JP2014160194A - Toner and image forming apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner for electrostatic charge image development that achieves both low-temperature fixability and heat-resistant storage stability even in a high-speed machine, provides high image quality even after a long-term storage, exhibits good releasability and hot offset resistance, and prevents the occurrence of in-apparatus contamination.SOLUTION: There is provided a toner containing at least a binder resin, a mold release agent, and a colorant. The binder resin contains a crystalline polyester resin and an amorphous polyester resin; and the crystalline polyester resin has a melting point Tmp of 55 to 80°C. When an endothermic peak temperature derived from the crystalline polyester resin in the toner in DSC measurement of the toner is Tm1, and a melt viscosity at 100°C of the mold release agent is η(w), the following formulas (1) and (2) are satisfied. (1): 5°C≤Tmp-Tm1≤15°C; and (2): 2mPa s≤η(w)≤20 mPa s.

Description

  The present invention relates to a toner suitably used in electrophotography, electrostatic recording, electrostatic printing, and the like, and an image forming apparatus using the toner.

2. Description of the Related Art Conventionally, in an electrophotographic type or electrostatic recording type image forming apparatus, an electric latent image or a magnetic latent image is visualized with toner to form an image. For example, in electrophotography, an electrostatic latent image is formed on a photoconductor, and then the electrostatic latent image is developed with toner to form a toner image. The toner image is transferred onto a recording medium such as paper and then fixed by melting with heating.
In recent years, copiers have been required to be small, high-speed and capable of copying many sheets while maintaining high image quality. For toner, the particle size has been reduced to improve the quality of output images, and energy saving has been achieved. There is a demand for improvement in low-temperature fixability for making it easier.
High image quality has been studied from various angles, and in particular, there is a growing recognition that toner particle size reduction and spheroidization are extremely effective. However, as the particle size of the toner is reduced, the transferability and the fixing property are lowered, and a tendency to become a poor image is observed.

Incidentally, toner production methods are roughly classified into a kneading pulverization method and a polymerization method.
In the pulverization method, a toner composition is prepared by pulverizing and classifying a toner composition in which a colorant, a charge control agent, an anti-offset agent, and the like are melt-mixed and uniformly dispersed in a thermoplastic resin. However, it is difficult to reduce the particle size of the toner obtained by the kneading and pulverizing method, its shape is indefinite, and its particle size distribution is broad. In addition, since a pulverizable resin requires a certain degree of hardness, the pulverized toner has a high fixing temperature and is difficult to save energy.
Further, in the kneading and pulverization method, during the pulverization, cracks occur at the interface between the resin and the release agent (wax), and therefore there are many release agents (wax) on the toner particle surfaces. For this reason, although the releasing effect at the time of fixing is produced, internal contamination such as adhesion of toner to the carrier, the photoconductor and the blade is likely to occur, and the performance is not satisfactory from the viewpoint of the entire image forming process.

In order to overcome such problems due to the kneading and pulverizing method, a toner manufacturing method by a polymerization method has been proposed. The toner produced by the polymerization method can be easily reduced in particle size, the particle size distribution is sharper than the particle size distribution of the toner obtained by the pulverization method, and wax can be included.
In addition, in the polymerization method, in order to achieve further energy saving and lower the glass transition temperature, the use of a crystalline polyester resin as the binder resin has produced a toner that can be fixed at a lower temperature than before. Yes.

  Since the crystalline polyester resin has crystallinity, the crystalline polyester resin exhibits a heat-melting characteristic showing a rapid viscosity decrease near the fixing start temperature. In other words, the heat-resistant storage stability due to crystallinity is good until just before the melting start temperature, and at the melting start temperature, a sharp viscosity drop (sharp melt property) is caused and fixing is performed. Toner can be designed. For example, Patent Document 1 (Japanese Patent No. 4533061) includes a styrene / acrylate copolymer, a crystalline polyester, and a release agent having a melting point lower than the melting point of the crystalline polyester, and the melting point of the crystalline polyester. In which the difference between the toner flow start temperature and the toner outflow start temperature is within 12 ° C. is excellent in low-temperature fixability and storage stability, and high image density is obtained without fogging or toner fusion even in long-term use. Is disclosed.

However, with further improvement in low-temperature fixability, it is desired that the heat resistant storage stability and hot offset resistance of the toner are not inhibited. In response to these issues, instead of styrene-acrylic resins, which have been widely used as a binder resin for toners, attempts have been made to use polyester resins with excellent low-temperature fixability and relatively good heat storage stability. It has been.
For example, Patent Document 2 (Patent No. 4267427) discloses a toner containing a polyester resin and a crystalline polyester, and Patent Document 3 (Patent No. 4347174) discloses a dispersion of a crystalline polyester resin. In which a crystalline polyester resin is introduced into a toner.
In these toners, toner materials such as crystalline polyester and polyester resin are appropriately compatible, and this compatibilized portion serves as a starting portion where melting starts at the time of fixing, and the entire toner is efficiently melted to achieve low-temperature fixability. It has been disclosed to develop sharp melt properties.

  Further, Patent Document 4 (Japanese Patent No. 4729950) discloses an electrostatic charge image developing toner containing a binder resin and a colorant, wherein the binder resin comprises a crystalline polyester resin and an amorphous resin. In the DSC chart obtained by differential scanning calorimetry of the toner, by adjusting the endothermic amount at the endothermic peak derived from the crystalline polyester in the toner and the softening temperature of the toner to a specific range, low temperature fixability and storage stability can be obtained. It is described that compatibility can be achieved. By adjusting the endothermic amount, it is possible to adjust the affinity of the crystalline polyester and the non-crystalline resin that are compatible with each other by heating at the time of fixing within a preferable range, and at the same time, the low temperature fixability is improved as compared with conventional toners. It is said that it is possible to achieve both preservation and storage.

  In Patent Document 5 (Japanese Patent No. 4973129), in a differential scanning calorimetric analysis of a crystalline polyester resin in a toner having colored particles including a crystalline polyester resin, an amorphous polyester resin, and a colorant. A method for producing a toner capable of achieving both low-temperature fixability and storage stability and good chargeability by adjusting the relationship between the endothermic peak and the endothermic peak derived from the crystalline polyester resin in the differential scanning calorimetric analysis of the toner. Is disclosed. Inside the toner, the crystalline polyester is dispersed in an incompatible state inside the colored particles containing the amorphous polyester resin as the main binder resin, so that both low-temperature fixability and storability can be achieved, and good chargeability is exhibited. It is described that toner can be provided.

  In attempts to lower the fixing temperature as described above, it is important to lower the fixing temperature of the toner itself and prevent hot offset on the high temperature side. Methods for preventing hot offset include controlling the viscoelasticity of the toner by introducing a polymer polymer into the toner, and using a release agent such as wax to improve the releasability from the fixing member. It is well known to suppress it by raising it. In particular, regarding the use of a mold release agent, it has been proposed to use paraffinic wax as described in Patent Document 6 (Japanese Patent No. 3376019), and the range of the melting point by the DSC method is specified. Although many proposals have been made, many of them have an effect on releasability.

  However, in recent years, copiers have been required to take environmental measures. Among them, the generation of dust in the external exhaust has been regulated in recent years as environmental protection, which is a very big issue that has a negative impact on the human body. Yes. In particular, external exhaust of dust and organic volatile substances (VOC) due to wax volatilization to the outside of the machine is regulated. Further, the volatilization of the wax leads to contamination of the optical equipment inside the copying machine.

  In addition, in the high-speed printing field, there is a demand for high image quality that is the same as the initial image even when a large amount of printing is performed with a large image area. On the other hand, when used in an electrophotographic image forming apparatus that prints a large amount of the wax having been proposed in the past, contamination of various image forming apparatus members with a highly volatile paraffin wax or transfer medium It has been found that problems such as contaminating itself occur.

For the generation of such volatile substances, it has been proposed to use an ester wax for the toner. For example, Patent Document 7 (Japanese Patent No. 3287733) discloses R ₁ —COO—R ₂ having a melting point of 40 to 90 ° C. [wherein R ₁ and R ₂ are linear alkyl having 15 to 45 carbon atoms] Each group is shown. And a toner containing an ester wax containing 50 to 95% by weight of an ester compound having the same total carbon number is low-temperature fixability, anti-blocking property, and transparent when used for an OHP film. It is disclosed that a fixed image excellent in the above can be obtained. In Patent Document 8 (Japanese Patent No. 4435434), an ester wax synthesized from a monocarboxylic acid having a predetermined number of carbon atoms and a monohydric or polyhydric alcohol exhibits a sharp heat melting behavior, which is used as a toner. It is disclosed that, by using it, good release properties can be exhibited and volatile substances can be reduced.

However, by incorporating crystalline polyester into the toner, it is possible to achieve both low-temperature fixability and heat-resistant storage stability. In particular, as described in Patent Documents 2 and 4, some of the crystalline polyester and the binder resin are used. In the compatible toner, the softened part due to the compatibility may be exposed on the toner surface, and the toner particles are fused with a weak force (slow aggregation) and are transferred to the image forming apparatus as they are. If this happens, abnormal images such as white streaks will be generated.
As described in Patent Document 5, when the crystalline polyester and the non-crystalline polyester in the toner particles before fixing are substantially incompatible, the starting portion where the melting starts is fixed particularly when fixing at a high process linear velocity. And low temperature fixability is insufficient.
In attempts to lower the fixing temperature, as described above, it is important to prevent hot offset on the high temperature side while lowering the fixing temperature of the toner itself. Although a method for improving the hot offset resistance by adjusting the resin acid value and increasing the affinity between the paper and the melted toner has been described, until the separation of the paper from the fixing member, that is, the improvement of the releasability Not considered.
Regarding the use of a release agent, paraffin wax as described in Patent Document 6 has high volatility, contaminates various image forming apparatus members, the transfer medium itself, and the outside of the apparatus. There is concern that it will be exhausted and affect the human body. In addition, according to the inventions described in Patent Documents 1, 7, and 8, low-temperature fixability can be obtained, but no study has been made on suppressing the amount of volatile components and increasing the speed of the copying machine. In the polymerized toner using polyester, there is a problem that the toner material and the release agent are compatible with each other and the releasability and fixability are deteriorated.

  Therefore, the present invention solves the above-mentioned problems of the prior art, achieves both low-temperature fixability and heat-resistant storage stability even in a high-speed machine, and provides high image quality even after long-term storage. An object of the present invention is to provide a toner for developing an electrostatic charge image that exhibits an offset property and has no in-machine contamination.

As a result of intensive studies, the present inventors have found that the above problems can be solved by the invention described below, and have reached the present invention.
That is, the present invention is a toner containing at least a binder resin, a release agent, and a colorant, and the binder resin contains a crystalline polyester and an amorphous polyester, and the crystalline polyester resin The melting point Tmp of the toner is 55 to 80 ° C., the endothermic peak temperature derived from the crystalline polyester in the toner is Tm1 in the toner DSC measurement, and the melt viscosity of the release agent at 100 ° C. is η (w). When the following formulas (1) and (2)
5 ° C. ≦ Tmp−Tm1 ≦ 15 ° C. (1)
2 mPa · s ≦ η (w) ≦ 20 mPa · s (2)
It is characterized by satisfying the requirements.

  The toner of the present invention uses crystalline polyester and non-crystalline polyester as a binder resin, and uses a release agent having a specified melt viscosity. In the measurement of the melting point of the crystalline polyester and the DSC of the toner, Because it has a certain relationship with the endothermic peak temperature derived from crystalline polyester, it enables both low-temperature fixability and storage stability, as well as excellent hot offset resistance and releasability, as well as high-speed machines (processes). Even when used at a linear velocity of 300 to 1500 mm / s, the release agent does not volatilize and a stable image can be obtained.

It is a figure which shows the flow curve of a flow tester. 1 is a schematic diagram illustrating an example of an image forming apparatus according to an exemplary embodiment. It is the schematic which shows the other example of the image forming apparatus of this embodiment. FIG. 3 is a schematic view showing a tandem developing device of FIG. 2. It is the schematic which shows an example of the process cartridge of this embodiment.

The toner for developing an electrostatic charge image of the present invention is a toner containing a binder resin, a release agent, and a colorant, and the binder resin contains a crystalline polyester and an amorphous polyester, and the crystal The melting point (Tmp) of the conductive polyester resin is 55 to 80 ° C., the endothermic peak temperature derived from Cpes (crystalline polyester resin) in the toner is Tm1 in the toner DSC measurement, and the melt viscosity of the release agent at 100 ° C. is η. When (w), the following formulas (1) and (2) are satisfied.
5 ° C. ≦ Tmp−Tm1 ≦ 12 ° C. (1)
1 mPa · s ≦ η (w) ≦ 20 mPa · s (2)

<Binder resin>
The binder resin of the present invention contains a crystalline polyester resin and an amorphous polyester resin.

(Crystalline polyester resin)
Since the crystalline polyester resin present in the toner particles has high crystallinity, it has a heat-melting characteristic that it shows a sharp decrease in viscosity near the fixing start temperature. In other words, by using a crystalline polyester resin, the heat-resistant storage stability is good due to crystallinity until just before the melting start temperature, and it is fixed by causing a sharp viscosity decrease (sharp melt property) at the melting start temperature. A toner having both heat-resistant storage stability and low-temperature fixability can be designed.

(Physical properties of crystalline polyester resin)
The crystalline polyester resin (single) of the present invention has a melting point (Tmp) of 55 ° C. or higher and 80 ° C. or lower, and more preferably 58 ° C. to 70 ° C. When the melting point is less than 55 ° C., the heat-resistant storage stability is deteriorated, and when it is higher than 80 ° C., the low-temperature fixability is deteriorated.
In the present invention, the melting point (Tmp) of the crystalline polyester resin (simple substance) refers to the temperature at which the maximum endothermic peak is shown in the DSC curve measured using a differential scanning calorimeter.
Further, the endothermic peak temperature (Tm1) derived from the crystalline polyester in the toner may satisfy the formula 1, but is preferably 40 ° C to 75 ° C, and more preferably 55 ° C to 70 ° C. When the temperature is lower than 40 ° C., the heat resistant storage stability deteriorates. When it exceeds 75 ° C., the low-temperature fixability is deteriorated.
The endothermic peak temperature (Tm1) derived from the crystalline polyester in the toner of the present invention is determined from the DSC curve obtained at the first temperature increase in the DSC measurement of the toner. In general, a crystalline resin shows a sharp endothermic peak at the time of temperature rise in DSC measurement. However, when heated together with an amorphous resin, the compatibility with the amorphous resin proceeds during the temperature rise process in DSC. In the DSC measurement conditions, the endothermic peak temperature is greatly decreased or not observed in the second temperature raising process. On the other hand, the release agent used in the toner of the present invention also shows a sharp endothermic peak. However, since the release agent is not compatible with the binder resin used in the present invention, the endotherm is also absorbed during the second temperature increase process. Peaks are observed at approximately the same temperature. Therefore, it can be determined that the endothermic peaks derived from the release agent are those that show substantially the same temperature in the first and second temperature raising processes. In the present invention, among the endothermic peak temperatures observed in the first temperature raising process, the endothermic peak temperature (Tm2) of the release agent that is not changed even in the second time as described above is defined as the second temperature raising process. The endothermic peak that disappeared or decreased was defined as the endothermic peak temperature (Tm1) of the crystalline polyester.

