solubles
Proportion of molecular weight above 100,000
250,000 or more: For gel diffusion chromatography measurement of tetrahydrofuran solubles in toner
Ratio in which molecular weight is 250,000 or more Urethane: Whether crystalline resin has urethane bond or not Urea: Whether crystalline resin has urea bond or not ΔH (T): Differential scanning calorimeter of toner Endothermic amount ΔH (H) in toner: mixed solvent of toner tetrahydrofuran (THF) / ethyl acetate
Endothermic amount in differential scanning calorimeter with respect to (mass ratio 50/50) <shoulder temperature of maximum endothermic peak>
The ratio Tsh2nd / Tsh1st of the maximum endothermic peak shoulder temperature Tsh1st of the first temperature rise by the differential scanning calorimeter (DSC) of the toner and the maximum endothermic peak shoulder temperature Tsh2nd of the second temperature rise is 0.90 or more. It is preferable that it is 1.10 or less because the sharp melt property of the toner is maintained and both low-temperature fixability and storage stability can be achieved.
The shoulder temperature (Tsh1st, Tsh2nd) of the maximum endothermic peak of the toner can be measured using a differential scanning calorimeter (DSC) (for example, TA-60WS and DSC-60 (manufactured by Shimadzu Corporation)). That is, first, 5.0 mg of toner is placed in an aluminum sample container, and the sample container is placed on a holder unit and set in an electric furnace. Next, the temperature was raised from 0 ° C. to 150 ° C. at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and then the temperature was lowered from 150 ° C. to 0 ° C. at a temperature lowering rate of 10 ° C./min. The temperature is raised to 150 ° C. in min and the DSC curve is measured. In the obtained DSC curve, the endothermic peak temperature at the first temperature rise is Tm1st, and the endothermic peak temperature at the second temperature rise is Tm2nd. At this time, when there are a plurality of endothermic peaks, the one with the largest endothermic amount is selected. For each endothermic peak, the intersections of the base line on the lower temperature side than the endothermic peak and the tangent line on the lower temperature side forming the endothermic peak are defined as Tsh1st and Tsh2nd, respectively.

(Career)
Next, a specific production example of the carrier used for evaluation is shown.
Acrylic resin solution (solid content 50 wt%) 21.0 parts guanamine solution (solid content 70 wt%) 6.4 parts alumina particles [0.3 μm, specific resistance 1014 (Ω · cm)] 7.6 parts silicone resin solution 65. 0 parts [solid content 23 wt% (SR2410: manufactured by Toray Dow Corning Silicone)]
Aminosilane 1.0 part [100 wt% solid content (SH6020: manufactured by Toray Dow Corning Silicone)]
60 parts of toluene 60 parts of butyl cellosolve was dispersed with a homomixer for 10 minutes to obtain a blend coating film forming solution of acrylic resin and silicone resin containing alumina particles. A fired ferrite powder [(MgO) 1.8 (MnO) 49.5 (Fe ₂ O ₃ ) 48.0: average particle size; 35 μm] was used as the core material, and the coating film forming solution was formed on the surface of the core material. It was applied by a Spira coater (Okada Seiko Co., Ltd.) so as to have a thickness of 0.15 μm and dried. The obtained carrier was baked by standing in an electric furnace at 150 ° C. for 1 hour. After cooling, the ferrite powder bulk was crushed using a sieve having an aperture of 106 μm to obtain a carrier. The measurement of the binder resin film thickness was performed by observing the cross section of the carrier with a transmission electron microscope so that the coating film covering the carrier surface could be observed. Thus, a carrier having a weight average particle diameter of 35 μm was obtained.

(Development of developer)
7 parts of each of toners (1) to (17) and 93 parts of the carrier were mixed to prepare and evaluate the developers of Examples 1 to 11 and Comparative Examples 1 to 6. The results are shown in Table 2.

