JP6032064B2 - Toner, image forming apparatus, and process cartridge - Google Patents

Description

  The present invention relates to an image forming toner in electrophotography, an image forming apparatus using the toner, and a process cartridge.

In recent years, there has been a demand for low-temperature fixing of toner in electrophotography. This is due not only to energy saving by reducing the energy required for fixing, but also to the demand for higher speed and higher image quality of the electrophotographic image forming apparatus.
In general, the image quality decreases as the speed of an electrophotographic image forming apparatus increases. There are various factors in this, and among them, the greatest contribution is the influence of fixing failure in the fixing step of the image forming process.

  In the fixing process, an unfixed toner image on a recording medium represented by paper is fixed on the recording medium by heat and pressure to become a fixed image. If the system speed is high, the unfixed toner image is not fixed in the fixing process. The toner image cannot obtain a sufficient amount of heat, and as a result, fixing failure occurs, the surface of the final toner image becomes rough, or an afterimage phenomenon called cold offset occurs, resulting in a defective image. Therefore, when the system speed is increased, it is conceivable to raise the fixing temperature in order to prevent the image quality from being lowered. However, from the viewpoints of side effects of heat leaking from the fixing device on other processes in the image forming apparatus, acceleration of the consumption speed of the fixing member, and increase in energy consumption, increasing the fixing temperature cannot always be the best countermeasure.

  Therefore, particularly in a high-speed image forming apparatus, improvement in the fixing performance of the toner itself is required, and more specifically, in the fixing step, a toner having sufficient fixability at a lower temperature is required. .

  Conventionally, various studies have been made to improve toner fixing properties. For example, in order to improve the toner fixing performance, a method for controlling the thermal characteristics of the binder resin itself contained in the toner, represented by the glass transition temperature (Tg) and the softening temperature (T1 / 2), is known. . However, lowering the Tg of the resin causes deterioration in heat-resistant storage stability, and lowering the T1 / 2 temperature due to lowering the molecular weight of the resin causes problems such as occurrence of hot offset. For this reason, it is impossible to obtain a toner having all of the low-temperature fixability, the heat-resistant storage stability, and the hot offset resistance by simply controlling the thermal characteristics of the resin itself.

  As a proposal for modifying the type of binder resin in order to cope with low-temperature fixing, for example, instead of styrene-acrylic resin that has been widely used, polyester that has excellent low-temperature fixability and relatively good heat-resistant storage stability It has been proposed to use a resin (see Patent Documents 1 to 6).

For the purpose of improving low-temperature fixability, it has been proposed to add a specific non-olefinic crystalline polymer having sharp melt properties at the glass transition temperature to the binder (see Patent Document 7). However, in these proposals, it cannot be said that the molecular structure and molecular weight of the toner are optimized, and there is a problem that the toner does not have sufficient low-temperature fixability.

Further, it has been proposed to improve fixability by using a crystalline polyester having a sharp melt property as in the above-mentioned specific non-olefinic crystalline polymer for the toner (see Patent Documents 8 and 9). . However, in this proposal, the acid value and hydroxyl value of the crystalline polyester used in the toner are as low as 5 or less and 20 or less, respectively, and the affinity between paper and the crystalline polyester is low, so that the low-temperature fixability is not sufficient. There is a problem.
Furthermore, in this proposal, the molecular weight of the finally obtained toner and the presence state of the crystalline polyester are not optimized. Therefore, the toner using the proposed crystalline polyester has a problem that the excellent low-temperature fixability and heat-resistant storage stability due to the crystalline polyester cannot be sufficiently exhibited after the toner is actually made into a toner. Further, there is a problem that a temperature range capable of fixing a good image cannot be secured because no countermeasure against hot offset is taken.

  As a method for controlling the presence state of the crystalline polyester, for example, it has been proposed that an incompatible crystalline polyester resin and an amorphous polyester resin have a sea-island phase separation structure (Patent Document 10). reference). However, in this proposal, three types of resins including a crystalline polyester resin are used as a binder resin for the toner. However, when the sea-island structure of the crystalline polyester resin is maintained, the dispersion diameter of the crystalline polyester resin is increased. There is a problem that the film becomes too large, hindering heat-resistant storage stability, or the electric resistance becomes too low, resulting in a transfer defect in the transfer process, resulting in a rough image.

  In addition, in the DSC curve measured by the differential scanning calorimeter, by controlling the endothermic amount of the peak appearing on the endothermic side, the presence state of the crystalline polyester resin is controlled, and the effect of the crystalline polyester resin is exhibited significantly. It has been proposed to impart low-temperature fixability and heat-resistant storage stability to the toner (see Patent Document 11). However, in this proposal, it is assumed that a resin having a relatively high softening temperature is used as the amorphous polyester resin used in combination with the crystalline polyester resin. For this reason, the role of low-temperature fixability is secured by the crystalline polyester resin, so that the amount of the crystalline polyester resin inevitably increases, and the crystalline polyester resin and the non-crystalline polyester resin are compatible. There is a problem that the heat storage stability is deteriorated by melting.

  As a method for simultaneously satisfying low-temperature fixability, heat-resistant storage stability and hot offset resistance, it has been proposed that a crystalline polyester resin having an ester bond having a specific structure is contained in the toner (see Patent Document 12). However, in this proposal, since the content of the crystalline polyester resin is very large, there is a problem that the heat resistant storage stability is deteriorated due to the compatibility with the amorphous resin.

  As another method, it has been proposed to use two or more types of resins having different softening temperatures as the binder resin by defining the peak and half width of the molecular weight distribution of the toner and the amount of chloroform insoluble matter (Patent Document 13). reference). However, since this proposal does not use a crystalline polyester resin, there is a problem that the low-temperature fixability is insufficient as compared with the case where a crystalline polyester resin is used.

As described above, the present situation is that a toner that satisfies all of the low-temperature fixability, the hot offset resistance, and the heat stability at the same time in a balanced manner has not been obtained.
Further, in the above-mentioned patent documents, although the problems with respect to low-temperature fixability, heat-resistant storage stability, and hot offset resistance can be improved, there is a concern about deterioration of stress resistance in the developing process, which is a concern due to low-temperature fixing of toner. No countermeasure has been taken, and there is a concern that the toner may deteriorate due to development stress and the transferability, developability, and cleaning property may be deteriorated.
In particular, with the recent increase in development speed, there is an increasing demand for stress resistance for toner.

Patent Document 14 discloses that medium-sized inorganic fine particles having an average particle size of 20 to 40 μm are used in combination with external additives in order to improve the transferability, developability, and cleaning properties.
In addition, it is disclosed that inorganic fine particles having a large particle diameter are used in order to suppress burying of the external additive due to stress in the developing machine (see Patent Documents 15 to 17).
Initially, good cleaning properties, transferability, and developability can be obtained, but the adhesion of inorganic fine particles is non-uniform for each particle, and the inorganic fine particles are released over time, so that the inside of the developing machine or photosensitive Contamination around the body and sufficient transfer and cleaning properties may not be obtained.

  In addition, it is disclosed that external additive particles formed by combining a plurality of particles are used as external additives to improve stress resistance (see Patent Document 18). Utilizing the fact that these are amorphous, the burial resistance to the base material and the resistance to detachment from the base material are improved, but the primary particle size and the particle size ratio with the secondary particles constituting the particle are Since it is very wide, there is a concern that the particle size distribution of the composed particles may be very wide although not described. As a result, a large amount of particles having a small particle size or a small particle size ratio (close to a true sphere) are present, making it impossible to utilize the characteristics of the irregular shape and maintaining the burying resistance and separation resistance.

  An object of the present invention is to solve the above-described problems and achieve the following objects. That is, the present invention satisfies all of low-temperature fixability, hot offset resistance, and heat-resistant storage stability in a well-balanced manner, and can form a high-quality image with excellent chargeability and transferability over the long term. The object is to provide toner.

Means for solving the problems are as follows. That is,
The toner of the present invention is
A toner comprising at least a binder resin and a colorant, and toner having inorganic fine particles as external additives on the surface of the mother body,
The binder resin contains a crystalline polyester resin (A), an amorphous resin (B), and a composite resin (C) including a condensation polymerization resin unit and an addition polymerization resin unit,
The toner contains 1% by mass to 30% by mass of chloroform insoluble matter
The molecular weight distribution determined by gel permeation chromatography (GPC) determined by the tetrahydrofuran soluble content of the toner has a main peak between 1,000 and 10,000, and the half width of the molecular weight distribution is 15,000 or less. Yes,
In the endothermic peak measurement by differential scanning calorimetry (DSC) of the toner, the toner has an endothermic peak in the range of 90 ° C to 130 ° C,
Secondary particles observed by FE-SEM of the inorganic fine particles (D) having inorganic fine particles (D) in which a plurality of primary particles are combined to form secondary particles as the inorganic fine particles. When the average particle diameter of the 50% measured from the small particle side of the diameter Db is Db50 and the average particle diameter of the 10% measured from the small particle side is Db10, Db50 / Db10 is 1.20 or less. This is a characteristic toner.

  According to the present invention, the conventional problems can be solved and the object can be achieved, and the low temperature fixability, the hot offset resistance, and the heat resistant storage stability can be satisfied in a well-balanced manner. And toner capable of forming a high-quality image excellent in transferability and transferability.

It is a graph which shows the X-ray-diffraction result of crystalline polyester resin a6 used in the Example. 10 is a graph showing the X-ray diffraction results of the toner obtained in Example 24. It is a FE-SEM image of the amorphous silica particle which is an external additive, the arrow in (a) shows a secondary particle diameter, and the arrow in (b) shows a primary particle diameter. 1 is a schematic diagram illustrating an example of an image forming apparatus of the present invention. It is the schematic which shows an example of the image development apparatus used by this invention. It is a figure which shows an example of the image forming apparatus of this invention provided with the image development apparatus of FIG. It is a figure which shows another example of the image forming apparatus of this invention. It is a figure which shows an example of the process cartridge of this invention.

The technical idea of the present invention will be described in detail below.
In recent years, there has been a demand for low-temperature fixing of toner in electrophotography. This is due not only to the demand for energy saving by reducing the energy required for fixing, but also to the demand for higher speed and higher image quality of the electrophotographic image forming apparatus. Coupled with this trend, the demand for low-temperature fixing is increasing.

  To simply fix the toner at a low temperature, the softening temperature (T1 / 2) of the toner may be lowered. However, when the softening temperature is lowered, the glass transition temperature is also lowered, and the heat resistant storage stability is deteriorated. In addition, since the lower limit of the fixable temperature (fixing lower limit temperature) at which no problem occurs in image quality is lowered, the upper limit of fixing temperature (fixing upper limit temperature) is also lowered, so that the hot offset resistance is also impaired. Therefore, satisfying the three factors of low-temperature fixability, heat-resistant storage stability, and hot-offset resistance in a well-balanced manner is a very difficult proposition for electrophotographic image forming toner designers.

  As a result of intensive studies on the proposition, the present inventors have found the following technical concept and have solved the above problems.

When the crystalline polyester resin (A) is used as the binder resin used in the electrophotographic image forming toner, the toner can be provided with low-temperature fixability and heat-resistant storage stability due to its sharp melt property.
However, when the crystalline polyester resin (A) is used alone as the binder resin, the hot offset resistance is extremely deteriorated, so that the fixing temperature range becomes very narrow and cannot be practically used.
Therefore, the present inventors use a non-crystalline resin (B) containing a chloroform-insoluble content together with the crystalline polyester resin (A), thereby improving hot offset resistance and having a wide range of fixing temperatures. I thought I could make it.

  However, in the case of a toner formulated only with the crystalline polyester resin (A) and the amorphous resin (B), if the content of the amorphous resin (B) is large, the low-temperature fixability is reduced. End up. On the other hand, if the content of the crystalline polyester resin (A) is large, it will be compatible with components other than the chloroform-insoluble component of the amorphous resin (B) when melt-kneaded in the production process, and will not be bonded. Since the glass transition temperature of the entire resin is significantly reduced, the heat resistant storage stability is extremely deteriorated.

  Accordingly, as a result of further investigations, the present inventors have found that the main peak of the toner molecular weight distribution between 1,000 and 10,000 determined by gel permeation chromatography (GPC) determined from the tetrahydrofuran (THF) soluble content. And the half-width of the molecular weight distribution is 15,000 or less, the absolute amount of the low molecular weight is large and the molecular weight distribution is sharp, and the distribution of the crystalline polyester resin (A) is reduced. It was found that the hot-offset resistance of the non-crystalline resin (B) is not inhibited while the compatibility with the non-crystalline resin (A) is suppressed.

  However, even in this case, the risk to heat-resistant storage is not completely eliminated. Even if the compatibility of the crystalline polyester resin (A) is suppressed and the decrease in the glass transition temperature of the entire binder resin is suppressed, if the crystalline polyester resin (A) exists with a large dispersion diameter, In addition, the interface between the crystalline polyester resin (A) and the other binder resin tends to be a pulverized interface, and the crystalline polyester resin (A) tends to appear on the toner surface as a result even in the polymerization method. Since the crystalline polyester resin (A) is a sharp melt material, when it is present inside the toner particles, it exhibits excellent heat-resistant storage stability as described above, but it melts slightly even at temperatures below the glass transition temperature. When present on the surface of the toner particles, the slightly melted crystalline polyester resin (A) acts as a binder between the toner particles, and as a result, the heat resistant storage stability of the toner is deteriorated. This phenomenon is particularly remarkable in a crystalline polyester resin having a low crystallinity.