The crystalline polyester resin has a weight average molecular weight (Mw) of 10,000 to 30,000, a number average molecular weight (Mn) of 500 to 6000, and Mw / Mn of G-PC molecular weight distribution of soluble o-dichlorobenzene. It is preferable that it is 2-10.
When the weight average molecular weight (Mw) exceeds 30000, the low-temperature fixability decreases, and when it is less than 10,000, the heat resistant storage stability decreases. On the other hand, when Mw / Mn exceeds 10, the molecular weight distribution becomes broad and it is difficult to achieve both low temperature fixability and heat resistant storage stability.
In addition, the peak position of the molecular weight distribution diagram in which the horizontal axis of the molecular weight distribution by GPC and the vertical axis of the soluble part of o-dichlorobenzene is expressed in log (M) and the vertical axis in weight% is in the range of 3.5 to 4.0. Yes, those having a peak half-value width of 1.5 or less can be preferably used.
The content of the crystalline polyester resin in the binder resin is preferably 5% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 15% by mass or less. If it is less than 5% by mass, the compatibility with the non-crystalline polyester becomes insufficient and the fixing property may be deteriorated. If it exceeds 30% by mass, the crystalline polyester is filmed on the fixing member or carrier. There may be a problem such as.

When the acid value of the crystalline polyester resin used in the toner of the present invention is A (KOH / g) and the hydroxyl value of the crystalline polyester resin is B (KOH / g), the following relational expression is satisfied. preferable.
10 mgKOH / g <A <40 mgKOH / g
0 mgKOH / g <B <20 mgKOH / g
20 mgKOH / g <A + B <40 mgKOH / g
When the acid value A of the crystalline polyester resin is 10 mgKOH / g or less, the affinity with paper as a recording member may be deteriorated, and heat resistant storage stability may be deteriorated. On the other hand, when the acid value A of the crystalline polyester resin is 40 mgKOH / g or more, or the hydroxyl value B is 20 mgKOH / g or more, the charging ability of the toner under high temperature and high humidity may be lowered. Further, if the sum of the acid value and the hydroxyl value (A + B) is 20 mgKOH / g or less, the compatibility with the amorphous polyester resin is lowered, and the low-temperature fixability may not be sufficiently obtained. On the other hand, if the total of the acid value and the hydroxyl value (A + B) is 40 mgKOH / g or more, the compatibility between the crystalline polyester resin and the amorphous polyester resin is excessively increased, so that the heat resistant storage stability may be deteriorated. . Here, the acid value can be measured by a method defined in JIS K0070-1992, and the hydroxyl value can be measured by a method defined in JIS K0070-1966.

(Monomer component constituting crystalline polyester resin)
In the present invention, the monomer component constituting the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. However, the alcohol contains a diol compound having 2 to 20 carbon atoms and a derivative thereof. A polyester resin that can be synthesized using a component and an acid component containing a polyvalent carboxylic acid compound such as aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and alicyclic dicarboxylic acid, and derivatives thereof can be used.
Therefore, in the present invention, the crystalline polyester resin includes a modified polyester resin, for example, a prepolymer described later, and a modified polyester resin obtained by crosslinking and / or elongation reaction of the prepolymer (that is, urethane bond and Modified polyester resin having at least one of urea bonds) is not included.

  Examples of the saturated aliphatic diol compound having 2 to 12 carbon atoms as the alcohol component include 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 1, Examples include 12-dodecanediol and derivatives thereof.

As the acidic component, a C2-C12 dicarboxylic acid having a double bond (C = C bond), or a C2-C12 saturated dicarboxylic acid, particularly fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8 octanedioic acid, 1,10-decanedioic acid, 1,12-dodecanedioic acid and derivatives thereof can be used.
In particular, a saturated diol component having 4 to 12 carbon atoms such as 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, and 1,12-dodecanediol; C4-C12 saturation of any of 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid and 1,12-dodecanedioic acid An aliphatic polyester resin composed of a dicarboxylic acid component is preferably used from the viewpoint of high crystallinity and a rapid change in viscosity near the melting point.

[Amorphous polyester resin]
In the present invention, an amorphous polyester resin is included as the binder resin component. As this non-crystalline polyester resin, non-crystalline unmodified polyester resin is preferably used, and is preferably an aromatic polyester resin.

(Physical properties of non-crystalline polyester resin)
The amorphous polyester resin of the present invention preferably has a glass transition temperature (Tg) of 35 to 55 ° C, and more preferably 39 to 45 ° C, from the viewpoint of toner storage stability. When Tg is less than 35 ° C., the toner may be easily deteriorated in a high temperature atmosphere, and offset may be easily generated during fixing. On the other hand, when Tg exceeds 55 ° C., fixability may be deteriorated.

(Monomer component constituting non-crystalline polyester resin)
The alcohol component used in the amorphous polyester resin is a divalent alcohol (diol), specifically, an alkylene glycol having 2 to 36 carbon atoms (ethylene glycol, 1,2-propylene glycol, 1,3-propylene). Glycols, 1,4-butylene glycol and 1,6-hexanediol); alkylene ether glycols having 4 to 36 carbon atoms (such as diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol); C6-C36 alicyclic diol (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); C2-C4 alkylene oxide of the above alicyclic diol [ethylene oxide (hereinafter referred to as E ), Propylene oxide (hereinafter abbreviated as PO), butylene oxide (hereinafter abbreviated as BO), etc.] adducts (addition mole number 1-30); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) And C 2-4 alkylene oxide (EO, PO, BO, etc.) adducts (addition mole number 2-30).

  Further, in addition to the above divalent diol, an alcohol component having 3 or more valences (3 to 8 valences or more) may be contained, specifically, 3 to 8 valences having 3 to 36 carbon atoms or more. The above aliphatic polyhydric alcohols (alkane polyols and intramolecular or intermolecular dehydrates thereof such as glycerin, triethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, polyglycerin, and dipentaerythritol; Derivatives such as sucrose and methyl glucoside; etc.]; C 2-4 alkylene oxide (EO, PO and BO etc.) adducts (addition moles 1-30) of the above aliphatic polyhydric alcohols; Trisphenols (Tris) C2-C4 alkyloxides (such as phenol PA) (EO, PO and Adduct (number of added moles 2-30); novolak resin (phenol novolak, cresol novolak, etc .: average degree of polymerization 3-60) adduct with 2-4 carbon atoms (e.g., EO, PO, BO) (Addition mole number 2-30) etc. are mentioned.

  The carboxylic acid component used in the amorphous polyester resin is a divalent carboxylic acid (dicarboxylic acid), specifically, an alkanedicarboxylic acid having 4 to 36 carbon atoms (such as succinic acid, apidic acid, and sebacic acid). And alkenyl succinic acid (such as dodecenyl succinic acid); alicyclic dicarboxylic acid having 4 to 36 carbon atoms [dimer acid (dimerized linoleic acid) and the like]; alkenedicarboxylic acid having 4 to 36 carbon atoms (maleic acid, fumaric acid, citracone) Acid and mesaconic acid); aromatic dicarboxylic acids having 8 to 36 carbon atoms (phthalic acid, isophthalic acid, terephthalic acid or derivatives thereof, and naphthalenedicarboxylic acid). Of these, preferred are alkene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. In addition, as a polycarboxylic acid, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

  Further, in addition to the above divalent carboxylic acid, it may contain a trivalent or higher (3 to 6 or higher) carboxylic acid component, specifically, an aromatic polycarboxylic acid having 9 to 20 carbon atoms. Acid (trimellitic acid, pyromellitic acid, etc.); vinyl polymer of unsaturated carboxylic acid [number average molecular weight (hereinafter referred to as Mn, according to gel permeation chromatography (GPC)): 450 to 10,000] (styrene / maleic acid co Polymer, styrene / acrylic acid copolymer, α-olefin / maleic acid copolymer, styrene / fumaric acid copolymer, etc.). Among these, preferred are aromatic polycarboxylic acids having 9 to 20 carbon atoms, and particularly preferred are trimellitic acid and pyromellitic acid. In addition, as a polycarboxylic acid more than trivalence, you may use the acid anhydride of the above-mentioned thing, or a lower alkyl (C1-C4) ester (Methyl ester, ethyl ester, isopropyl ester, etc.).

[Temperature, melting point, etc.]
The toner of the present invention containing the binder resin has an endothermic peak temperature derived from the crystalline polyester resin when the toner is subjected to differential calorimetry (DSC) as Tm1, and the crystalline polyester resin (the crystalline polyester resin used in the toner). When the melting point of the simple substance is Tmp, the following formula (1) is satisfied, and it is more preferable that the following formula (1 ′) is satisfied.
5 ° C. ≦ Tmp−Tm1 ≦ 15 ° C. (1)
8 ° C. ≦ Tmp−Tm1 ≦ 12 ° C. (1 ′)

  If there are many portions where the crystalline polyester resin and the non-crystalline polyester are compatible, the toner is easily softened, and the start-up temperature of the toner is lowered. Some of the compatible parts of the crystalline polyester resin can be known from the difference between the melting point Tmp of the crystalline polyester alone and the endothermic peak temperature (Tm1) derived from the crystalline polyester when the toner is DSCed. It can be adjusted by the affinity between the crystalline polyester resin and the amorphous polyester resin, the content of the crystalline polyester resin in the toner particles, the dispersion diameter, and the like.

  When crystalline polyester and non-crystalline polyester are partially compatible inside the toner, this compatible portion serves as a starting point where melting starts at the time of fixing, and the entire toner is efficiently melted to achieve low-temperature fixability and sharpness. It has been found that it develops melt properties. However, if there are too many compatible parts or the toner particles are exposed on the surface of the toner particles, the toner particles may be fused with each other, and an abnormal image may be generated after long-term storage or when used on a high-speed machine. In addition, a rubbery material in which crystalline polyester and amorphous polyester exposed on the surface are mixed with each other adheres to the fixing member, and filming occurs. Furthermore, when most of the crystalline polyester and the amorphous polyester are compatible in the toner, Tm1 is not observed or Tmp-Tm1 is 15 ° C. or higher. In this case, it is considered that the crystalline polyester and the amorphous polyester are compatible with each other in the production process of the toner, and both the low-temperature fixability and the heat-resistant storage stability are deteriorated. On the other hand, when there are too few compatibilized parts, Tmp-Tm1 will be less than 5 degreeC, the affinity of crystalline polyester and binder resin in the vicinity of fixing temperature will worsen, and it will become impossible to express desired sharp-melt property, so low temperature. Fixability is hindered.

  In an image forming method having an image forming apparatus with a process linear velocity of about 300 to 1500 mm / s in which the toner of the present invention is used, while satisfying the formula (1), both low temperature fixability and heat resistant storage stability are achieved. A toner having good image quality after long-term storage can be obtained.

[Measurement method of Tmp, Tm1]
Here, Tmp and Tm1 in the present invention are specifically determined by the following procedure. Using Shimadzu TA-60WS and DSC-60 as measuring devices, the measurement was performed under the following measurement conditions.
Measurement conditions Sample container: Aluminum sample pan (with lid)
Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10mg)
Atmosphere: Nitrogen (flow rate 50ml / min)
Temperature conditions Starting temperature: 20 ° C
Temperature increase rate (first temperature increase): 10 ° C./min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate (second temperature increase): 10 ° C./min
End temperature: 150 ° C
From the obtained DSC curve, using the analysis program in the DSC-60 system, using the “endothermic peak temperature” in the analysis program, find the peak where the endothermic amount is maximum in the DSC curve at the first temperature rise. By selecting, the maximum endothermic peak temperature in the first temperature rising process of the target sample can be obtained. Similarly, the second maximum endothermic peak temperature can be determined from the DSC curve during the second temperature increase.
Here, the melting point (Tmp) of the crystalline polyester resin was determined from the maximum endothermic peak temperature in the second temperature rising process using the crystalline polyester resin alone used for the toner as a sample.
Further, the endothermic peak temperature (Tm1) derived from the crystalline polyester in the toner was obtained by specifying the endothermic peak derived from the crystalline polyester resin at the first temperature increase using the toner as a sample.

<Melting viscosity of release agent>
The release agent used in the toner of the present invention satisfies the following formula (2) when the melt viscosity at 100 ° C. is η (w), and more preferably satisfies the following formula (5).
1 mPa · s ≦ η (w) ≦ 20 mPa · s (2)
5 mPa · s ≦ η (w) ≦ 18 mPa · s (5)

Equations (2) and (5) are both the melt viscosity of the release agent at 100 ° C. As described above, in order to save energy, the low-temperature fixing is progressing and the set temperature of the fixing machine is decreasing. Further, the temperature applied to the toner when fixing the toner on the paper is lower than the actual setting temperature of the fixing machine. As a result of intensive studies, it was found that the melt viscosity at 100 ° C. of the release agent is important. When the melt viscosity of the release agent at the time of fixing is lowered, the hot offset and the friction resistance performance of the fixed image are improved. However, when the melt viscosity of the release agent at the time of fixing is less than 1 mPa · s, the low-temperature fixability may be deteriorated. On the other hand, if it exceeds 20 mPa · s, the release of the release agent from the toner becomes insufficient, and there may be a problem that the release property and hot offset resistance deteriorate.

  Conventionally, in order to improve the low temperature fixability, the viscosity of the toner and the viscosity of the release agent have been lowered. However, the low temperature fixability is deteriorated only by reducing the viscosity of the release agent. In particular, in a toner whose viscosity decreases in a short time at the time of fixing, such as the toner of the present invention, the occurrence of offset can be suppressed by controlling the amount of the release agent that exudes from the toner at the time of fixing to a constant amount. I understood that I could do it.

<Toner melt viscosity>
In the toner of the present invention, it is preferable that the following formula (3) is satisfied when the melt viscosity at 100 ° C. of the toner is η (t). Moreover, it is more preferable that the following formula (4) is satisfied.
500 mPa · s ≦ η (t) ≦ 8000 mPa · s (3)
1000 mPa · s ≦ η (t) ≦ 6000 mPa · s (4)

When the melt viscosity of the toner at the time of fixing is too low (η (t) is less than 500 mPa · s), the hot offset and cold offset, and further the separation between the paper and the fixing member deteriorates, and the melt viscosity of the toner at the time of fixing is low. If it is too high (η (t) exceeds 8000 mPa · s), the low-temperature fixability deteriorates.
The reason for the excellent low-temperature fixability is not obvious, but it is necessary to satisfy the requirements of the above formulas (1) and (2) in order to control the amount of the release agent that exudes from the toner at the time of fixing to a constant amount. I think there is.

