JP6132679B2 - Toner production method - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, and a toner jet method.

In recent years, for electrophotographic apparatuses such as printers, high-definition, high-quality images, and energy savings have been achieved more than ever, and higher-speed printing is possible and low running costs are strong. It is desired. Along with this, the properties required for toners are becoming increasingly sophisticated and diverse, and development is being carried out from various viewpoints.
Among these, from the viewpoint of energy saving, it is desired to realize a toner that can be fixed quickly and at low energy by melting at a lower temperature than before.
In order to satisfy these requirements, it is necessary to soften the toner, but it cannot be achieved simply by softening the toner from the viewpoint of heat-resistant storage stability and durability. Therefore, a toner has been proposed in which a low-temperature fixing performance of a toner is improved without softening the binder resin of the toner by adding a crystalline resin having an excellent response speed to heat, that is, a sharp melt property.

For example, Patent Document 1 proposes a toner in which 90% or more of the dispersed domain of the crystalline polyester has a diameter of 0.1 to 2 μm in order to obtain excellent low-temperature fixability (see Patent Document 1). .
The toner described above is prepared by a pulverization method, and in such a toner, crystalline polyester is exposed on the toner surface in some cases. As a result, the crystalline polyester acts as a leak site, and sufficient toner triboelectric chargeability may not be obtained. Further, when the crystalline polyester is dispersed and present as in the toner described above, the glass transition point of the toner is lowered due to the plasticizing effect of the crystalline polyester. As a result, the heat resistant storage stability of the toner may be reduced.
In addition, in order to maintain heat-resistant storage stability and durability while maintaining low-temperature fixing performance with crystalline polyester, a core layer containing amorphous polyester and crystalline polyester as a binder resin, and a shell layer covering the core layer A toner having a toner has been proposed (Patent Document 2).
In the toner described above, toner particles are produced by an agglomeration method, so that the crystalline polyester is clumped without being dispersed in the toner, or the amount of crystalline polyester present in each toner particle is non-uniform. It may become. For this reason, when the speed of the fixing process is increased, the crystalline polyester present in the domain shape loses heat, and the low-temperature fixability sufficient as the toner may not be maintained.

JP 2002-287426 A JP 2007-093809 A

When a crystalline substance such as ester wax or crystalline polyester is added to the toner, the viscosity of the toner rapidly decreases in a temperature range above the melting point of the crystalline substance. This is an effect obtained by rapidly melting the crystalline substance and plasticizing the binder resin of the toner. In particular, crystalline polyester has a wider range of resin physical properties such as acid value and molecular weight than ester wax. Therefore, from the viewpoint of dispersibility and compatibility of the toner with respect to the binder resin, a suitable resin design can be performed, and a more excellent plastic effect can be obtained. The present inventors tried to fully utilize the plastic effect of this crystalline polyester.

In order to maximize the plastic effect of the crystalline polyester on the toner, it is essential that the crystalline polyester is finely dispersed in the toner. This is because the crystalline polyester is finely dispersed, the contact area between the crystalline polyester and the binder resin is increased, and the crystalline polyester instantly liquefied in the fixing process does not flow out to the outside. This is because the binder resin can be plasticized. As a result, the plastic effect can be sufficiently exhibited, and the low-temperature fixability can be dramatically improved.
In general, a crystalline polyester having an ester bond has a property that it is easily adapted to a polyester-based binder resin and easily finely dispersed in a toner. However, when the binder resin of the toner is a copolymer of vinyl monomers such as styrene-acrylic resin, it is difficult for the crystalline polyester and the binder resin to become familiar, and the crystalline polyester is difficult to be finely dispersed in the toner. There was a nature. For this reason, it has been clarified that when a vinyl binder resin is used, the effect of plasticizing the crystalline polyester toner is small, and it is difficult to sufficiently improve the low-temperature fixability.

Further, for the purpose of improving the storage stability and durability of the toner, a surface layer resin having a high glass transition temperature (hereinafter also referred to as Tg) may be contained in the toner. In that case, since the surface layer resin has a higher Tg than the binder resin, the crystalline polyester liquefied in the fixing step cannot sufficiently plasticize the surface layer resin, and the surface layer resin becomes a fixability inhibiting substance and has low temperature fixability. It has become clear that it is difficult to improve sufficiently.
An object of the present invention is to solve the above problems. That is, it is an object of the present invention to provide a toner to which a crystalline resin is added that exhibits sufficient low-temperature fixability even during high-speed fixing, and that has sufficient durability even in a development system in which the toner is loaded.

As a result of intensive studies to solve the problems of the prior art, the present inventors have found that the problems can be solved by the following configuration, and have reached the present invention.
That is, the present invention adds a polymerizable monomer composition containing a polymerizable monomer, a colorant, a polar resin, and a crystalline resin to an aqueous medium, and the polymerizable monomer composition in the aqueous medium. Forming particles of the polymerizable monomer composition by granulating the product, and polymerizing the polymerizable monomer composition contained in the particles of the polymerizable monomer composition to form toner particles A method for producing a toner comprising a step of obtaining
The polymerizable monomer is a vinyl monomer,
The polar resin is a carboxyl group-containing vinyl polar resin,
The crystalline resin is a hybrid resin having a crystalline polyester portion and an amorphous vinyl portion,
The mass ratio (crystalline part / amorphous part) of the crystalline polyester part and the amorphous vinyl part of the crystalline resin is 70/30 or more and 98/2 or less,
When the melting point of the crystalline resin is Tm (C) (° C.) and the glass transition temperature of the polar resin is Tg (H) (° C.), the following formulas (1) and (2) are satisfied:
55.0 ≦ Tm (C) ≦ 90.0 (1)
5.0 ≦ Tg (H) −Tm (C) ≦ 30.0 (2)
When the acid value of the crystalline resin is Av (C) (mg KOH / g) and the acid value of the polar resin is Av (H) (mg KOH / g), the following formulas (3) to (5) are satisfied. A toner manufacturing method characterized by satisfying the above.
0.1 ≦ Av (C) ≦ 5.0 (3)
5.0 ≦ Av (H) ≦ 30.0 (4)
0.02 ≦ Av (C) / Av (H) ≦ 0.50 (5)

  According to the present invention, it is possible to provide a toner to which a crystalline resin is added that exhibits sufficient low-temperature fixability even during high-speed fixing, and that has sufficient durability even in a development system in which the toner is loaded. it can.

FIG. 4 is a cross-sectional explanatory view of a process cartridge according to the present invention. It is a schematic block diagram of an example of the apparatus which implements the image forming method of this invention.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention.
The toner used in the present invention is prepared by adding a polymerizable monomer composition containing a polymerizable monomer, a colorant, a polar resin, and a crystalline resin to an aqueous medium, and then adding the polymerizable monomer in the aqueous medium. A step of granulating a body composition to form particles of the polymerizable monomer composition, and polymerization for polymerizing the polymerizable monomer composition contained in the particles of the polymerizable monomer composition Toner particles obtained by a method including the steps are contained.
When the above manufacturing method is used, a so-called “core shell, in which a crystalline resin or a low Tg binder resin exists in the toner and a high Tg polar resin exists on the surface of the toner particles due to the difference in polarity of each material. A “structure” is easily formed. As a result, it is possible to improve the heat resistance and durability of the toner while maintaining the low-temperature fixability of the toner. Further, the circularity of the toner particles increases, and the developability and transferability are further improved. Moreover, according to the said manufacturing method, crystalline resin is melt | dissolved in a polymerizable monomer composition on heating conditions. Thereafter, the mixture is granulated through a suspending process while maintaining the heated state, and a polymerization initiator is added to produce toner particles by adding a polymerization initiator. At this time, by proceeding the polymerization reaction in the state where the crystalline resin is melted from the start of polymerization, the crystalline polyester is finely dispersed in the binder resin without causing phase separation of the crystalline resin as much as possible until the end of the polymerization. It is possible to produce toner particles as they are.

Such a structure control of toner particles is technically difficult in a method in which a toner composition is melt-mixed and simply pulverized as in a pulverization method. Further, as in a method of emulsion aggregation, a method in which a fine particle dispersion such as a resin particle dispersion is aggregated in an aqueous medium to obtain aggregated particles, and then the aggregated particles are fused to obtain an electrophotographic toner. In the internal structure, the dispersion state of each fine particle tends to be biased.
Here, the aqueous medium is a medium containing water as a main component. Specific examples include water itself, water added with a small amount of surfactant, water added with a pH adjuster, and water added with an organic solvent.

Hereinafter, an example of a method for producing toner particles by a suspension polymerization method preferably used in the present invention will be described, but the present invention is not limited to this.
First, the above-mentioned polymerizable monomer, colorant, polar resin, crystalline resin, etc. (further, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, other additives) are uniformly dissolved or dispersed. A polymerizable monomer composition is obtained. Thereafter, the polymerizable monomer composition is dispersed and granulated using a suitable stirrer in a continuous layer (for example, an aqueous phase) containing a dispersion stabilizer, and particles of the polymerizable monomer composition are dispersed. Let it form. Then, a polymerization reaction of the polymerizable monomer composition contained in the formed particles is performed to obtain toner particles having a desired particle size. The polymerization initiator may be added at the same time as other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.
After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

The polar resin used in the present invention is a carboxyl group-containing vinyl polar resin. Specifically, copolymers of styrene and acrylic acid, copolymers of styrene and methacrylic acid, copolymers of styrene and unsaturated carboxylic acid esters, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, etc. Examples thereof include polymers such as acids, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, copolymers of these monomers with styrene monomers, maleic acid copolymers, and the like.
Among them, in the present invention, the polar resin is preferably a styrene acrylic resin prepared using styrene and acrylic acid or methacrylic acid as a copolymerization component. When toner particles are prepared by suspension polymerization using styrene and an acrylic polymerizable monomer and further using a styrene acrylic resin as a polar resin, the styrene toward the toner particle surface is formed in the internal structure of the toner particles. A gently inclined structure is formed so that the proportion of the acrylic resin present increases. Therefore, even if a brittle crystalline resin is present, the durability of the entire toner particles is kept constant, and member contamination due to toner cracking is suppressed.