  Further, from the viewpoint of the electrical characteristics of the toner, there is a concern with a toner having a prescription combining the crystalline polyester resin (A) and the amorphous resin (B). That is, since the polyester resin having crystallinity has a relatively low electric resistance, the electric resistance of the toner tends to be low if it exists in the toner with a large dispersion diameter. If the electrical resistance is low and exceeds the allowable range, it may cause transfer failure in the transfer process during image formation. In particular, when the compatibility of the crystalline polyester resin (A) is suppressed for the purpose of maintaining the low-temperature fixability as described above, the crystalline polyester resin (A) can easily maintain a state with a large dispersion diameter, and the crystalline Since the electrical characteristics of the polyester resin (A) tend to be dominant in the toner, the electrical resistance tends to decrease.

  In addition, when a resistance adjusting agent (hereinafter, also referred to as “charge control agent”) is included as described later, the resistance adjusting agent cannot enter the domain of the crystalline polyester resin (A). In other binder resins, it exists in a relatively high concentration state. For this reason, the resistance adjusting agent tends to be confined in the toner as an aggregate, and the resistance tends to be excessively lowered. If the resistance adjuster is used only for the purpose of reducing the resistance, it may be solved by adjusting the prescription amount of the resistance adjuster. When serving also as a colorant, the prescription amount may not be reduced from the viewpoint of coloring power, and may not be adjusted to an optimum electrical resistance.

  The present inventors have intensively studied to solve these problems. As a result, a composite resin (C) including a condensation polymerization resin unit and an addition polymerization resin unit is further added to the combination of the crystalline polyester resin (A) and the amorphous resin (B). By prescribing, simultaneously solve the concern about the decrease in heat storage stability and the concern about the decrease in electrical resistance that are characteristically expressed when the crystalline polyester resin (A) and the amorphous resin (B) are combined. Found that is possible.

  The molecular weight distribution of the toner by GPC determined by the crystalline polyester resin (A) and the THF-soluble content has a main peak between 1,000 and 10,000, and the half width of the molecular weight distribution is 15 When the low molecular weight non-crystalline resin (B) having a molecular weight of 1,000 or less is used in combination with melt kneading, the viscosity of the resin is remarkably lowered, so that it is difficult to share the raw material, and the crystalline polyester resin (A) The dispersion diameter tends to be larger. Therefore, when the composite resin (C) is added together with the crystalline polyester resin (A) and the amorphous resin (B) and melt-kneaded, a moderate share is applied. Decentralization is encouraged.

  When the crystalline polyester resin (A) is in a finely dispersed state, the frequency of the crystalline polyester resin (A) appearing on the toner surface during pulverization decreases, and the heat resistant storage stability is dramatically improved. Moreover, since the crystalline polyester resin (A) is finely dispersed, it is possible to maintain an appropriate electrical resistance.

Furthermore, when the composite resin (C) is harder than the amorphous resin (B) having a molecular weight distribution peak in a relatively low molecular weight region, it is likely to exist at the pulverization interface at the time of pulverization. For this reason, there is an effect of reducing the probability that the amorphous resin (B) that is relatively easily present on the toner surface and has a low softening temperature appears on the toner surface, which contributes to improvement in heat-resistant storage stability.
In addition, since the hardness of the toner surface can be increased, there is little toner deterioration when physical stress is applied to the toner. In particular, when external additives are used, the phenomenon that the external additives are embedded in the toner base particles is improved, so the change in charging characteristics before and after stress is reduced, and stable image quality is provided over a long period of time. It becomes possible to do.

  In addition, a combination of the crystalline polyester resin (A) and the amorphous resin (B) and the composite resin (C) includes inorganic fine particles (D) in which a plurality of primary particles are combined to form secondary particles. And the average particle diameter of the 50% measured from the small particle side of the secondary particle diameter Db observed by the FE-SEM of the inorganic fine particles (D) is Db50, the 10% measured from the small particle side. When the average particle diameter of Db10 is Db10, the use of external additive inorganic fine particles having Db50 / Db10 of 1.20 or less has an effect on the stress resistance in the development process.

  By using the inorganic fine particles, the embedding of the additive, which is a concern due to the low softening of the base material due to low-temperature fixing, is suppressed. The electrostatic adhesion force is reduced, and sufficient transfer efficiency can be obtained. Furthermore, when mechanical stress over time is high as in a high-speed machine, or when the toner surface hardness becomes too high and the fixation of the additive becomes weak due to the use of composite resin (C), the removal of external additives is suppressed. In addition, since the external additive itself does not easily roll, the external additive rolls into the recess, and the function of the external additive is not lost, and sufficient transfer efficiency can be maintained over a long period of time.

  In the present invention, it is necessary that Db50 / Db10 is 1.20 or less in the particle size distribution of the average secondary particle diameter Db, and particularly preferably 1.15 or less. Here, Db50 represents the 50% average particle diameter measured from the small particle side of the secondary particle diameter observed by FE-SEM, and Db10 represents the 10% average particle diameter measured from the small particle side. . Db50 / Db10 indicates the ratio of small particles having a secondary particle size and center particle, and an increase in this value indicates that there are many particles having a small secondary particle size. That is, either the particle A existing in the state of primary particles in which coalescence has not progressed, or the coalescence has progressed, but the primary particles themselves have many particles B having a small particle diameter, or both. It means that. Such particles A or B do not have sufficient functions. The particle A cannot function as an irregular additive and is inferior in embedment resistance, so there is a concern that an abnormal image may be generated. On the other hand, B cannot function as a spacer effect, and is buried due to external stress. There is a high possibility that it cannot be suppressed. It is desirable to reduce these particles, that is, Db10 is large. When Db50 / Db10 exceeds 1.2, the number of the above-described particles A and B is too large, so that it is difficult to perform the function as a deformed additive characterized for suppressing burial.

The average value of the degree of adhesion G is preferably in the range of 1.5 to 4.0, and particularly preferably in the range of 2.0 to 3.0. When this is smaller than 1.5, the external additive tends to be buried in the base material, and the function of maintaining high transferability tends to be slightly inferior, for example, because the external additive tends to roll into the recess. On the other hand, when the ratio is larger than 4.0, the external additive is easily peeled off from the toner, and carrier contamination and the photoconductor are easily damaged.
Further, it is preferable that the number of inorganic fine particles having the above-mentioned degree of adhesion G of less than 1.3 is 10% by number or less. The degree of coalescence G has a distribution in production, and particles having a degree of coalescence of less than 1.3 are particles that have not undergone coalescence, and are present in a substantially spherical state. For this reason, it is difficult to perform the function as a variant additive characterized for suppressing burial.
Further, the secondary particle diameter of the fused silica is preferably in the range of 80 nm to 200 nm, particularly preferably in the range of 100 nm to 160 nm. If it is less than 80 nm, it is difficult to perform the function of the spacer effect, and it is difficult to suppress burying due to external stress. On the other hand, if it exceeds 200 nm, release from the toner tends to occur, and photoconductor filming tends to occur.

  However, even if the crystalline polyester resin (A), the non-crystalline resin (B) and the composite resin (C) are used in combination, if the kneaded toner is melt-kneaded in the manufacturing process, the heat of each resin of the toner raw material Each advantage due to the characteristics may not be exhibited. The main reason for this is that in the melt-kneading step, the molecular chains of the resin are cut and the molecular weight changes. In particular, when the chain of molecules insoluble in chloroform contained in the binder resin is broken, the molecular weight distribution of the entire toner becomes broad, which adversely affects the thermal characteristics caused by the non-crystalline resin (B). Fixability is impaired.

  As a result of extensive studies by the present inventors, for example, as described later, the crystalline polyester resin (A) is cooled while optimizing the share of the raw material resin by appropriately heating and kneading. By adopting a technique such as recrystallization in the process, the molecular weight distribution of the toner by GPC determined from the THF soluble content has a main peak between 1,000 and 10,000, and the molecular weight distribution By setting the full width at half maximum to 15,000 or less, the absolute amount of the low molecular weight is large and the molecular weight distribution becomes sharp, and the crystalline polyester resin (A), amorphous resin (B) and composite resin (C The present inventors have found that it is possible to provide a toner having a well-balanced balance of low-temperature fixability, heat-resistant storage stability, and hot-offset resistance, utilizing each of the above characteristics.

(toner)
The toner of the present invention contains at least a binder resin and a colorant, and further contains other components such as a charge control agent, a fatty acid amide compound, a release agent, and an external additive as necessary.
The binder resin contains a crystalline polyester resin (A), an amorphous resin (B), and a composite resin (C) including a condensation polymerization resin unit and an addition polymerization resin unit.
The toner is preferably manufactured by melt-kneading and further pulverizing.

<Crystalline polyester resin (A)>
The crystalline polyester resin (A) is not particularly limited as long as it is a polyester resin having crystallinity, and conventionally known ones can be appropriately used depending on the purpose. It preferably has an ester bond represented by the general formula (1).
_{- [OCO-R-COO- (} CH 2) n] - ··· formula (1)
(In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20).
The presence of the structure of the general formula (1) in the crystalline polyester resin (A) can be confirmed by, for example, solid C ¹³ NMR.

The linear unsaturated aliphatic divalent carboxylic acid residue is not particularly limited and may be appropriately selected depending on the intended purpose. For example, maleic acid, fumaric acid, 1,3-n-propene dicarboxylic acid And a linear unsaturated aliphatic residue derived from a linear unsaturated divalent carboxylic acid such as 1,4-n-butenedicarboxylic acid.
In the general formula (1), (CH ₂ ) _n represents a linear aliphatic dihydric alcohol residue. The linear aliphatic dihydric alcohol residue in this case is not particularly limited and may be appropriately selected depending on the intended purpose. For example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol , Residues derived from linear aliphatic dihydric alcohols such as 1,6-hexanediol.

The crystalline polyester resin (A) has an advantage that a linear unsaturated aliphatic dicarboxylic acid is used as its acid component, so that a crystal structure can be formed more easily than when an aromatic dicarboxylic acid is used, The function of the crystalline polyester resin can be exhibited more effectively.
The crystalline polyester resin (A) includes, for example, (I) a linear unsaturated aliphatic divalent carboxylic acid or a reactive derivative thereof (for example, acid anhydride, lower alkyl ester having 1 to 4 carbon atoms, acid halide) Etc.) and a polyhydric alcohol component consisting of (II) a linear aliphatic diol can be produced by a polycondensation reaction.

If necessary, a small amount of other polyvalent carboxylic acid may be added to the polyvalent carboxylic acid component. Examples of the other polyvalent carboxylic acid include (i) an unsaturated aliphatic having a branched chain. Divalent carboxylic acids, (ii) saturated aliphatic polyvalent carboxylic acids such as saturated aliphatic divalent carboxylic acids, saturated aliphatic trivalent carboxylic acids, (iii) aromatic divalent carboxylic acids, aromatic trivalent carboxylic acids, etc. Aromatic polyvalent carboxylic acid and the like.
There is no restriction | limiting in particular as content of these polyhydric carboxylic acid, Although it can select suitably according to the objective, 30 mol% or less is preferable with respect to all the carboxylic acids, and 10 mol% or less is more preferable. The obtained polyester resin is appropriately added within the range having crystallinity.

  Examples of the polyvalent carboxylic acid added as necessary include divalent carboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, citraconic acid, phthalic acid, isophthalic acid, and terephthalic acid. Acid; trimellitic anhydride, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2 , 5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, trivalent or higher polyvalent carboxylic acid such as 1,2,7,8-octanetetracarboxylic acid and the like.

If necessary, the polyhydric alcohol component may further contain a trivalent or higher polyhydric alcohol in addition to a small amount of an aliphatic branched dihydric alcohol or cyclic dihydric alcohol.
There is no restriction | limiting in particular as content of these polyhydric alcohol, Although it can select suitably according to the objective, 30 mol% or less is preferable with respect to all the alcohols, and 10 mol% or less is more preferable, and obtained. The polyester to be added is appropriately added within the range having crystallinity.

  Examples of the polyhydric alcohol added as necessary include 1,4-bis (hydroxymethyl) cyclohexane, polyethylene glycol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, and glycerin.

The molecular weight distribution of the crystalline polyester resin (A) is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably sharp from the viewpoint of low-temperature fixability, and the molecular weight is compared. Preferably, the molecular weight is low.
As the molecular weight of the crystalline polyester resin (A), the weight average molecular weight (Mw) is 5,500 to 6,500 and the number average molecular weight (Mn) is 5500-6500 in GPC molecular weight distribution of o-dichlorobenzene soluble matter. It is preferable that it is 1,300-1,500, and it is preferable that ratio (Mw / Mn) of the said weight average molecular weight and the said number average molecular weight is 2-5.

  For example, the GPC stabilizes the column in a heat chamber at 40 ° C., and o-dichlorobenzene as a solvent is allowed to flow through the column at this temperature at a flow rate of 1 mL / min. It can be measured by injecting 50 μL to 200 μL of o-dichlorobenzene sample solution of the resin prepared to 6 mass%. In the molecular weight measurement, the molecular weight distribution of the sample can be calculated from the relationship between the logarithmic value of the prepared calibration curve and the count number using several types of monodisperse polystyrene standard samples.

  The molecular weight distribution of the crystalline polyester resin (A) is based on a molecular weight distribution diagram in which the horizontal axis is log (M: molecular weight) and the vertical axis is mass%. In the case of the crystalline polyester resin (A), in this molecular weight distribution diagram, it is preferable to have a molecular weight peak in the range of 3.5 mass% to 4.0 mass%, and the half width of the peak is 1.5. The following is preferable.