<Release agent>
The release agent used in the present invention is not particularly limited as long as it satisfies the above formula (2), and can be appropriately selected according to the purpose. For example, the following materials are used. Can do.
As waxes and waxes, plant waxes such as carnauba wax, cotton wax, wood wax, rice wax; animal waxes such as beeswax and lanolin; mineral waxes such as ozokerite and cercin; paraffin, microcrystalline, petrolatum, etc. And petroleum wax.
Examples of waxes other than these natural waxes include synthetic hydrocarbon waxes such as Fischer-Tropsch wax and polyethylene wax; synthetic waxes such as esters, ketones and ethers.
Furthermore, fatty acid amides such as 1,2-hydroxystearic acid amide, stearic acid amide, phthalic anhydride imide, chlorinated hydrocarbons; low molecular weight crystalline polymers such as poly (n-stearyl methacrylate), poly (methacrylic acid n-) A crystalline polymer having a long-chain alkyl group in the side chain such as a homopolymer or copolymer of polyacrylate such as lauryl (for example, n-stearyl acrylate-ethyl methacrylate copolymer) can also be used as the wax.

Among these, ester waxes are particularly preferable in terms of hot offset property, volatile matter derived from wax at the time of fixing, separability, and low temperature fixability. The wax preferably has a melting point (Tm2) of 65 to 80 ° C, and more preferably 68 to 75 ° C. When the melting point (Tm2) is less than 65 ° C., the heat-resistant storage stability tends to deteriorate, and when it exceeds 80 ° C., the low-temperature fixability tends to deteriorate.
The ester wax satisfying these conditions preferably has a carbon number of 26 or more, a lower carbon number is preferable for low-temperature fixability, and a higher carbon number is preferable for improving hot offset. In order to achieve both, it is more preferable to mix ester waxes having different carbon numbers.
As said ester wax, what was synthesize | combined suitably may be used and a commercial item may be used.

The ester wax is usually synthesized by esterifying a long-chain fatty acid or polyvalent carboxylic acid with a long-chain higher alcohol or polyhydric alcohol.
The long-chain fatty acid or polyvalent carboxylic acid and the long-chain higher alcohol or polyhydric alcohol are usually obtained from natural products and are generally composed of a mixture having an even number of carbon atoms. .

  The long-chain fatty acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid and the like. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the polyvalent carboxylic acid include alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or anhydrides thereof, maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid and the like. Unsaturated dibasic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride, etc., trimellitic acid, pyromellitic acid, 1,2,4 Benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5 -Hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetrakis (methylene carbonate) Bokishi) methane, 1,2,7,8-octane tetracarboxylic acid, Empol trimer acid, anhydrides thereof, such as partial lower alkyl esters. These may be used individually by 1 type and may use 2 or more types together.

  The long chain higher alcohol is not particularly limited and may be appropriately selected depending on the intended purpose.For example, caprylic alcohol, capric alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, aratidyl alcohol, behenyl alcohol And lignoceryl alcohol. These may be used individually by 1 type and may use 2 or more types together.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol,
1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl- 1,3-hexanediol, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2 , 5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene, and the like. These may be used individually by 1 type and may use 2 or more types together.

  As the esterification reaction, for example, the reaction temperature is normal pressure or less than 250 ° C., preferably in an inert gas such as nitrogen. The reaction rate of the long chain fatty acid or polyvalent carboxylic acid and the long chain higher alcohol or polyhydric alcohol is not particularly limited and may be appropriately selected depending on the purpose. In the esterification reaction, a small amount of an esterification catalyst or a solvent may be present.

Examples of the esterification catalyst include organic titanium compounds such as tetrabutoxy titanate and tetrapropoxy titanate, organic tin compounds such as dibutyltin dilaurate and dibutyltin oxide, and other organic lead compounds. As said solvent, aromatic solvents, such as toluene, xylene, a mineral spirit, are used, for example.
When the long-chain fatty acid or polyhydric carboxylic acid and the long-chain higher alcohol or polyhydric alcohol are esterified as they are, by-products having various similar structures in addition to the target ester compound are by-produced. Therefore, the toner characteristics are liable to be adversely affected. Therefore, the ester wax used by this invention can be obtained by refine | purifying a raw material and a product using solvent extraction or vacuum distillation operation.

  Since such a wax can effectively act as a wax between the fixing roller and the toner interface, the high temperature offset resistance can be improved without applying a wax such as oil to the fixing roller.

The content of the release agent in the toner is preferably 3 parts by mass to 15 parts by mass, and more preferably 4 parts by mass to 12 parts by mass with respect to 100 parts by mass of the binder resin.
When the addition amount is less than 3 parts by mass, the high-temperature offset resistance is lowered, and further, the image on the back side tends to exhibit an offset phenomenon when fixing a double-sided image. On the other hand, when the amount exceeds 15 parts by mass, in the production by the pulverization method, fusion in the apparatus is likely to occur, and also in the production by the polymerization method, the toner particles are likely to coalesce during granulation. As a result, a toner having a wide particle size distribution is likely to be generated, the durability of the toner may be lowered, and the heat resistant storage stability and charging characteristics may be deteriorated.

  The average particle diameter of the release agent in the toner particles is preferably 0.2 to 1.5 μm in major axis diameter. When it is smaller than 0.2 μm, the mold release effect is small. If it exceeds 1.5 μm, there is a high possibility that filming on the photoreceptor and spent on the carrier will be caused. Therefore, the average particle size is preferably 0.2 to 1.5 μm, and more preferably 0.4 to 1.0 μm.

<Wax dispersant>
The dispersant used in the present invention is not particularly limited, but a styrene acrylic resin shown below is preferably grafted with a hydrocarbon wax or a crystalline polyester. Having a hydrocarbon wax or crystalline polyester as the affinity part for the release agent is preferable in that the dispersant is easily adsorbed to the binder resin and the release agent, and the dispersion stabilizing effect is easily exhibited.
The styrene acrylic resin is preferably composed of the following monomers.

(Styrene monomer)
Examples of the styrene monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethyl. Styrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene Styrene and its derivatives such as pn-dodecylstyrene.

(Acrylic monomer)
Examples of N-containing vinyl monomers include amino group-containing α-methylene aliphatic monocarboxylic acid esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide. Can be mentioned.

  Examples of the carboxyl group-containing monomer include unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic acid Unsaturated dibasic acid anhydrides such as acid anhydride; maleic acid methyl half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itacon Half-esters of unsaturated dibasic acids such as acid methyl half ester, alkenyl succinic acid methyl half ester, fumaric acid methyl half ester, mesaconic acid methyl half ester; dimethyl maleic acid, unsaturated dibasic such as dimethyl fumaric acid Esters; α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride, the α, β-unsaturated acid Examples include anhydrides of saturated acids and lower fatty acids; alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid, acid anhydrides thereof and monoesters thereof.

  Examples of the hydroxyl group-containing monomer include acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1 -Hydroxy-1-methylhexyl) styrene.

  Examples of the acrylate monomer include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, and stearyl acrylate. And acrylic acid esters such as 2-chloroethyl acrylate and phenyl acrylate.

  Examples of the methacrylic acid ester monomer include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate. And methacrylic acid esters such as phenyl methacrylate.

In the molecular weight distribution by GPC of the styrene acrylic resin, the weight average molecular weight (Mw) is 5000 to 100,000, the number average molecular weight (Mn) is 1500 to 15000, the weight average molecular weight (Mw) and the number average molecular weight (Mn). ) (Mw / Mn) is preferably 2 to 40.
When the weight average molecular weight (Mw) is less than 5000, or when the number average molecular weight (Mn) is less than 1500, or the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is less than 2. In this case, the anti-blocking performance of the toner is significantly impaired.
When the weight average molecular weight (Mw) exceeds 100,000, the number average molecular weight (Mn) exceeds 15,000, or the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 40. If it exceeds the upper limit, the release agent cannot quickly migrate to the surface of the molten toner at the time of fixing and melting, and the releasability is deteriorated, so that high temperature offset tends to occur.

(Hydrocarbon wax, crystalline polyester resin)
The hydrocarbon wax used for graft polymerization with a styrene acrylic resin and the crystalline polyester resin have a maximum endothermic peak maximum value of 60 to 120 ° C. in the endothermic curve at the time of temperature rise measured by DSC. Is good.
When the maximum value of the maximum endothermic peak of the hydrocarbon wax and the crystalline polyester resin is less than 60 ° C. or exceeds 120 ° C., the branched structure with respect to the styrene acrylic resin is impaired, so that the release agent and the crystalline polyester When the toner is made into a toner, the release agent and the crystalline polyester resin are unevenly distributed on the toner surface, resulting in poor filming properties.

  Crystalline polyester resins graft-polymerized to styrene acrylic resins are, for example, saturated aliphatic diol compounds having 2 to 12 carbon atoms as alcohol components, particularly 1,4-butanediol, 1,6-hexanediol, 1,8- Octanediol, 1,10-decanediol, 1,12 dodecanediol and derivatives thereof, and a dicarboxylic acid having 2 to 12 carbon atoms having at least a double bond (C═C bond) as an acidic component, or 2 carbon atoms ~ 12 saturated dicarboxylic acids, in particular fumaric acid, 1,4-butanedioic acid, 1,6-hexanedioic acid, 1,8-octanedioic acid, 1,10-decanedioic acid, 1,12 dodecanedioic acid and Crystalline polyesters synthesized using these derivatives are preferred.

  Examples of the hydrocarbon wax that is graft-polymerized to the styrene acrylic resin include paraffin, microcrystalline, Fischer-Tropsch wax, polyethylene, and polypropylene.

(Glass transition temperature and content of wax dispersant)
The glass transition temperature of the wax dispersant is preferably 55 ° C to 80 ° C, more preferably 55 ° C to 70 ° C. When the glass transition temperature of the wax dispersant exceeds 80 ° C., the low-temperature fixability may be impaired, and when it is less than 55 ° C., the hot offset resistance may be deteriorated.
The content of the wax dispersant is preferably 0.01% by mass to 8% by mass and more preferably 0.5% by mass to 6% by mass with respect to the toner. When the amount is within the above preferable range (0.01% by mass to 8% by mass with respect to the toner), the amount of wax present on the toner surface is appropriately maintained, and in particular, releasability from the fixing roller and the belt is improved. The effect which was excellent in smear resistance can be exhibited. In addition, when the amount is within the preferable range, the amount of the wax present on the toner surface can be appropriately maintained, in particular, the releasability from the fixing roller and the belt can be improved, and the effect of excellent smear resistance can be exhibited. .

<Colorant>
As the colorant used in the present invention, all known dyes and pigments can be used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide , Ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent yellow (NCG), Vulcan fast yellow ( 5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Phisera Red , Parachlor Rutonitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carnmin BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Resol Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Tolujing Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake , Thioindigo red B, thioindigo maroon, oil red, quinacridone red, pyrazo Red, polyazo red, chrome vermillion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkali blue rake, peacock blue rake, Victoria blue rake, metal free phthalocyanine blue, phthalocyanine blue, fast sky blue, indance Ren Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide, Pyridian, Emerald Green , Pigment Green B, Naphthol Green B, Green Gold, Acid Green Lake, Malachite Green , Phthalocyanine green, anthraquinone green, titanium oxide, zinc white, lithopone and mixtures thereof can be used.
The content of the colorant is usually 1 to 15% by mass, preferably 3 to 10% by mass with respect to the toner.

〔Master Badge〕
The colorant used in the present invention can also be used as a master batch combined with a binder resin. As the binder resin to be kneaded together with the production of the masterbatch or the masterbatch, in addition to the above-mentioned modified and unmodified polyester resins, styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and polymers of substitution products thereof. Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer Polymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α -Methyl chloromethacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid Styrenic copolymers such as ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacryl Acid resins, rosins, modified rosins, terpene resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes and the like can be used, and these can be used alone or in combination.

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

<Preferred production method of toner>
Next, a method for producing the toner of the present invention will be described.
The toner of the present invention can be produced by a polymerization method.
That is, the toner of the present invention emulsifies or disperses an oil phase in which a toner material such as a binder resin, a release agent, and a colorant is dissolved or dispersed in an organic solvent, for example, It can be produced by removing the organic solvent, and it is important that the crystalline polyester and the amorphous polyester are not compatible in the toner production process.
As a method for preventing the crystalline polyester resin and the amorphous polyester resin from being compatible in the toner production process, a resin fine particle dispersion in which the crystalline polyester resin is dispersed in the amorphous polyester resin can be used.

  As the method for preparing the resin fine particle dispersion, the crystalline polyester resin is added alone to an organic solvent, dissolved by heating at high temperature, and cooled to precipitate the crystalline polyester resin particles by recrystallization. A method in which the non-crystalline polyester resin is dissolved in the subsequent dispersion to make the crystalline polyester fine particles is preferable. When the crystalline polyester is dispersed in an organic solvent, as the pulverization of the crystalline polyester particles proceeds, the viscosity of the dispersion becomes high, and it becomes difficult to disperse more than a certain degree. Therefore, when an amorphous polyester solution is added, the viscosity of the dispersion decreases, and the crystalline polyester can be pulverized to a finer particle size.

However, when the crystalline polyester resin is heated and melted and cooled, non-crystalline polyester resin is mixed, or when fine dispersion is performed with a mechanical pulverizer, the dispersion increases as the viscosity increases and dispersion occurs. When the liquid temperature is increased, the crystalline polyester resin and the amorphous polyester resin are compatible with each other, and the sharp melt property of the crystalline polyester is not utilized in the toner.
Therefore, the crystalline polyester resin and the non-crystalline polyester resin are not compatible by further micronizing with a mechanical pulverizer so that the dispersion temperature does not rise above the temperature at which the crystalline polyester resin dissolves in the organic solvent. A resin fine particle dispersion can be prepared.

The dispersion diameter of the crystalline polyester resin in the toner particles is preferably 0.1 μm or more and 2.0 μm or less in terms of the major axis diameter from the viewpoint of fine dispersion of the crystalline polyester resin and surface uneven distribution. More preferably, it is 0 μm or less.
When it is smaller than 0.1 μm, the viscosity of the crystalline polyester dispersion becomes high, and it becomes difficult to control the viscosity within the range of 0.1 μm to 2.0 μm. Moreover, since it becomes compatible with non-crystalline polyester, heat-resistant storage stability may deteriorate. If the dispersion diameter exceeds 2.0 μm, it becomes difficult to granulate the toner, so the dispersion diameter needs to be 2.0 μm or less.
The dispersed particle diameter of the crystalline polyester resin particles can be adjusted by the concentration of the solution and the cooling rate when the crystalline polyester resin particles are precipitated, in addition to mechanically pulverizing the resin fine particle dispersion.

