JP2019028123A - toner - Google Patents

Abstract

To provide a toner which has excellent thin line reproducibility and low temperature fixability in various environments.SOLUTION: A toner contains toner base particles containing a vinyl resin, a colorant and amorphous polyester, where in a toner cross section of the toner observed with a transmission electron microscope (TEM), a matrix-domain structure is observed, a vinyl resin forms a matrix, the amorphous polyester forms a plurality of domains, 30 area% or more and 70 area% or less of the domain exists to the total area of the domain of the amorphous polyester with a distance from a contour of the toner cross section to a center point between the contour and the toner cross section of 25% or less, a softening point (Tm) of the amorphous polyester is 85°C or higher and 105°C or lower, and a theoretical specific surface area A (m/g) obtained from number-based particle size distribution and true density of the toner base particles and a specific surface area B (m/g) measured by a BET method satisfy the following expression (1): 0.450≤B≤1.500 and expression (2): 1.00≤B/A≤1.26.SELECTED DRAWING: None

Description

  The present invention relates to a toner used in a recording method using an electrophotographic method, an electrostatic recording method, a toner jet recording method, or the like.

In recent years, copiers and printers using electrophotography have come to be used in various countries and regions due to market expansion, and high-definition and high-quality images are stable even in a wide variety of environments and media. Thus, there is a demand for a printer obtained. Further, with the expansion of the market scale, various needs are demanded. For example, energy saving and downsizing are considered as major technical issues.
In order to obtain a high-definition and high-quality image, in addition to increasing the resolution of the image, excellent dot reproducibility as a toner is desired, and therefore a toner having uniform charge is required.
As for the media, for example, when paper with low smoothness is used, the concave portions of the paper are not easily pressed or heated in the fixing step, and the toner deformation tends to be insufficient. Therefore, in order to improve dot reproducibility, it is also necessary for the toner to instantaneously melt and deform with respect to heat.
As a means for downsizing, it is effective to mainly reduce the size of the fixing device and the size of the cartridge.
In order to reduce the size of the fixing device, it is easy to apply the heat fixing and the device configuration when film fixing is used. In such film fixing, a toner that can be fixed with a small amount of heat and light pressure is required.
In addition, since it is effective to reduce the size of the cartridge containing the developer, the one-component development method is preferable to the two-component development method using a carrier, and in order to obtain a high-quality image at the same time, the contact development method is used. preferable. Therefore, in order to satisfy the above performance, the contact one-component development method is an effective means.
To reduce the size of the contact one-component developing process cartridge, it is conceivable to reduce the diameter of the toner carrier or to reduce the supply roller for supplying toner to the sleeve toner carrier. Here, when the supply roller is eliminated, the toner transportability to the sleeve toner carrier is deteriorated, and it is difficult to uniformly transport the toner to the regulating portion, which is a severe condition for uniform charge application.
As described above, in order to obtain a high-definition image on a wide variety of media while downsizing the printer, the toner has excellent charging characteristics in various environments and has excellent low-temperature fixability. It is hoped that.
As a method for imparting excellent charging characteristics to the toner, Patent Document 1 proposes a method for producing toner mother particles having high circularity in order to make the charge amount distribution uniform in addition to the sharp particle size distribution. .
This technique has a step of forming droplets of a polymerizable monomer composition, and a step of polymerizing the polymerizable monomer composition to obtain toner mother particles. An aqueous medium containing is used. By using an aqueous medium containing a dispersion stabilizer also in the polymerization step, toner base particles having a high degree of circularity are obtained.
As a technique for improving low-temperature fixability, Patent Document 2 discloses a binder resin and a colorant containing an amorphous resin and an amorphous polyester resin (B) different from the amorphous resin (A). The toner base particles have a domain-matrix structure in which the amorphous polyester resin (B) is dispersed as a domain phase in a matrix phase made of the amorphous resin (A). In the observation image of the cross section of the toner base particle, the number average domain diameter of the domain phase of the amorphous polyester resin (B) having a domain diameter of 100 nm or more is 100 to 200 nm, and the domain with respect to the total area of the domain phase An electrostatic charge image developing toner has been proposed in which the area ratio of a domain phase having a diameter of 500 nm or more is 0 to 10%.