  The glass transition temperature (Tga) and softening temperature (T1 / 2a) of the crystalline polyester resin (A) are not particularly limited and may be appropriately selected depending on the intended purpose. However, the heat resistant storage stability of the toner is deteriorated. It is preferable that it is as low as possible. As said Tga, 80 to 130 degreeC is preferable and 80 to 125 degreeC is more preferable. Moreover, as said T1 / 2a, 80 to 130 degreeC is preferable and 80 to 125 degreeC is more preferable. If the Tga and T1 / 2a exceed the above range, the lower limit fixing temperature of the toner does not increase, and the low temperature fixability does not deteriorate.

  Here, the glass transition temperature (Tg) of the binder resin is increased from 20 ° C. to 150 ° C. at 10 ° C./min using a differential scanning calorimeter (eg, DSC-60, manufactured by Shimadzu Corporation). It can be determined by measuring. In addition, the measurement of the endothermic peak and the glass transition temperature in the present invention is derived using an endothermic curve at the first temperature increase.

In addition, the softening temperature (T1 / 2) of the binder resin was measured using an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation), a die hole diameter of 1 mm, a pressure of 20 kgf / cm ² , and a temperature rising rate of 6 ° C. / It is measured by a temperature corresponding to ½ from the outflow start point to the outflow end point when a 1 cm ³ sample is melted out under the condition of minutes.

In the present invention, whether or not the polyester resin has crystallinity can be confirmed by whether or not a peak exists in the X-ray diffraction pattern by the powder X-ray diffractometer.
The crystalline polyester resin (A) preferably has at least one diffraction peak at a position where 2θ is 19 ° to 25 ° in the diffraction pattern, and 2θ is (i) 19 ° to 20 °, (ii More preferably, diffraction peaks exist at positions of 21 ° to 22 °, (iii) 23 ° to 25 °, and (iv) 29 ° to 31 °. In addition, in the melt-kneaded and pulverized toner, if a diffraction peak exists at a position of 2θ = 19 ° to 25 °, this indicates that the crystalline polyester resin (A) maintains the crystallinity. It is preferable because the function of the crystalline polyester resin (A) can be surely exhibited.

  The powder X-ray diffraction measurement can be performed using, for example, a powder X-ray diffractometer RINT1100 (manufactured by Rigaku Electric Co., Ltd.), using a wide-angle goniometer under conditions of Cu as the tube and tube voltage-current as 50 kV-30 mA. it can. As a specific example of the measurement, FIG. 1 shows the X-ray diffraction result of the crystalline polyester resin a6 used in the example, and FIG. 2 shows the toner obtained in Example 24 (including the crystalline polyester resin a6 and its crystalline properties). X-ray diffraction results are shown.

  There is no restriction | limiting in particular as content in the toner of the said crystalline polyester resin (A), Although it can select suitably according to the objective, 1 mass%-15 mass% are preferable, and 1 mass%-10 mass are preferable. % Is more preferable.

<Amorphous resin (B)>
The non-crystalline resin (B) is not particularly limited, and a conventionally known material can be appropriately used according to the purpose. For example, polystyrene, chloropolystyrene, poly α-methylstyrene, styrene / chlorostyrene copolymer can be used. Polymer, styrene / propylene copolymer, styrene / butadiene copolymer, styrene / vinyl chloride copolymer, styrene / vinyl acetate copolymer, styrene / maleic acid copolymer, styrene / acrylic acid ester copolymer ( Styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / phenyl acrylate copolymer, etc.), styrene / methacryl Acid ester copolymer (styrene / methyl methacrylate copolymer, styrene / Ethyl tacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / phenyl methacrylate copolymer, etc.), styrene / α-methyl chloroacrylate copolymer, styrene / acrylonitrile / acrylate ester copolymer, etc. Styrene resin (homopolymer or copolymer containing styrene or styrene-substituted product), vinyl chloride resin, styrene / vinyl acetate copolymer, rosin-modified maleic acid resin, phenol resin, epoxy resin, polyethylene resin, polypropylene resin , Ionomer resins, polyurethane resins, silicone resins, ketone resins, ethylene / ethyl acrylate copolymers, petroleum resins such as xylene resins and polyvinyl butyral resins, and hydrogenated petroleum resins. These may be used individually by 1 type and may use 2 or more types together.
There is no restriction | limiting in particular as a manufacturing method of these resin, Any of block polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be utilized.

The amorphous resin (B) is preferably a polyester resin from the viewpoint of low-temperature fixability. As the polyester resin, for example, those usually obtained by condensation polymerization of alcohol and carboxylic acid can be used. is there.
There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1, 4-bis (hydroxymethyl) cyclohexane, And ethylated bisphenols such as bisphenol A, other divalent alcohol monomers, and trivalent or higher polyhydric alcohol monomers.

  The carboxylic acid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include divalent organic compounds such as maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and malonic acid. Acid monomer, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,5 -Trivalent or higher polyvalent carboxylic acid monomers such as hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxypropane, 1,2,7,8-octanetetracarboxylic acid and the like.

  The polyester resin preferably has a glass transition temperature Tgb of 55 ° C or higher, more preferably 60 ° C or higher, from the viewpoint of heat-resistant storage stability.

  The non-crystalline resin (B) preferably contains a chloroform-insoluble component. In particular, when the amount of insoluble chloroform in the toner is 1% by mass to 30% by mass after toner formation, distribution of resins other than the amorphous resin (B) can be secured while maintaining hot offset resistance. Therefore, it is preferable.

The chloroform insoluble content of the non-crystalline resin (B) is measured as follows.
About 1.0 g of the amorphous resin (B) is weighed, and about 50 g of chloroform is added thereto. The sufficiently dissolved solution is separated by centrifugation, and filtered at room temperature using JIS standard (P3801) type 5 C qualitative filter paper. The filter paper residue is an insoluble matter, and the content (% by mass) of the used binder resin or toner and the filter paper residue mass represents the content of the chloroform insoluble matter.

  The amorphous resin (B) has a main peak between 1,000 and 10,000 in the molecular weight distribution by GPC determined by the THF soluble content, and the half width of the molecular weight distribution is 15,000 or less. It is preferable that Such an amorphous resin (B) exhibits a very good low-temperature fixability, and therefore sufficiently assists the low-temperature fixability even when the amount of the crystalline polyester resin (A) is reduced when formulated into a toner. Can do. As a result of repeated studies by the present inventors, when a toner is produced with a combination of the crystalline polyester resin (A), the amorphous resin (B), and the composite resin (C), the amorphous resin is obtained. When the proportion of (B) is increased, the balance is the best, and side effects due to excessive crystalline polyester resin and excessive THF insoluble matter and the adverse effect on the lower limit of fixing due to the hardness of the composite resin (C) are manifested. In other words, the inventors have found that the functions of the respective resins are effectively exhibited and the low-temperature fixability, heat-resistant storage stability, and hot offset resistance are improved.

  There is no restriction | limiting in particular as content in the toner of the said amorphous resin (B), Although it can select suitably according to the objective, 60 mass%-95 mass% are preferable, and 75 mass%-90 mass are preferable. % Is more preferable.

<Composite resin (C)>
The composite resin (C) includes a condensation polymerization resin unit and an addition polymerization resin unit. That is, a resin in which a condensation polymerization resin unit and an addition polymerization resin unit are chemically bonded (hereinafter also referred to as “hybrid resin”).
The composite resin (C) is prepared by performing a condensation polymerization reaction and an addition polymerization reaction in parallel in the same reaction vessel in a mixture containing a condensation polymerization monomer and an addition polymerization monomer as raw materials. It can be obtained by sequentially performing a polymerization reaction, or an addition polymerization reaction and a condensation polymerization reaction.

  The polycondensation monomer in the composite resin (C) is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a polyhydric alcohol, a polycarboxylic acid, and a polyamide resin unit that form a polyester resin unit Or the polyhydric carboxylic acid and amine or amino acid which form a polyester-polyamide resin unit are mentioned.

Among the polyhydric alcohols, examples of the divalent alcohol component include 1,2-propanediol, 1,3-propanediol, ethylene 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, hydrogenated bisphenol A, bisphenol A and ethylene oxide And diols obtained by polymerizing cyclic ethers such as propylene oxide.
Among the polyhydric alcohols, trihydric or higher polyhydric alcohols include, for example, 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.
Among these, bisphenol A skeletons such as diols obtained by polymerizing cyclic ethers such as ethylene oxide and propylene oxide to hydrogenated bisphenol A or bisphenol A in terms of imparting heat-resistant storage stability and mechanical strength to the binder resin. The alcohol component is preferred.

Among the polyvalent carboxylic acids, examples of the divalent carboxylic acid component include benzene dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, or anhydrides thereof; succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Alkyl dicarboxylic acids or anhydrides thereof; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride, And unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride.
Among the polyvalent carboxylic acids, trivalent or higher polyvalent carboxylic acid components include, for example, 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- Examples include 2-methylenecarboxypropane, tetra (methylenecarboxy) methane, 1,2,7,8-octanetetracarboxylic acid, empole trimer acid, anhydrides thereof, and partial lower alkyl esters.
These may be used individually by 1 type and may use 2 or more types together.
Among these, aromatic polyvalent carboxylic acid compounds such as phthalic acid, isophthalic acid, terephthalic acid, and trimellitic acid are preferable from the viewpoint of heat-resistant storage stability and mechanical strength of the binder resin.

As the amine and the amino acid, for example, diamine (C1), trivalent or higher polyamine (C2), aminoalcohol (C3), aminomercaptan (C4), amino acid (C5), and amino groups of C1 to C5 are blocked. (C6) etc. are mentioned.
Examples of the diamine (C1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.) and alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexyl). Methane, diaminocyclohexane, isophorone diamine, etc.), aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
Examples of the trivalent or higher polyamine (C2) include diethylenetriamine and triethylenetetramine.
Examples of the amino alcohol (C3) include ethanolamine and hydroxyethylaniline.
Examples of the amino mercaptan (C4) include aminoethyl mercaptan and aminopropyl mercaptan.
Examples of the amino acid (C5) include aminopropionic acid, aminocaproic acid, and ε-caprolactam.
(C6) obtained by blocking the amino group of (C1) to (C5) (C6) and a ketimine compound obtained from the amines of (C1) to (C5) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.) And oxazolidine compounds.

The molar ratio of the condensation polymerization monomer component in the composite resin (C) is preferably 5 mol% to 40 mol%, and more preferably 10 mol% to 25 mol%.
When the molar ratio is less than 5 mol%, dispersibility with the crystalline polyester resin (A) may be deteriorated, and when it exceeds 40 mol%, dispersion of the release agent may be deteriorated. .
In addition, when performing a polycondensation reaction, you may use a well-known esterification catalyst.

There is no restriction | limiting in particular as an addition polymerization type monomer in the said composite resin (C), According to the objective, it can select suitably, For example, a vinyl-type monomer is mentioned.
Examples of the vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, Styrenic vinyl monomers such as p-tert-butylstyrene, pn-hexylstyrene, pn-4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene; acrylic acid, acrylic acid Methyl, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-nomer acrylate; methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n methacrylate -Butyl, isobutyl methacrylate, methacryl Methacrylic vinyl monomers such as n-octyl, n-dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; other vinyl monomers or co-polymers Other monomers that form a polymer may be mentioned. These may be used individually by 1 type and may use 2 or more types together.

Examples of the other vinyl monomers or other monomers forming the copolymer include monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene; vinyl chloride, vinylidene chloride and vinyl bromide. Vinyl halides such as vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl methyl ketone and vinyl hexyl ketone Vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; vinyl naphthalenes; acrylonitrile, methacrylonitrile , Acrylic acid or methacrylic acid derivatives such as acrylamide; unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic anhydride, itaconic anhydride , Unsaturated dibasic acid anhydrides such as alkenyl succinic anhydride; maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester Monoesters of unsaturated dibasic acids such as itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, and mesaconic acid monomethyl ester; unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid Α, β-unsaturated acids such as crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; the α, β-unsaturated acid and lower fatty acid Monomers having a carboxyl group such as anhydrides, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides or monoesters thereof; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl And monomers having a hydroxy group such as acrylic acid or methacrylate hydroxyalkyl esters such as methacrylate, 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-1-methylhexyl) styrene, and the like. It is done. These may be used individually by 1 type and may use 2 or more types together.
Among these, styrene, acrylic acid, n-butyl acrylate, 2-ethylhexyl acrylate, methacrylic acid, n-butyl methacrylate, 2-ethylhexyl methacrylate are preferably used, and a combination containing at least styrene and acrylic acid Is particularly preferred in that the dispersibility of the release agent is extremely good.

In the production of the composite resin (C), an addition polymerization monomer crosslinking agent may be added as necessary.
The crosslinking agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aromatic divinyl compounds, diacrylate compounds linked by an alkyl chain, and alkyl chains including an ether bond. Examples include diacrylate compounds and polyester type diacrylates.

  Examples of the aromatic divinyl compound include divinylbenzene and divinylnaphthalene.

  Examples of diacrylate compounds linked by the alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1, Examples include 6-hexanediol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing the acrylate of these compounds with methacrylate.

Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include dipropylene glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.
Other examples include diacrylate compounds and dimethacrylate compounds linked by a chain containing an aromatic group and an ether bond.

  Examples of the polyester-type diacrylates include trade name MANDA (manufactured by Nippon Kayaku Co., Ltd.).