The styrene acrylic resin can be prepared by the following method. (1) Solid-phase polymerization method in which monomers are polymerized in a substantially solvent-free state, (2) All monomers to be used for polymerization, all polymerization initiators and solvent are added, and polymerization is performed collectively Solution polymerization method, (3) A dropping polymerization method in which a monomer is added during the polymerization reaction. Moreover, what was manufactured by the normal pressure polymerization method and the pressure polymerization method can be used.
The following compounds are mentioned as a copolymerization component used for preparation of a styrene acrylic resin. Styrene; α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, and other styrenic monomers; acrylic acid, methacrylic acid; methyl acrylate, ethyl acrylate, acrylic Acrylic acid esters such as n-butyl acid, isobutyl acrylate, n-propyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-methacrylic acid 2- Methacrylic acid esters such as hydroxyethyl; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; vinyl Ethyl ketone, vinyl hexyl ketone, such as vinyl ketones of methyl isopropenyl ketone; N- vinyl pyrrole, N- vinyl carbazole, N- vinyl indole, N- vinylpyrrolidone, such as N- vinyl compounds, vinyl naphthalenes.

The crystalline resin used in the present invention is a hybrid resin having a crystalline polyester moiety and an amorphous vinyl moiety, and the mass ratio of the crystalline polyester moiety to the amorphous vinyl moiety of the crystalline resin (crystal moiety / The amorphous portion is 70/30 or more and 98/2 or less. Preferably, it is 75/25 or more and 95/5 or less. Since the crystalline resin has an amorphous vinyl moiety, the compatibility between the amorphous vinyl moiety of the crystalline resin and the binder resin is improved, and the crystalline resin is further increased in the toner than in the past. Fine dispersion is possible. Thereby, it is possible to obtain excellent low-temperature fixability and durability.
Furthermore, since the polar resin used in the present invention is a resin having a vinyl moiety, when the crystalline resin is melted in the fixing step, it can be instantaneously compatible with the polar resin having the same vinyl structure. The polar resin can be sufficiently plasticized. Therefore, it becomes possible to sufficiently suppress the fixing inhibition property of the polar resin having a high Tg, and the low temperature fixing property can be further improved.
When the mass ratio of the amorphous vinyl portion in the crystalline resin is greater than 30, the compatibility between the crystalline resin and the binder resin proceeds excessively, and the heat resistance of the toner decreases. It becomes. Further, since the crystallinity of the crystalline resin is too low, sufficient sharp melt property cannot be exhibited in the fixing step. When the mass ratio of the amorphous vinyl moiety in the crystalline resin is smaller than 2, the compatibility between the crystalline resin and the binder resin becomes too small, so that the crystalline resin in the binder resin The dispersibility in the water is reduced. Therefore, the contact area between the crystalline resin and the binder resin is reduced, and the plasticizing effect during the fixing process is reduced. As a result, the low-temperature fixability of the toner is deteriorated.

Further, when the melting point of the crystalline resin used in the present invention is Tm (C) (° C.) and the glass transition temperature of the polar resin is Tg (H) (° C.), they are represented by the following formulas (1), ( The relationship of 2) is satisfied.
55.0 ≦ Tm (C) ≦ 90.0 (1)
5.0 ≦ Tg (H) −Tm (C) ≦ 30.0 (2)
The melting point Tm (C) of the crystalline resin in the present invention indicates the endothermic peak top temperature in differential scanning calorimetry (DSC). In the present invention, when Tm (C) is 55.0 ° C. or higher and 90.0 ° C. or lower, storability and fixability can be maintained, and when toner particles are produced by a polymerization method, The solubility is increased, which is preferable. In addition, the crystalline resin can maintain a crystalline state in the toner particles even in a high temperature environment, and the crystalline resin finely dispersed in the toner particles melts rapidly even under low temperature fixing conditions and high speed fixing conditions. To do. Therefore, sufficient heat storage stability and excellent low-temperature fixing performance as a toner can be obtained. A more preferable range of Tm (C) is 60.0 ° C. or higher and 85.0 ° C. or lower.
When Tm (C) is lower than 55.0 ° C., toner blocking is likely to occur, and storage stability may be deteriorated. On the other hand, if Tm (C) is higher than 90.0 ° C., the low-temperature fixability is impaired. In the case where toner particles are obtained by suspension polymerization, which is a preferable method for producing toner particles in the present invention, the solubility of the crystalline resin in the polymerizable monomer is likely to deteriorate, and the colorant and the Since the dispersibility of the toner particle constituent material such as a crystalline resin is deteriorated, fog is likely to increase.
Tm (C) can be adjusted by the type of alcohol monomer or carboxylic acid monomer used, the degree of polymerization, and the like.

  The melting point Tm (C) of the crystalline resin used in the present invention and the glass transition temperature Tg (H) of the polar resin satisfy the relationship of the above formula (2). In the fixing step, in order to suppress the fixing inhibition property of the high-Tg polar resin, it is necessary that the molten crystalline resin be instantaneously compatible with the polar resin. For this purpose, as described above, the polar resin has a vinyl structure, and immediately after the crystalline resin is melted at the melting point Tm (C), the Tg of the polar resin is reached. It is effective that the molecular chain starts to move. More specifically, it is necessary that Tg (H) is higher than Tm (C) and that Tg (H) and Tm (C) are close to some extent. When Tm (C) and Tg (H) satisfy the above relationship, it has been clarified that the plasticization of the crystalline resin to the vinyl polar resin during fixing is the largest. As a result, the low-temperature fixability can be dramatically improved. Tg (H) -Tm (C) is more preferably 5.0 ° C. or higher and 20.0 ° C. or lower. Tg (H) can be adjusted by the monomer composition ratio at the time of manufacturing the polar resin.

Further, when the acid value of the crystalline resin used in the present invention is Av (C) (mg KOH / g) and the acid value of the polar resin is Av (H) (mg KOH / g), they are represented by the following formula ( 3) to (5) are satisfied.
0.1 ≦ Av (C) ≦ 5.0 (3)
5.0 ≦ Av (H) ≦ 30.0 (4)
0.02 ≦ Av (C) / Av (H) ≦ 0.50 (5)
When the acid value of the crystalline resin used in the present invention satisfies the formula (3), the distribution state of the crystalline resin in the binder resin is less likely to be biased, and the crystalline resin is appropriately dispersed. A state is obtained. Therefore, a desired plastic effect for the binder resin can be obtained, and excellent low-temperature fixing performance can be satisfied. In addition, the crystallinity of the crystalline resin can be increased, and the heat resistance is improved. Furthermore, by controlling the acid value within the above range, the adhesion between the toner and the paper during image formation is improved. Further, when toner particles are produced by a polymerization method, if the acid value of the crystalline resin is 5.0 mg KOH / g or less, aggregation of the toner particles tends to hardly occur. This is desirable because charging stability and durability stability are improved.
The acid value of the crystalline resin can be controlled by the ratio between the alcohol component and the acid component constituting the crystalline resin, the type of monomer, and the end group treatment of the crystalline resin. A method for measuring the acid value of the crystalline resin will be described later.
When Av (C) is smaller than 0.1 mgKOH / g, the crystalline resin forms a large domain inside the binder resin, and the crystalline resin is finely dispersed in the binder resin. It becomes difficult. Therefore, the low temperature fixability of the toner is deteriorated. Further, when Av (C) is larger than 5.0 mgKOH / g, the crystalline resin tends to be unevenly distributed near the toner surface. As a result, the triboelectric chargeability and heat resistance are likely to deteriorate due to the exposure of the crystalline resin. A preferable range of Av (C) is 0.2 ≦ Av (C) ≦ 3.5.

When the acid value of the polar resin used in the present invention satisfies the formula (4), the polar resin easily migrates to the surface of the toner particle when producing toner particles by suspension polymerization. Covered with a polar resin shell. Thereby, even when the Tg of the binder resin is reduced by containing the crystalline resin, sufficient heat-resistant storage stability as the toner can be maintained. Further, since the crystalline resin is difficult to be exposed on the toner surface, charge leakage is less likely to occur and the triboelectric charging property is stabilized.
When Av (H) is smaller than 5.0 mgKOH / g, the crystalline resin is likely to be exposed on the surface of the toner particles, resulting in a decrease in heat resistance and a decrease in triboelectric chargeability. On the other hand, when Av (H) is larger than 30.0 mgKOH / g, the dispersibility of the crystalline resin is lowered and the low-temperature fixability is deteriorated. Further, the dispersibility of the colorant is deteriorated, and the coloring power of the toner is reduced. The acid value Av (H) of the polar resin can be controlled by the ratio of the acid component of the polar resin and the type of monomer. A method for measuring the acid value of the polar resin will be described later. A preferable range of Av (H) is 8 ≦ Av (H) ≦ 25.

As described above, since the polar resin used in the present invention is a vinyl-based resin, it has good compatibility with the vinyl-based binder resin, and the presence of the polar resin gradually from the inside of the toner particles toward the toner particle surface. A gently sloping structure is formed so that the ratio increases. On the other hand, when the acid value Av (C) of the crystalline resin used in the present invention and the acid value Av (H) of the polar resin satisfy the formula (5), toner particles were prepared by suspension polymerization. In addition, the distribution of the crystalline resin in the toner particles is not concentrated in the core portion, but is distributed over a certain ratio in the middle and the vicinity of the surface layer. Therefore, it becomes possible for the crystalline resin to be present in a moderately finely dispersed manner in the inclined portion. Further, since the crystalline resin has the amorphous vinyl portion, when the crystalline resin is melted during the fixing process, not only the binder resin but also the polar resin can be plasticized instantaneously. It becomes possible. As a result, the sharp melt effect of the crystalline resin is exerted to the maximum with respect to both the binder resin and the polar resin, and the low-temperature fixability is dramatically improved. The value of Av (C) / Av (H) is preferably 0.04 ≦ Av (C) / Av (H) ≦ 0.35.
When Av (C) / Av (H) is smaller than 0.02, the crystalline resin exists only in the binder resin, and the polar resin can be sufficiently plasticized during the fixing step. become unable. Therefore, the low temperature fixability of the toner is deteriorated. If Av (C) / Av (H) is greater than 0.50, the crystalline resin is unevenly distributed only near the toner particle surface, or a part of the crystalline resin is easily exposed on the toner particle surface. turn into. As a result, the heat resistance and durability of the toner are deteriorated.