As an organic solvent used in the dispersion process of the crystalline polyester resin, the crystalline polyester resin can be completely dissolved at a high temperature to form a uniform solution. On the other hand, when cooled to a low temperature, the crystalline polyester resin is precipitated, Those that form an opaque heterogeneous solution can be used.
Specifically, with reference to the temperature (Tm) at which the crystalline polyester is dissolved in the organic solvent, the temperature is less than (Tm-40) ° C., indicating non-solvent characteristics, and the temperature higher than that indicates good solvent characteristics. As a specific example, toluene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.

  Examples of the mechanical pulverization apparatus used in the step of micronizing the crystalline polyester resin precipitated in the cooling process include commercially available pulverization apparatuses such as a bead mill apparatus, a ball mill apparatus, a wet pulverization apparatus (Altima manufactured by Sugino Machine). Iser device).

  In addition, the toner of the present invention is bonded to a toner material liquid in which a toner material such as a binder resin containing a crystalline polyester resin and an amorphous polyester, a release agent, and a colorant is dissolved or dispersed in an organic solvent. An emulsified dispersion is obtained by dispersing an oily phase in which an adhesive resin precursor and a compound that undergoes an elongation reaction or a crosslinking reaction with the binder resin precursor are dissolved in an aqueous medium in which a fine particle dispersant is present. The binder resin precursor is preferably subjected to a crosslinking reaction and / or an extension reaction in the dispersion to remove the organic solvent. In other words, the binder is bonded to an oil phase including a binder resin component containing a binder resin precursor composed of a crystalline polyester resin, an amorphous polyester, and a modified polyester resin, a colorant, and a release agent. After dissolving a resin precursor and a compound that extends or crosslinks, an oil phase in which the compound is dissolved is dispersed in an aqueous medium containing a dispersant to obtain a dispersion, and the binder resin is dispersed in the dispersion A toner obtained by reacting a precursor with the compound to cause a crosslinking reaction and / or elongation reaction and then removing the organic solvent is preferable.

<Prepolymer>
As the binder resin precursor, a binder resin precursor made of a modified polyester resin is preferable, and examples thereof include a polyester prepolymer modified with isocyanate or epoxy.
This is because the binder resin precursor undergoes an extension reaction with a compound having an active hydrogen group (for example, amines), and has an effect of improving the release width (difference between the minimum fixing temperature and the hot offset occurrence temperature).
As a method for synthesizing this polyester prepolymer, it can be easily synthesized by reacting a base polyester resin with a conventionally known isocyanate agent or epoxidizing agent.

  The polyester prepolymer is preferably at least partially compatible with the above-described non-crystalline polyester resin (unmodified polyester resin). The polyester resin used as the base of the polyester prepolymer has an alcohol component and a carboxylic acid component. The alcohol component and carboxylic acid component constituting the amorphous polyester resin are preferably similar in composition. Moreover, as a polyester resin used as a base, you may use the non-crystalline polyester resin (unmodified polyester resin) mentioned above.

Examples of the isocyanate agent include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; And a combination of two or more of these.
Moreover, as an epoxidizing agent, epichlorohydrin etc. can be mentioned as the representative example.

  The ratio of the isocyanate agent is usually 5/1 to 1/1, preferably 4/1 to 1 as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the base polyester. 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. When the molar ratio of [NCO] is less than 1, the urea content of this polyester prepolymer becomes low, and the hot offset resistance deteriorates.

  The content of the isocyanate agent in the polyester prepolymer is usually 0.5 to 40% by mass, preferably 1 to 30% by mass, and more preferably 2 to 20% by mass. If it is less than 0.5% by mass, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by mass, the low-temperature fixability deteriorates.

The number of isocyanate groups contained per molecule in the polyester prepolymer is usually 1 or more, preferably 1.5 to 3 on average, and more preferably 1.8 to 2.5 on average. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester resin after the elongation reaction is lowered, and the hot offset resistance is deteriorated.
The binder resin precursor preferably has a weight average molecular weight of 5 × 10 ³ or more and 5 × 10 ⁴ or less.

<Compound that undergoes elongation reaction or cross-linking reaction with binder resin precursor>
Examples of the compound that undergoes an elongation reaction or a cross-linking reaction with the binder resin precursor include compounds having an active hydrogen group, and representative examples thereof include amines. Examples of amines include diamine compounds, trivalent or higher polyamine compounds, amino alcohol compounds, amino mercaptan compounds, amino acid compounds, and compounds in which these amino groups are blocked.

Examples of diamine compounds include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, isophoronediamine). Etc.); and aliphatic diamines (ethylenediamine, tetramethylenediamine, hexamethylenediamine, etc.) and the like.
Examples of the trivalent or higher polyamine compound include diethylenetriamine and triethylenetetramine.

Examples of amino alcohol compounds include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan compound include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of amino acid compounds include aminopropionic acid and aminocaproic acid.
Examples of the compounds in which these amino groups are blocked include ketimine compounds and oxazoline compounds obtained from the amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).

  Among these amines, preferred are a diamine compound, a mixture of a diamine compound and a small amount of a polyamine compound, and a compound in which the amino group of the diamine compound is blocked.

  The urea-modified polyester resin can be used in combination with a polyester resin modified with a chemical bond other than a urea bond, for example, a polyester resin modified with a urethane bond, in addition to an unmodified amorphous polyester resin. .

When a modified polyester resin such as a urea-modified polyester resin is contained in the organic solvent, the modified polyester resin can be produced by a one-shot method or the like.
As an example, a method for producing a urea-modified polyester resin will be described.
First, a polyol and a polycarboxylic acid are heated to 150 to 280 ° C. in the presence of a catalyst such as tetrabutoxy titanate or dibutyltin oxide, and if necessary, water generated while removing pressure is removed to have a hydroxyl group. A polyester resin is obtained. Next, a polyester resin having a hydroxyl group is reacted with polyisocyanate at 40 to 140 ° C. to obtain a polyester prepolymer having an isocyanate group. Furthermore, the polyester prepolymer having an isocyanate group is reacted with amines at 0 to 140 ° C. to obtain a urea-modified polyester resin.
The number average molecular weight of the urea-modified polyester resin is usually 1000 to 10000, preferably 1500 to 6000.

In addition, when making the polyester resin which has a hydroxyl group and polyisocyanate react, and when making the polyester prepolymer which has an isocyanate group, and amines react, a solvent can also be used as needed.
Solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.); ethers (tetrahydrofuran) And the like which are inert with respect to the isocyanate group.
The unmodified polyester resin may be mixed with a solution produced in the same manner as the polyester resin having a hydroxyl group in the solution after the reaction of the urea-modified polyester resin.

Among the toners produced by the production method as described above, in the case of a toner containing a crystalline polyester resin and an amorphous polyester resin, and the release agent is an ester wax,
The melting point Tm2 of the releasing agent and the endothermic peak temperature derived from the crystalline polyester resin when the toner is DSC satisfies the following formula (5), and the outflow start temperatures Tfb and Tm1 of the toner satisfy the following formula (6). It is preferable that the melting point Tmp of the crystalline polyester is 55 to 80 ° C.
When Tm1, Tm2, and Tfb satisfy a specific relationship, both low-temperature fixability and heat-resistant storage stability can be achieved, and high image quality can be obtained even after long-term storage.
Tm1 ≦ Tm2 ≦ Tm1 + 20 ° C. (5)
Tm1 + 12 ° C. <Tfb <Tm1 + 25 ° C. (6)

[Regarding Formula (5)]
In the fixing process, the toner receives heat from the fixing machine, and the heat is transferred to the inside, so that the binder resin and the release agent are melted and the toner is plasticized and deformed to obtain a fixed image. Here, the behavior of the release agent and the binder resin at the time of fixing was examined. After the crystalline polyester resin and the amorphous polyester resin contained in the binder resin were compatible and viscoelasticity decreased rapidly, It has been found that when the mold is melted and oozes out on the surface of the fixed image, a good release effect is exhibited. Generally, it is known that a crystalline substance expands in volume when it is melted, and the crystalline polyester resin and ester wax contained in the toner of the present invention exhibit the same behavior.
The melting of the release agent contained in the toner is faster than that of the crystalline polyester resin, that is, the endothermic peak temperature derived from the crystalline polyester resin when the melting point (Tm2) of the release agent is DSC of the toner is higher than (Tm1). If it is low, the crystalline polyester resin and the non-crystalline polyester resin will be non-uniformly arranged inside the toner particles, which may impair sharp melt properties. In addition, the release agent having a low melting point deteriorates heat-resistant storage stability and may cause in-machine contamination due to volatilization. Therefore, it is preferable to satisfy Tm1 ≦ Tm2.
On the other hand, when Tm2 is higher than Tm1 + 20 ° C., the low-temperature fixability may deteriorate due to the high melting point (Tm2) of the release agent. Therefore, it is preferable to satisfy | fill Formula (5), and it is more preferable to satisfy | fill Tm1 + 3 degreeC <= Tm2 <= Tm1 + 10 degreeC.

[Regarding Formula (6)]
Next, when the temperature of the toner exceeds the endothermic peak temperature derived from the crystalline polyester resin when the toner is DSC (Tm1), the toner is compatible with other binder resin contained in the toner and becomes a molten state. At this time, if there is a partially compatible part, the thermal characteristics of the partially compatible part approach those of the amorphous polyester resin contained in the main resin. That is, the compatibility of the entire toner is started with the compatible portion as a base point, and the temperature at which the deformation of the toner starts approaches Tm1. On the other hand, the compatibilized portion is easily softened due to an increase in the ambient temperature of the toner, and the toner may adhere to the softened portions with a loose force, which causes deterioration of image quality in the fixing process. For this reason, the number of compatibilizing parts must be reduced as much as possible in high-speed machines where the temperature inside the copying machine tends to rise, and when long-term storage is required. In view of the ease of deformation of the toner with respect to a certain pressure, the relationship between the starting temperature (Tfb) of the colored toner and Tm1 was examined. As a result, it was found that if Tm1 + 12 ° C. <Tfb, the toner has little partial compatibility. . On the other hand, at a temperature higher than Tm1 + 25 ° C., the compatibility between the crystalline polyester resin and the amorphous polyester resin is poor and the sharp melt property is not exhibited, so that the low temperature fixability is not exhibited. Therefore, it is preferable to satisfy Expression (6).

Here, the outflow start temperature (Tfb) of the toner can be measured using an elevated flow tester CFT500 type manufactured by Shimadzu Corporation. The flow curve based on the data from the flow tester becomes the data shown in FIGS. 1A and 1B, from which each temperature can be read. In the figure, Ts is the softening temperature of the toner, and the melting temperature in the 1/2 method is the “T1 / 2 temperature”.
"Measurement condition"
Load: 10 kg / cm ² , temperature rising rate: 3.0 ° C./min,
Die diameter: 0.50 mm, Die length: 1.0 mm

<Adjustment method for satisfying formula (5)>
Tm1 and Tm2 can be adjusted by selecting an appropriate one from an arbitrary release agent and crystalline polyester resin.

<Adjustment method to satisfy Expression (6)>
Tfb depends on the manufacturing method of the toner, and changes depending on the crystalline state of the crystalline polyester resin in the binder resin changed in the manufacturing process.
Examples of a method for preventing the crystalline polyester resin and the amorphous polyester resin from being compatible in the toner production process include the following methods.
An oil phase containing at least a crystalline polyester resin and an amorphous polyester resin as a binder resin component is dispersed in an aqueous medium in an organic solvent, and a toner is obtained by removing the organic solvent from the obtained dispersion. In the toner production method, a crystalline polyester resin dissolves when heated to a high temperature in an organic solvent, and recrystallizes when cooled. It is possible to prevent the polyester resin and the amorphous polyester resin from being compatible. If an amorphous polyester resin is mixed in this step, the crystalline polyester resin and the amorphous polyester resin are compatible at the time of heating and dissolving, and the sharp melt property of the crystalline polyester resin is not utilized in the toner. Therefore, it is necessary to carry out the crystalline polyester resin alone in the organic solvent in the heating dissolution / cooling step. At this time, the dispersed particle diameter of the crystalline polyester resin precipitated in the cooling process is determined by the concentration of the solution and the cooling rate. Then, after cooling, the non-crystalline polyester resin is dissolved in the dispersion, and finely divided by a mechanical pulverizer, whereby a resin fine particle dispersion can be produced. In the fine dispersion using a mechanical pulverizer, the dispersion temperature increases as the viscosity increases, the dispersion temperature rises, and the crystalline polyester resin and the amorphous polyester resin become compatible. If the dispersion is performed so that the temperature does not become higher than the temperature at which the polyester resin is dissolved in the organic solvent, the compatibility between the crystalline polyester resin and the amorphous polyester resin can be prevented.

  As described above, it has been found that the toner manufactured by the above-described manufacturing method satisfies the formulas (5) and (6), thereby achieving a more preferable compatible state inside the toner.

<Other toner materials>
Further, the toner of the present invention may contain, as necessary, a charge control agent, an external additive, and the like that are well-known and commonly used as toners. An additive may be attached.

(Charge control agent)
The toner of the present invention may contain a charge control agent as necessary. All known charge control agents can be used, such as nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified). Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine-based activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives.

  Specifically, Nitronine-based dye Bontron 03, quaternary ammonium salt Bontron P-51, metal-containing azo dye Bontron S-34, oxynaphthoic acid metal complex E-82, salicylic acid metal complex E- 84, E-89 of a phenol-based condensate (manufactured by Orient Chemical Industry Co., Ltd.), TP-302 of a quaternary ammonium salt molybdenum complex, TP-415 (manufactured by Hodogaya Chemical Industry Co., Ltd.), quaternary ammonium Copy charge PSY VP2038 of salt, copy blue PR of triphenylmethane derivative, copy charge of quaternary ammonium salt NEG VP2036, copy charge NX VP434 (manufactured by Hoechst), LRA-901, LR-147 which is a boron complex (Nippon Carlit), copper phthalocyanine, perylene, quinaclide And azo pigments, and other high molecular compounds having a functional group such as a sulfonic acid group, a carboxyl group, and a quaternary ammonium salt.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Preferably, the range of 0.2-5 mass parts is good. When the amount exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. If the amount is less than 0.1 parts by mass, the effect of the charge control agent cannot be sufficiently obtained.

  These charge control agents can be melted and kneaded together with the masterbatch and binder resin and then dissolved and dispersed. Of course, they can be added directly when dissolved and dispersed in organic solvents, and fixed on the toner surface after toner particles are prepared. You may make it.

(External additive)
The toner of the present invention may contain an external additive in order to assist fluidity, developability, chargeability, or cleaning properties.
As an external additive capable of assisting fluidity, developability and chargeability, inorganic fine particles can be preferably used. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, bengara, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

The primary particle diameter of the inorganic fine particles is preferably 5 nm to 2 μm (2000 nm), particularly preferably 5 nm to 500 nm. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The use ratio of the inorganic fine particles is preferably 0.01 to 5% by mass of the toner, and particularly preferably 0.01 to 2.0% by mass.

  Other polymer fine particles, such as polystyrene, methacrylic acid ester and acrylic acid ester copolymer obtained by soap-free emulsion polymerization, suspension polymerization, and dispersion polymerization, polycondensation systems such as silicone, benzoguanamine, and nylon, thermosetting resins And polymer particles.