  As the polyfunctional type crosslinking agent, for example, pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and those obtained by replacing the acrylate of the above compounds with methacrylate, Examples include triallyl cyanurate and triallyl trimellitate.

  There is no restriction | limiting in particular as content of the said crosslinking agent, Although it can select suitably according to the objective, 0.01 mass part-10 mass parts are used with respect to 100 mass parts of addition polymerization type monomers used. Preferably, 0.03 mass part-5 mass parts are more preferable.

There is no restriction | limiting in particular as a polymerization initiator used when superposing | polymerizing an addition polymerization type monomer, According to the objective, it can select suitably, For example, 2,2'- azobisisobutyronitrile, 2,2 Azo polymerization initiators such as' -azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile); methyl ethyl ketone peroxide, acetylacetone peroxide, 2, Peroxide polymerization initiators such as 2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, benzoyl peroxide, n-butyl-4,4-di- (tert-butylperoxy) valerate Is mentioned.
These may be used alone or in combination of two or more for the purpose of adjusting the molecular weight and molecular weight distribution of the resin.

  There is no restriction | limiting in particular as content of the said polymerization initiator, Although it can select suitably according to the objective, 0.01 mass part-15 mass parts are used with respect to 100 mass parts of addition polymerization type monomers used. Is preferable, and 0.1 to 10 parts by mass is more preferable.

In order to chemically bond the condensation polymerization resin unit and the addition polymerization resin unit, for example, a monomer that can be reacted by either condensation polymerization or addition polymerization can be used.
Examples of such bireactive monomers include unsaturated carboxylic acids such as acrylic acid and methacrylic acid; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof; and hydroxy groups. Examples thereof include vinyl monomers.
There is no restriction | limiting in particular as content of the said both reactive monomer, Although it can select suitably according to the objective, 1 mass part-25 mass parts are used with respect to 100 mass parts of addition polymerization type monomers used. Preferably, 2 parts by mass to 20 parts by mass is more preferable.

As long as the composite resin (C) is in the same reaction vessel, both the condensation polymerization reaction and the addition polymerization reaction proceed and / or complete at the same time, and each reaction temperature and time are selected independently. The progress of the reaction can be completed.
For example, a mixture of an addition polymerization monomer and a polymerization initiator is added dropwise to a mixture of condensation polymerization monomers in a reaction vessel and mixed in advance. There is a method of performing condensation polymerization by raising the temperature.
In this way, it is possible to effectively disperse or combine two types of resin units by advancing two independent reactions in the reaction vessel.

  The composite resin (C) is preferably a composite resin having a polyester resin polycondensation resin unit and a vinyl resin addition polymerization unit. The combination of these units makes the function of the composite resin (C) more effective. Can be demonstrated.

There is no restriction | limiting in particular as softening temperature (T1 / 2c) of the said composite resin (C), Although it can select suitably according to the objective, 90 to 130 degreeC is preferable and 100 to 120 degreeC is more preferable. .
When the softening temperature (T1 / 2c) is 90 ° C. or higher, heat-resistant storage stability and hot offset resistance are not deteriorated, and when it is 130 ° C. or lower, low-temperature fixability is not deteriorated. .
The glass transition temperature (Tgc) of the composite resin (C) is preferably 50 ° C. to 80 ° C., and more preferably 55 ° C. to 70 ° C. from the viewpoints of fixability, storage stability and durability.
The Tgc and T1 / 2c can be measured in the same manner as the Tga and T1 / 2a.

  The acid value of the composite resin (C) is not particularly limited and may be appropriately selected depending on the intended purpose. However, from the viewpoint of chargeability and environmental stability, 5 mgKOH / g to 80 mgKOH / g is preferable, and 15 mgKOH / G to 40 mgKOH / g is more preferable. The acid value can be determined by a method according to JIS K-0070.

  There is no restriction | limiting in particular as content in the toner of the said composite resin (C), Although it can select suitably according to the objective, 3 mass%-20 mass% are preferable.

(Inorganic fine particles)
The inorganic fine particles are used as an external additive for imparting fluidity, developability, chargeability and the like to the toner particles. The inorganic fine particles are not particularly limited and can be appropriately selected from known ones according to the purpose. For example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, titanate Strontium, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, carbonized Silicon, silicon nitride, or the like can be used. These may be used individually by 1 type and may use 2 or more types together.

Fused silica refers to silica that is secondarily aggregated by chemically bonding primary particles of silica and / or fused silica using a treating agent.
The fused silica used in the present invention is prepared by chemically bonding primary particles of crystalline silica and / or fused silica using a treating agent. Examples of the treating agent include alkoxysilanes and silane coupling agents. Silane type processing agents such as chlorosilanes and silazanes or epoxy type processing agents such as liquid epoxy resins are preferably used.
When the silica primary particles are treated with a silane treatment agent such as alkoxysilanes or silane coupling agents, silanol groups bonded to the silica primary particles react with alkoxy groups bonded to the silane treatment agent. A new Si—O—Si bond is formed by dealcoholization.
That is, as shown in the following formula, the silica primary particles are secondarily aggregated by chemical bonding through the silane-based treatment agent.

When the silica primary particles are treated with chlorosilanes, the chloro group of the chlorosilanes and the silanol group bonded to the silica primary particles form a new Si-O-Si bond by the dehydrochlorination reaction. When coexisting with water, chlorosilanes first hydrolyze into water to form silanol groups, and the silanol groups and the silanol groups bonded to the silica primary particles are each subjected to a new Si-O-Si bond by a dehydration reaction. To produce secondary agglomeration.
Silazanes form a new Si—O—Si bond and secondary agglomerate when the amino group and the silanol group bonded to the silica primary particles are deammoniated.
On the other hand, when silica primary particles are treated with an epoxy-based treatment agent, silanol groups bonded to the silica primary particles add an epoxy group oxygen atom of the epoxy-based treatment agent and a carbon atom bonded to the epoxy group. Then, a new Si—O—C bond is formed.
That is, as shown in the following formula, the silica primary particles are secondarily aggregated by a chemical bond via an epoxy-based treatment agent.

  The fused silica used in the present invention is prepared by preparing silica as primary particles, and then preparing fused silica by treating the silica with the above-described silane-based treatment agent or epoxy-based treatment agent to fill the epoxy resin. However, for example, when silica is synthesized by a sol-gel method, a fused silica may be prepared by a one-step reaction in the presence of the silane-based treatment agent or epoxy-based treatment agent.

  In addition, since the Si—O—Si bond to be produced is more stable to heat than the Si—O—C bond, the silane-based treatment agent is preferable to the epoxy-based treatment agent. . Specific examples of alkoxysilanes that are the silane-based treatment agents include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, Examples include methyldiethoxysilane, diphenyldimethoxysilane, isobutyltrimethoxysilane, and decyltrimethoxysilane.

  Specific examples of the silane coupling agent that is the silane treatment agent include γ-aminopropyltoluethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyldiethoxysilane. , Γ-methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltriethoxysilane, methylvinyldimethoxysilane, and the like.

  Furthermore, as silane-based treatment agents other than the above alkoxysilanes or silane-based coupling agents, specifically, vinyltrichlorosilane, dimethyldichlorosilane, methylvinyldichlorosilane, methylphenyldichlorosilane, phenyltrichlorosilane, N, Examples thereof include N'-bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) acetamide, dimethyltrimethylsilylamine, hexamethyldisilazane, and cyclosilazane mixture.

Specific examples of the epoxy-based treatment agent include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenol type epoxy resin, Examples thereof include glycidylamine type epoxy resins and alicyclic epoxy resins.
The fused silica used in the present invention is prepared by chemically bonding primary particles of crystalline silica and / or fused silica using the above-mentioned treatment agent. Mixing is performed at a weight ratio of 100: 0.01 to 100: 50 using a known mixer such as a spray dryer.
At that time, for example, water or a 1% aqueous acetic acid solution may be appropriately added as a processing aid.

The mixture of the silica primary particles and the treating agent is then fired, and the firing temperature is selected from a temperature range of 100 to 2500 ° C.
The firing time may be 0.5 to 30 hours.

The degree of coalescence of silica (the definition of the degree of coalescence will be described later) can be arbitrarily controlled by adjusting the primary particle diameter, the type and amount of the treatment agent, and the treatment conditions.
That is, the cohesive strength is stronger when a silane-based treatment agent is used than when an epoxy-based treatment agent is used, when the amount of the treatment agent is increased with respect to primary silica particles, and when the firing temperature is higher. And the degree of adhesion tends to be high. On the other hand, the proportion of non-fused particles can be reduced by extending the firing time. However, excessive time extension promotes agglomeration of the coalesced particles, which may cause a problem in adhesion to the toner.

(Measurement of degree of adhesion)
The degree of adhesion in the present invention is defined as follows.
The measurement of the degree of adhesion is obtained by image observation. After the fused silica is dispersed in a suitable solvent (such as THF), the solvent is removed from the substrate and dried, and the sample is observed with an FE-SEM. The secondary particle diameter is measured for silica in the field of view at an acceleration voltage of 5 to 8 kV and an observation magnification of 8 to 10 k times. The secondary particle system measures the longest length of agglomerated particles. An example is shown in FIG. The number of silica to be observed is 100 or more particles.

Similarly, the primary particle diameter is observed with FE-SEM. The entire embedded image is predicted from the outer frame of the fused silica, and the longest length of the entire image is measured. An example is shown in FIG. Their average value is taken as the primary particle size. The number of silica to be observed is 100 or more particles.
When the length of the arrow in FIG. 3A is the secondary particle diameter (Db) and the average length of the arrow in FIG. 3B is the primary particle diameter (Da), the degree of coalescence is as follows: Defined in
Degree of adhesion = Db / Da
The degree of adhesion is calculated by the above-described measurement method, and Db50 and Db10 are calculated.

<Colorant>
The colorant is not particularly limited and may be appropriately selected from conventionally known dyes and pigments according to the purpose. Examples thereof include carbon black, lamp black, iron black, aniline blue, phthalocyanine blue, phthalocyanine green, and hansa yellow. G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dyes and the like. These may be used individually by 1 type and may use 2 or more types together.

The toner of the present invention can be used as a black toner or a full color toner by using the colorant.
Among the colorants, carbon black has a particularly good black coloring power, but at the same time, since it is also a good conductive material, it has an electric resistance if it is contained in a large amount or in an aggregated state in the toner. Decreases, which causes a transfer failure in the transfer process. In particular, when used in combination with the crystalline polyester resin (A), carbon black particles cannot enter the domains of the crystalline polyester resin (A), so that the crystalline polyester resin (A) has a large dispersion diameter. When present in the resin, it exists in a relatively high concentration in the resin other than the crystalline polyester resin (A). For this reason, the aggregate is easily confined in the toner, and the resistance is likely to be excessively reduced.

  In the case of the present invention, since the composite resin (C) is also used in combination, the dispersion of carbon black is improved, and the above risk can be reduced. In addition, when carbon black is contained, the viscosity of the melted toner can be increased when fixing the toner to the recording medium. Therefore, when a large amount of the amorphous resin (C) is formulated, the viscosity is reduced. The effect that the hot offset generated can be suppressed can also be imparted.

  There is no restriction | limiting in particular as content of the said coloring agent, Although it can select suitably according to the objective, It is 1 mass%-30 mass% normally with respect to the resin component of a toner, and 3 mass%-20 Mass% is preferred.

<Other ingredients>
The toner of the present invention can be blended with other components such as a charge control agent, a fatty acid amide compound, and a release agent as required.

<< Charge Control Agent >>
The charge control agent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include modified products of nigrosine and fatty acid metal salts, onium salts such as phosphonium salts, lake pigments thereof, and triphenylmethane. Dyes and their lake pigments, metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotin borates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate, organometallic Examples include complexes, chelate compounds, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, aromatic dicarboxylic acid metal complexes, quaternary ammonium salts, and salicylic acid metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- or polycarboxylic acids and metal salts thereof, anhydrides, esters, phenol derivatives such as bisphenol, and the like. These may be used individually by 1 type and may use 2 or more types together.

  There is no restriction | limiting in particular as content of the said charge control agent, Although it can select suitably according to the objective, 0.1 mass part-10 mass parts are preferable with respect to a toner resin component, and 1 mass part-5 Part by mass is more preferable.

Among these charge control agents, inclusion of a metal salicylic acid compound is preferable in that it can improve hot offset resistance at the same time. In particular, a complex having a tri- or higher-valent metal capable of a hexacoordinate configuration reacts with a highly reactive part of the resin and wax to form a light cross-linked structure, and thus has a large effect on hot offset resistance. Moreover, dispersibility improves by using together with the said composite resin (C), and the function of charge polarity control can be exhibited more effectively.
Here, there is no restriction | limiting in particular as a metal more than trivalence, According to the objective, it can select suitably, For example, Al, Fe, Cr, Zr etc. are mentioned.
Moreover, as a salicylic acid metal compound, the compound represented by following General formula (2) can be used, for example, Bontron E-84 (made by Orient Chemical Industry Co., Ltd.) is mentioned as a metal complex whose M is zinc. .