On the other hand, the hydroxyl value of the polar resin in the present invention is preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less, more preferably 7.0 mgKOH / g or more and 16.0 mgKOH / g or less. preferable. When the hydroxyl value is in the above range, the dispersibility of the crystalline resin in the inclined portion of the binder resin and the polar resin is further improved. Therefore, the sharp melt effect of the crystalline resin is further improved particularly during the high-speed fixing process. Further, when the hydroxyl value is 5.0 mgKOH / g or more, sufficient tribo can be secured even in a high-temperature and high-humidity environment, so that fog is improved. Further, when the hydroxyl value is 20.0 mgKOH / g or less, the fog (left fog) when left in a high temperature and high humidity environment becomes good. This is because when the hydroxyl value is 20.0 mgKOH / g or less, it is possible to suppress the amount of water adsorbed to the polar resin existing in the vicinity of the toner particle surface, and the toner left in a high-temperature and high-humidity environment. This is because the decrease in tribo is suppressed. Moreover, if the hydroxyl value of the polar resin is within the above range, the cross-linked state and polarity of the polar resin can be more suitably controlled. As a result, the weight average molecular weight (Mw) of the polar resin can be controlled to a more suitable value. The hydroxyl value of the polar resin can be controlled by adjusting the amount of the hydroxyl group-containing monomer used in producing the polar resin.

  The content of the polar resin with respect to 100 parts by mass of the polymerizable monomer used for the toner particles is preferably 3.0 parts by mass or more and 20.0 parts by mass or less, and preferably 4.0 parts by mass or more and 15. More preferably, it is 0 parts by mass or less. When the content of the polar resin is within the above range, the toner particle surface sufficiently forms a layer of the polar resin and has excellent elasticity of the entire toner, and the crystalline resin is finely contained in the binder resin. Even in the dispersed state, the toner is difficult to break against pressure. Therefore, member durability can be prevented and excellent durability can be obtained.

The crystalline resin preferably has a weight average molecular weight (Mw) of 10,000 or more and 80000 or less, and more preferably 13000 or more and 40000 or less. When the Mw is 10,000 or more and 80,000 or less, the plasticity effect by the crystalline resin can be quickly obtained in the fixing process while maintaining the crystallinity of the crystalline resin high in the toner manufacturing process. . Therefore, it is possible to achieve both excellent heat resistance storage stability and excellent fixability under low temperature conditions and high speed conditions.
The weight average molecular weight (Mw) of the crystalline resin can be controlled by various production conditions of the crystalline resin, for example, the substance amount ratio of the raw polyvalent carboxylic acid and diol, the reaction temperature, the reaction time, and the like. . The method for measuring the weight average molecular weight (Mw) of the crystalline resin will be described later.

The weight average molecular weight (Mw) of the amorphous vinyl portion of the crystalline resin is preferably 2000 or more and 12000 or less. When the weight average molecular weight (Mw) is 2000 or more and 12000 or less, the amorphous vinyl portion is further uniformly dispersed in the crystalline resin. As a result, the compatibility between the crystalline resin and the binder resin is further improved, and the low-temperature fixability is improved. The weight average molecular weight (Mw) of the amorphous vinyl moiety is more preferably 3000 or more and 11000 or less.
The weight average molecular weight (Mw) of the amorphous vinyl moiety can be controlled by various production conditions of the polyester, such as the amount of both reactive monomers added during the production of the crystalline resin. A method for measuring the weight average molecular weight (Mw) of the amorphous vinyl moiety will be described later.

The toner particles according to the present invention are more preferably heated and held at a temperature T1 (° C.) represented by the following formula (5) in the polymerization step.
T1 ≧ Tm (C) +5 (5)

In the polymerization step of the toner particles, the crystalline resin is sufficiently melted by being heated and held at a temperature equal to or higher than the melting point Tm (C) of the crystalline resin, and compatibility with the binder resin proceeds. To do. As a result, the fine dispersibility of the crystalline resin is improved and the low-temperature fixability is improved. T1 is more preferably higher by 10 ° C. than Tm (C). On the other hand, the upper limit is not particularly limited, but is usually Tm + 40 ° C. or lower.

The toner particles are subjected to the polymerization step, and then the temperature T2 (° C.) represented by the following formula (6).
It is more preferable to heat and hold at 60 to 500 minutes.
Tm (C) -30 ≦ T2 ≦ Tm (C) -5 (6)
The crystalline resin is partly amorphous during the production of the toner, and the crystallinity tends to decrease. The amorphous resin that has been amorphized is compatible with the binder resin and may soften the binder resin. After the polymerization step of the toner particles, the crystallinity of the crystalline resin is improved by heating and holding at the temperature T2 represented by the above formula (6) for 60 minutes or more. That is, even when the crystalline resin is finely dispersed, the crystallinity is sufficiently maintained, and excellent fixability can be obtained while maintaining the heat resistant storage stability and durability of the toner. A more preferable range of T2 is Tm (C) -25 ≦ T2 ≦ Tm (C) -7.
The dispersion state of the crystalline resin in the toner can also be controlled by physical properties such as the acid value and molecular weight of the crystalline resin and the conditions of the melting point and polymerization temperature of the crystalline resin.

Next, the crystalline polyester as the crystalline polyester portion in the crystalline resin according to the present invention can be obtained by the reaction of a divalent or higher polyvalent carboxylic acid and a diol. Among these, a polyester mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid is preferable because of high crystallinity. Only one type of crystalline polyester may be used, or a plurality of types may be used in combination. Furthermore, in addition to the crystalline polyester, an amorphous polyester may be included in the toner.
Examples of alcohol monomers for obtaining such a crystalline polyester include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, trimethylene glycol, and tetramethylene. Examples include glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, dodecamethylene glycol, neopentyl glycol, 1,4-butadiene glycol and the like. In the present invention, the alcohol monomer as described above is used as a main component. In addition to the above components, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A, 1,4-cyclohexanedimethanol, etc. Divalent alcohol, aromatic alcohol such as 1,3,5-trihydroxymethylbenzene, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol, 1,2,5-pentanetriol, Trivalent alcohols such as glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, and trimethylolpropane may be used.

Examples of the carboxylic acid monomer for obtaining the crystalline polyester include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, peric acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, Decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, isophthalic acid, terephthalic acid, n-dodecyl succinic acid, n-dedecenyl succinic acid, cyclohexanedicarboxylic acid, these Examples include acid anhydrides and lower alkyl esters.
In the present invention, the carboxylic acid monomer as described above is used as a main component, but a trivalent or higher polyvalent carboxylic acid may be used in addition to the above components.
Trivalent or higher polyvalent carboxylic acid components include trimellitic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, pyromellitic acid, 1,2,4-butanetricarboxylic acid, Examples thereof include 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, and derivatives such as acid anhydrides or lower alkyl esters thereof.

Particularly preferable crystalline polyesters include polyesters obtained by reacting 1,4-cyclohexanedimethanol and adipic acid, polyesters obtained by reacting tetramethylene glycol and ethylene glycol and adipic acid, hexamethylene glycol and sebacine. Polyester obtained by reacting acid, polyester obtained by reacting ethylene glycol and succinic acid, polyester obtained by reacting ethylene glycol and sebacic acid, obtained by reacting tetramethylene glycol and succinic acid Polyester obtained by reacting diethylene glycol and decanedicarboxylic acid, polyester obtained by reacting nonamethylene glycol and sebacic acid, reacting decamethylene glycol and sebacic acid It is polyester, and polyester obtained by reacting a dodecamethylene glycol and sebacic acid.
More preferably, the crystalline polyester is a saturated polyester. Compared with the case where the crystalline polyester has an unsaturated portion, a crosslinking reaction does not occur in the reaction with the peroxide-based polymerization initiator, which is advantageous in terms of the solubility of the crystalline polyester. . The crystalline polyester resin used in the present invention can be produced by an ordinary polyester synthesis method. For example, it can be obtained by subjecting a dicarboxylic acid component and a dial alcohol component to an esterification reaction or a transesterification reaction, and then performing a polycondensation reaction under reduced pressure or by introducing nitrogen gas according to a conventional method.

In the esterification or transesterification reaction, a normal esterification catalyst or a transesterification catalyst such as sulfuric acid, tertiary butyl titanium butoxide, dibutyl tin oxide, manganese acetate, magnesium acetate can be used as necessary. For polymerization, it is possible to use conventional polymerization catalysts such as tertiary butyl titanium butoxide, dibutyl tin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. it can. The polymerization temperature and the amount of catalyst are not particularly limited, and may be arbitrarily selected as necessary.
As the catalyst, a titanium catalyst is preferably used, and a chelate-type titanium catalyst is more preferable. This is because the reactivity of the titanium catalyst is appropriate, and a polyester having a desirable molecular weight distribution can be obtained in the present invention. In addition, the crystalline polyester produced using a titanium catalyst is superior in terms of toner chargeability from the titanium or titanium catalyst incorporated into the polyester during production. The chelate-type titanium catalyst is highly effective, and the catalyst hydrolyzed during the reaction is incorporated into the polyester, so that the hydrogen abstraction reaction from the peroxide-based polymerization initiator is appropriately performed. Desirable for control. Furthermore, the durability of the toner is also improved.

  Moreover, the acid value of crystalline polyester can also be controlled by sealing the carboxyl group of a polymer terminal. Monocarboxylic acid and monoalcohol can be used for end-capping. Examples of monocarboxylic acids include benzoic acid, naphthalenecarboxylic acid, salicylic acid, 4-methylbenzoic acid, 3-methylbenzoic acid, phenoxyacetic acid, biphenylcarboxylic acid, acetic acid, propionic acid, butyric acid, octanoic acid, decanoic acid, dodecanoic acid, And monocarboxylic acids such as stearic acid. As the monoalcohol, methanol, ethanol, propanol, isopropanol, butanol, and higher alcohol can be used.