Japanese Patent No. 3972709 Japanese Patent Laying-Open No. 2015-152703

In the toner described in Patent Document 1, when an aqueous medium containing a dispersion stabilizer is used in the polymerization step, toner base particles having high circularity are surely obtained, irregularly shaped particles are reduced, and the chargeability of the toner base particles is improved. There is a possibility to improve it evenly. However, in the above-described film fixing, if a thin line is output using the toner with low smoothness, such as rough paper, the adhesion between the toners at the time of heat welding tends to decrease with a thin line with a small amount of toner. . Further, the toner present in the concave portion of the paper is not easily subjected to sufficient pressure and heat. For this reason, it is easy to peel off from the paper, and the reproducibility of the thin line is likely to deteriorate, and there is room for improvement.
In the toner described in Patent Document 2, since the polyester is exposed on the toner surface, it is difficult to uniformly charge the toner, it is difficult to obtain dot reproducibility, and there is room for improvement.
Further, in the contact development method in which the supply roller is omitted, there is room for improvement in durability and charging stability due to environmental fluctuations.
In addition, since the polyester is dispersed in the styrene acrylic resin by forming a small domain, the compatibility is high when sufficient heat is applied, and it is assumed that the heat deformation is easy. However, in a fixing machine with a small amount of heat and a light pressure such as the film fixing, the melt deformation of the toner in the concave portion tends to be insufficient, and the adhesion between paper and toner tends to be insufficient. For this reason, the separation of the molten toner tends to become more prominent when a high-print image is output.
The present invention provides a toner that solves the above problems. More specifically, the present invention provides a toner having excellent fine line reproducibility and low-temperature fixability in various environments.

As a result of intensive studies, the present inventors have adjusted the presence state of the amorphous polyester (domain) in the vinyl resin (matrix) in the vicinity of the surface layer in addition to controlling the shape of the outermost surface of the toner base particles. The present inventors have found a means for solving the above problems and completed the present invention.
That is, the present invention is a toner having toner base particles containing a binder resin, a colorant, and amorphous polyester,
In the toner cross section observed with a transmission electron microscope (TEM) of the toner, a matrix-domain structure is observed, the vinyl resin forms a matrix, and the amorphous polyester forms a plurality of domains,
The domain is present within 30% or more of the total area of the amorphous polyester domain within 25% of the distance between the outline and the center point of the toner cross section from the outline of the toner cross section. The softening point (Tm) of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower,
The theoretical specific surface area A (m ² / g) obtained from the number-based particle size distribution and true density of the toner base particles and the specific surface area B (m ² / g) measured by the BET method are expressed by the following formula (1): , (2) is satisfied.
0.450 ≦ B ≦ 1.500 (1)
1.00 ≦ B / A ≦ 1.26 (2)

  According to the present invention, it is possible to provide a toner capable of obtaining excellent fine line reproducibility and low-temperature fixability even for media having low smoothness.

It is a figure which shows an example of a developing device. 1 is an example of an image forming apparatus in which a developing device is incorporated. It is a schematic diagram of a flow curve.

  As described above, the toner of the present invention is a toner having toner base particles containing a vinyl resin, an amorphous polyester, and a colorant, and a matrix-domain structure is observed in the toner cross section. Is a toner in which the theoretical specific surface area A and the actual specific surface area B of the toner base particles are adjusted to a specific range in addition to the presence of the domain in the vicinity of the toner surface. It is characterized by.

  The present inventors consider the reason why the present invention has solved the above problems as follows.

  First, in order to solve the problems of the present invention, it is important that the vinyl resin has an amorphous polyester and the vinyl polyester has a plurality of domains.