[General formula (2)]

(In the general formula (2), R ² , R ³ and R ⁴ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. M represents chromium, zinc, calcium, zirconium or aluminum, m represents an integer of 2 or more, and n represents an integer of 1 or more)

<< Fatty acid amide compound >>
The toner of the present invention preferably contains a fatty acid amide compound.
When a fatty acid amide compound is blended with a crystalline polyester resin in a pulverized toner including a melt-kneading process at the time of toner production, recrystallization in the kneaded product is accelerated when the crystalline polyester resin melted at the time of kneading is cooled. Therefore, the compatibility with the resin is reduced, and the decrease in the glass transition temperature of the toner can be suppressed, so that the heat resistant storage stability can be improved.
Further, when used in combination with a mold release agent, which will be described later, the mold release agent can be retained on the surface of the fixed image, so that it is strong against rubbing (improved smear resistance).
The content of the fatty acid amide compound in the toner is preferably 0.5% by mass to 10% by mass.

There is no restriction | limiting in particular as said fatty acid amide compound, According to the objective, it can select suitably, For example, the compound etc. which are represented with the following general formula (I) or the following general formula (II) are mentioned.
R ₁ —CO—NR ₂ R ₃ ... General formula (I)
(In the general formula (I), R ₁ represents an aliphatic hydrocarbon group having 10 to 30 carbon atoms, and R ₂ and R ₃ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, Represents an aryl group having 6 to 10 carbon atoms or an aralkyl group having 7 to 10 carbon atoms.)

(In the general formula (II), R ₁ and R ₃ represent an alkyl group or alkenyl group having 5 to 21 carbon atoms, and R ₂ represents an alkylene group having 1 to 20 carbon atoms.)
Among these, the alkylene bis fatty acid amide represented by the general formula (II) is particularly preferable.

Here, the alkyl group, aryl group and aralkyl group of R ₂ and R ₃ in the general formula (I) are usually inactive substituents such as fluorine atom, chlorine atom, cyano group, alkoxy group and alkylthio group. May be substituted with an unsubstituted one.

  Examples of the compound represented by the general formula (I) include stearic acid amide, stearic acid methylamide, stearic acid diethylamide, stearic acid benzylamide, stearic acid phenylamide, behenic acid amide, behenic acid dimethylamide, and myristic acid amide. And palmitic acid amide. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the alkylene bis saturated fatty acid amide represented by the general formula (II) include methylene bis stearic acid amide, ethylene bis stearic acid amide, methylene bis palmitic acid amide, ethylene bis palmitic acid amide, methylene bis behenic acid amide, ethylene Examples thereof include bisbehenic acid amide, hexamethylene bisstearic acid amide, hexaethylene bispalmitic acid amide, and hexamethylene bisbehenic acid amide. These may be used individually by 1 type and may use 2 or more types together. Among these, ethylene bis stearamide is particularly preferable.

  Specific examples of the alkylene bis fatty acid amide compound that can be used in addition to the above include propylene bis stearic acid amide, butylene bis stearic acid amide, methylene bis oleic acid amide, ethylene bis oleic acid amide, propylene bis oleic acid amide, Butylene bis oleic acid amide, methylene bis lauric acid amide, ethylene bis lauric acid amide, propylene bis lauric acid amide, butylene bis lauric acid amide, methylene bis myristic acid amide, ethylene bis myristic acid amide, propylene bis myristic acid amide, butylene bis Myristic acid amide, Propylene bispalmitic acid amide, Butylene bispalmitic acid amide, Methylene bispalmitoleic acid amide, Ethylene bispalmitoleic acid amide, Propylene vinyl Palmitoleic acid amide, butylene bispalmitoleic acid amide, methylene bisarachidic acid amide, ethylene bisarachidic acid amide, propylene bisarachidic acid amide, butylene bisarachidic acid amide, methylene biseicosenoic acid amide, ethylene biseicosenoic acid Amide, Propylene biseicosenoic acid amide, Butylene biseicosenoic acid amide, Methylene bis behenic acid amide, Ethylene bis behenic acid amide, Propylene bis behenic acid amide, Butylene bis behenic acid amide, Methylene bis Examples thereof include alkylene bis fatty acid amide compounds of saturated or 1 to 2 unsaturated fatty acids such as erucic acid amide, ethylene biserucic acid amide, propylene biserucic acid amide, and butylene biserucic acid amide.

  These fatty acid amide compounds can also serve as a release agent on the surface of the fixing member when the softening temperature (T1 / 2) is lower than the temperature of the surface of the fixing member at the time of fixing.

<< Releasing agent >>
The release agent is not particularly limited and may be appropriately selected from conventionally known ones according to the purpose. Examples thereof include low molecular weight polyolefin waxes such as low molecular weight polyethylene and low molecular weight polypropylene; Fischer-Tropsch wax and the like. Synthetic hydrocarbon waxes; natural waxes such as beeswax, carnauba wax, candelilla wax, rice wax and montan wax; petroleum waxes such as paraffin wax and microcrystalline wax; stearic acid, palmitic acid, myristic acid, etc. Higher fatty acids, metal salts and amides thereof; synthetic ester waxes; and various modified waxes thereof. These may be used individually by 1 type and may use 2 or more types together.
Among these, carnauba wax and its modified wax, polyethylene wax, and synthetic ester wax are preferable, and the toner is moderately finely dispersed in the polyester resin and polyol resin, and has excellent hot offset resistance, transferability, and durability. Carnauba wax is particularly preferable because it is easy to achieve. Further, when used in combination with a fatty acid amide compound, the effect of staying on the fixed image surface becomes very strong, and smear resistance is further improved.

  There is no restriction | limiting in particular as content of the said mold release agent, Although it can select suitably according to the objective, 2 mass%-15 mass% are preferable with respect to a toner. When the content is less than 2% by mass, the effect of preventing hot offset may be insufficient. When the content exceeds 15% by mass, transferability and durability may be deteriorated.

There is no restriction | limiting in particular as melting | fusing point of the said mold release agent, Although it can select suitably according to the objective, 70 to 150 degreeC is preferable. When the melting point is less than 70 ° C., the heat-resistant storage stability of the toner may be lowered, and when it exceeds 150 ° C., the releasability may not be sufficiently achieved.
In addition, the said melting | fusing point can be measured using a differential scanning calorimeter (DSC-60, Shimadzu Corporation make), for example.

<Chloroform insoluble matter in toner>
The toner of the present invention contains 1% by mass to 30% by mass, preferably 2% by mass to 20% by mass, and more preferably 3% by mass to 20% by mass. When the chloroform-insoluble content is less than 1% by mass, the hot offset resistance due to the chloroform-insoluble content becomes dilute. When the chloroform-insoluble content is more than 30% by mass, the distribution of the binder resin that contributes to the low-temperature fixability is reduced. Since it becomes relatively small, the low-temperature fixability deteriorates.

The chloroform insoluble content of the toner is measured as follows.
About 1.0 g of toner is weighed, and about 50 g of chloroform is added thereto. The sufficiently dissolved solution is separated by centrifugation, and filtered at room temperature using JIS standard (P3801) type 5 C qualitative filter paper. The filter paper residue is an insoluble component, and the ratio of the used toner mass to the filter paper residue mass (mass%) represents the content of the chloroform insoluble component. When measuring the chloroform-insoluble content of the toner, solid matter such as pigment is present in the filter paper residue, and therefore it is obtained separately by thermal analysis.

<Endothermic peak of toner and its endothermic amount>
The toner of the present invention has an endothermic peak in the range of 90 ° C. to 130 ° C. in measuring the endothermic peak of the toner by DSC. The endothermic peak is preferably an endothermic peak due to the crystalline polyester resin (A). If the endothermic peak due to the crystalline polyester resin (A) is in the range of 90 ° C. to 130 ° C., the crystalline polyester resin does not melt at room temperature and the toner melts in a relatively low fixing temperature range. Since it can be fixed on a recording medium, heat-resistant storage stability and low-temperature fixability can be expressed more effectively.

  There is no restriction | limiting in particular as the endothermic amount of the said endothermic peak, Although it can select suitably according to the objective, 1J / g-15J / g are preferable. If the endothermic amount is less than 1 J / g, the amount of the crystalline polyester resin (A) that works effectively in the toner is too small, and the function of the crystalline polyester resin (A) may not be sufficiently exhibited. . If the endothermic amount exceeds 15 J / g, the amount of the crystalline polyester resin (A) effective in the toner is excessive, so it is absolutely compatible with the amorphous resin (B) and the composite resin (C). The amount increases, the glass transition temperature of the toner decreases, and heat resistant storage stability may decrease.

The DSC measurement (endothermic peak) in the present invention is measured by using a differential scanning calorimeter (“DSC-60”; manufactured by Shimadzu Corporation) at a temperature of 20 ° C. to 150 ° C. at 10 ° C./min.
In the present invention, the endothermic peak derived from the crystalline polyester resin (A) exists in the vicinity of 80 ° C. to 130 ° C., which is the melting point of the crystalline polyester resin (A), and the endothermic amount is surrounded by the baseline and the endothermic curve. It is obtained from the area of the specified range. In general, the endothermic amount in DSC measurement is often measured by increasing the temperature twice, but the measurement of the endothermic peak in the present invention is derived using the endothermic curve at the first temperature rise.
When the endothermic peak derived from the crystalline polyester resin (A) overlaps with the endothermic peak of the wax, the endothermic amount of the wax is subtracted from the endothermic amount of the overlapped peak. The endothermic amount of the wax is calculated from the endothermic amount of the wax alone and the wax content in the toner.

<Molecular weight distribution of toner>
The toner of the present invention has a main peak between 1,000 and 10,000 as the molecular weight distribution by gel permeation chromatography (GPC) determined from the tetrahydrofuran (THF) soluble content, and half of the molecular weight distribution. The price range is 15,000 or less. Moreover, it is preferable that the molecular weight distribution by GPC calculated | required by the THF soluble part has a main peak between 1,200-9,000, and the half value width of the said molecular weight distribution is 14,000 or less.

The GPC is measured as follows. That is, the column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was allowed to flow through the column at this temperature at a flow rate of 1 mL per minute, so that the sample concentration was 0.05 mass% to 0.6 mass%. Measurement is performed by injecting 50 μL to 200 μL of the THF sample solution of the prepared resin.
In measuring the molecular weight of the toner, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the calibration curve prepared and the count number using several types of monodisperse polystyrene standard samples.
As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical Co. Alternatively Tosoh Co. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 3, 4 × 10 3, 1.75 × 10 4, 5.1 × 10 4, 1.1 × 10 5, 3.9 × It is appropriate to use 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ , and use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector.

<Toner particle size>
The particle size of the toner of the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. From the viewpoint of obtaining high image quality excellent in fine line reproducibility and the like, the volume average particle size is 4 μm to 10 μm. Preferably there is. When the volume average particle size is less than 4 μm, the cleaning property in the development process and the transfer efficiency in the transfer process may be hindered, and the image quality may deteriorate. When the volume average particle size exceeds 10 μm, the fine line reproducibility of the image may deteriorate.
Here, the volume average particle diameter of the toner can be measured by various methods. For example, the toner can be measured using a Coulter Counter TAII manufactured by Coulter Electronics, USA.

<Toner production method>
The toner of the present invention is produced by, for example, a pulverization method or a polymerization method.
There is no restriction | limiting in particular as said polymerization method, According to the objective from conventionally well-known, it can select suitably, For example, a suspension polymerization method, a solution suspension method, an emulsion aggregation method, an ester extension method etc. are mentioned.
The pulverization method includes at least a melt-kneading step and a pulverization step, and further includes other steps such as a cooling step and a classification step as necessary. That is, the crystalline polyester resin (A), the amorphous resin (B), the composite resin (C), and a toner material containing a colorant are dry-mixed, melt-kneaded in a kneader, and pulverized. Thus, a pulverized toner is obtained.

  The melt kneading step is a step of melt kneading a mixture obtained by mixing the above-described toner materials. As the melt kneader used in the melt kneading step, for example, a uniaxial continuous kneader, a biaxial continuous kneader, or a batch kneader using a roll mill can be used. Specifically, KTK type twin screw extruder manufactured by Kobe Steel, TEM type extruder manufactured by Toshiba Machine Co., Ltd., twin screw extruder manufactured by Casey Kay Co., Ltd., PCM type twin screw extruder manufactured by Ikekai Iron Works Co., Ltd., manufactured by Busus A kneader or the like is preferably used. The melt-kneading is preferably performed under appropriate conditions that do not cause the molecular chain of the binder resin to be broken. Specifically, the melt-kneading temperature is determined with reference to the softening point of the binder resin, and the higher the temperature, the more severe the cutting, and the lower the temperature, the less the dispersion.

The pulverization step is a step of pulverizing the kneaded product obtained in the melt-kneading step. In this pulverization, it is preferable that the kneaded material is first coarsely pulverized and then finely pulverized. At this time, a method of pulverizing by colliding with a collision plate in a jet stream, pulverizing particles by colliding with each other in a jet stream, or pulverizing with a narrow gap between a mechanically rotating rotor and a stator is preferably used.
The classification step is a step of classifying the pulverized product obtained in the pulverization step, and the toner can be adjusted to particles having a predetermined particle diameter. Classification can be performed, for example, by removing fine particle portions by a cyclone, a decanter, centrifugation, or the like.
After the pulverization and classification are completed, the pulverized product is classified in an air stream with a centrifugal force or the like to produce a toner having a predetermined particle size.