The toner particles of the present invention preferably contain 3.0 to 30.0 parts by mass of the crystalline resin with respect to 100 parts by mass of the polymerizable monomer constituting the binder resin. More preferably, it is contained in an amount of from 0.0 part by mass to 25.0 parts by mass, particularly preferably from 3.0 parts by mass to 20.0 parts by mass.
A crystalline resin content of 3.0 parts by mass or more is desirable because the above-described effects of the present invention are great. Furthermore, when the content of the crystalline resin is 3.0 parts by mass or more, the fixability is better, and it is more desirable from the viewpoint of suppressing a decrease in the rubbing density. In addition, since the crystalline resin easily absorbs moisture, if the content is more than 30.0 parts by mass with respect to the binder resin, the uniformity of charging of the toner is liable to be lost, and fog is likely to increase. There is a tendency. Further, when the content of the crystalline resin is larger than 30.0 parts by mass, compatibility with the binder resin due to the presence of excess crystalline resin is likely to occur, resulting in a decrease in melt viscosity. Therefore, the offset tends to occur easily. Further, in the polymerized toner, since the smoothness of the surface shape of the toner particles tends to decrease, the charging characteristics tend to decrease and the image density tends to decrease.

  Examples of a method for producing the hybrid resin include a method in which a polymerization reaction is allowed to proceed under a pressurized environment when an amorphous vinyl moiety is created. Specifically, transesterification reaction between hydroxyl group contained in polyester and (meth) acrylic ester contained in amorphous vinyl polymer, hydroxyl group contained in polyester and contained in amorphous vinyl polymer To generate a radical in the polyester by an esterification reaction with a carboxyl group, an esterification reaction between a carboxyl group contained in the polyester and a hydroxyl group contained in the amorphous vinyl polymer, a hydrogen abstraction reaction, Examples thereof include a method of adding a monomer and polymerizing under a pressurized environment. At that time, the degree of pressurization is preferably 0.20 MPa or more and 0.45 MPa or less.

  A monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used as the vinyl polymerizable monomer used when the amorphous vinyl moiety in the hybrid resin is produced. Examples of the monofunctional polymerizable monomer include styrene; styrene derivatives such as α-methylstyrene, o-methylstyrene, m-methylstyrene, and p-methylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso- Acrylic materials such as propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate Polymerizable monomer; Methacrylic polymerizable monomer in which the acrylic polymerizable monomer is changed to methacrylate.

As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Acrylic polyfunctional polymerizable monomers such as diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate; Methacrylic polyfunctional polymerizable monomer obtained by replacing the acrylic polyfunctional polymerizable monomer with methacrylate; divinylbenzene, divinylnaphthalene, divinylacetate Tell.
As the vinyl monomer, those having a carboxyl group or a hydroxyl group and those containing (meth) acrylic acid esters are preferable. This is because when a functional group having a strong polarity such as a carboxyl group is present in the amorphous vinyl portion of the hybrid resin, the amorphous vinyl portion has an appropriate polarity, and toner particles in an aqueous medium This is preferable because the toner particles are stabilized during the production.
In addition, if the amorphous vinyl portion of the hybrid resin is a copolymer of a vinyl-based polymerizable monomer and acrylic acid, the hydrogen surface due to the carboxyl group of acrylic acid will make the toner surface stronger and more durable. It is preferable because it is excellent. However, when the content of acrylic acid in the hybrid resin exceeds 3.0% by mass, the hygroscopicity tends to increase in a high-temperature and high-humidity environment, and the triboelectric chargeability of the toner tends to decrease.

As a polymerization initiator used for polymerizing the above-mentioned vinyl-based polymerizable monomer when producing the hybrid resin, as long as it does not inhibit the effects of the present invention other than those used in the present invention, Oil-soluble initiators and / or water-soluble initiators can be used as appropriate. For example, as an oil-soluble initiator, azo compounds such as 2,2′-azobisisobutyronitrile; t-butylperoxyneodecanoate, t-hexylperoxypivalate, lauroyl peroxide, t- Examples thereof include peroxides such as butyl peroxy 2-ethylhexanoate, t-butyl peroxyisobutyrate, di-t-butyl peroxyisophthalate, and di-t-butyl peroxide.
Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salt, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2 -Hydroxyethyl] propionamide}, 2,2′-azobis {2-methyl-N- [2- (1-hydroxybutyl)]-propionamide}, hydrochloride ferrous sulfate or hydrogen peroxide.
In particular, it is preferably a peroxide, and when the polyester resin is vinyl-modified by a hydrogen abstraction reaction, the 10-hour half-life temperature is preferably 70 ° C. or higher and 170 ° C. or lower, and 75 ° C. or higher and 130 ° C. or lower. When used, it is more preferable because it has an appropriate reactivity.

The polymerizable monomer composition used for the production of toner particles according to the present invention contains a polymerizable monomer. The polymerizable monomer constitutes a binder resin.
As the polymerizable monomer used in the present invention, a vinyl monomer capable of radical polymerization is used. As the vinyl monomer, a monofunctional vinyl monomer or a polyfunctional vinyl monomer can be used.

  The following are mentioned as a monofunctional vinyl-type monomer. Styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, p- Styrenic polymerizable monomers such as n-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene Body; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n- Octyl Acryle Acrylic monomers such as methyl methacrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; methyl methacrylate , Ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n -Nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate Methacrylic polymerizable monomers such as ethyl acetate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl ethyl ether, Vinyl ethers such as vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

The following are mentioned as a polyfunctional vinyl-type monomer. Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2 '-Bis (4- (acryloxy-diethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-buty Lenglycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2′-bis (4- (methacryloxy-diethoxy) phenyl) propane, 2,2′-bis ( 4-methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, divinyl ether.

In the present invention, the above monofunctional vinyl monomers are used alone or in combination of two or more, or the above monofunctional vinyl monomers and polyfunctional vinyl monomers are used in combination.
The polyfunctional vinyl monomer can also act as a crosslinking agent. A crosslinking agent can be normally used in the ratio of 0.001-15 mass parts with respect to 100 mass parts of monofunctional vinylic monomers. Examples of the polyfunctional vinyl-based monomer include divinyl compounds such as divinylaniline, divinyl sulfide and divinyl sulfone, and compounds having three or more vinyl groups, in addition to those described above.

In the present invention, a colorant is used. Examples of the colorant include a black colorant, a yellow colorant, a magenta colorant, and a cyan colorant.
Examples of the black colorant include carbon black, a magnetic material, and a toned color of each color using the following yellow / magenta / cyan colorants.
Examples of the yellow colorant include compounds typified by monoazo compounds, disazo compounds, condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment
Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, 155 168, 180, 185, 214, C.I. I. Solvent Yellow 93, 162 etc. can be illustrated.
Examples of the magenta colorant include monoazo compounds, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 150, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Violet 19 etc. can be illustrated.
Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner. The amount of the colorant added is usually 1 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Furthermore, the toner particles according to the present invention can be made into magnetic toner particles by containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. Magnetic materials include the following iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium and bismuth of these metals. And alloys of metals such as cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.
The magnetic material is preferably a surface-modified magnetic material, more preferably a material subjected to a hydrophobic treatment with a surface modifying agent that is a substance that does not inhibit polymerization. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.
These magnetic materials preferably have a number average particle diameter of 2 μm or less, more preferably 0.1 to 0.5 μm. The amount to be contained in the toner particles is preferably 20 to 200 parts by mass, more preferably 40 to 150 parts by mass with respect to 100 parts by mass of the polymerizable monomer, with respect to 100 parts by mass of the polymerizable monomer.

  As the polymerization initiator, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 40,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

  The following are mentioned as an example of a polymerization initiator. 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis Azo or diazo polymerization initiators such as -4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylper Oxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide Such peroxide polymerization initiators. A polymerization initiator that generates an ether compound at the time of decomposition during the polymerization reaction is preferable.

  An inorganic or organic dispersion stabilizer is preferably added to the aqueous medium. The type of inorganic compound used as the dispersion stabilizer is not particularly limited. For example, calcium phosphate salts, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silicon oxide, An aluminum oxide is mentioned. Among them, it is particularly preferable to use calcium phosphate salts. Specific examples of calcium phosphate salts include hydroxyapatite, fluoroapatite, calcium deficient apatite, carbonate apatite, tricalcium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, calcium diphosphate, tetracalcium phosphate, octacalcium phosphate And mixtures thereof are preferably used. In view of the positive chargeability and acid solubility of these calcium phosphates, it is more preferable that the calcium phosphates used in the present invention contain hydroxyapatite.

The kind of the organic compound as the dispersion stabilizer is not particularly limited. Examples thereof include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer.
Further, a surfactant may be used for fine dispersion of these dispersion stabilizers. This is to promote the intended action of the dispersion stabilizer. There are no particular limitations on the type of surfactant. Examples include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like.
When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is,
In order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium.
For example, in the case of calcium phosphates such as hydroxyapatite and tricalcium phosphate, an aqueous phosphate solution and an aqueous calcium salt solution may be mixed with high stirring.
In the present invention, a known chain transfer agent or polymerization inhibitor may be used to control the degree of polymerization of the polymerizable monomer.

The toner particles according to the present invention may further contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group (hereinafter also referred to as a polymer having a sulfonic acid group or the like).
Charge stability at the time of high temperature use which contains a polymer having a sulfonic acid group and the like is further increased. The amount to be contained in the toner particles is preferably 0.1 to 3.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer constituting the binder resin.
Examples of the monomer having a sulfonic acid group for producing the polymer include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, 2-methacrylamide-2-methylpropane sulfonic acid, vinyl sulfonic acid, Examples thereof include methacrylsulfonic acid.
The polymer containing a sulfonic acid group or the like used in the present invention may be a homopolymer of the above monomer, or may be a copolymer of the above monomer and another monomer. Good. Examples of the monomer that forms a copolymer with the above monomer include the vinyl monomers shown in the section of the polymerizable monomer constituting the binder resin.