  For example, the vinyl resin is a resin that can easily control the rigidity of the toner and easily improve the mechanical stress resistance of the toner. In addition, since amorphous polyester easily introduces a portion that melts in a specific temperature range, it tends to improve the melting characteristics of the toner by changing the monomer composition.

  In other words, the above-described matrix-domain structure enables the toner to have both stress resistance and fixing properties.

  In addition, when outputting images that do not contain dense toner such as fine lines on media with low smoothness, excellent charging uniformity, heat and pressure can be transferred to the media properly regardless of the unevenness of the paper. Excellent melt adhesion between toners is indispensable even in concave portions that are difficult to be applied.

  Accordingly, in the present invention, in terms of melt adhesion, the presence of the above-described amorphous polyester domains is made near the surface to promote thermal melting and to control the unevenness of the toner itself, thereby charging the toner. The above problem was solved by making the distribution uniform.

  Considering generation of toner base particles in an aqueous medium, for example, generation of toner base particles by a suspension polymerization method, the polymerizable monomer composition repeats coalescence, shearing, and coalescence in the granulation step. Of these two phenomena, when shearing is likely to occur compared to coalescence, the amorphous polyester has a domain shape and is present in the vicinity of the surface of the toner droplet, so the droplet tends to become unstable. In addition, the generation of fine particles and the droplets themselves tend to be unstable. As a result, extremely fine irregularities are formed on the surface of the toner particle diameter.

  In the present invention, it is necessary to suppress fine irregularities by uniformly covering the surface of the toner base particles with a polar resin having high affinity with the vinyl resin. Furthermore, by controlling the interfacial tension of the polar resin and the amorphous polyester with respect to the aqueous phase, it is possible to easily suppress variations in the amorphous polyester between and inside the toner during granulation. As a result, the balance between shearing and coalescence of the oil droplets formed with the polymerizable monomer composition in the granulation process can be controlled to some extent, so that it is easy to suppress the generation of fine particles and toner destabilization. It is thought that the unevenness of the surface could be suppressed.

  From the viewpoint of enhancing the adhesion between the toner when melted, the amorphous polyester domain is within 30% of the distance between the contour and the center point of the cross section from the contour of the cross section, based on the total area of the domain. It is necessary to exist in an area of 70% by area or more.

  The area ratio (hereinafter also referred to as “25% area ratio”) of the amorphous polyester domain existing within 25% of the distance between the outline and the center point of the cross section from the outline of the toner cross section is the melting of the toner at the time of melting. This parameter has a high correlation with deformation, and if it is high, the adhesion force between the toners at the time of melting or between the toner and paper increases.

  When the 25% area ratio is 30 area% or more, the adhesive force between the toner in the concave portion and between the toner and paper at the time of melting described above tends to increase, and the reproducibility of the thin line is increased. Further, if it is 70 area% or less, the ratio of the amorphous polyester on the surface layer can be controlled within a desired range, so that the brittleness and chargeability of the toner can be easily maintained, and it tends to be noticeable particularly in a high humidity environment. . From the viewpoint of further improving the above effects, the 25% area ratio is preferably 45 area% or more and 70 area%.

  Next, as the amorphous polyester, it is important that the softening point of the amorphous polyester is 85 ° C. or more and 105 ° C. or less because the toner is easily deformed by heating. When the amorphous polyester has a softening point of 85 ° C. or higher, the brittleness of the toner is easily maintained, the toner is less prone to cracking, and the reproducibility of fine lines can be stably obtained for long-term image printing. It tends to be easy. Also, if the softening point is 105 ° C. or less, it tends to melt and deform due to heat, so that the adhesive force between the toners in the recesses tends to be improved, and reproducibility of fine lines on paper with low smoothness tends to be obtained. is there.

  Means for controlling the softening point of the amorphous polyester within a preferable range of the present invention include a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms and a monomer unit derived from a dialcohol. The content ratio of the monomer unit derived from a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms is preferably 10 mol% or more and 50 mol% or less with respect to all monomer units derived from the carboxylic acid of the amorphous polyester.