(About FIGS. 2 to 4)
10, 10Y, 10M, 10C, 10K Photoconductor 11, 11Y, 11M, 11C, 11K Charging member 12, 12Y, 12M, 12C, 13K Image exposure member 13, 13Y, 13M, 13C, 13K Developing member 14 Transport roller 15 Transfer Paper 16, 16Y, 16M, 16C, 16K Transfer member 17, 17Y, 17M, 17C, 17K Cleaning member 18 Static eliminating member 20Y, 20M, 20C, 20K Image forming element 21 Paper feed roller 22 Registration roller 23 Transfer member (secondary transfer) Element)
24 Fixing member

JP 2010-0777419 A JP 2009-014926 A JP 2010-151996 A JP 2009-069222 A JP 2009-198972 A JP 2011-237608 A

Claims (12)

At least in a toner comprising a binder resin, a colorant and a release agent,
The gradient F / L up to the peeling point P of the curve showing the relationship between the scratch distance L and the sensor output F in the micro scratch test for the fixed image of the toner satisfies the relationship of 8 ≦ F / L ≦ 12. Toner.   In the diffraction spectrum obtained by the toner X-ray diffractometer, the binder resin contains a crystalline resin, and (C) represents the integrated intensity of the spectrum derived from the crystal structure, and FIG. 2. The toner according to claim 1, wherein a ratio (C) / ((C) + (A)) is 0.15 or more, where is (A). The maximum endothermic peak temperature T1 at the first temperature increase in the range of 0 ° C. to 100 ° C. and the maximum exothermic peak temperature T2 at the time of temperature decrease satisfy the following relational expression (1) in the differential scanning calorimeter (DSC) of the toner. The toner according to claim 1, wherein:
T1-T2 ≦ 30 ° C. and T2 ≧ 30 ° C. (1)
(However, the rate of temperature increase from 0 ° C. to 100 ° C. in the first temperature increase is 10 ° C./min, and the rate of temperature decrease from 100 ° C. to 0 ° C. is 10 ° C./min.)   The ratio of the molecular weight in terms of polystyrene of 100,000 or more in gel diffusion chromatography (GPC) measurement of the tetrahydrofuran (THF) soluble content of the toner is 5% or more, and the weight average molecular weight (Mw) is 20,000 or more. The toner according to claim 1, wherein the toner is 70,000 or less.   The endothermic amount of the toner in a differential scanning calorimeter (DSC) is ΔH (T) (J / g), and the difference in insoluble content of the toner with respect to the tetrahydrofuran (THF) / ethyl acetate mixed solvent (50/50 by mass). 2. The heat absorption amount in a scanning calorimeter (DSC) is ΔH (H) (J / g), and ΔH (H) / ΔH (T) is 0.2 to 1.25. The toner according to any one of -4.   The toner according to claim 2, wherein the crystalline resin has a urethane bond and / or a urea bond.   The toner according to claim 2, wherein the crystalline resin is a resin having a crystalline polyester unit.   A developer comprising the toner according to claim 1 and a carrier. An image carrier, charging means for charging the image carrier, latent image forming means for forming an electrostatic latent image on the image carrier, and developing the electrostatic latent image on the image carrier with toner In an image forming apparatus comprising a developing unit,
An image forming apparatus using the toner according to claim 1 as a toner to be replenished to the developing means.   The image forming apparatus according to claim 9, wherein a plurality of the image carriers are provided, and toner images formed on the image carriers are sequentially transferred onto a transfer medium. An image comprising an image carrier, a charging unit for charging the image carrier, a developing unit for developing a latent image on the image carrier, and a cleaning unit for cleaning the transfer residual toner remaining on the image carrier. In a process cartridge used in a forming apparatus, wherein at least one selected from the image carrier, the charging unit, and the cleaning unit and the developing unit are integrated and detachable from the main body of the image forming apparatus.
A process cartridge, wherein the image forming apparatus is the image forming apparatus according to claim 9. A fixed image formed using the toner according to claim 1,
A fixed image in which a gradient F / L up to a peeling point P of a curve indicating a relationship between a scratch distance L and a sensor output F in a micro scratch test satisfies a relationship of 8 ≦ F / L ≦ 12.