The toner particles according to the present invention may further contain a charge control agent. As the charge control agent used for the toner particles, a conventionally known charge control agent can be used without any particular limitation. Specifically, as the negative charge control agent, the following metal compounds of aromatic carboxylic acids represented by salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, etc .; metal salts or metals of azo dyes or azo pigments Complexes: boron compounds, silicon compounds, calixarenes, etc. Examples of the positive charge control agent include the following quaternary ammonium salts, polymer compounds having a quaternary ammonium salt in the side chain; guanidine compounds; nigrosine compounds; imidazole compounds.
The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100.0 parts by mass of the binder resin. In the case of external addition, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100.0 parts by mass of the toner particles.

The toner particles according to the present invention may further contain a wax as a release agent. There is no restriction | limiting in particular as a mold release agent which can be used for this invention, A well-known thing can be utilized. For example, the following compounds are mentioned. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax or block copolymers thereof; Waxes mainly composed of fatty acid esters such as waxes, sazol waxes, ester waxes, and montanic acid ester waxes; those obtained by partially or fully deoxidizing fatty acid esters such as deoxidized carnauba wax; aliphatic hydrocarbon waxes Waxes grafted with vinyl monomers such as styrene and acrylic acid; partially esterified products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride; obtained by hydrogenation of vegetable oils and the like And methyl ester compounds having a Dorokishiru group.
The wax preferably contains 1.0 to 40.0 parts by mass with respect to 100.0 parts by mass of the polymerizable monomer constituting the binder resin. More preferably, it is 3.0-25.0 mass parts.

The toner of the present invention may contain inorganic fine powder in addition to toner particles containing at least a binder resin and a colorant, and the inorganic fine powder is preferably externally added. For example, the toner of the present invention can be obtained by externally mixing an inorganic fine powder with toner particles and adhering them to the surface of the toner particles. A known method may be adopted as the external addition method of the inorganic fine powder. For example, the method of performing a mixing process using a Henschel mixer (Mitsui Miike Kako Co., Ltd.) is mentioned.
The amount of the inorganic fine powder added is preferably 0.01 to 5.0 parts by mass, more preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner particles. If the addition amount is within the above range, a sufficient fluidity improving effect can be obtained while suppressing a decrease in fixing property. The inorganic fine powder preferably has a number average primary particle size of 4 to 80 nm, and more preferably 4 to 60 nm.
Examples of the inorganic fine powder include metal oxides such as titanium oxide powder, aluminum oxide powder, and zinc oxide powder; silica fine powder such as wet process silica and dry process silica. In the present invention, silica fine powder is preferred. The metal oxide or silica fine powder may be surface-treated with a treatment agent such as a silane coupling agent, a titanium coupling agent, or silicone oil. Furthermore, aluminum dope silica, strontium titanate, and hydrotalcite are mentioned. In addition, as an external additive, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder; fatty acid metal salt such as zinc stearate, calcium stearate, lead stearate, etc. can be added. .

The physical property value measuring method of the present invention will be described below.
(Weight average molecular weight of toner)
The weight average molecular weight (Mw) of the toner is measured by gel permeation chromatography (GPC) as follows.
First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

(Weight average molecular weight of crystalline resin)
The weight average molecular weight of the crystalline resin is measured by gel permeation chromatography (GPC) as follows.
First, 0.03 g of a crystalline resin is dispersed in 10 ml of o-dichlorobenzene and dissolved, and then allowed to stand at 135 ° C. for 24 hours for dissolution. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, measurement is performed under the following conditions.
[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71
In calculating the molecular weight of the sample, standard polystyrene resin (TSK manufactured by Tosoh Corporation)
Standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500) are used.

(Measurement of weight average molecular weight of amorphous vinyl part in crystalline resin and mass ratio of crystalline polyester part to amorphous vinyl part in crystalline resin)
Measurement of the molecular weight of the amorphous vinyl part in the crystalline resin and measurement of the mass ratio of the crystalline polyester part to the amorphous vinyl part in the crystalline resin are carried out by hydrolyzing the polyester part of the crystalline resin. Measure. Specifically, 50 ml of dioxane and 10 ml of a 10 wt% aqueous potassium hydroxide solution were added to 300 mg of crystalline resin, and a commercially available horizontal shaker was used at a temperature of 70 ° C. for about 2 reciprocations per second for 6 hours. Shake to hydrolyze the polyester part. Thereafter, the solvent is distilled off under reduced pressure, and further dried in a 90 ° C. atmosphere under reduced pressure for 24 hours to prepare a sample for measuring the molecular weight of the vinyl part. The mass of the obtained measurement sample is A (mg). And the mass ratio (wt%) of the amorphous vinyl site | part in crystalline resin is computed by following Formula.

Mass ratio of amorphous vinyl moiety in crystalline resin (wt%) = A / 300 × 100
Next, 0.03 g of the measurement sample is dispersed in 10 ml of o-dichlorobenzene and dissolved, and then allowed to stand at 135 ° C. for 24 hours for dissolution. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. Using this sample solution, analysis is performed under the same conditions as the weight average molecular weight of the crystalline resin.

(Glass transition temperature Tg of toner and melting point of crystalline resin Tm (C))
The glass transition temperature Tg of the toner and the melting point of the crystalline resin are measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, 5 mg of toner or 1 mg of crystalline resin is precisely weighed, placed in an aluminum pan, and an empty aluminum pan is used as a reference, and the temperature is raised between 20 ° C. and 140 ° C. Modulation measurement is performed at a speed of 1 ° C./min and an amplitude temperature range of ± 0.318 ° C./min. In this temperature raising process, a specific heat change is obtained in the temperature range of 20 ° C to 140 ° C. The glass transition temperature Tg of the toner is defined as an intersection point between the baseline intermediate line and the differential heat curve before and after the specific heat change of the reversible specific heat change curve. The melting point Tm (C) of the crystalline resin is the maximum endothermic peak temperature in the specific heat change curve. In the present invention, whether or not a crystalline site exists in the crystalline resin is determined by the presence or absence of the maximum endothermic peak temperature in the specific heat change curve.

(Glass transition temperature Tg (H) of polar resin)
The glass transition temperature Tg (H) of the polar resin is determined by the differential scanning calorimeter “Q1000” (TA
Measured in accordance with ASTM D3418-82 using Instruments, Inc.).
The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.
Specifically, about 10 mg of polar resin is precisely weighed and placed in an aluminum pan, and an empty aluminum pan is used as a reference. Measure in min. In this temperature rising process, a specific heat change is obtained in the temperature range of 40 to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the specific heat change and the differential heat curve is defined as the glass transition temperature Tg of the polar resin.

(Molecular weight of polar resin)
The molecular weight distribution of the polar resin is measured by gel permeation chromatography (GPC) as follows.
First, a polar resin is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. Then, the obtained solution is filtered through a solvent-resistant membrane filter “Mysholy disk” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

(Acid value Av (C) of crystalline resin and acid value Av (H) of polar resin)
The acid values of the crystalline resin and the polar resin were measured by the following method.
The acid value is the number of mg of potassium hydroxide necessary for neutralizing the acid contained in 1 g of the sample. Although the acid value of crystalline resin and polar resin is measured according to JIS K 0070-1992, specifically, it measures according to the following procedures.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test 2.0 g of the pulverized crystalline resin and polar resin sample are precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added over 5 hours. Dissolve. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

(Hydroxyl value of polar resin)
In the present invention, the hydroxyl value (JIS hydroxyl value) of the polar resin is determined by the following method.
The hydroxyl value is the number of mg of potassium hydroxide required to neutralize acetic acid bonded to a hydroxyl group when 1 g of a sample is acetylated. The hydroxyl value of the binder resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(A) Preparation of reagent 25 g of special grade acetic anhydride is placed in a 100 ml volumetric flask, pyridine is added to make a total volume of 100 ml, and shaken sufficiently to obtain an acetylating reagent. The obtained acetylating reagent is stored in a brown bottle so as not to come into contact with moisture, carbon dioxide gas and the like.
Dissolve 1.0 g of phenolphthalein in 90 ml of ethyl alcohol (95 vol%) and add ion exchange water to make 100 ml to obtain a phenolphthalein solution.
Dissolve 35 g of special grade potassium hydroxide in 20 ml of water and add ethyl alcohol (95 vol%) to make 1 liter. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.5 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.5 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(A) Operation (A) Main test A 1.0 g sample of the pulverized binder resin is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added to the sample using a whole pipette. At this time, if the sample is difficult to dissolve in the acetylating reagent, a small amount of special grade toluene is added and dissolved.
A small funnel is placed on the mouth of the flask, and the bottom of the flask is immersed in a glycerin bath at about 97 ° C. and heated. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, it is preferable to cover the base of the neck of the flask with a cardboard having a round hole.
After 1 hour, the flask is removed from the glycerin bath and allowed to cool. After standing to cool, 1 ml of water is added from the funnel and shaken to hydrolyze acetic anhydride. The flask is again heated in the glycerin bath for 10 minutes for further complete hydrolysis. After cooling, wash the funnel and flask walls with 5 ml of ethyl alcohol.
Add several drops of the phenolphthalein solution as an indicator and titrate with the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration similar to the above operation is performed except that no binder resin sample is used.
(C) Substituting the obtained results into the following equation to calculate the hydroxyl value.
A = [{(BC) × 28.05 × f} / S] + D
Here, A: hydroxyl value (mg KOH / g), B: addition amount (ml) of potassium hydroxide solution in blank test, C: addition amount (ml) of potassium hydroxide solution in this test, f: potassium hydroxide Factor of solution, S: sample (g), D: acid value of binder resin (mgKOH / g).