The toner of the present invention has a theoretical specific surface area A (m ² / g) obtained from the particle size distribution and true density of the toner base particles, and a specific surface area B (m ² / g) measured by the BET method. Must satisfy the following formulas (1) and (2).
0.450 ≦ B ≦ 1.500 (1)
1.00 ≦ B / A ≦ 1.26 (2)

  This B / A (hereinafter referred to as the surface irregularity index) is a value calculated from the BET specific surface area measured by the BET multipoint method. is there. The theoretical specific surface area A is a numerical value when all the particles are true spheres. Therefore, as the surface unevenness index deviates from 1.00, the unevenness is formed on the particle surface. As a result of investigations by the present inventors, it is possible to impart uniform chargeability to the toner base particles by suppressing the occurrence of this extremely fine unevenness from the surface of the toner base particles, so even in media with low smoothness. Since a tendency to transfer with high accuracy is obtained, high reproducibility of fine lines tends to be easily obtained.

  When B is 0.450 or more, the particle size can be controlled within a certain range without increasing the particle size, and the surface roughness index tends to be easily controlled within the above range. In addition, since charging is easily maintained, the above-described fine line reproducibility tends to be easily obtained. Also, if B is 1.500 or less, the particle size can be maintained without a small particle size, so that the charge distribution is easily sharpened and the toner can be easily transferred uniformly to the paper, so that fine line reproducibility is obtained. There is a tendency to be easily.

  Moreover, as an ideal state with respect to the surface unevenness index, a state close to 1.00 where the extremely fine unevenness is minimal is most preferable.

  The surface roughness index required for the present invention is 1.26 or less. If it is 1.26 or less, fine irregularities can be suppressed, so that the chargeability tends to be uniform, and the dots for media with low smoothness tend to be reproducible, and the reproducibility of fine lines is obtained. It tends to be easy. When the surface roughness index is preferably 1.00 or more and 1.19 or less, stable uniform chargeability tends to be obtained even in a high humidity environment.

  In order to make the surface irregularity index within the above range, it is preferable that a material having high affinity with the vinyl resin forming the matrix is present in the vicinity of the surface, and in consideration of the chargeability of the toner base particles, the polar resin is a vinyl resin. It is preferable that it exists on the surface.

  In addition, by controlling the interfacial tension of polar resin and amorphous polyester in tricalcium phosphate aqueous solution, and by controlling the distillation process in suspension polymerization, such as the heating process of toner base particles, the surface roughness index Is preferably controlled.

  Further, the specific surface area B measured by the BET method is preferably adjusted by controlling the toner base particle diameter and the degree of fine unevenness of the particles.

  Hereinafter, preferred embodiments of the toner of the present invention will be described.

  As described above, the toner of the present invention contains a vinyl resin and an amorphous polyester.

  Examples of the vinyl resin include the following.

Homopolymers of styrene such as polystyrene and polyvinyltoluene and substituted products thereof;
Styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, Styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-methacrylic acid Dimethylaminoethyl acid copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene -Maleic acid copolymerization , Styrene - styrene copolymer and maleic acid ester copolymers;

  Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, and polyacrylic acid resin can be used, and these can be used alone or in combination. Among these, styrene copolymers, and styrene-butyl acrylate copolymers are particularly preferable from the viewpoints of development characteristics and ease of control of fixability.

  As the amorphous polyester that can be used in the toner of the present invention, a condensate of any dicarboxylic acid and dialcohol can be used. From the viewpoint of achieving both low-temperature fixability and charge stability in various environments, the amorphous polyester in the toner can be used. It is preferable to control the presence state of the conductive polyester within an arbitrary range.

  Specifically, as described above, a matrix-domain structure is observed in a toner cross section observed with a transmission electron microscope (TEM), a vinyl resin forms a matrix, and an amorphous polyester forms a plurality of domains. It is preferable that the 25% area ratio is 30 to 70 area%.