  The toner production method of the present invention preferably includes a cooling step between the melt-kneading step and the pulverizing step. The cooling step is a step of cooling the kneaded product obtained in the melt-kneading step. In the cooling step, when the average thickness of the kneaded product is 2.5 mm or more, the cooling rate of the kneaded product becomes slow, and the crystalline polyester resin (A) melted in the kneaded product is recrystallized. Therefore, the recrystallization is promoted and the function of the crystalline polyester resin (A) can be exhibited more effectively. In order to promote recrystallization, it is effective to add a fatty acid amide compound as described above, but such a method is also effective. The upper limit value of the average thickness of the kneaded material is not particularly limited and can be appropriately selected according to the purpose. However, if it exceeds 8 mm, the pulverization efficiency is significantly reduced in the subsequent pulverization step. preferable. In addition, there is no restriction | limiting in particular as how to obtain | require the said average thickness, It can obtain | require by applying the method of measuring a well-known thickness conventionally and calculating the average value of a measured value.

  In order to improve the fluidity, storage stability, developability, and transferability of the toner, an external additive is prepared by adding an external additive such as hydrophobic silica fine powder to the toner (toner base particle) produced as described above. A mixing step may be further included.

The mixing device that can be used in the external additive mixing step is not particularly limited as long as the powder can be mixed, and a known device can be used. For example, a V-type mixer, a rocking mixer, a Ladige mixer, a now-known device can be used. Turmixer, Henschel mixer, etc. These mixing devices are preferably those equipped with a jacket or the like and capable of adjusting the internal temperature.
In order to change the load history applied to the external additive, for example, the external additive may be added in the middle of the mixing or gradually, and the rotation speed, rolling speed, time, temperature, etc. of the mixer may be changed as appropriate. You may let them. Further, a strong load may be applied first, and then a relatively weak load may be applied, or vice versa.

  In addition, after giving the said external additive mixing process, you may pass a 250 mesh or more sieve, and may remove a coarse particle and an aggregated particle.

(Developer)
The developer relating to the present invention comprises the toner of the present invention. The developer is not particularly limited, and may be used as a one-component developer composed only of toner or a two-component developer containing a carrier. When used in a printer or the like, it is preferably used as a two-component developer from the viewpoint of improving the service life.
There is no restriction | limiting in particular as said carrier and its content, According to the objective, it can select suitably.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention includes an electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit, and further, other units appropriately selected as necessary, for example, fixing. Means, cleaning means, static elimination means, recycling means, control means, and the like.
The image forming method used in the present invention includes a charging step, an exposure step, a development step, and a transfer step, and other steps appropriately selected as necessary, for example, a fixing step, a cleaning step, and a static elimination step. A recycling process, a control process, and the like.

  The image forming method used in the present invention can be preferably implemented by the image forming apparatus of the present invention, the charging step can be performed by the charging unit, and the exposure step can be performed by the exposing unit. The developing step can be performed by the developing unit, the transferring step can be performed by the transferring unit, and the other steps can be performed by the other unit.

<Charging step and charging means>
The charging step is a step of charging the surface of the electrophotographic photosensitive member, and is performed by the charging unit.
The charging means is not particularly limited as long as it is a means for charging the surface of the electrophotographic photosensitive member, and can be appropriately selected according to the purpose. A charging means of the type is preferable.
The non-contact charging means includes, for example, a non-contact charger and a needle electrode device using a corona discharge, a solid discharge element; a conductive or semiconductive material disposed with a small gap with respect to the electrophotographic photosensitive member. And a charging roller. Among these, corona discharge is particularly preferable.

The corona discharge is a non-contact charging method that gives positive or negative ions generated by corona discharge in the air to the surface of the electrophotographic photosensitive member, and has a characteristic of giving a certain amount of charge to the electrophotographic photosensitive member. There are a charger and a scorotron charger having a characteristic of giving a constant potential.
The coroton charger is composed of a casing electrode that occupies a half space around the discharge wire, and a discharge wire placed almost at the center thereof.
The scorotron charger is obtained by adding a grid electrode to the corotron charger, and the grid electrode is provided at a position 1.0 mm to 2.0 mm away from the surface of the electrophotographic photosensitive member.

<Exposure process and exposure means>
The exposure can be performed, for example, by exposing the surface of the electrophotographic photosensitive member imagewise using the exposure unit.
The optical system in the exposure is roughly classified into an analog optical system (analog system) and a digital optical system (digital system). The analog optical system is an optical system that directly projects an original onto an electrophotographic photosensitive member by an optical system, and the digital optical system receives image information as an electrical signal, converts this into an optical signal, and converts it into an electrophotographic image. It is an optical system that exposes a photoreceptor to form an image.
The exposure unit is not particularly limited as long as it is a unit that exposes the charged surface of the electrophotographic photosensitive member to form an electrostatic latent image, and can be appropriately selected according to the purpose. Examples include various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, a liquid crystal shutter optical system, and an LED optical system. Among these, an exposure unit that has at least one of a semiconductor laser and a light emitting diode and forms an electrostatic latent image on an electrophotographic photosensitive member by a digital method is preferable.
In the present invention, an optical backside system that performs imagewise exposure from the backside of the electrophotographic photosensitive member may be employed.

<Development process and development means>
The developing step is a step of developing the electrostatic latent image using a toner or a developer to form a visible image.
The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer, and can be performed by the developing unit.
The developing unit is not particularly limited as long as it is a unit that develops the electrostatic latent image with toner to form a visible image, and can be appropriately selected according to the purpose. For example, the toner Or a developer containing at least a developer and capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image.
The toner is the toner of the present invention.

  The developing unit may be a dry developing type, a wet developing type, a single color developing unit, or a multi-color developing unit. For example, a toner having a stirrer for charging the toner or the developer by frictional stirring and a rotatable magnet roller is preferable.

  In the developing device, for example, the toner and the carrier are mixed and agitated, 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. . Since the magnet roller is disposed in the vicinity of the electrophotographic photosensitive member (photosensitive member), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is caused by an electric attractive force. It moves to the surface of the electrophotographic photoreceptor. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrophotographic photosensitive member.

<Transfer process and transfer means>
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.
The transfer can be performed, for example, by charging the visible image with the electrophotographic photosensitive member using a transfer charger, and can be performed by the transfer unit.
The transfer means is not particularly limited as long as it is a means for transferring the visible image to a recording medium, and can be appropriately selected according to the purpose, but the visible image is transferred onto an intermediate transfer member. An embodiment having a primary transfer unit for forming a composite transfer image and a secondary transfer unit for transferring the composite transfer image onto a recording medium is preferable.
The intermediate transfer member is not particularly limited and can be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

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

<Other processes and other means>
-Fixing process and fixing means-
The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.

The fixing unit is not particularly limited and may be appropriately selected depending on the intended purpose. A fixing unit and a heat source for heating the fixing unit are used.
Examples of the fixing unit include a combination of an endless belt and a roller, a combination of a roller and a roller, etc., but the warm-up time can be shortened, and in terms of realizing energy saving, A combination of an endless belt and a roller having a small heat capacity is preferable in terms of expansion of the fixable width.

-Static elimination process and static elimination means-
The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrophotographic photosensitive member, and can be suitably performed by a neutralization unit.
The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrophotographic photosensitive member. For example, a neutralization lamp is preferable. Can be mentioned.

-Cleaning process and cleaning means-
The cleaning step is a step of removing the toner remaining on the electrophotographic photosensitive member, and can be suitably performed by a cleaning unit. In addition, it is also possible to employ a method in which the charge of the residual toner is made uniform by the rubbing member and collected by the developing roller without using the cleaning means.
The cleaning means is not particularly limited, and may be selected from known cleaners as long as the electrophotographic toner remaining on the electrophotographic photosensitive member can be removed. For example, a magnetic brush cleaner Suitable examples include electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

-Recycling process and recycling means-
The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.
There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

-Control process and control means-
The control step is a step of controlling each of the steps, and can be suitably performed by a control unit.
The control means is not particularly limited as long as the movement of each means can be controlled, and can be appropriately selected according to the purpose. Examples thereof include devices such as a sequencer and a computer.

Hereinafter, an image forming method and an image forming apparatus of the present invention will be described in detail with reference to the drawings.
An example of the image forming apparatus of the present invention is shown in FIG.
In FIG. 4, reference numeral 101A is a driving roller, 101B is a driven roller, 102 is a photosensitive belt, 103 is a charger, 104 is a laser writing system unit, and 105A to 105D store toners of yellow, magenta, cyan, and black, respectively. Development unit 106, paper feed cassette 107, intermediate transfer belt 107, drive shaft roller 107A for driving the intermediate transfer belt, 107B driven shaft roller for supporting the intermediate transfer belt 108, cleaning device 108, fixing roller 109 Reference numeral 109A denotes a pressure roller, 110 denotes a paper discharge tray, and 113 denotes a paper transfer roller.

In this color image forming apparatus, a flexible intermediate transfer belt 107 is used as a transfer drum, and the intermediate transfer belt 107 as an intermediate transfer member is stretched between a driving shaft roller 107A and a pair of driven shaft rollers 107B. The belt is circulated and conveyed in the clockwise direction, and the belt surface between the pair of driven shaft rollers 107B is in contact with the photosensitive belt 102 on the outer periphery of the driving roller 101A from the horizontal direction.
During normal color image output, each color toner image formed on the photoreceptor belt 102 is transferred to the intermediate transfer belt 107 each time it is formed, and the color toner images are combined, and this is fed into the paper feed cassette 106. The transfer sheet is transferred onto the transfer sheet by the paper transfer roller 113, and the transferred transfer sheet is transferred between the fixing roller 109 and the pressure roller 109A of the fixing device, and is fixed by the fixing roller 109 and the pressure roller 109A. After fixing, the paper is discharged onto the paper discharge tray 110.

  When the developing units 105A to 105E develop toner, the toner concentration of the developer stored in the developing unit is lowered. A decrease in the toner density of the developer is detected by a toner density sensor (not shown). When a decrease in toner density is detected, a toner replenishing device (not shown) connected to each developing unit operates to replenish the toner and increase the toner density. At this time, the replenished toner may be a so-called trickle developing system developer in which a carrier and toner are mixed as long as the developing unit has a developer discharging mechanism.

  In FIG. 4, an image is formed by superimposing a toner image on an intermediate transfer belt. However, the electrophotography of the present invention is also applied to a system that transfers directly from a transfer drum to a recording medium without using an intermediate transfer belt. An image forming apparatus can be obtained.

FIG. 5 is a diagram showing an example of a developing device used in the present invention, and modifications as will be described later also belong to the category of the present invention.
In FIG. 5, a developing device disposed opposite to the photosensitive member 20 as a latent image carrier includes a developing sleeve 41 as a developer carrier, a developer containing member 42, and a developer supply regulating member as a regulating member. 43, a support case 44, and the like.
To a support case 44 having an opening on the side of the photoconductor 20, a toner hopper 45 serving as a toner storage unit that stores the toner 21 is joined. A developer containing portion 46 containing toner 21 and a carrier 23 adjacent to the toner hopper 45 is used to stir the toner 21 and the carrier 23 and impart friction / release charge to the toner 21. A developer stirring mechanism 47 is provided.
Inside the toner hopper 45, a toner agitator 48 and a toner replenishing mechanism 49 are disposed as toner supplying means rotated by a driving means (not shown). The toner agitator 48 and the toner replenishing mechanism 49 send out the toner 21 in the toner hopper 45 toward the developer accommodating portion 46 while stirring.

A developing sleeve 41 is disposed in a space between the photoconductor 20 and the toner hopper 45. The developing sleeve 41, which is rotationally driven in the direction of the arrow in the figure by a driving means (not shown), is disposed in the interior thereof so as to be in a relative position with respect to the developing device 40 in order to form a magnetic brush by the carrier 23. It has a magnet (not shown) as means.
A developer supply regulating member 43 is integrally attached to the side of the developer containing member 42 that faces the side attached to the support case 44. In this example, the developer supply regulating member 43 is disposed in a state where a certain gap is maintained between the tip of the developer supply regulating member 43 and the outer peripheral surface of the developing sleeve 41.

Using such a device without limitation, the image forming method of the present invention is performed as follows.
That is, with the above configuration, the toner 21 sent out from the toner hopper 45 by the toner agitator 48 and the toner replenishing mechanism 49 is conveyed to the developer container 46 and stirred by the developer agitating mechanism 47, so The friction / peeling charge is applied, and is carried on the developing sleeve 41 as a developer together with the carrier 23 and conveyed to a position facing the outer peripheral surface of the photoconductor 20, and only the toner 21 is formed on the photoconductor 20. A toner image is formed on the photoreceptor 20 by electrostatically coupling with the electrostatic latent image.

  FIG. 6 is a diagram illustrating an example of an image forming apparatus having the developing device of FIG. Around the drum-shaped photoconductor 20, a charging member 32, an image exposure system 33, a developing device 40, a transfer device 50, a cleaning device 60, and a charge eliminating lamp 70 are arranged. In this example, the surface of the charging member 32 Is in a non-contact state with a gap of about 0.2 mm from the surface of the photoconductor 20, and when charging the photoconductor 20 by the charging member 32, direct current is applied to the charging member 32 by a voltage applying means (not shown). By charging the photoconductor 20 with an electric field in which an AC component is superimposed on the component, charging unevenness can be reduced, which is effective. The image forming method including the developing method is performed by the following operation.