(Toner particles and toner weight average particle diameter (D4) and number average particle diameter (D1))
The weight average particle diameter (D4) and the number average particle diameter (D1) of the toner particles and the toner are the precision particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark) by the pore electric resistance method equipped with an aperture tube of 100 μm. Using Beckman Coulter Multisizer 3 Version 3.51 (manufactured by Beckman Coulter, Inc.) and the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.). Measurements were taken with 55,000 channels, and the measurement data was analyzed and calculated.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software was set as follows.
In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.
In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and "Contaminone N" (nonionic surfactant, anionic surfactant, organic builder pH 7 precision measurement is used as a dispersant therein. About 0.3 ml of a diluted solution obtained by diluting a 10% by weight aqueous solution of a neutral detergent for washing a vessel (made by Wako Pure Chemical Industries, Ltd.) 3 times with ion exchange water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated in a state where the phase is shifted by 180 degrees, and is placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikka Ki Bios) with an electrical output of 120 W. A predetermined amount of ion-exchanged water is put, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

(Particle ratio of toner and toner particles 4 μm or less)
The particle ratio (number%) of 4 μm or less in the toner is calculated by analyzing the data after measuring the Multisizer 3 described above.
The number% of particles of 4.0 μm or less in the toner is calculated by the following procedure. First, graph / number% is set with the dedicated software, and the measurement result chart is displayed in number%. Then, check “<” in the particle size setting portion on the “format / particle size / particle size statistics” screen, and enter “4” in the particle size input section below. The numerical value of the “<4 μm” display portion when the “analysis / number statistics (arithmetic mean)” screen is displayed is the number% of particles of 4.0 μm or less in the toner.

(Measuring method of average circularity of toner particles)
The average circularity of the toner particles was measured with a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.
A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (for example, “VS-150” (manufactured by Velvo Crea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
For the measurement, the above-mentioned flow type particle image analyzer equipped with “LUCPLFLN” (magnification 20 ×, numerical aperture 0.40) as an objective lens is used, and particle sheath “PSE-900A” (manufactured by Sysmex Corporation) is used as the sheath liquid. It was used. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 2000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis was set to 85%, the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm, and the average circularity of the toner particles was determined.
In the measurement, automatic focus adjustment is performed using standard latex particles (for example, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5100A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.
In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle diameter was limited to a circle equivalent diameter of 1.977 μm or more and less than 39.54 μm.

Next, an example of an image forming method using the toner of the present invention will be described with reference to FIGS. However, the present invention is not limited to this.
<Process cartridge>
FIG. 1 is a schematic sectional view of a process cartridge 7 (hereinafter also referred to as “cartridge”) that can be suitably used in an image forming apparatus using the toner of the present invention.
The cartridge 7 includes a photosensitive drum 1, a cleaner unit 50 including a charging unit 2 and a cleaning unit 6, and a developing unit 4A having a developing unit 4 that develops an electrostatic latent image formed on the photosensitive drum 1. Have. The photosensitive drum 1 is rotatably attached to the cleaning frame 31 constituting the cleaner unit 50 via a bearing member.
The photosensitive drum 1 has a charging roller 2 for uniformly charging the photosensitive layer provided on the outer peripheral surface of the photosensitive drum 1, and a developer (residual toner) remaining on the photosensitive drum 1 after transfer is removed. The cleaning blade 60 for making contact is in contact. The toner (removed toner) removed from the surface of the photosensitive drum 1 by the cleaning blade 60 is stored in a removed toner storage chamber 35 provided in the cleaning frame 31.

The developing unit 4A has a developing frame body 45 (45a, 45b, 45e) that accommodates toner, and the developing roller 40 (rotated in the direction of arrow Y) is rotatably attached to the developing frame body 45 via a bearing member. It is supported. Further, a toner supply roller 43 (rotated in the arrow Z direction) and a toner regulating member 44 are provided in contact with the developing roller 40. Further, the developing device frame 45 is provided with a toner transport mechanism 42 for stirring the toner contained therein and transporting the toner to the toner supply roller 43.
The developing unit 4A is supported so as to be swingable with respect to the cleaner unit 50. That is, the coupling holes 47, 48 provided at both ends of the developing device frame 45 and the support holes (not shown) provided at both ends of the cleaning frame 31 of the cleaner unit 50 are aligned, and pins (not shown) are inserted from both ends of the cleaner unit 50. It is out.
Further, the developing unit 4A is always urged by a pressure spring (not shown) so that the developing roller 40 contacts the photosensitive drum 1 with the support hole as the rotation axis.

At the time of development, the toner stored in the toner container 41 is conveyed to the toner supply roller 43 by the toner stirring mechanism 42. The toner supply roller 43 supplies toner to the developing roller 40 by rubbing with the developing roller 40, and causes the toner to adhere on the developing roller 40. The toner adhered on the developing roller 40 reaches the toner regulating member 44 as the developing roller 40 rotates. Then, the toner regulating member 44 regulates the toner to form a predetermined toner thin layer, and gives a desired charge amount. The toner thinned on the developing roller 40 is conveyed to the developing unit in which the photosensitive drum 1 and the developing roller 40 come close as the developing roller 40 rotates. Then, in the developing unit, the latent image is developed by attaching to the electrostatic latent image formed on the surface of the photosensitive drum 1 by a developing bias applied to the developing roller 40 from a power source (not shown). The toner remaining on the surface of the developing roller 40 without contributing to the development of the electrostatic latent image is returned into the developing frame 45 as the developing roller 40 rotates. Then, it is peeled off and collected from the developing roller 40 at the rubbing portion with the toner supply roller 43. The collected toner is stirred and mixed with the remaining toner by the toner stirring mechanism 42.
Here, an elastic roller is used as the developing roller 40, and a method of bringing the roller into contact with the surface of the photosensitive drum 1 can be used. In general, in a developing method in which a toner carrier and a photoreceptor are in contact with each other, damage and deformation of the toner are likely to occur. preferable.

<Image forming apparatus>
FIG. 2 is a schematic cross-sectional view showing an example of an image forming apparatus using the toner of the present invention. The image forming apparatus 100 has four image forming stations Pa, Pb, Pc, and Pd arranged in parallel in the vertical direction. The process cartridges 7 (7a, 7b, 7c, 7d) are detachably attached to the image forming stations Pa, Pb, Pc, Pd by attachment means (not shown). The magenta, cyan, yellow, and black cartridges 7a, 7b, 7c, and 7d have the same configuration.
In this schematic diagram, the image forming stations Pa, Pb, Pc, and Pd are arranged side by side with a slight inclination in the vertical direction, but they may be arranged in the vertical direction without being inclined. Further, the process cartridge 7 may be the same as that illustrated in FIG. 1 or may be different.

Each cartridge 7 (7a, 7b, 7c, 7d) has a photosensitive drum 1 (1a, 1b, 1c).
1d). The photosensitive drum 1 is driven to rotate counterclockwise in the drawing by a driving means (not shown). The following means are provided around the photosensitive drum 1 in order according to the rotation direction. (A) Charging means 2 (2a, 2b, 2c, 2d) for uniformly charging the surface of the photosensitive drum 1. (B) A scanner unit 3 (3a, 3b, 3c, 3d) that irradiates a laser beam based on image information to form an electrostatic latent image on the photosensitive drum 1. (C) Developing means 4 (4a, 4b, 4c, 4d) for developing a toner image by attaching a developer (hereinafter referred to as “toner”) to the electrostatic latent image. (D) A transfer device 5 that transfers the toner image on the photosensitive drum 1 to the recording medium S. (E) Cleaning means 6 (6a, 6b, 6c, 6d) for removing toner remaining on the surface of the photosensitive drum 1 after transfer.
Here, the photosensitive drum 1 and the charging means 2, the developing means 4, and the cleaning means 6, which are process means, are integrally constituted by a cartridge frame to form a cartridge to constitute a cartridge 7.
The photosensitive drum 1 (1a, 1b, 1c, 1d) is configured by providing a photosensitive layer on the outer peripheral surface of a cylinder. Both ends of the photosensitive drum 1 are rotatably supported by support members. Then, when a driving force from a driving motor (not shown) is transmitted to one end portion, it is rotationally driven counterclockwise.

As the photoconductor, a photoconductor drum having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used. Further, the binder resin of the organic photosensitive layer in the OPC photoreceptor is not particularly limited. Of these, polycarbonate resins, polyester resins, and acrylic resins are particularly preferable because they are excellent in transferability and hardly cause toner fusion to the photoreceptor and filming of external additives.
As the charging means 2 (2a, 2b, 2c, 2d), a contact charging type is used. The charging means 2 is a conductive roller formed in a roller shape. The roller is brought into contact with the surface of the photosensitive drum 1 and a charging bias voltage is applied to the roller. As a result, the surface of the photosensitive drum 1 is uniformly charged.
In the scanner unit 3 (3a, 3b, 3c, 3d), a laser diode (not shown) passes image light corresponding to an image signal through a polygon mirror (not shown) and an imaging lens (not shown) rotated at high speed. Then, the surface of the charged photosensitive drum 1 is exposed according to image information. As a result, an electrostatic latent image is formed on the photosensitive drum.

The developing means 4 (4a, 4b, 4c, 4d) is composed of a toner container 41 that stores magenta, cyan, yellow, and black toners, respectively, and feeds toner in the toner container 41. To the toner supply roller 43.
The toner supply roller 43 rotates in the clockwise direction in the figure, and supplies toner to the developing roller 40 as a toner carrying member and does not contribute to the development of the electrostatic latent image. Perform stripping.
The toner supplied to the developing roller 40 is applied to the outer periphery of the developing roller 40 (rotated clockwise) by the toner regulating member 44 pressed against the outer periphery of the developing roller 40, and is given an electric charge. Then, a developing bias is applied to the developing roller 40 facing the photosensitive drum 1 on which the latent image is formed. Then, toner development is performed on the photosensitive drum 1 in accordance with the latent image.

The transfer device 5 is provided with an electrostatic transfer belt 11 that circulates and moves so as to face and contact all the photosensitive drums 1 (1a, 1b, 1c, 1d). The transfer belt 11 is stretched around a driving roller 13, driven rollers 14a and 14b, and a tension roller 15, and electrostatically attracts the recording medium S to the outer peripheral surface on the left side in the drawing. The transfer belt 11 circulates so that the recording medium S is brought into contact with the photosensitive drum 1. As a result, the recording medium S is conveyed to the transfer position by the transfer belt 11 and the toner image on the photosensitive drum 1 is transferred.
Abutting on the inside of the transfer belt 11, the four photosensitive drums 1 (1a, 1b, 1c, 1d)
), Transfer rollers 12 (12a, 12b, 12c, 12d) are arranged in parallel. A bias is applied to the transfer rollers 12 at the time of transfer, and an electric charge is applied to the recording medium S via the electrostatic transfer belt 11. The toner image on the photosensitive drum 1 is transferred to the recording medium S in contact with the photosensitive drum 1 by the electric field generated at this time.