  Next, the domain of the amorphous polyester is within 80% of the distance between the contour and the center point of the cross section from the contour of the cross section, based on the total area of the domain, 80 area% or more and 100 area% or less Preferably it is present. More preferably, it is 90 area% or more and 100 area% or less.

  The area ratio (hereinafter also referred to as “50% area ratio”) of the amorphous polyester domain existing within 50% of the distance between the outline and the center point of the cross section from the outline of the toner cross section is 80 area% or more. If it exists, it can be melted instantaneously at the time of fixing, so that the low-temperature fixing property and the fine line reproducibility at the concave portion are likely to be good. Further, the presence of 80% by area or more of the domain can be said in other words that the existing amount of the domain in the region from the center point of the toner to 50% of the contour of the toner cross section is 20% by area or less. In such a state, it is easy to maintain the brittleness at the time of long-term use, and good fine line reproducibility is easily obtained even after long-term use. The domain formed by the amorphous polyester component preferably has a domain diameter of 0.3 μm or more and 3.0 μm or less, and more preferably 0.3 μm or more and 2.0 μm or less.

  When the number average diameter of the domains of the amorphous polyester is 0.3 μm or more, the adhesion between paper and toner is improved when melted at the time of fixing, and the fine line reproducibility is more easily improved.

  On the other hand, when the number average diameter of the amorphous polyester domains is 3.0 μm or less, the presence state of the amorphous polyester domains in the toner base particles can be easily controlled. In addition, it is possible to reduce the variation in the domain of the amorphous polyester between the toner base particles. Therefore, it becomes easier to improve the fine line reproducibility.

  As a method for controlling the number average diameter of amorphous polyester domains by forming amorphous polyester domains near the toner surface, adjustment of acid value of amorphous polyester, molecular chain terminal of amorphous polyester In addition, the addition of a lipophilic portion, adjustment of the softening point of the amorphous polyester and the toner, and adjustment of the production conditions of the toner base particles are exemplified.

  The content of the amorphous polyester is preferably 5.0 parts by mass or more and 30.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. If it is 5.0 parts by mass or more, the domain state in the vinyl resin can be easily controlled, and if it can be distributed in the vicinity of the surface layer, the melting effect in the vicinity of the surface layer during melting can be easily exerted, and the low-temperature fixability is improved. It becomes a trend. Moreover, it is easy to lead to a brittle improvement in it being 30.0 mass parts or less.

Furthermore, the non-crystalline polyester has an interfacial tension C (mN / m) in an aqueous solution of tricalcium phosphate having a pH of 6.0 dissolved in styrene / butyl acrylate = 80/20 (mass ratio). Interfacial tension D (mN / m) measured by changing amorphous polyester to polar resin is 13 ≦ C−D ≦ 25 (4)
It is preferable from the viewpoint of controlling an extremely fine uneven shape on the surface of the toner base particles.

  As described above, considering the generation of toner base particles by, for example, suspension polymerization, which generates toner base particles in an aqueous medium, the polymerizable monomer composition repeats coalescence, shearing, and coalescence in the granulation process. . Of these two phenomena, when shearing is likely to occur compared to coalescence, the amorphous polyester has a domain shape and is present in the vicinity of the surface of the toner droplet, so the droplet tends to become unstable. In addition, the generation of fine particles and the droplets themselves tend to be unstable. As a result, particles having a rough toner particle surface are formed. Although the reason is not clear, the interfacial tension C in the aqueous solution of tricalcium phosphate at pH 6.0 of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) of the amorphous polyester When the difference in the interfacial tension D measured by changing the crystalline polyester to a polar resin is 13 mN / m or more and 25 mN / m or less, the toner base particle surface is uniformly covered with the polar resin, and the amorphous polyester toner Alternatively, variations in the toner can be suppressed. Therefore, since the balance between the shearing and coalescence of oil droplets formed with the polymerizable monomer composition in the granulation step can be controlled, generation of fine particles and toner destabilization can be suppressed. thinking.