A series of image forming processes can be described as a negative-positive process. A photoconductor 20 typified by a photoconductor (OPC) having an organic photoconductive layer is neutralized by a static elimination lamp 70, and is uniformly negatively charged by a charging member 32 such as a charging charger or a charging roller. A latent image is formed by the laser light L emitted from the image exposure system 33 (in this example, the absolute value of the exposed portion potential is lower than the absolute value of the non-exposed portion potential).
Laser light L is emitted from a semiconductor laser and scans the surface of the photoconductor 20 in the direction of the rotation axis of the photoconductor 20 by a polygonal polygonal mirror (polygon) that rotates at high speed. The latent image formed in this manner is developed with a developer composed of a mixture of toner and carrier supplied onto a developing sleeve 41 which is a developer carrying member in the developing device 40, and a toner image is formed. At the time of developing the latent image, a DC voltage having an appropriate magnitude or an AC voltage is superimposed on the developing sleeve 41 from a voltage application mechanism (not shown) between the exposed portion and the non-exposed portion of the photoreceptor 20. A development bias is applied.

On the other hand, a transfer medium (for example, paper) 80 is fed from a paper feed mechanism (not shown), and is synchronized with the leading edge of the image by a pair of upper and lower registration rollers (not shown), and the photoreceptor 20 and the transfer device 50. And the toner image is transferred. At this time, it is preferable that a potential having a polarity opposite to that of toner charging is applied to the transfer device 50 as a transfer bias. Thereafter, the transfer medium 80 is separated from the photoreceptor 20, and a transfer image is obtained.
Further, the toner remaining on the photoreceptor 20 is collected in a toner collecting chamber 62 in the cleaning device 60 by a cleaning blade 61 as a cleaning member.
The collected toner may be transported to the developer container 46 and / or the toner hopper 45 by a toner recycling means (not shown) and reused.
The image forming apparatus may be a device in which a plurality of the developing devices described above are arranged, and the toner images are sequentially transferred onto the transfer medium, then sent to the fixing mechanism, and the toner is fixed by heat or the like. An apparatus may be used in which a plurality of toner images are transferred to a transfer medium and transferred together onto a transfer medium and fixed in the same manner.

FIG. 7 shows another example of the image forming apparatus used in the present invention. The photosensitive member 20 is provided with at least a photosensitive layer on a conductive support, and is driven by driving rollers 24a and 24b. The photosensitive member 20 is charged by a charging member 32, image exposure by an image exposure system 33, development by a developing device 40, and transfer. Transfer using the apparatus 50, pre-cleaning exposure by the pre-cleaning exposure light source 26, cleaning by the brush-like cleaning means 64 and the cleaning blade 61, and static elimination by the static elimination lamp 70 are repeatedly performed.
In FIG. 7, pre-cleaning exposure is performed on the photoconductor 20 (of course, in this case, the support is translucent) from the support side.

(Process cartridge)
The process cartridge of the present invention has at least an electrophotographic photosensitive member and developing means for developing an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a visible image. In addition, other means appropriately selected as necessary are provided.
The developing means includes at least a developer container that contains the toner, and a developer carrier that carries and conveys the developer contained in the developer container, and A layer thickness regulating member for regulating the toner layer thickness to be carried may be provided.
The process cartridge can be detachably provided in various electrophotographic image forming apparatuses, and is preferably provided detachably in the image forming apparatus of the present invention.

  FIG. 8 shows an example of the process cartridge of the present invention. This process cartridge uses the toner or developer of the present invention, the photosensitive member 20, the proximity brush-like contact charging means 32, the developing means 40 for storing the developer of the present invention, and the cleaning blade 61 as a cleaning means. Is a process cartridge that integrally supports at least a cleaning unit that is detachable from the image forming apparatus main body. In the present invention, the above-described components can be integrally combined as a process cartridge, and the process cartridge can be configured to be detachable from a main body of an image forming apparatus such as a copying machine or a printer.

  Hereinafter, the present invention will be described with reference to examples and comparative examples. In addition, this invention is not limited to the Example illustrated here. In the following, “parts” represents parts by mass.

<Production Example 1: Synthesis of crystalline polyester resin (A)>
Using a compound selected from 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol as the alcohol component, and a compound selected from fumaric acid, maleic acid, and terephthalic acid as the carboxylic acid component Crystalline polyester resins a1 to a6 were obtained.
Specifically, the alcohol component and carboxylic acid component monomers shown in Table 1 were esterified under normal pressure at 170 to 260 ° C. under non-catalytic conditions, and then the reaction system was charged with respect to all carboxylic acid components. 400 ppm of antimony trioxide was added, and polycondensation was performed at 250 ° C. while removing glycol out of the system under a vacuum of 3 Torr to obtain a crystalline resin. The crosslinking reaction was carried out until the stirring torque reached 10 kg · cm (100 ppm), and the reaction was stopped by releasing the reduced pressure state of the reaction system.

  The obtained crystalline polyester resins a1 to a6 have an X-ray diffraction pattern (tube: Cu, tube voltage-current: 50 kV-30 mA, goniometer: wide angle) by a powder X-ray diffractometer (manufactured by Rigaku Electric Co., Ltd., RINT1100). Goniometer, Sampling width: 0.020 °, Scanning speed: 2.0 ° / min, Scanning range: 5-50 °, Diffraction peak: Peak detected by processing peak search 11) , At least one diffraction peak was present at a position of 2θ = 19 ° to 25 °, confirming that the polyester was crystalline. The X-ray diffraction result of the crystalline polyester resin a6 is shown in FIG.

  The glass transition temperatures Tga of the crystalline polyester resins a1 to a6 are measured with a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation), and the DSC measurement is performed at a temperature of 10 ° C / min to 20 ° C to 150 ° C. Went.

The softening temperatures (T1 / 2a) of the crystalline polyester resins a1 to a6 are as follows: an elevated flow tester CFT-500 (manufactured by Shimadzu Corporation), a die hole diameter of 1 mm, a pressure of 20 kg / cm ² , and a heating rate of 6 A temperature corresponding to ½ from the outflow start point to the outflow end point when 1 cm ³ of the sample was melted out under the conditions of ° C / min.

Whether or not the crystalline polyester resins a1 to a6 have an ester bond represented by the following general formula (1) in the molecular main chain was confirmed by solid C ¹³ NMR. The results are shown in Table 1.
_{- [OCO-R-COO- (} CH 2) n] - ··· formula (1)
(In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20).

<Production Example 2: Synthesis of amorphous resin (B)>
Amorphous resins b1-1 to b1-3, b2-1 and b2-3 were obtained as follows.
After an esterification reaction of an aromatic diol component and a monomer selected from ethylene glycol, glycerin, adipic acid, terephthalic acid, isophthalic acid, and itaconic acid under conditions of 170 ° C to 260 ° C and no catalyst under normal pressure Then, 400 ppm of antimony trioxide was added to the reaction system, and polycondensation was performed at 250 ° C. while removing glycol out of the system under a vacuum of 3 Torr (399.966 Pa) to obtain a resin. The crosslinking reaction was carried out until the stirring torque reached 10 kg · cm (100 ppm), and the reaction was stopped by releasing the reduced pressure state of the reaction system.
As the non-crystalline resins b1-4 and b2-2, styrene-acrylic resins were used.
The obtained non-crystalline resins b1-1 to b1-4 and b2-1 to b2-3 are non-crystalline due to the absence of a diffraction peak due to the X-ray diffraction pattern measured in the same manner as in Production Example 1. It was confirmed.
Further, the glass transition temperatures Tgb and softening temperatures T1 / 2b of the obtained amorphous resins b1-1 to b1-4 and b2-1 to b2-3 were measured in the same manner as in Production Example 1. The results are shown in Table 2-1 and Table 2-2.

  The content of chloroform in the obtained amorphous resins b1-1 to b1-4 was determined as follows. That is, 1.0 g of the obtained resin was weighed, a solution in which 50 g of chloroform was added and sufficiently dissolved was separated by centrifugation, and filtered at room temperature using JIS standard (P3801) type 5 C qualitative filter paper. . The filter paper residue is an insoluble matter, and is expressed as a ratio (mass%) between the mass of the resin used and the mass of the filter paper residue. The results are shown in Table 2-1.

The measurement of the main peak and the half width in GPC (gel permeation chromatography) of the obtained amorphous resins b2-1 to b2-3 was performed as follows. The results are shown in Table 2-2.
The column was stabilized in a heat chamber at 40 ° C., THF as a solvent was passed through the column at this temperature at a flow rate of 1 mL / min, and the concentration of the sample was adjusted to 0.05% to 0.6% by weight. The sample solution was measured by injecting 50 μL to 200 μL.
In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of the prepared calibration curve and the number of counts using several types of monodisperse polystyrene standard samples.
As a standard polystyrene sample for preparing a calibration curve, Pressure Chemical Co. Alternatively Tosoh Co. having a molecular weight of ^{6 × 10 2, 2.1 × 10} 3, 4 × 10 3, 1.75 × 10 4, 5.1 × 10 4, 1.1 × 10 5, 3.9 × 10 ⁵ , 8.6 × 10 ⁵ , 2 × 10 ⁶ , 4.48 × 10 ⁶ were used, and at least about 10 standard polystyrene samples were used. An RI (refractive index) detector was used as the detector.

<Production Example 3: Synthesis of composite resin c1>
Condensation polymerization monomers, terephthalic acid 0.8 mol, fumaric acid 0.6 mol, trimellitic anhydride 0.8 mol, bisphenol A (2,2) propylene oxide 1.1 mol, and bisphenol A (2,2) ethylene oxide 0.5 mol and 9.5 mol of dibutyltin oxide as an esterification catalyst were put in a four-necked flask of a 5-liter container equipped with a nitrogen introduction tube, a dehydration tube, a stirrer, a dropping funnel, and a thermocouple, and a nitrogen atmosphere Under heating to 135 ° C.
An addition polymerization monomer, 10.5 mol of styrene, 3 mol of acrylic acid, 1.5 mol of 2-ethylhexyl acrylate, and 0.24 mol of t-butyl hydroperoxide as a polymerization initiator were put into a dropping funnel to obtain a mixture.
The obtained mixture was dropped into the four-necked flask over 5 hours, and the reaction was performed for 6 hours while stirring.
Subsequently, the temperature was raised to 210 ° C. over 3 hours, and the reaction was performed at 210 ° C. and 10 kPa to the desired softening point to synthesize composite resin c1.

By the reaction described above, the condensation polymerization monomer, the addition polymerization monomer, and the acrylic resin that is both reactive monomers are reacted to form a hybrid resin in which the condensation polymerization resin unit and the addition polymerization resin unit are chemically bonded. Was made. At 135 ° C., an addition polymerization (both reactive system) reaction is promoted, and by raising the reaction temperature to 210 ° C., a condensation polymerization reaction is promoted.
The obtained composite resin c1 had a softening point (T1 / 2c) of 115 ° C., a glass transition temperature (Tgc) of 58 ° C., and an acid value of 25 mgKOH / g.

The acid value of the composite resin c1 was determined by the following method according to JIS K-0070.
Samples 0.5 g to 2.0 g obtained by pulverizing the obtained resin were precisely weighed, and the weight W (g) was measured. Next, the sample was put in a 300 mL beaker, and 150 mL of a mixed solution of toluene / ethanol (volume ratio 4/1) was added and dissolved. Titration was performed using a potentiometric titrator using a 0.1 mol / L ethanol solution of KOH. The amount of KOH solution used at this time was S (mL), and a blank was measured at the same time. The amount of KOH solution used at this time was B (mL), and the following formula (1) was calculated. However, f is a factor of KOH.
Acid value (mgKOH / g) = {(SB) × f × 5.61} / W Formula (1)

<Production Example 4: Synthesis of composite resin c2>
Hexamethylenediamine and ε-caprolactam as the condensation polymerization monomers and styrene, acrylic acid, and 2-ethylhexyl acrylate as the addition polymerization monomers were reacted in the same manner as in Production Example 3 to obtain a composite resin c2.

<Other toner materials>
Tables 3 and 4 below show toner materials other than the crystalline polyester resin (A), the amorphous resin (B), and the composite resin (C) used in Examples and Comparative Examples.

Example 1
<Production of toner>
The toner raw materials listed in Tables 1 to 3 were pre-mixed with the formulation shown in Table 5-1 below using a Henschel mixer (FM20B, manufactured by Mitsui Miike Chemical Co., Ltd.), and then a twin-screw kneader (stock) It was melted and kneaded at a temperature of 100 ° C. to 130 ° C. with a product of Ikekai, PCM-30). The obtained kneaded product was rolled to an average thickness of 2.8 mm with a roller, cooled to room temperature with a belt cooler, and coarsely pulverized to 200 μm to 300 μm with a hammer mill. Subsequently, after finely pulverizing using a supersonic jet pulverizer lab jet (manufactured by Nippon Pneumatic Industry Co., Ltd.), the weight average particle diameter is 5. Classification was performed while appropriately adjusting the louver opening so as to be 6 ± 0.2 μm to obtain toner base particles. Next, with respect to 100 parts of the toner base particles, 2.0 parts of the coalesced fused silica a classified in Table 4 and 0.8 parts of silica fine particles (manufactured by Clariant Co., Ltd., HDK-2000) are stirred and mixed with a Henschel mixer, and the toner is mixed. 1 was produced.
The molecular weight distribution of the produced toner 1 was measured in the same manner as in Production Example 2, and the main peak of the molecular weight and the half width of the molecular weight distribution were obtained. The results are shown in Table 5-2.
Further, the DSC peak temperature and endothermic amount in the range of 90 ° C. to 130 ° C. due to the crystalline polyester resin (A) of the toner 1 were measured using a differential scanning calorimeter (DSC-60, manufactured by Shimadzu Corporation). It calculated | required from the DSC chart at the time of heating up at 20 degreeC-150 degreeC at a C / min. The results are shown in Table 5-2.
Further, the content of chloroform-insoluble matter in the toner was confirmed in the same manner as in Production Example 2. The results are shown in Table 5-2.