The feeding unit 16 feeds and transports the recording medium S to the image forming stations Pa, Pb, Pc, and Pd. A plurality of recording media S are stored in the cassette 17 in the feeding unit 16. At the time of image formation, the feeding roller 18 (half-moon roller) and the registration roller 19 are driven and rotated according to the image forming operation. The feeding roller 18 separates and feeds the recording medium S in the cassette 17 one by one, and then stops the recording medium S by abutting against the registration roller 19. Thereafter, the registration roller 19 feeds the recording medium S to the electrostatic transfer belt 11 in synchronization with the rotation of the transfer belt 11 and the image writing position.
The fixing unit 20 fixes the toner images of a plurality of colors transferred to the recording medium S. The fixing unit 20 includes a heating roller 21a and a pressure roller 21b that presses against the heating roller 21a and applies heat and pressure to the recording medium S. That is, the recording medium S to which the toner image formed on the photosensitive drum 1 has been transferred is conveyed by the pressure roller 21b and applied with heat and pressure by the heating roller 21a when passing through the fixing unit 20. As a result, a plurality of color toner images are fixed on the surface of the recording medium S.
As an image forming operation, the cartridges 7 (7a, 7b, 7c, 7d) are sequentially driven in accordance with the image forming timing. In response to the driving, the photosensitive drums 1a, 1b, 1c, and 1d are rotationally driven in the counterclockwise direction. Then, the scanner units 3 corresponding to the respective cartridges 7 are sequentially driven. By this driving, the charging roller 2 applies a uniform charge to the peripheral surface of the photosensitive drum 1. The scanner unit 3 exposes the circumferential surface of the photosensitive drum in accordance with the image signal to form an electrostatic latent image on the circumferential surface of the photosensitive drum. The developing roller 40 in the developing unit 4 forms (develops) a toner image on the circumferential surface of the photosensitive drum 1 by transferring the toner to the low potential portion of the electrostatic latent image.

At the timing when the leading edge of the toner image formed on the circumferential surface of the most upstream photosensitive drum 1 is rotated and conveyed to the point facing the transfer belt 11, the print start position of the recording medium S coincides with the point facing the transfer belt 11. Thus, the registration roller 19 rotates to feed the recording medium S to the transfer belt 11.
The recording medium S is pressed against the outer periphery of the transfer belt 11 so as to be sandwiched between the suction roller 22 and the transfer belt 11. A voltage is applied between the transfer belt 11 and the suction roller 22. Electric charges are induced in the recording medium S that is a dielectric and the dielectric layer of the transfer belt 11, and the recording medium S is electrostatically adsorbed on the outer periphery of the transfer belt 11. Thereby, the recording medium S is stably adsorbed to the electrostatic transfer belt 11 and conveyed to the most downstream transfer unit.
The toner images on the respective photosensitive drums 1 are sequentially transferred to the recording medium S while being conveyed in this manner by an electric field formed between the respective photosensitive drums 1 and the transfer roller 12.
The recording medium S to which the four color toner images are transferred is separated from the electrostatic transfer belt 11 by the curvature of the belt driving roller 13 and is carried into the fixing unit 20. After the toner image is thermally fixed by the fixing unit 20, the recording medium S is discharged out of the main body by the paper discharge roller 23 with the image surface facing down from the paper discharge unit 24.
Although FIG. 2 illustrates a method using a heating roller for the fixing unit 20, the toner of the present invention can be suitably used for other fixing methods. As an example, there is an apparatus for fixing a toner image by heating a heat-resistant polymer film using a heating element.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass.

(Production example of crystalline resin)
(Crystalline resin 1)
Under a nitrogen atmosphere, 50 parts of xylene, 175.0 parts of sebacic acid, and 210.1 parts of 1,12-dodecanediol were added to a pressure resistant reactor equipped with a dropping funnel, a Liebig condenser and a stirrer, and the temperature was raised to 210 ° C. Warm up. The pressure at this time was 0.32 MPa. A mixture of 52.3 parts of styrene, 5.43 parts of acrylic acid, and 3.67 parts of di-tert-butyl peroxide (Perbutyl D, manufactured by NOF Corporation) as a polymerization initiator in 10 parts of xylene. What was charged in the dropping funnel was dropped under pressure (0.31 MPa) over 2 hours. After the dropping, the reaction was further performed at 210 ° C. for 3 hours to complete the solution polymerization. Thereafter, 0.80 part of tetrabutoxy titanate was charged, and a polycondensation reaction was performed at 210 ° C. under a nitrogen atmosphere for 3 hours under normal pressure. Thereafter, 0.010 part of tetrabutoxy titanate was added and reacted at 210 ° C. for 2 hours. Thereafter, the pressure was returned to normal pressure, 33.1 parts of benzoic acid and 4.00 parts of trimellitic acid were added, and the mixture was further reacted at 220 ° C. for 5 hours to obtain a crystalline resin 1. Since the mass ratio of the crystalline polyester part and the amorphous vinyl part in the crystalline resin 1 was equal to the mass ratio in the raw material, it was confirmed that there was no unreacted amorphous vinyl part. Table 2 shows the physical properties of the obtained crystalline resin 1.

(Crystalline resin 2-24)
In the production example of the crystalline resin 1, except that the addition amount of the monomer, the bireactive monomer (acrylic acid), the initiator, other additives, and the polycondensation reaction conditions were changed as shown in Table 1, the crystal The reaction was carried out in the same manner as in the production example of the crystalline resin 1 to obtain crystalline resins 2 to 24.
Table 2 shows the physical properties of the obtained crystalline resins 2 to 24.

(Production example of polar resin)
(Polar resin 1)
After putting 300 parts by mass of xylene (boiling point 144 ° C.) into an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirring device, the inside of the container was sufficiently replaced with nitrogen while stirring. The temperature was raised to reflux.
Under this reflux,
Styrene 91.50 parts by weight butyl acrylate 1.00 parts by weight methyl methacrylate 2.50 parts by weight methacrylic acid 2.50 parts by weight 2-hydroxyethyl methacrylate 2.50 parts by weight initiator di- After adding 2.00 parts by mass of a mixed solution of tert-butyl peroxide, polymerization was carried out for 5 hours at a polymerization temperature of 160 ° C. and a reaction pressure of 0.150 MPa. Then, the solvent removal process was performed under reduced pressure for 3 hours, xylene was removed, and the polar resin 1 was obtained by grinding.
Table 4 shows the physical properties of the polar resin 1.

(Polar resin 2-15)
In the production example of the polar resin 1, polar resins 2 to 15 were obtained in the same manner except that the addition amount of the monomer and the reaction conditions were changed as shown in Table 3.
Table 4 shows the physical properties of the polar resins 2 to 15.

(Polar resin 16)
In an autoclave equipped with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device, and a stirrer. Parts · Bisphenol A-propylene oxide 3 mol adduct 23.0 parts by mass · Potassium oxalate titanate 0.030 parts by mass The above polyester monomer was charged and reacted at 220 ° C for 15 hours under nitrogen atmosphere and normal pressure. Furthermore, it was made to react under reduced pressure of 10-20 mmHg for 1 hour, and the polar resin 16 was obtained. Table 4 shows the physical properties of the polar resin 16.

(Example of toner production)
(Toner 1)
A suspension polymerization toner was produced by the following method.
First, the following materials were uniformly dissolved and mixed at 100 r / min with a propeller type stirring device to prepare a polymerizable monomer composition.
-Styrene 70.0 parts by mass-n-butyl acrylate 30.0 parts by mass-Polar resin 1 10.0 parts by mass-Crystalline resin 1 10.0 parts by mass-Pigment Blue 15: 3 7.5 parts by mass-Paraffin wax (HNP-5: Nippon Seiki, melting point 60 ° C.) 9.0 parts by mass / sulfonic acid group-containing copolymer FCA-1001-NS (manufactured by Fujikura Kasei Co., Ltd.) 1.0 part by mass / charge control agent Bontron E-88 (Orient Chemical Co., Ltd.) 0.5 parts by mass Next, the polymerizable monomer composition was heated to 60 ° C., Cavitron (manufactured by Eurotech) was introduced, and the preparation solution was mixed. The circumferential speed G (m / s) of the rotor was 40, and the mixing time was 30 minutes. Thereafter, 8.0 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.
On the other hand, 850 parts of a 0.1 mol / L-Na ₃ PO ₄ aqueous solution and 8.0 parts by mass of 10% hydrochloric acid were added to a container equipped with a high-speed agitator CLEARMIX (M Technique Co., Ltd.), and the rotational speed was 80 rps. And heated to 60 ° C. To this, 68 parts of a 1.0 mol / L-CaCl ₂ aqueous solution was added to prepare an aqueous medium containing a slight sparingly water-soluble dispersant Ca ₃ (PO ₄ ) ₂ . After 5 minutes after adding the polymerization initiator to the polymerizable monomer composition, the polysynthetic monomer composition at 60 ° C. is put into an aqueous medium heated to 60 ° C., and the CLEARMIX is rotated at 80 rps. And granulated for 15 minutes. Thereafter, the stirrer was changed from a high-speed stirrer to a propeller stirring blade, and the mixture was reacted at 70 ° C. for 5 hours while refluxing. After completion of the polymerization, the liquid temperature was lowered to about 20 ° C., diluted hydrochloric acid was added to adjust the pH of the aqueous medium to 3.0 or less, and the poorly water-soluble dispersant was dissolved. Further, washing and drying were performed to obtain toner particles. For the obtained toner particles, the weight average particle diameter (D4) (μm), the number average particle diameter (D1) (μm), and the particle ratio (number%) of 4 μm or less were measured. The results are shown in Table 6.
To 100 parts of the obtained toner particles, 1.6 parts of silica fine particles having an average primary particle size of 40 nm are added as an external additive, and mixed using a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. Obtained. Table 6 shows the physical properties of Toner 1.