  Amorphous polyester can easily introduce a specific site in the molecular chain. Therefore, as a method for controlling the relationship of the interfacial tension, amorphous polyester has a molecular chain structure and composition ratio in the chain. It is preferable to change the terminal structure or the terminal structure. Moreover, although it mentions later regarding polar resin, it is possible to control by the polar site | part in polar resin.

  Therefore, as an amorphous polyester, from the viewpoint of control of the surface roughness index of toner base particles, brittleness and low-temperature fixability, a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms and a dialcohol are used. The content ratio of monomer units derived from linear aliphatic dicarboxylic acids having a monomer unit derived from 8 to 14 carbon atoms is 10 mol% to 50 mol% with respect to all monomer units derived from the carboxylic acid of the amorphous polyester. The following is preferable.

  When the number of carbon atoms is 8 or more, the value of the interfacial tension C can be easily controlled within a desired range, and a structure such as a pseudocrystalline state can be easily obtained. Therefore, the reproducibility of thin lines tends to be improved because the resin tends to be plasticized while suppressing surface irregularities. In addition, when the number of carbon atoms is 14 or less, the value of the interfacial tension C can be easily controlled within a desired range, and the softening point of the amorphous polyester can be easily lowered in a state where the peak molecular weight of the amorphous polyester is increased. Therefore, it is possible to easily improve the plasticity at the time of fixing while maintaining the durability as a resin, and to suppress the unevenness of the toner surface.

  Next, the amorphous polyester preferably has a carboxylic acid component containing 10 to 50 mol% of a linear aliphatic dicarboxylic acid with respect to the total carboxylic acid component. It is preferable for the linear aliphatic dicarboxylic acid to be 10 mol% or more with respect to the total carboxylic acid component because the softening point tends to be lowered. Further, when the linear aliphatic dicarboxylic acid content is 50 mol% or less with respect to the total carboxylic acid component, it is difficult to reduce the peak molecular weight of the amorphous polyester, which is preferable from the viewpoint of improving the durability of the toner.

  Examples of the carboxylic acid component for obtaining the amorphous polyester include linear aliphatic dicarboxylic acids having 8 to 14 carbon atoms and other carboxylic acids. Examples of the linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms include suberic acid, sebacic acid, dodecanedioic acid, and tetradecanedioic acid. Examples of the carboxylic acid other than the linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms include the following. Examples of the divalent carboxylic acid component include maleic acid, fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, glutaric acid, n-dodecenyl succinic acid, anhydrides of these acids, and lower alkyl esters. It is done. Examples of the trivalent or higher polyvalent carboxylic acid component include 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, pyromellitic acid, emporic trimer acid and acid anhydrides thereof, lower Examples include alkyl esters. Among these, terephthalic acid is preferably used because it can maintain a high peak molecular weight and easily maintain durability.

  Examples of the alcohol component for obtaining the amorphous polyester include a propylene oxide adduct of bisphenol A and an ethylene oxide adduct of bisphenol A. Examples of other alcohols include the following. Examples of the divalent alcohol component include ethylene glycol, 1,3-propylene glycol, neopentyl glycol and the like. Examples of the trivalent or higher alcohol component include sorbitol, pentaerythritol, dipentaerythritol, and the like. The dihydric alcohol component and the trihydric or higher polyhydric alcohol component can be used alone or in combination of a plurality of compounds. Among them, an alcohol component derived from bisphenol A is preferably used as the alcohol component from the viewpoint of easy control of the presence state in the toner.

The amorphous polyester can be produced by an esterification reaction or a transesterification reaction using the above alcohol component and carboxylic acid component. In the case of polycondensation, a known esterification catalyst such as dibutyltin oxide may be appropriately used to promote the reaction.
The molar ratio (carboxylic acid component / alcohol component) between the alcohol component and the carboxylic acid component, which are raw material monomers of the amorphous polyester resin, is preferably 0.60 or more and 1.00 or less.