<Production of developer>
5% by mass of the produced toner 1 and 95% by mass of the coated ferrite carrier are uniformly mixed at 48 rpm for 5 minutes using a tumbler mixer (manufactured by Willy et Bacchofen (WAB)) to produce developer 1. did.

<Evaluation of low-temperature fixability, hot offset resistance, and fine line reproducibility (initial)>
The image of the developer 1 was output using the above-described image forming apparatus (manufactured by Ricoh Co., Ltd.). The developer 1 was accommodated in the developing unit 105D of the image forming apparatus schematically shown in FIG. 7 (the developing units 105A to 105C were not used).
A solid image having an adhesion amount of 0.4 mg / cm ² was output on paper (Type 6200, manufactured by Ricoh Co., Ltd.) through exposure, development, and transfer processes. The linear speed of fixing was 180 mm / second. The fixing temperature was sequentially output in increments of 5 ° C., and the lower limit temperature at which no cold offset occurred (fixing lower limit temperature: low temperature fixability) and the upper limit temperature at which hot offset did not occur (fixing upper limit temperature: hot offset resistance) were measured. The NIP width of the fixing device was 11 mm. Separately, a character chart (image size is about 2 mm × 2 mm) with a toner image area ratio of 5% is output at a fixing lower limit temperature + 20 ° C. and fine line reproducibility is determined by visual inspection. (Initial) was evaluated. The results are shown in Table 6. In addition, the evaluation criteria in each evaluation are as follows.

<< Evaluation criteria for low-temperature fixability >>
◎: Less than 130 ° C ○: 130 ° C or more and less than 140 ° C △: 140 ° C or more and less than 150 ° C △△: 150 ° C or more and less than 160 ° C ×: 160 ° C or more

<< Evaluation criteria for hot offset resistance >>
◎: 200 ° C. or higher ○: 190 ° C. or higher and lower than 200 ° C. Δ: 180 ° C. or higher and lower than 190 ° C. ΔΔ: 170 ° C. or higher and lower than 180 ° C.

<< Evaluation criteria for fine line reproducibility (initial) >>
◎: Very good ○: Good △: General level △△: No problem in practical use ×: Unacceptable

<Reproducibility of fine lines (over time)>
After evaluating the initial fine line reproducibility, a chart with an image area ratio of 2% is output continuously with 200K sheets while replenishing the toner. % Character chart (the size of one character is about 2 mm × 2 mm) and visual judgment was performed to evaluate reproducibility of fine lines over time. The criterion was the same as the initial thin line reproducibility evaluation. The results are shown in Table 6.

<Smear resistance>
At the minimum fixing temperature, a halftone image having an image coverage of 60% with a toner adhesion amount of 0.40 ± 0.1 mg / cm ² is output on paper (Type 6200 paper manufactured by Ricoh Co., Ltd.), and a fixed image portion Was rubbed 10 times with a white cotton cloth (JIS L0803 Cotton No. 3) using a clock meter, and the ID of dirt adhering to the cloth (hereinafter referred to as smear ID) was measured. The smear ID was measured with a colorimeter (X-Rite 938, manufactured by X-Rite). The measurement was performed with black. The results are shown in Table 6.

<< Smear resistance evaluation criteria >>
◎: Smear ID is 0.20 or less ○: Smear ID is more than 0.20 and less than 0.35 △: Smear ID is more than 0.35 and less than 0.55 ×: Smear ID is more than 0.55

<Heat resistant storage stability>
10 g of the obtained toner is put into a 30 mL screw vial, tapped 100 times with a tapping machine, stored in a constant temperature bath at 50 ° C. for 24 hours, returned to room temperature, and then used with a needle penetration tester. The penetration was measured, and the heat resistant storage stability was evaluated according to the following criteria. The results are shown in Table 6.

<< Evaluation criteria for heat-resistant storage stability >>
◎: Penetrating ○: 20 mm or more △: 15 mm or more and less than 20 mm △△: 10 mm or more and less than 15 mm ×: Less than 10 mm

(Examples 2 to 24 and Comparative Examples 1 to 9)
In Example 1, the formulation of the toner raw materials was changed as shown in Table 5-1, and in some examples, the rolling average thickness was changed to the thickness shown in Table 5-2. Except for the addition of the stated amount of fatty acid amide compound, mixing, kneading, pulverization, and additive mixing were carried out in the same manner as in Example 1 to obtain toners 2-33, and a developer was prepared. These toners and developers were evaluated in the same manner as in Example 1.
However, in Example 17 (toner 26), the dispersion of the colorant p2 in the binder resin is poor. Therefore, before mixing with other raw materials, the amorphous resin b2-3 and pure water are used according to the following prescription. Was preliminarily kneaded, masterbatched, and a toner was prepared using the colorant p2. In making the toner, the amount of the amorphous resin b2-3 contained in the masterbatch was calculated backward, and the final raw material ratio was adjusted to the amount shown in Table 5-1. In Example 17, the smear resistance was evaluated in cyan.

<Master batch formulation of Example 17 (Toner 26)>
Amorphous resin: b2-3 100 parts Colorant: p2 50 parts Pure water 50 parts In the present invention, the production method of the masterbatch is not limited to the above.

(Examples 25-31 and Comparative Example 10)
Toners 34 to 41 were obtained in the same manner as in Example 1 except that the classified fused silica a in Table 4 was changed to b to i, and developers were produced. These toners and developers were evaluated in the same manner as in Example 1 to give Examples 25 to 31 and Comparative Example 10.

The aspect of the present invention is as follows.
<1> A toner comprising at least a binder resin and a colorant, and toner having inorganic fine particles as external additives on the surface of the mother body,
The binder resin contains a crystalline polyester resin (A), an amorphous resin (B), and a composite resin (C) including a condensation polymerization resin unit and an addition polymerization resin unit,
The toner contains 1% by mass to 30% by mass of chloroform insoluble matter
The molecular weight distribution determined by gel permeation chromatography (GPC) determined by the tetrahydrofuran soluble content of the toner has a main peak between 1,000 and 10,000, and the half width of the molecular weight distribution is 15,000 or less. Yes,
In the endothermic peak measurement by differential scanning calorimetry (DSC) of the toner, the toner has an endothermic peak in the range of 90 ° C to 130 ° C,
Secondary particles observed by FE-SEM of the inorganic fine particles (D) having inorganic fine particles (D) in which a plurality of primary particles are combined to form secondary particles as the inorganic fine particles. When the average particle diameter of the 50% measured from the small particle side of the diameter Db is Db50 and the average particle diameter of the 10% measured from the small particle side is Db10, Db50 / Db10 is 1.20 or less. This is a characteristic toner.
<2> The toner according to <1>, wherein the endothermic amount of the endothermic peak is 1 J / g to 15 J / g.
<3> The toner according to any one of <1> to <2>, wherein the toner contains 2% by mass to 20% by mass of a chloroform-insoluble component.
<4> The toner according to any one of <1> to <3>, further including a fatty acid amide compound.
<5> The toner according to any one of <1> to <4>, further including a metal salicylic acid compound.
<6> The toner according to any one of <1> to <5>, wherein the crystalline polyester resin (A) has an ester bond represented by the following general formula (1) in the molecular main chain.
_{- [OCO-R-COO- (} CH 2) n] - ··· formula (1)
(In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20).
<7> The toner according to any one of <1> to <6>, wherein the composite resin (C) includes a polyester resin condensation polymerization resin unit and a vinyl resin addition polymerization resin unit.
<8> When the primary particle diameter of the external additive of the inorganic fine particles (D) is Da and the degree of adhesion G is Db / Da, the average value of the degree of adhesion G is 1.5 to 4.0. The toner according to any one of <1> to <7>.
<9> The toner according to any one of <1> to <8>, wherein the inorganic fine particles (D) contain 10% by number or less of particles having an adhesion degree G of less than 1.3.
<10> The inorganic fine particle (D) is the toner according to any one of <1> to <9>, wherein an average secondary particle diameter Db is in a range of 80 nm to 200 nm.
<11> An electrophotographic photosensitive member, a charging unit that charges the surface of the electrophotographic photosensitive member, an exposure unit that exposes the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image, and the electrostatic An image forming apparatus comprising: a developing unit that develops a latent image with toner to form a visible image; and a transfer unit that transfers the visible image to a recording medium.
An image forming apparatus, wherein the toner is the toner according to any one of <1> to <10>.
<12> At least an electrophotographic photosensitive member and a developing unit that develops the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a visible image, and is attached to and detached from the main body of the image forming apparatus A possible process cartridge,
A process cartridge, wherein the toner is the toner according to any one of <1> to <10>.

20 Photoconductor 21 Toner 23 Carrier 24a Drive roller 24b Drive roller 26 Exposure light source before cleaning 32 Charging means (charging member)
33 Image exposure system 40 Developing device (developing means)
DESCRIPTION OF SYMBOLS 41 Developing sleeve 42 Developer accommodating member 43 Developer supply regulating member 44 Support case 45 Toner hopper 46 Developer accommodating portion 47 Developer agitating mechanism 48 Toner agitator 49 Toner replenishing mechanism 50 Transfer device 60 Cleaning device 61 Cleaning means (cleaning blade)
62 Toner recovery chamber 64 Brush-like cleaning means 70 Static elimination lamp 80 Transfer medium 101A Drive roller 101B Follower roller 102 Photoreceptor belt 103 Charger 104 Laser writing system unit 105A Development unit containing yellow toner 105B Development unit 105C containing magenta toner Developing unit for storing cyan toner 105D Developing unit for storing black toner 106 Paper feed cassette 107 Intermediate transfer belt 107A Drive shaft roller for driving intermediate transfer belt 107B Drive shaft roller for supporting intermediate transfer belt 108 Cleaning device 109 Fixing roller 109A Pressure roller 110 Paper discharge tray 113 Paper transfer roller L Laser light

JP 60-90344 A JP-A 64-15755 Japanese Patent Laid-Open No. 2-82267 JP-A-3-229264 JP-A-3-41470 JP-A-11-305486 JP 62-63940 A Japanese Patent No. 2931899 JP 2001-222138 A JP 2004-46095 A JP 2007-33773 A JP 2005-338814 A Japanese Patent No. 4118498 Japanese Patent Laid-Open No. 3-100161 Patent No. 033828013 JP-A-9-319134 Japanese Patent No. 03056122 JP 2010-224502 A

Claims (12)

A toner comprising at least a binder resin and a colorant, and toner having inorganic fine particles as external additives on the surface of the mother body,
The binder resin contains a crystalline polyester resin (A), an amorphous resin (B), and a composite resin (C) including a condensation polymerization resin unit and an addition polymerization resin unit,
The toner contains 1% by mass to 30% by mass of chloroform insoluble matter
The molecular weight distribution determined by gel permeation chromatography (GPC) determined by the tetrahydrofuran soluble content of the toner has a main peak between 1,000 and 10,000, and the half width of the molecular weight distribution is 15,000 or less. Yes,
In the endothermic peak measurement by differential scanning calorimetry (DSC) of the toner, the toner has an endothermic peak in the range of 90 ° C to 130 ° C,
Secondary particles observed by FE-SEM of the inorganic fine particles (D) having inorganic fine particles (D) in which a plurality of primary particles are combined to form secondary particles as the inorganic fine particles. When the average particle diameter of the 50% measured from the small particle side of the diameter Db is Db50 and the average particle diameter of the 10% measured from the small particle side is Db10, Db50 / Db10 is 1.20 or less. Features toner.   The toner according to claim 1, wherein the endothermic amount of the endothermic peak is 1 J / g to 15 J / g.   The toner according to claim 1, wherein the toner contains 2% by mass to 20% by mass of a chloroform-insoluble component.   The toner according to claim 1, further comprising a fatty acid amide compound.   The toner according to claim 1, further comprising a metal salicylic acid compound. The toner according to claim 1, wherein the crystalline polyester resin (A) has an ester bond represented by the following general formula (1) in the molecular main chain.
_{- [OCO-R-COO- (} CH 2) n] - ··· formula (1)
(In the general formula (1), R represents a linear unsaturated aliphatic divalent carboxylic acid residue having 2 to 20 carbon atoms, and n represents an integer of 2 to 20).   The toner according to claim 1, wherein the composite resin (C) includes a polyester resin condensation polymerization resin unit and a vinyl resin addition polymerization resin unit.   When the primary particle diameter of the external additive of the inorganic fine particles (D) is Da and the degree of adhesion G is Db / Da, the average value of the degree of adhesion G is 1.5 to 4.0. The toner according to claim 1.   The toner according to claim 1, wherein the inorganic fine particles (D) contain 10% by number or less of particles having a degree of coalescence G of less than 1.3.   The electrostatic image developing toner according to claim 1, wherein the inorganic fine particles (D) have an average secondary particle diameter Db in the range of 80 nm to 200 nm. An electrophotographic photosensitive member; a charging unit that charges the surface of the electrophotographic photosensitive member; an exposure unit that exposes the surface of the charged electrophotographic photosensitive member to form an electrostatic latent image; and An image forming apparatus comprising: a developing unit that develops a visible image by developing with toner; and a transfer unit that transfers the visible image to a recording medium.
An image forming apparatus, wherein the toner is the toner according to claim 1. A process having at least an electrophotographic photosensitive member and a developing unit that develops an electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a visible image, and is detachable from the main body of the image forming apparatus A cartridge,
A process cartridge, wherein the toner is the toner according to claim 1.