(Toner 2 to Toner 47)
In the toner 1 production example, toners 2 to 47 are obtained in the same manner as in the toner 1 production example except that the crystalline resin type, polar resin type, addition amount, and polymerization conditions are changed to those shown in Table 5. It was. Table 6 shows the physical properties of Toner 2 to Toner 47.

(Examples 1-37, Comparative Examples 1-10)
The toners 1 to 47 were evaluated according to the combinations shown in Table 7.
[Example 1]
Using toner 1 as a non-magnetic one-component developer, and a remodeling machine of a commercially available laser printer LBP-5400 (manufactured by Canon) as the image forming apparatus, temperature 23 ° C., relative humidity 50%
Image evaluation was performed using an A4 color laser copier paper (manufactured by Canon, 80 g / m ² ) under the environment. The remodeling points of the evaluation machine are as follows.
By changing the gear and software of the evaluation machine main body, the process speed was set to 360 mm / sec.
The cartridge used for evaluation was a cyan cartridge. That is, the product toner was extracted from a commercially available cyan cartridge, the inside was cleaned by air blow, and 150 g of the toner according to the present invention was filled for evaluation. In addition, the product toner was extracted from each of the magenta, yellow, and black stations, and evaluation was performed by inserting magenta, yellow, and black cartridges in which the toner remaining amount detection mechanism was disabled.

(1) Low-temperature fixability during high-speed fixing Using the above-mentioned evaluation machine, using basis 4105 (manufactured by Xerox) having a basis weight of 105 g / m ² as an evaluation paper, setting temperature adjustment in a temperature range from 130 ° C. to 220 ° C. The original image was output at each temperature while changing the temperature every 5 ° C.
As the original image, a 10 mm square solid patch image (toner applied amount 0.90 mg / cm ² ) was output at the center when the paper surface was divided into 9 parts.
Subsequently, the lowest fixable temperature was determined by performing a rubbing resistance test of the fixed image output at each temperature.
The minimum fixable temperature is the average of the density reduction rate obtained by measuring the fixed image density and the image density after rubbing the fixed image with Sylbon paper applied with a load of 50 g / cm ² five times for each patch. It is defined as a fixing state where the value satisfies 10% or less.
For measurement of the density, “Macbeth reflection densitometer RD918” (manufactured by Macbeth) was used. A: A stable fixed image can be obtained when the minimum fixable temperature is 160 ° C. or lower B: A stable fixed image can be obtained when the minimum fixable temperature is higher than 160 ° C. and lower than 175 ° C. C: The minimum fixable temperature is 175 A stable fixed image is obtained at a temperature higher than 190 ° C. and lower than 190 ° C. D: The minimum fixing temperature is higher than 190 ° C. or has no fixing temperature

(2) High-temperature offset resistance The toner is applied to the center of the front end of the recording material, a solid image of 5 cm × 5 cm area is formed at an amount of 0.20 mg / cm ² , and the rear end of the recording material in the paper feeding direction when passing through the fixing device Measure the temperature of the surface of the fixing heating part when a hot offset phenomenon occurs (a phenomenon in which a part of the fixed image adheres to the surface of the fixing member and then fixes on the recording material in the next round), The temperature was determined as the hot offset phenomenon occurrence temperature, and was evaluated based on the following evaluation criteria.
A: 180 ° C. or higher B: 175 ° C. or higher, lower than 180 ° C. C: 170 ° C. or higher, lower than 175 ° C. D: less than 170 ° C.

(3) Charge uniformity The charge uniformity was evaluated as follows.
That is, the particle size distribution of the toner in the cartridge at the initial stage and after 10,000 sheets is measured in accordance with the above-described method for measuring the weight average particle diameter (D4). The particle size change rate was calculated based on the above and evaluated based on the following criteria. The more uniform the charge distribution of each toner, the more uniformly the toner of each particle size is consumed by durable use, so the change rate of the weight average particle size (D4) becomes smaller.
Initial weight average particle diameter (D4) / weight average particle diameter after 10,000 sheets (D4) × 100 = Particle size change rate (%)
A: 95 ≦ particle size change rate (%) ≦ 100
B: 85 ≦ particle size change rate (%) <95
C: 75 ≦ particle size change rate (%) <85
D: Particle size change rate (%) <75

(4) Image fog The durability of the toner was evaluated by performing a durability test using the modified machine described above.
The durability test is performed under high temperature and high humidity environment (30 ° C, 80% RH), normal temperature and normal humidity environment (23 ° C, 50% RH), and low temperature and low humidity environment (15 ° C, 10% RH). An original image with a ratio of 2% was printed out 3000 sheets a day, and a total of 12000 sheets were output in 4 days. The evaluation timing was every 1000 sheets, and a solid white image was output on the first sheet on each evaluation day, and the following evaluation criteria were used.
Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printout image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured with a blue filter attached.
In addition, the evaluation criteria judged the worst value through durability with the following criteria.
A: Less than 1.0% B: 1.0% or more and less than 2.0% C: 2.0% or more and less than 3.0% D: 3.0% or more Fog (reflectance;%) = (standard Paper reflectance;%)-(Sample reflectance;%)

(5) Storage stability In order to evaluate storage stability, blocking resistance was evaluated. About 10 g of toner was put in a 100 ml polycup and allowed to stand at 55 ° C. for 3 days, and then visually evaluated.
A: Aggregates are not seen.
B: Although the aggregate is slightly seen, the aggregate is easily broken.
C: Aggregates are observed, but the aggregates are easily broken.
D: Although many agglomerates are observed, the agglomerates can be broken by shaking the cup.
E: Aggregates are very much observed and the aggregates cannot be easily broken.

  When the toner 1 was evaluated under the above conditions, the toner 1 showed a very good result in the low-temperature fixability at the time of high-speed output. In addition, the hot offset resistance, charging uniformity, fogging, and storage stability were also good. Detailed results are shown in Table 7.

[Examples 2 to 37]
Toner 2 to toner 37 were evaluated under the same conditions as in Example 1. Detailed results are shown in Table 7. [Comparative Examples 1 to 10]
Comparative toners 1 to 10 were evaluated under the same conditions as in Example 1. Detailed results are shown in Table 7.

Pa, Pb, Pc, Pd Image forming station 1 (1a to 1d) Photosensitive drum (image carrier)
2 (2a to 2d) Charging means 3 (3a to 3d) Scanner unit 4 (4a to 4d) Developing means 4A Developing unit 5 Electrostatic transfer device 6 (6a to 6d) Cleaning means 7 (7a to 7d) Process cartridge 11 Static Electrotransfer belt 12 (12a to 12d) Transfer roller 13 Belt drive rollers 14a and 14b Driven roller 15 Tension roller 16 Feeding unit 17 Cassette 18 Feeding roller 19 Registration roller 20 Fixing unit 21a Heating roller 21b Pressure roller 22 Adsorption roller 23 Paper discharge roller 24 Paper discharge unit 31 Cleaning frame (cartridge frame)
35 Removal toner storage chamber 40 Developing roller (toner carrier)
41 Toner container (developer storage part)
42 Toner transport mechanism 43 Toner supply roller 44 Toner regulating member (blade)
45 (45a, 45b, 45e) Development frame (cartridge frame)
47, 48 Bonding hole 50 Cleaner unit 60 Cleaning blade 100 Image forming apparatus main body S Recording medium (recording material sheet)

Claims (6)

A polymerizable monomer composition containing a polymerizable monomer, a colorant, a polar resin, and a crystalline resin is added to an aqueous medium, and the polymerizable monomer composition is granulated in the aqueous medium. A toner comprising: forming particles of the polymerizable monomer composition; and polymerizing the polymerizable monomer composition contained in the particles of the polymerizable monomer composition to obtain toner particles. A manufacturing method of
The polymerizable monomer is a vinyl monomer,
The polar resin is a carboxyl group-containing vinyl polar resin,
The crystalline resin is a hybrid resin having a crystalline polyester portion and an amorphous vinyl portion,
The mass ratio (crystalline part / amorphous part) of the crystalline polyester part and the amorphous vinyl part of the crystalline resin is 70/30 or more and 98/2 or less,
When the melting point of the crystalline resin is Tm (C) (° C.) and the glass transition temperature of the polar resin is Tg (H) (° C.), the following formulas (1) and (2) are satisfied:
55.0 ≦ Tm (C) ≦ 90.0 (1)
5.0 ≦ Tg (H) −Tm (C) ≦ 30.0 (2)
When the acid value of the crystalline resin is Av (C) (mg KOH / g) and the acid value of the polar resin is Av (H) (mg KOH / g), the following formulas (3) to (5) are satisfied. A toner manufacturing method characterized by satisfying the above.
0.1 ≦ Av (C) ≦ 5.0 (3)
5.0 ≦ Av (H) ≦ 30.0 (4)
0.02 ≦ Av (C) / Av (H) ≦ 0.50 (5)   The polar resin has a hydroxyl value of 5.0 mgKOH / g or more and 20.0 mgKOH / g or less, and the content of the polar resin with respect to 100 parts by mass of the polymerizable monomer used in the toner particles is 3.0 parts by mass or more. The toner production method according to claim 1, wherein the toner content is 20.0 parts by mass or less.   The crystalline resin has a weight average molecular weight of 10,000 or more and 80,000 or less, and the amorphous vinyl portion of the crystalline resin has a weight average molecular weight of 2,000 or more and 12,000 or less. A method for producing the toner according to the description. Polar resin The method for producing a toner according to any one of claims 1 to 3, characterized in that a styrene-acrylic resin. The method for producing a toner according to any one of claims 1 to 4 , wherein the amorphous vinyl portion of the hybrid resin is a copolymer of a vinyl polymerizable monomer and acrylic acid. The polymerizable monomer 100 parts by constituting the binder resin, a crystalline resin 3.0 parts by mass or more, claim 1-5, characterized in that it contains less 30.0 parts by The toner production method according to one item.

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