  Such a fluidizing agent is surface-treated with a surface treating agent to increase hydrophobicity and prevent deterioration of fluidity characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  On the other hand, as an external additive capable of assisting the cleaning property, that is, as a cleaning property improving agent for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium, for example, zinc stearate, calcium stearate, stearic acid And fatty acid metal salts such as polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  The volume average particle size of the toner of the present invention is preferably 3 μm or more and 7 μm or less, and the ratio of the volume average particle size to the number average particle size is preferably 1.2 or less. Moreover, it is preferable that the component whose particle size is 2 micrometers or less is 10 number% or less.

<Developer>
Further, the developer of the present invention has the toner of the present invention, but may further include a component such as a carrier. As a one-component developer composed of a toner, a two-component developer composed of a toner and a carrier, etc. Although it can be used, it is preferable to use a two-component developer in a high-speed printer or the like corresponding to the recent improvement in information processing speed from the viewpoint of improving the life. Such a developer can be used in various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

  When the developer of the present invention is used as a one-component developer, there is little fluctuation in the particle size of the toner even if the balance of the toner is performed, and the blade for filming the toner on the developing roller and thinning the toner The toner can be prevented from being fused to a member such as the above, and good and stable developability can be obtained even in the long-term use (stirring) of the developing device.

In addition, when the developer of the present invention is used as a two-component developer, even if the toner balance for a long period of time is performed, there is little fluctuation in the particle size of the toner, and it is good and stable even with long-term stirring in the developing device. Developability is obtained.
The content of the carrier in the two-component developer is preferably 90 to 98% by mass, and more preferably 93 to 97% by mass.

[Carrier]
The carrier is not particularly limited, but preferably has a core material and a resin layer covering the core material.

(Core material)
As a material of the core material, for example, 50 to 90 emu / g of manganese-strontium (M
n-Sr) -based materials, manganese-magnesium (Mn-Mg) -based materials and the like may be mentioned, and two or more of them may be used in combination. In terms of securing image density, it is preferable to use a highly magnetized material such as iron powder (100 emu / g or more) or magnetite (75 to 120 emu / g) as the core material. In addition, a copper-zinc (Cu-Zn) system (30 to 80 emu / g) is used as a core material in that it can weaken the hitting of the photoconductor in which the toner is in a spiked state, and is advantageous in improving the image quality. It is preferable to use a weakly magnetized material such as

  The core material preferably has a volume average particle size (D50) of 10 to 150 μm, more preferably 20 to 80 μm. If D50 is less than 10 μm, fine particles increase in the particle size distribution of the carrier, so that the magnetization per particle may decrease and carrier scattering may occur. On the other hand, if D50 exceeds 150 μm, the specific surface area of the carrier may decrease and toner scattering may occur. As a result, the reproducibility of the solid portion may be deteriorated particularly in a full color with many solid portions.

(Resin layer)
Examples of the material of the resin layer include amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, polyester resins, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoro Ethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, terpolymer of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Examples thereof include fluoroterpolymers such as polymers, silicone resins, and the like, and two or more of them may be used in combination.

  Examples of the amino resin include urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin. Examples of the polyvinyl resin include acrylic resin, polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, and polyvinyl butyral. Examples of polystyrene resins include polystyrene and styrene-acrylic copolymers. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester-based resin include polyethylene terephthalate and polybutylene terephthalate.

  Moreover, a resin layer may contain conductive powder etc. as needed. Examples of the conductive powder material include metals, carbon black, titanium oxide, tin oxide, and zinc oxide. The conductive powder preferably has an average particle size of 1 μm or less. When the average particle size exceeds 1 μm, it may be difficult to control the electric resistance.

The resin layer is formed by, for example, preparing a coating solution by dissolving a silicone resin or the like in a solvent, and then applying the coating solution to the surface of the core material by a known coating method, followed by drying and baking. Can do. Examples of the application method include a dipping method, a spray method, and a brush coating method. Examples of the solvent include toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, celsol butyl acetate and the like. Furthermore, the baking method may be either an external heating method or an internal heating method, for example, a method using a fixed electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, or the like, or using a microwave. Methods and the like.
The content of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. If the content is less than 0.01% by weight, a uniform resin layer may not be formed on the surface of the core material. If the content exceeds 5.0% by weight, the resin layer becomes too thick and the carriers are formed. Particles may be generated and a uniform carrier may not be obtained.

<Development method, etc.>
Furthermore, the developer of the present invention can be suitably used for image formation by various known electrophotographic methods such as a magnetic one-component development method, a non-magnetic one-component development method, and a two-component development method.

<Developer container>
The developer container of the present invention contains the developer of the present invention, but the container is not particularly limited and can be appropriately selected from known ones, but has a container body and a cap. Etc.
In addition, the size, shape, structure, material, etc. of the container body are not particularly limited, but the shape is preferably cylindrical, etc., spiral irregularities are formed on the inner peripheral surface, and by rotating, It is particularly preferable that the developer as the contents can move to the discharge port side, and that some or all of the spiral irregularities have a bellows function. Furthermore, the material is not particularly limited, but is preferably one having good dimensional accuracy. For example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, Examples thereof include resin materials such as polyacetal resin.
Since the developer container is easy to store and transport and has excellent handleability, the developer container can be detachably attached to a process cartridge, an image forming apparatus, etc., which will be described later, and used for replenishing the developer.

<Image forming method>
The image forming method of the present invention includes at least an electrostatic latent image forming step, a developing step, a transfer step, and a fixing step, and the toner is used in the developing step. In addition to the above steps, the image forming method of the present invention preferably further includes a cleaning step, and may include, for example, a static elimination step, a recycling step, a control step, and the like as necessary.

<Image forming apparatus>
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and the developing unit uses the toner. It is. Further, the image forming method of the present invention preferably further includes a cleaning unit in addition to the above units, and may include, for example, a static elimination unit, a recycling unit, a control unit, etc. as necessary. The speed is preferably 300 mm / s or more and 1500 mm / s or less.

  The image forming method of the present invention can be carried out using the image forming apparatus of the present invention, the electrostatic latent image forming step using an electrostatic latent image forming unit, and the developing step using a developing unit. The transfer step can be performed using a transfer unit, the fixing step can be performed using a fixing unit, and the other steps can be performed using other units.

  The electrostatic latent image forming step is a step of forming an electrostatic latent image on an electrostatic latent image carrier such as a photoconductive insulator or a photoconductor. The material, shape, structure, size and the like of the electrostatic latent image carrier are not particularly limited and can be appropriately selected from known ones, but the shape is preferably a drum shape. Examples of the photoreceptor include inorganic photoreceptors such as amorphous silicon and selenium, and organic photoreceptors such as polysilane and phthalopolymethine. Among these, an amorphous silicon photoconductor is preferable because of its long life.

  The electrostatic latent image is formed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then exposing it like an image, and can be formed using electrostatic latent image forming means. The electrostatic latent image forming means includes, for example, a charger that applies a voltage to the surface of the electrostatic latent image carrier and uniformly charges it, and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Have at least.

  The charger is not particularly limited. For example, a known contact charger including a conductive or semiconductive roll, brush, film, rubber blade, etc., non-contact charging using corona discharge such as corotron and scorotron. A vessel or the like can be used.

  The exposure device is not particularly limited as long as it can be exposed like an image to be formed on the surface of the electrostatic latent image carrier charged by the charger. For example, a copying optical system, a rod lens array system, a laser optical Various exposure devices such as an optical system and a liquid crystal shutter optical system can be used. In addition, you may employ | adopt the light back system which performs imagewise exposure from the back surface side of an electrostatic latent image carrier.

The developing step is a step of developing the electrostatic latent image with the developer of the present invention to form a toner image, and the visible image can be formed using a developing unit.
The developing means is not particularly limited as long as it can be developed with the developer of the present invention. For example, a developing device that contains the developer of the present invention and can apply toner to the electrostatic latent image in a contact or non-contact manner. A developing device equipped with the developer container of the present invention is preferable.

  The developing device may be either a dry developing method or a wet developing method, and may be either a single color developing device or a multicolor developing device. For example, the developer of the present invention may be obtained by friction stirring. Examples include a stirrer to be charged and a rotatable magnet roller. In the developing device, for example, the toner and the carrier are mixed and stirred, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. The magnet roller is disposed in the vicinity of the electrostatic latent image carrier, and a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted by the electrostatic latent image carrier. Move to the surface. As a result, the electrostatic latent image is developed with toner, and a toner image is formed on the surface of the electrostatic latent image carrier. The developer housed in the developing device is the developer of the present invention, but may be a one-component developer or a two-component developer.

  The transfer step is a step of transferring the toner image to a recording medium by charging the electrostatic latent image carrier on which the toner image is formed using, for example, a transfer charger, and transferring the image using a transfer unit. be able to. At this time, the transfer step preferably includes a primary transfer step of transferring the toner image onto the intermediate transfer member and a secondary transfer step of transferring the toner image transferred onto the intermediate transfer member onto the recording medium. The transfer process includes a primary transfer process in which a toner image of two or more colors, preferably a full color toner, is used to transfer a toner image of each color onto an intermediate transfer member to form a composite toner image, and on the intermediate transfer member. It is more preferable to have a secondary transfer step of transferring the formed composite toner image onto a recording medium.

The transfer unit includes a primary transfer unit that transfers a toner image onto an intermediate transfer member to form a composite toner image, and a secondary transfer unit that transfers the composite toner image formed on the intermediate transfer member onto a recording medium. It is preferable. The intermediate transfer member is not particularly limited, and examples thereof include an endless transfer belt. The transfer means (primary transfer means and secondary transfer means) preferably has at least a transfer device that charges and separates the toner image formed on the electrostatic latent image carrier on the recording medium side. The transfer means can have one or more transfer devices.
Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.
The recording medium is not particularly limited, and can be appropriately selected from known recording media (recording paper).

  The fixing step is a step of fixing the toner image transferred to the recording medium, and can be fixed using a fixing unit. When two or more color toners are used, the toner may be fixed each time the toner of each color is transferred to the recording medium, or the toner of all colors may be transferred to the recording medium and fixed in a stacked state. Also good. The fixing unit is not particularly limited, and a heat fixing method using a known heating and pressing unit can be employed. Examples of the heating and pressing means include a combination of a heating roller and a pressing roller, a combination of a heating roller, a pressing roller, and an endless belt. At this time, heating temperature is 80-200 degreeC normally. If necessary, for example, a known optical fixing device may be used together with the fixing means.

Conventionally, when such a heat fixing method is employed, more than half of the power consumption in the image forming apparatus is consumed for the heat treatment in the heat fixing method fixing device. On the other hand, from the viewpoint of measures against environmental problems in recent years, an image forming apparatus with low power consumption (energy saving) is desired.
For example, in the 1999 International Energy Agency (IEA) DSM (Demand-Side Management) program, there is a technology procurement project for next-generation copiers, and the required specifications are published. For copiers of 30 cpm or more, achieve dramatic energy savings compared to conventional copiers so that standby time is within 10 seconds and standby power consumption is 10 to 30 watts (depending on the copying speed). Is required. For this reason, it is essential to save energy in a fixing device with high power consumption.

In order to achieve the above requirements and shorten the waiting time, it is considered that it is an essential technical achievement matter to lower the melting start temperature of the toner to lower the fixing temperature when it can be used. In order to cope with such low-temperature fixing, the above-described toner of the present invention is used in the image forming apparatus of the present invention.
Further, on the fixing device side, improvements for energy saving are being promoted. Among the heat fixing methods, a heat roller fixing method in which fixing is performed by directly pressing a heating roller against a toner image on a recording medium is widely used because of its high thermal efficiency. Further, it is possible to use a heating roller having a low heat capacity to improve the temperature responsiveness of the toner. However, since the specific heat capacity is reduced, the temperature difference between the portion through which the recording medium passes and the portion through which the recording medium does not pass increases, and toner adheres to the fixing roller. For this reason, a so-called hot offset phenomenon occurs in which the toner is fixed to the non-image portion on the recording medium after the fixing roller makes one round. Therefore, the demand for toner with respect to hot offset resistance as well as low-temperature fixability is becoming stricter. For this reason, the toner of the present invention is used which has a low temperature fixability and a hot offset resistance.

  The neutralization step is a step of neutralizing by applying a neutralization bias to the electrostatic latent image carrier, and the neutralization can be performed using a neutralization unit. The neutralization means is not particularly limited as long as a neutralization bias can be applied to the electrostatic latent image carrier. For example, a neutralization lamp can be used.

  The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be cleaned using a cleaning unit. The cleaning means is not particularly limited as long as the toner remaining on the electrostatic latent image carrier can be removed. For example, a magnetic brush cleaner, electrostatic brush cleaner, magnetic roller cleaner, blade cleaner, brush cleaner, web A cleaner or the like can be used.

  The recycling step is a step of recycling the toner removed in the cleaning step to the developing unit, and can be recycled using the recycling unit. The recycling unit is not particularly limited, and a known transport unit or the like can be used.

A control process is a process of controlling each process, and can be controlled using a control means.
The control means is not particularly limited as long as the operation of each means can be controlled. For example, a sequencer, a computer, or the like can be used.

  FIG. 2 shows an example of the image forming apparatus of the present invention. The image forming apparatus (100A) includes a photosensitive drum (10) as an electrostatic latent image carrier, a charging roller (20) as a charging unit, an exposure device (not shown) as an exposure unit, and a developing unit. A developing device (40), an intermediate transfer member (50), a cleaning device (60) having a cleaning blade as a cleaning means, a static elimination lamp (70) as a static elimination means, and a fixing device as a fixing means. .

  The intermediate transfer member (50) is an endless belt, is stretched by three rollers (51) arranged on the inner side thereof, and can move in the direction of the arrow. A part of the three rollers (51) also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member (50). Further, a cleaning device (90) having a cleaning blade is disposed in the vicinity of the intermediate transfer member (50). Further, a transfer roller (80) as a transfer means capable of applying a transfer bias for transferring (secondary transfer) the toner image onto the recording paper (95) is disposed to face the intermediate transfer member (50). Has been. Further, around the intermediate transfer member (50), a corona charger (52) for applying a charge to the toner image on the intermediate transfer member (50) includes a photosensitive drum (10) and the intermediate transfer member (50). ) And the contact portion between the intermediate transfer member (50) and the recording paper (95).

  A developing device (40) for each color of black (K), yellow (Y), magenta (M), and cyan (C) includes a developer container (41), a developer supply roller (42), a developing roller ( 43). The fixing device includes a heating roller and a pressure roller.

  In the image forming apparatus (100A), the photosensitive drum (10) is uniformly charged by the charging roller (20), and then the exposure light L is imaged onto the photosensitive drum (10) by an exposure apparatus (not shown). Exposure is performed to form an electrostatic latent image. Next, the electrostatic latent image formed on the photosensitive drum (10) was developed by supplying a developer from the developing device (40) to form a toner image, and then applied from the roller (51). The toner image is transferred (primary transfer) onto the intermediate transfer member (50) by the transfer bias. Further, the toner image on the intermediate transfer member (50) is given a charge by the corona charger (52) and then transferred (secondary transfer) onto the recording paper (95). The recording paper (95) onto which the toner image has been transferred is heated while being pressurized by the heating roller and the pressure roller of the fixing device, thereby being heated and melted and fixed on the recording paper (95). On the other hand, the toner remaining on the photosensitive drum (10) is removed by the cleaning device (60), and the photosensitive drum (10) is once discharged by the discharging lamp (70).

  FIG. 3 shows another example of the image forming apparatus of the present invention. The image forming apparatus (100B) is a tandem color image forming apparatus, and includes a copying apparatus main body (150), a paper feed table (200), a scanner (300), and an automatic document feeder (ADF) (400). Have.

  The copying machine main body (150) is provided with an endless belt-like intermediate transfer member (50) at the center. The intermediate transfer member (50) is stretched around the support rollers (14), (15) and (16), and can rotate in the direction of the arrow. A cleaning device (17) for removing toner remaining on the intermediate transfer member (50) is disposed in the vicinity of the support roller (15). The intermediate transfer member (50) stretched by the support roller (14) and the support roller (15) is provided with four image forming units (18, yellow, cyan, magenta, and black) along the transport direction. ) Are arranged in parallel with each other, and a tandem developing device (120) is arranged.

As shown in FIG. 4, the image forming means (18) for each color includes a photosensitive drum (10), a charging roller (20) for uniformly charging the photosensitive drum (10), and a photosensitive drum (10). A developing device (40) for developing a toner image by developing the electrostatic latent image formed on the toner with a developer of each color of black (K), yellow (Y), magenta (M), and cyan (C); A transfer roller (80) for transferring the toner image onto the intermediate transfer member (50), a cleaning device (60), and a static elimination lamp (70).
An exposure device (30) is disposed in the vicinity of the tandem developing device (120). The exposure device (30) exposes the exposure light L on the photosensitive drum (10) to form an electrostatic latent image.

  Further, a secondary transfer device (22) is arranged on the opposite side of the intermediate transfer member (50) from the side where the tandem developing device (120) is arranged. The secondary transfer device (22) includes a secondary transfer belt (24), which is an endless belt stretched between a pair of rollers (23), and a recording sheet conveyed on the secondary transfer belt (24). The intermediate transfer members (50) can contact each other.

A fixing device (25) is arranged in the vicinity of the secondary transfer device (22). Fixing device (2
5) has a fixing belt (26) which is an endless belt, and a pressure roller (27) which is arranged to be pressed against the fixing belt (26). One of the tension rollers of the fixing belt (26) is a heating roller. In addition, a reversing device (28) for reversing the recording paper in order to form images on both sides of the recording paper is disposed in the vicinity of the secondary transfer device (22) and the fixing device (25).

  A full color image formation (color copy) in the image forming apparatus (100B) having such a configuration will be described. First, a document is set on the document table (130) of the automatic document feeder (ADF) (400) or the automatic document feeder (400) is opened and the document is placed on the contact glass (32) of the scanner (300). Is set and the automatic document feeder (400) is closed. Next, when a start switch (not shown) is pressed, when the document is set on the automatic document feeder (400), the document is transported and moved onto the contact glass (32), and then the contact glass ( 32) When an original is set on the scanner (300), the scanner (300) is immediately driven, and the first traveling body (33) and the second traveling body (34) travel. At this time, light from the light source is irradiated by the first traveling body (33), and reflected light from the document surface is reflected by the mirror in the second traveling body (34) and read through the imaging lens (35). Light is received by the sensor (36). Thus, a color original (color image) is read, and image information of each color of black, yellow, magenta, and cyan is obtained.

  Further, after the electrostatic latent image of each color is formed on the photosensitive drum (10) based on the obtained image information of each color by the exposure device (30), the electrostatic latent image of each color is developed for each color. Development is performed with the developer supplied from the container (40), and a toner image of each color is formed. The formed toner images of the respective colors are sequentially transferred (primary transfer) on the intermediate transfer body (50) that is rotated and moved by the support rollers (14), (15), and (16). ) To form a composite toner image.

  In the paper feed table (200), one of the paper feed rollers (142) is selectively rotated to feed the recording paper from one of the paper feed cassettes (144) provided in multiple stages in the paper bank (143) for separation. Each sheet is separated by a roller (145), sent to a paper feed path (146), transported by a transport roller (147), guided to a paper feed path (148) in the copier body (150), and a registration roller (49 ) And stop. Alternatively, the recording paper on the manual feed tray (54) is fed out, separated one by one by the separation roller (58), put into the manual feed path (53), and abutted against the registration roller (49) and stopped. The registration roller (49) is generally used while being grounded, but may be used in a state where a bias is applied in order to remove paper dust from the recording paper.

  Then, the registration roller (49) is rotated in time with the composite toner image formed on the intermediate transfer member (50), and the recording paper is placed between the intermediate transfer member (50) and the secondary transfer device (22). The composite toner image is transferred (secondary transfer) onto the recording paper.

The recording paper on which the composite toner image has been transferred is conveyed by the secondary transfer device (22) and sent out to the fixing device (25). In the fixing device (25), the composite toner image is fixed on the recording paper by being heated and pressed by the fixing belt (26) and the pressure roller (27). Thereafter, the recording paper is switched by the switching claw (55), discharged by the discharge roller (56), and stacked on the discharge tray (57). Alternatively, it is switched by the switching claw (55), reversed by the reversing device (28), guided again to the transfer position, and after an image is formed on the back surface, it is ejected by the ejection roller (56) and ejected by the ejection tray ( 57) Stacked on top.
The toner remaining on the intermediate transfer member (50) after the composite toner image is transferred is removed by the cleaning device (17).

FIG. 5 shows an example of the process cartridge of the present invention. The process cartridge (110) includes a photosensitive drum (10), a corona charger (52), a developing device (40), a transfer roller (80), and a cleaning device (90).
The process cartridge of the present invention is detachably molded in various image forming apparatuses, and includes an electrostatic latent image carrier that carries an electrostatic latent image, and an electrostatic latent image carried on the electrostatic latent image carrier. And at least developing means for forming a toner image by developing with the developer of the present invention. The process cartridge of the present invention may further include other means as necessary.
The developing means includes at least a developer container that contains the developer of the present invention and a developer carrier that carries and conveys the developer contained in the developer container. The developing means may further include a regulating member or the like for regulating the thickness of the developer carried.

EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. The “parts” described here are “parts by mass”.
First, the measurement method used in the present invention will be described.

<Measurement of melt viscosity of release agent>
The melt viscosity of the release agent was measured under the following conditions.
First, 60 g of a sample is put into a 100 ml test tube, set in a drive lock bath EB-303 (manufactured by ASONE), and the temperature is raised to 100 ° C. After reaching 100 ° C., the viscosity is measured at 100 rpm using a rotary viscometer DV-E (Brookfield) and rotor LV # 1. The viscosity after 3 minutes from the start of rotation was measured, and the melt viscosity of the release agent at 100 ° C .: η (w) was measured.

<Toner melt viscosity>
The melt viscosity of the toner was measured under the following conditions.
First, as a sample, 1 g of toner was pressed with a molding machine to produce pellets for a flow tester. The pellet was set in an elevated flow tester CFT100 type (manufactured by Shimadzu Corporation), and the viscosity at 100 ° C. when measured under the following conditions was measured to measure the melt viscosity of the release agent at 100 ° C .: η (t) it can.
"Measurement condition"
-Die diameter: 0.50 mm, Die length: 1.0 mm
-Measurement temperature: 40 ° C to 200 ° C
・ Raising rate: 3.0 ° C / min
・ Test weight: 30kgf
・ Stroke: 8.0mm

<Glass transition temperature (Tg) of toner>
The glass transition point (Tg) is specifically determined by the following procedure. The measurement was performed under the following measurement conditions using TA-60WS and DSC-60 manufactured by Shimadzu Corporation.
"Measurement condition"
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature condition Start temperature: 20 ℃
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. The analysis method is to specify a range of ± 5 ° C around the point showing the maximum peak on the lowest temperature side of the DrDSC curve, which is the DSC differential curve of the second temperature rise, and use the peak analysis function of the analysis software to determine the peak temperature. Ask. Next, the maximum endothermic temperature of the DSC curve is determined using the peak analysis function of the analysis software in the range of the peak temperature + 5 ° C. and −5 ° C. in the DSC curve. The temperature shown here corresponds to the Tg of the toner.

<Dispersion diameter of crystalline polyester>
Although it does not specifically limit as a measuring method of the dispersion diameter of crystalline polyester, For example, the following method can be used. First, toner particles are embedded in an epoxy resin, cut into ultrathin sections of about 100 nm, and dyed with ruthenium tetroxide. Next, using a transmission electron microscope (TEM), observation was performed at a magnification of 10,000 times, and the photographed photograph was subjected to image evaluation, and the crystalline polyester was completely crystallized (excluding the compatibilized portion). And the dispersion diameter can be measured.

<Dispersed diameter of release agent>
As the particle size of the release agent, an average major axis in 100 toner particles was calculated from a TEM image.

<Resin fine particle dispersion diameter in dispersion>
The dispersion particle size in the dispersion of resin fine particles was measured using “LA-920” (manufactured by Horiba Ltd.). During the measurement of LA-920, analysis was performed using an application dedicated to LA-920 (Ver3.32) (manufactured by Horiba Ltd.). Specifically, LA-920 is measured by adjusting the optical axis with a solvent in which a wax dispersion is dispersed, and then measuring the background. Thereafter, circulation is started and a wax dispersion is dropped. After confirming that the transmittance is stable, an ultrasonic wave is irradiated under the following conditions. The dispersion particle diameter was measured under the condition that the transmittance value was in the range of 70 to 95% after irradiation. It is important for this measuring apparatus to measure under the condition that the transmittance value of LA-920 is in the range of 70 to 95% from the viewpoint of measurement reproducibility of the particle diameter. In addition, if the transmittance deviates from the above value after ultrasonic irradiation, it is necessary to perform measurement again. In order to obtain the transmittance value, it is necessary to adjust the dripping amount of the dispersion.
Measurement and analysis conditions were set as follows.
・ Data acquisition frequency: 15 times ・ Relative refractive index: 1.20
・ Circulation: 5
・ Ultrasonic intensity: 7

<Weight average molecular weight (Mw) of crystalline polyester resin>
The weight average molecular weight in this invention can be measured with the following method, for example.
Gel permeation chromatography (GPC) measuring device: GPC-8220GPC (manufactured by Tosoh Corporation)
・ Column: TSKgel SuperHZM-H 15cm triple (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
Solvent: o-dichlorobenzene Flow rate: 0.35 ml / min
Sample: 0.4 ml of 0.15% sample was injected Sample pretreatment: The sample was dissolved in o-dichlorobenzene (containing a stabilizer, manufactured by Wako Pure Chemical Industries, Ltd.) at 0.15 wt% and then filtered through a 0.2 μm filter. The filtrate is used as a sample.
100 μl of the o-dichlorobenzene sample solution is injected and measured.
In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the number of counts. As a standard polystyrene sample for preparing a calibration curve, Showd 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.

<Number average molecular weight (Mn) of crystalline polyester resin>
The o-dichlorobenzene-soluble content of the resin alone was measured by GPC.
The conditions for molecular weight measurement by GPC are as follows.
Device: HLC-8120 manufactured by Tosoh Corporation
Column: TSK GEL GMH6 2 (Tosoh Corporation)
Measurement temperature: 25 ° C
Sample solution: 0.25 wt% o-dichlorobenzene solution Solution injection amount: 200 μl
Detector: Refractive index detector The molecular weight calibration curve was prepared using standard polystyrene.

<Average toner particle size>
In the present invention, the particle size distribution is measured using a Coulter counter method.
Examples of the particle size distribution measuring apparatus include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter).
In the present invention, a PC-9801 personal computer (manufactured by NEC Corporation) is connected to the Coulter Counter TA-II type measuring device via an interface (manufactured by Nikka Giken) which outputs the number distribution and volume distribution. Measure the particle size distribution.
Specifically, first, 0.1 to 5 ml of a surfactant (preferably alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of the electrolytic solution. The electrolytic solution is prepared by preparing an aqueous solution of about 1% by weight using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Next, 2 to 20 mg of the sample is added and suspended, and then dispersed with an ultrasonic disperser for 1 to 3 minutes. Using the 100 μm aperture, the volume and number of toners are measured from the obtained dispersion, and the volume distribution and number distribution are calculated.
The channel is 2.00 μm or more and less than 2.52 μm, 2.52 μm or more and less than 3.17 μm, 3.17 μm or more and less than 4.00 μm, 4.00 μm or more and less than 5.04 μm, 5.04 μm or more and less than 6.35 μm, 6.35 μm or more and less than 8.00 μm, 8.00 μm or more and less than 10.08 μm, 10.08 μm or more and less than 12.70 μm, 12.70 μm or more and less than 16.00 μm, 16.00 μm or more and less than 20.20 μm, 20.20 μm or more and 25 or more The target is particles having a particle size of 2.00 μm or more and less than 40.30 μm using 13 channels of less than 40 μm, 25.40 μm or more and less than 32.00 μm and 32.00 μm or more and less than 40.30 μm.

<Production Example 1>
Synthesis of crystalline polyester resin 1 In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1,120-decanedioic acid 2120 g, 1,8-octanediol 1520 g, 1,6-hexanediol and 4.9 g of hydroquinone were added, reacted at 180 ° C. for 10 hours, heated to 200 ° C. for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester. Resin 1 was obtained. The properties of the obtained resin are shown in Table 1.

<Production Example 2>
Synthesis of crystalline polyester 2 resin In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 2,120 g of 1,10-decanedioic acid, 1700 g of 1,8-octanediol, , 6-hexanediol 1000 g and hydroquinone 4.9 g, reacted at 180 ° C. for 10 hours, heated to 200 ° C. for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester. Resin 2 was obtained. The properties of the obtained resin are shown in Table 1.

<Production Example 3>
Synthesis of crystalline polyester resin 3 Adipic acid 2200 g, 1,6-hexanediol 1620 g, 1,4-butanediol were added to a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. After adding 1000 g and 5.2 g of hydroquinone and reacting at 170 ° C. for 8 hours, the temperature was raised to 190 ° C. and reacted for 3 hours, and further reacted at 8.3 kPa for 2 hours to obtain a crystalline polyester resin 3. . The properties of the obtained resin are shown in Table 1.

<Production Example 4>
Synthesis of crystalline polyester resin 4 In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 1,120-decanedioic acid 2120 g, 1,8-octanediol 1000 g, , 4-butanediol 1520 g and hydroquinone 3.9 g, reacted at 180 ° C. for 10 hours, heated to 200 ° C. for 3 hours, further reacted at 8.3 kPa for 1.5 hours to produce crystals Resin polyester resin 4 was obtained. The properties of the obtained resin are shown in Table 1.

<Production Example 5>
Synthesis of crystalline polyester resin 5 Adipic acid 2150 g, 1,6-hexanediol 1000 g, 1,4-butanediol were added to a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple. 1620 g and 5.2 g of hydroquinone were added, reacted at 180 ° C. for 7 hours, heated to 200 ° C. for 3 hours, further reacted at 8.3 kPa for 1.5 hours to obtain crystalline polyester resin 5. Obtained. The properties of the obtained resin are shown in Table 1.

<Production Example 6>
-Synthesis of mold release agent (ester wax) Fatty acid component and alcohol component are put in a reaction vessel together with a catalyst (effective amount) at a molar ratio shown in Table 2 and esterified at 240 ° C under a nitrogen stream. Release agents 1 to 5, 8 to 10, and 12 were synthesized.

(Note) In Table 2, the release agent 1 means that the composition comprises 10 parts of stearic acid, 90 parts of behenic acid, and 100 parts of lignoceryl alcohol. (The same applies hereinafter)
Table 3 shows the properties of the obtained release agent.

<Production Example 7>
-Synthesis of non-crystalline polyester resin 1 In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 229 parts of bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide Add 529 parts of 3-mole adduct, 100 parts of isophthalic acid, 108 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide, react at 230 ° C. for 10 hours at normal pressure, and further 5 hours under reduced pressure of 10-15 mmHg. After the reaction, 30 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 3 hours to obtain [Amorphous Polyester Resin 1]. [Amorphous polyester resin 1] had a weight average molecular weight of 6000 and a glass transition temperature (Tg) determined by DSC of 43 ° C.

<Production Example 8>
Synthesis of non-crystalline polyester resin 2 In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 250 parts of bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 500 parts of 3 mol adduct, 60 parts of isophthalic acid, 68 parts of terephthalic acid, 46 parts of adipic acid and 2 parts of dibutyltin oxide were added and reacted at 230 ° C. for 7 hours at normal pressure, and further for 6 hours at a reduced pressure of 10-15 mmHg. After the reaction, 50 parts of trimellitic anhydride was put in a reaction vessel and reacted at 180 ° C. and normal pressure for 2 hours to obtain [Amorphous Polyester Resin 2]. [Amorphous polyester resin 2] had a weight average molecular weight of 5500 and a glass transition temperature (Tg) determined by DSC of 35 ° C.

<Production Example 9>
Synthesis of non-crystalline polyester resin 3 In a 5-liter four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 229 parts of bisphenol A ethylene oxide side 2 mol adduct, bisphenol A propylene oxide 529 parts of 3-mole adduct, 70 parts of isophthalic acid, 98 parts of terephthalic acid, 46 parts of fumaric acid and 24 parts of -dodecenyl succinic acid, 2 parts of dibutyltin oxide, and inert by introducing nitrogen gas into the container After raising the temperature while maintaining the atmosphere, a copolycondensation reaction was performed at 230 ° C. for 12 hours, and then the pressure was gradually reduced at 230 ° C. to synthesize [Amorphous Polyester Resin 3]. [Amorphous polyester resin 3] had a weight average molecular weight of 6900 and a glass transition temperature (Tg) determined by DSC of 35 ° C.

<Production Example 10>
Preparation of Crystalline Polyester Resin Dispersion 1-1 Take 100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate in a 2 L metal container, heat and dissolve at 70 ° C., then in an ice-water bath at 20 ° C. / Quenched at the rate of minutes. After cooling, 200 g of amorphous polyester resin 1 was dissolved in the dispersion, 500 ml of glass beads (3 mmφ) were added thereto, and pulverized for 10 hours while maintaining the average liquid temperature at 23 ° C. with a batch type sand mill (made by Campehapio). [Crystalline polyester resin dispersion 1-1] having a volume average particle size of 0.8 μm was obtained.

<Production Example 11>
Preparation of Crystalline Polyester Resin Dispersion 1-2 100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate are placed in a metal 2 L container, heated and dissolved at 70 ° C., and then placed in an ice-water bath at 20 ° C. / Quenched at a minute rate. After cooling, 200 g of amorphous polyester resin 1 was dissolved in the dispersion, 500 ml of glass beads (3 mmφ) were added thereto, and pulverized for 10 hours while maintaining an average liquid temperature of 28 ° C. with a batch type sand mill (made by Campehapio). [Crystalline polyester resin dispersion 1-2] having a volume average particle size of 0.8 μm was obtained.

<Production Example 12>
-Preparation of Crystalline Polyester Resin Dispersion 1-3 100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were placed in a metal 2 L container and dissolved by heating at 70 ° C., then in an ice-water bath at 20 ° C. / Quenched at a minute rate. After cooling, 100 g of amorphous polyester resin 1 is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and pulverized for 8 hours while maintaining the average liquid temperature at 20 ° C. with a batch type sand mill (made by Campehapio). [Crystalline polyester resin dispersion 1-3] having a volume average particle size of 1.3 μm was obtained.

<Production Example 13>
Preparation of Crystalline Polyester Resin Dispersion 1-4 100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 70 ° C., and then placed in an ice-water bath at 20 ° C. / Quenched at a minute rate. After cooling, 200 g of amorphous polyester resin 1 is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and pulverized for 14 hours while maintaining an average liquid temperature of 23 ° C. with a batch type sand mill (made by Campehapio). [Crystalline polyester resin dispersion 1-4] having a volume average particle size of 0.5 μm was obtained.

<Production Example 14>
-Preparation of dispersion 1-5 of crystalline polyester resin-
100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate were placed in a metal 2 L container, heated and dissolved at 70 ° C., and then rapidly cooled in an ice water bath at a rate of 20 ° C./min. After cooling, 500 g of amorphous polyester resin 1 is dissolved in the dispersion, 500 ml of glass beads (3 mmφ) are added thereto, and pulverized for 10 hours while maintaining an average liquid temperature of 28 ° C. with a batch type sand mill device (Kampehapio). [Crystalline polyester resin dispersion 1-5] having a volume average particle size of 0.3 μm was obtained.

<Production Example 15>
Preparation of Crystalline Polyester Resin Dispersion 1-6 Take 100 g of [Crystalline Polyester Resin 1] and 400 g of ethyl acetate in a metal 2 L container, heat and dissolve at 70 ° C., then in an ice-water bath at 20 ° C. / Quenched at a minute rate. 500 ml of glass beads (3 mmφ) were added to this, and the mixture was pulverized for 10 hours while maintaining the average liquid temperature at 28 ° C. with a batch type sand mill (made by Campehapio Co., Ltd.). Liquid 1-6] was obtained.

<Production Example 16>
Production of Crystalline Polyester Resin Dispersion 2-1 In Production Example 10, the volume average particle size was 0 as in Production Example 10, except that crystalline polyester resin 2 was used instead of crystalline polyester resin 1. [Crystalline polyester resin dispersion 2-1] of 8 μm was obtained.

<Production Example 17>
-Production of Crystalline Polyester Resin Dispersion 2-2 In Production Example 13, the volume average particle size is 1 as in Production Example 13, except that the crystalline polyester resin 2 is used instead of the crystalline polyester 1. 2 μm of [Crystalline Polyester Resin Dispersion Liquid 2-2] was obtained.

<Production Example 18>
Production of Crystalline Polyester Resin Dispersion 3-1 In Production Example 10, the volume average particle size was 0 as in Production Example 10, except that crystalline polyester resin 3 was used instead of crystalline polyester resin 1. [Crystalline polyester resin dispersion 3-1] of 8 μm was obtained.

<Production Example 19>
-Preparation of Crystalline Polyester Resin Dispersion 3-2 100 g of [Crystalline Polyester Resin 3] and 400 g of ethyl acetate are placed in a metal 2 L container, heated and dissolved at 70 ° C, and then in an ice-water bath Quenched at a minute rate. After cooling, 300 g of amorphous polyester resin 1 was dissolved in the dispersion, 500 ml of glass beads (3 mmφ) were added thereto, and the mixture was pulverized for 10 hours while maintaining the average liquid temperature at 28 ° C. with a batch type sand mill (made by Campehapio). [Crystalline polyester resin dispersion 3-2] having a volume average particle size of 0.3 μm was obtained.

<Production Example 20>
Production of Crystalline Polyester Resin Dispersion 4-1 In Production Example 10, the volume average particle size is 1 as in Production Example 10 except that the crystalline polyester resin 4 is used instead of the crystalline polyester resin 1. 0.0 micrometer of [crystalline polyester resin dispersion 4-1] was obtained.

<Production Example 21>
Production of Crystalline Polyester Resin Dispersion 5-1 In Production Example 10, the volume average particle size is 1 as in Production Example 10 except that the crystalline polyester resin 5 is used instead of the crystalline polyester resin 1. [Crystalline polyester resin dispersion 5-1] of 0.0 μm was obtained.

<Production Example 22>
Production of Crystalline Polyester Resin Dispersion 1-7 In Production Example 10, the volume average particle diameter was the same as Production Example 10 except that amorphous polyester resin 2 was used instead of amorphous polyester resin 1. Of [Crystalline Polyester Resin Dispersion 1-7] having a thickness of 0.8 μm was obtained.

<Production Example 23>
Production of Crystalline Polyester Resin Dispersion 1-8 In Production Example 10, the volume average particle diameter was the same as Production Example 10 except that amorphous polyester resin 3 was used instead of amorphous polyester resin 1. Of [Crystalline Polyester Resin Dispersion 1-8] having a diameter of 0.8 μm was obtained.

<Production Example 24>
-Synthesis of wax dispersant In an autoclave reaction vessel equipped with a thermometer and a stirrer, 600 parts of xylene, 300 parts of low molecular weight polyethylene (Sunwax LEL-400, softening point 128 ° C, manufactured by Sanyo Chemical Industries, Ltd.) After sufficiently dissolving and purging with nitrogen, a mixed solution of 2310 parts of styrene, 270 parts of acrylonitrile, 150 parts of butyl acrylate, 78 parts of di-t-butylperoxyhexahydroterephthalate, and 455 parts of xylene was added at 175 ° C. over 3 hours. The solution was dropped to polymerize, and further kept at this temperature for 30 minutes. Next, the solvent was removed to synthesize a wax dispersant.

<Production Example 25>
Synthesis of masterbatch (MB) 1200 parts of water, carbon black (Printtex 35, manufactured by Dexa Corporation) [DBP oil absorption: 42 ml / 100 mg, pH: 9.5] 540 parts, 1200 parts of amorphous polyester resin, Henschel The mixture was mixed with a mixer (manufactured by Mitsui Mining Co., Ltd.), and the mixture was kneaded at 150 ° C. for 30 minutes using two rolls, rolled and cooled, and pulverized with a pulverizer to obtain [Masterbatch 1].

<Production Example 26>
Synthesis of polyester prepolymer In a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, 682 parts of bisphenol A ethylene oxide 2-mol adduct, 81 parts of bisphenol A propylene oxide 2-mol adduct, 283 parts terephthalic acid Then, 22 parts of trimellitic anhydride and 2 parts of dibutyltin oxide were added, reacted at 230 ° C. at normal pressure for 8 hours, and further reacted at reduced pressure of 10 to 15 mmHg for 5 hours to obtain [Intermediate Polyester 1]. [Intermediate Polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 51 mgKOH / g. Next, 410 parts of [Intermediate Polyester 1], 89 parts of isophorone diisocyanate and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours. Polymer 1] was obtained.
[Prepolymer 1] had a free isocyanate mass% of 1.53%.

[Example 1]
~ Creation of oil phase ~
In a container equipped with a stir bar and a thermometer, 378 parts of [Non-crystalline polyester resin 1], 110 parts of [Releasing agent 1], and 66 parts of [Wax dispersant] (60% by weight with respect to the releasing agent) %) And 947 parts of ethyl acetate were added, the temperature was raised to 80 ° C. with stirring, maintained at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour. Next, 500 parts of a master batch and 500 parts of ethyl acetate were placed in a container and mixed for 1 hour to obtain [Raw material solution 1]. [Raw material solution 1] 1324 parts are transferred to a container, and using a bead mill (Ultra Visco Mill, manufactured by Imex Co., Ltd.), a liquid feeding speed of 1 kg / hr, a disk peripheral speed of 6 m / sec, and 0.5 mm zirconia beads are 80 vol%. Carbon black and wax were dispersed under conditions of filling and 3 passes. Next, 1042.3 parts of a 65% ethyl acetate solution of [Amorphous Polyester Resin 1] was added, and one pass was performed with a bead mill under the above conditions to obtain [Pigment / Wax Dispersion 1]. The solid content concentration of [Pigment / Wax Dispersion 1] (130 ° C., 30 minutes) was 50%.

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

~ Synthesis of ketimine ~
In a reaction vessel equipped with a stirrer and a thermometer, 170 parts of isophoronediamine and 75 parts of methyltyl ketone were charged and reacted at 50 ° C. for 5 hours to obtain [ketimine compound 1].
The amine value of [ketimine compound 1] was 418 mgKOH / g.

~ Emulsification ~
[Pigment / wax dispersion 1] 664 parts, [Prepolymer 1] 111 parts, [Crystalline polyester resin dispersion 1-1] 258 parts, [Ketimine compound 1] 4.6 parts in a container, TK After mixing for 1 minute at 5000 rpm with a homomixer (made by Tokushu Kika), add 1200 parts of [Aqueous Phase 1] to the container and mix for 5 minutes at 11,000 rpm with a TK homomixer [Emulsion slurry 1] Got.
[Emulsion slurry 1] was put into a container equipped with a stirrer and a thermometer, and after removing the solvent at 30 ° C. for 8 hours, aging was carried out at 45 ° C. for 4 hours to obtain [Dispersion slurry 1].

~ Washing and drying ~
After 100 parts of [Dispersion Slurry 1] obtained above was filtered under reduced pressure, the following operations (1) to (4) were performed.
(1): 100 parts of ion-exchanged water was added to the filter cake, mixed with a TK homomixer (10 minutes at 12,000 rpm), and then filtered.
(2): 100 parts of a 10% aqueous sodium hydroxide solution was added to the filter cake of (1) above, mixed with a TK homomixer (30 minutes at 12,000 rpm), and then filtered under reduced pressure.
(3): 100 parts of 10% hydrochloric acid was added to the filter cake of (2) above, mixed with a TK homomixer (10 minutes at 12,000 rpm) and then filtered.
(4): 300 parts of ion-exchanged water was added to the filter cake of (3) above, dried with a TK homomixer at 45 ° C. for 48 hours with a mixed air dryer, and sieved with a mesh opening of 75 μm to obtain a toner base. .

~ Applying external additives ~
[Toner 1] was obtained by mixing 0.7 part of hydrophobic silica and 0.3 part of hydrophobic titanium oxide with 100 parts of the toner base using a Henschel mixer.

[Example 2]
In the emulsification step of Example 1, the same procedure as in Example 1 except that the crystalline polyester resin dispersion 2-1 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step [Toner 2] was obtained.

Example 3
In Example 1, [Toner 3] was prepared in the same manner as in Example 1 except that the crystalline polyester resin dispersion 3-1 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step. Obtained.

Example 4
In Example 1, [Toner 4] was prepared in the same manner as in Example 1 except that the crystalline polyester resin dispersion 1-2 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step. Obtained.

Example 5
[Toner 5] was obtained in the same manner as in Example 1 except that, in the emulsification step of Example 1, [Prepolymer 1] was changed to 100 parts and [Crystalline Polyester Resin Dispersion 1-3] was changed to 202 parts. It was.

Example 6
In Example 1, [Toner 6] was obtained in the same manner as in Example 1 except that the release agent 2 was used instead of the release agent 1 used in the oil phase preparation step.

Example 7
In Example 1, [Toner 7] was obtained in the same manner as in Example 1 except that the release agent 3 was used instead of the release agent 1 used in the oil phase preparation step.

Example 8
In Example 6, [Toner 8] was prepared in the same manner as in Example 6 except that the crystalline polyester resin dispersion 1-4 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step. Obtained.

Example 9
In Example 7, [Toner 9] was prepared in the same manner as in Example 7 except that the crystalline polyester resin dispersion 1-5 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step. Obtained.

Example 10
Example 6 In the emulsification step of Example 6, except that [Prepolymer 1] of the prepolymer and the crystalline polyester resin dispersion was changed to 100 parts and [Crystalline polyester resin dispersion 1-3] was changed to 202 parts. [Toner 10] was obtained in the same manner as above.

Example 11
Example 6 In the emulsification step of Example 7, except that [Prepolymer 1] of the prepolymer and the crystalline polyester resin dispersion was changed to 100 parts and [Crystalline polyester resin dispersion 1-3] was changed to 202 parts. [Toner 11] was obtained in the same manner as above.

Example 12
Example 8 except that in the emulsification step of Example 8, [Prepolymer 1] of the prepolymer and the crystalline polyester resin dispersion was changed to 100 parts and [Crystalline polyester resin dispersion 2-2] was changed to 202 parts. [Toner 12] was obtained in the same manner as above.

Example 13
Example 6 Except for changing the [Prepolymer 1] of the prepolymer and the crystalline polyester resin dispersion liquid to 124 parts and [Crystalline polyester resin dispersion liquid 3-2] to 202 parts in the emulsification step of Example 6. In the same manner as described above, [Toner 13] was obtained.

Example 14
[Toner 14] is the same as Example 6 except that [Prepolymer 1] is changed to 143.5 parts and [Crystalline polyester resin dispersion 1-1] is changed to 269 parts in the emulsification step of Example 6. Got.

Example 15
[Toner 15] was obtained in the same manner as in Example 6 except that, in the emulsification step of Example 6, [Prepolymer 1] was changed to 91 parts and [Crystalline Polyester Resin Dispersion 1-1] was changed to 252 parts. It was.

Example 16
[Toner 16] in the same manner as in Example 6 except that in the emulsification step of Example 7, [Prepolymer 1] was changed to 143.5 parts and [Crystalline Polyester Resin Dispersion 1-1] was changed to 269 parts. Got.

Example 17
[Toner 17] was obtained in the same manner as in Example 6, except that, in the emulsification step of Example 7, [Prepolymer 1] was changed to 91 parts and [Crystalline Polyester Resin Dispersion 1-1] was changed to 252 parts. It was.

Example 18
In Example 1, [Toner 18] was obtained in the same manner as in Example 1 except that the release agent 4 was used instead of the release agent 1 used in the oil phase preparation step.

Example 19
In Example 1, [Toner 19] was obtained in the same manner as in Example 1 except that the release agent 5 was used instead of the release agent 1 used in the oil phase preparation step.

Example 20
In Example 1, instead of the release agent 1 used in the oil phase preparation step, a release agent 6 (HNP-9, manufactured by Nippon Seiki Co., Ltd .: paraffin wax) was used. [Toner 20] was obtained.

Example 21
In Example 1, instead of the release agent 1 used in the oil phase preparation step, a release agent 7 (HNP-11, manufactured by Nippon Seiki Co., Ltd .: paraffin wax) was used. [Toner 21] was obtained.

[Example 22]
In Example 1, [Toner 22] was obtained in the same manner as in Example 1 except that the release agent 8 was used instead of the release agent 1 used in the oil phase preparation step.

Example 23
In the oil phase preparation step of Example 1, the amorphous polyester resin 2 is used instead of the amorphous polyester resin 1, and the crystalline polyester resin dispersion 1 is used instead of the crystalline polyester resin dispersion 1-1 in the emulsification step. [Toner 23] was obtained in the same manner as in Example 1 except that -7 was used.

Example 24
In the oil phase preparation step of Example 1, the amorphous polyester resin 3 is used instead of the amorphous polyester resin 1, and the crystalline polyester resin dispersion 1 is used instead of the crystalline polyester resin dispersion 1-1 in the emulsification step. [Toner 24] was obtained in the same manner as in Example 1 except that -8 was used.

[Comparative Example 1]
In the emulsification step of Example 1, the same procedure as in Example 1 except that the crystalline polyester resin dispersion 4-1 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step [Toner 25].

[Comparative Example 2]
In the emulsification step of Example 1, the same procedure as in Example 1 except that the crystalline polyester resin dispersion 5-1 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step [Toner 26].

[Comparative Example 3]
In the emulsification step of Example 1, the same procedure as in Example 1 except that the crystalline polyester resin dispersion 1-5 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step [Toner 27].

[Comparative Example 4]
In the emulsification step of Example 1, the same procedure as in Example 1 except that the crystalline polyester resin dispersion 1-6 was used instead of the crystalline polyester resin dispersion 1-1 used in the emulsification step [Toner 28].

[Comparative Example 5]
In Example 1, [Toner 29] was obtained in the same manner as in Example 1 except that the release agent 9 was used instead of the release agent 1 used in the oil phase preparation step.

[Comparative Example 6]
In Example 1, [Toner 30] was obtained in the same manner as in Example 1 except that the release agent 10 was used instead of the release agent 1 used in the oil phase preparation step.

[Comparative Example 7]
In Example 1, Example 1 was used except that the release agent 11 (Hi-Mic-1090, manufactured by Nippon Seiki Co., Ltd .: Microcrystalline wax) was used instead of the release agent 1 used in the oil phase preparation step. [Toner 31] was obtained in the same manner as above.

[Comparative Example 8]
In Example 1, [Toner 32] was obtained in the same manner as in Example 1 except that the release agent 12 was used instead of the release agent 1 used in the oil phase preparation step.

Table 4 shows the physical properties of the produced toner.

[Evaluation method and evaluation results]
The following evaluations were performed using the obtained developers (toners 1 to 32). The evaluation results in Examples 1 to 24 and Comparative Examples 1 to 8 are shown in Table 5.

<Fixability>
(Low temperature fixability)
A clear toner solid image and a solid image using colored toner are printed on type 6200 paper (Ricoh Co., Ltd.) with an image forming apparatus (Ricoh Co., Ltd .: Imagio MP C5000 modified machine) capable of printing 50 sheets of A4 size paper per minute using each developer. A copy test was conducted. Specifically, the cold offset temperature (fixing lower limit temperature) was determined by changing the fixing temperature, and evaluated according to the following criteria.
The lower fixing temperature is preferably lower because power consumption can be suppressed. If the temperature is 130 ° C. or lower, there is no problem in practical use.
(Low-temperature fixability evaluation criteria)
A: The lower limit fixing temperature is lower than 120 ° C .: The lower limit fixing temperature is 120 ° C. or higher and 130 ° C. or lower. Δ: The fixing lower limit temperature is equal to 130 ° C., but a slight cold offset occurs. Is higher than 130 ° C

(Hot offset property)
An unfixed image was produced in the same manner as described above, and the temperature was increased from 170 ° C. by 5 ° C. using an external fixing machine under the same conditions. At this time, the offset phenomenon in which the image was not sufficiently melted and the image was retransferred to the non-image area was observed on the fixing roller and the paper, and the temperature at which the image was not retransferred was defined as the non-offset temperature on the high temperature side.
[Evaluation criteria for hot offset resistance]
A: Hot offset generation temperature is 200 ° C. or higher. ○: Hot offset generation temperature is 185 ° C. or higher and lower than 195 ° C. Δ: Hot offset generation temperature is 175 ° C. or higher and lower than 185 ° C. ×: Hot offset generation temperature is 170 ° C. or lower.

<Releasability>
A clear toner solid image and a solid image using colored toner are copied and printed by NBS with an image forming apparatus (Ricoh Pro C751EX remodeling machine manufactured by Ricoh) that can print 75 sheets of A4 size paper per minute using each developer. The number of paper jams when 1,000 sheets were continuously output on paper <55> was measured, and the releasability was evaluated according to the following criteria.
[Evaluation criteria for releasability]
◎: No paper jam occurred ○: Paper jam occurred 1 to 3 times △: Paper jam occurred 3 times to 10 times or less ×: Paper jam occurred 10 times or more

<Image evaluation>
The toner was filled in a replenishing bottle and stored at 40 ° C. and 60% RH for 4 weeks. Using the image forming apparatus (Ricoh Pro C751EX remodeling machine manufactured by Ricoh Co., Ltd.) capable of printing 75 sheets of A4 size paper per minute with the developer and toner supply bottle, 100 solid sheets were continuously printed and evaluated according to the following criteria. did.
[Image Stability Evaluation Criteria]
◎: Uniform and good condition ○: Some white streaks with a width of less than 0.3 mm are seen, but no streaks appear in the image Δ: White streaks with a width of 0.3 mm or more are generated, and 20 out of 100 solid sheets State in which white streaks are observed in less than one sheet x: State in which white streaks having a width of 0.3 mm or more are generated and white streaks are observed in 20 or more of 100 solid sheets

<In-flight contamination>
In-machine contamination is measured by using a particle counter (KC01E, manufactured by Riontec Co., Ltd.) at the exhaust port of the main body using an image forming device (Ricoh Pro C751EX modified machine manufactured by Ricoh) that can print 75 sheets of A4 size paper per minute. The image was evaluated by the amount of dust when an image in which the printing area of each toner was 20% of the paper was output for 1 minute at 180 ° C. fixing using each developer of clear toner and colored toner.
[In-machine contamination resistance evaluation standard]
A: Dust is not detected.
○: Dust amount of less than 10,000 was detected.
○ to Δ: Dust amount of 10,000 or more and less than 50,000 was detected.
Δ: Dust amount of 50,000 or more and less than 100,000 was detected.
X: 100,000 or more dust amounts were detected.

<Heat resistant storage stability>
Each toner is filled in a 50 mL glass container, left in a constant temperature bath at 50 ° C. for 24 hours, cooled to 24 ° C., and measured for penetration by a penetration test (JIS K2235-1991). Thus, the heat resistant storage stability was evaluated. In addition, the greater the penetration, the better the heat-resistant storage stability. If the penetration is less than 5 mm, there is a high possibility that a problem will occur in use.
[Evaluation criteria for heat-resistant storage stability]
◎: Needle penetration is 25 mm or more ○: Needle penetration is 15 mm or more and less than 25 mm △: Needle penetration is 5 mm or more and less than 15 mm ×: Needle penetration is less than 5 mm

  From Table 5 above, the toners of Examples 1 to 24 enable both low-temperature fixability and storage stability, and are excellent in hot offset resistance and releasability. A toner that does not volatilize and can provide a stable image can be provided.

DESCRIPTION OF SYMBOLS 10 Photosensitive drum 18 Image forming means 20 Charging roller 22 Secondary transfer device 24 Secondary transfer belt 25 Fixing device 30 Exposure device 40 Developer 50 Intermediate transfer body 52 Corona charger 60 Cleaning device 70 Static elimination lamp 80 Transfer roller 90 Cleaning device 100A, 100B Image forming apparatus 110 Process cartridge 120 Tandem developer

Japanese Patent No. 4533061 Japanese Patent No. 4267427 Japanese Patent No. 4347174 Japanese Patent No. 4729950 Japanese Patent No. 4973129 Japanese Patent No. 3376019 Japanese Patent No. 3287733 Japanese Patent No. 4435434

Claims (9)

A toner containing at least a binder resin, a release agent, and a colorant, wherein the binder resin contains a crystalline polyester and an amorphous polyester, and the melting point Tmp of the crystalline polyester resin is 55 to 55. When the endothermic peak temperature derived from the crystalline polyester in the toner is Tm1 and the melt viscosity at 100 ° C. of the release agent is η (w) in the DSC measurement of the toner, the following formula (1 And a toner satisfying the requirements (2).
5 ° C. ≦ Tmp−Tm1 ≦ 15 ° C. (1)
2 mPa · s ≦ η (w) ≦ 20 mPa · s (2) The toner according to claim 1, wherein the toner satisfies the requirement of the following formula (3), where η (t) is a melt viscosity at 100 ° C. of the toner.
500 mPa · s ≦ η (t) ≦ 8000 mPa · s (3)   The toner according to claim 1, wherein the release agent is a wax having a melting point Tm2 of 65 to 80 ° C.   The toner according to claim 1, wherein the release agent is a monoester wax.   The molecular weight of the crystalline polyester resin is a weight average molecular weight (Mw) of 10,000 to 30,000, and a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) is 2 to 10. The toner according to any one of -4.   The toner according to claim 1, wherein the non-crystalline polyester resin has a glass transition temperature of 35 ° C. to 55 ° C.   The toner has toner base particles granulated from an aqueous medium dispersion or emulsion of an oil phase containing a toner material containing at least a crystalline polyester resin, an amorphous polyester resin, and a release agent. The toner according to claim 1, wherein the toner is a toner.   In an organic solvent, an active hydrogen group-containing compound, a binder resin precursor having a site capable of reacting with the active hydrogen group-containing compound, a crystalline polyester resin, an amorphous polyester resin, a colorant, a release agent, and a release agent An oil phase obtained by dissolving or dispersing a toner material containing at least a mold agent dispersant is dispersed in an aqueous medium to obtain an emulsified dispersion, and the binder resin precursor and the active hydrogen group are obtained in the emulsified dispersion. The toner according to claim 1, wherein the toner is obtained by reacting a contained compound with an organic solvent.   An electrostatic latent image carrier, a charging unit for charging the surface of the electrostatic latent image carrier, an exposure unit for exposing the charged electrostatic latent image carrier surface to form an electrostatic latent image, and a toner. And developing means for developing the electrostatic latent image to form a visible image, transfer means for transferring the visible image to a recording medium, and fixing means for fixing the transferred image transferred to the recording medium. An image forming apparatus having at least an image forming apparatus, wherein a process linear velocity of the image forming apparatus is 300 to 1500 mm / s, and the toner is the toner according to claim 1. apparatus.