  The method for producing the amorphous polyester is not particularly limited, and can be produced by an esterification reaction or a transesterification reaction using each of the above monomers. When polymerizing the raw material monomer, a commonly used esterification catalyst such as dibutyltin oxide may be appropriately used in order to accelerate the reaction.

  The glass transition temperature (Tg) of the amorphous polyester is preferably 45 ° C. or higher and 75 ° C. or lower from the viewpoint of fixability and brittleness.

  The peak molecular weight (Mp (P)) of the amorphous polyester is preferably 8000 or more and 13000 or less. When the peak molecular weight (Mp (P)) is 8000 or more, it becomes easy to suppress the cracking and crushing of the toner during long-term use. Further, when the peak molecular weight (Mp (P)) is 13000 or less, melting by heat occurs instantaneously, so that the toner layer can be sufficiently adhered on the paper.

  The acid value AvA of the amorphous polyester is preferably lower than the acid value AvB of the polar resin described later. AvA is preferably 1.0 mgKOH / g or more and 10.0 mgKOH / g or less, and more preferably 3.0 mgKOH / g or more and 8.0 mgKOH / g or less. If it is within the above range, it tends to be present in the vicinity of the surface of the toner base particles without hindering the shell formation of the polar resin.

  Next, the hydroxyl value OHv of the amorphous polyester is preferably 40.0 mgKOH / g or less. For example, when the toner is obtained by suspension polymerization, it is preferable that the hydroxyl value OHv of the amorphous polyester is 40.0 mgKOH / g or less because the amorphous polyester easily forms a plurality of domains in the vicinity of the toner surface. .

  In order to control the acid value Av of the amorphous polyester to 1.0 mgKOH / g or more and 10.0 mgKOH / g or less and the hydroxyl value OHv to 40.0 mgKOH / g or less, the end of the molecular chain of the amorphous polyester is controlled. It is preferable to have a lipophilic part.

  Since the terminal of the molecular chain of the amorphous polyester has a lipophilic part, it becomes easy to interact with the vinyl resin, and thus the domain size can be easily controlled.

  From the viewpoint of adjusting the acid value and hydroxyl value and controlling the interfacial tension C, the amorphous polyester preferably has an alkyl moiety at the end of the amorphous polyester.

  Further, at the end of the amorphous polyester, at least one of an aliphatic monocarboxylic acid having a peak value of 25 to 102 carbon atoms and an aliphatic monoalcohol having a peak value of 25 to 102 carbon atoms (hereinafter, These two are generally referred to as “long-chain monomer” at the terminal, and it is preferable that these long-chain monomers are condensed at the terminal. Specifically, when a carboxyl group is present at the terminal of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monoalcohol occurs to cause bonding. In addition, when a hydroxyl group is present at the terminal of the amorphous polyester before the long-chain monomer is bonded, a condensation reaction with a monocarboxylic acid occurs and a bond is generated. Here, the “peak value of the carbon number” is the number of carbons calculated from the main peak molecular weight of the long-chain monomer.

  Here, the “terminal” includes the end of the branched chain when the amorphous polyester has a branched chain. In the present invention, the amorphous polyester has a branched chain, and the condensed form at the end of the branched chain is one of preferred embodiments.

  An alkyl moiety can be introduced at the end of the amorphous polyester by bonding a long chain monomer to the end of the amorphous polyester. As a result, it is presumed that by taking a structure in which the alkyl moiety is easy to be folded, the amorphous polyester also takes a pseudo-crystallized state, so that it becomes easy to form a domain. Further, the above-described interfacial tension C of the amorphous polyester can be easily controlled and the surface roughness index tends to be easily controlled.

  Further, from the viewpoint of controlling the softening point of the amorphous polyester and the interfacial tension C, the aliphatic monocarboxylic acid and the aliphatic monoalcohol preferably have a peak value of 25 or more and 102 or less.

  The total content of the long-chain monomers is preferably 2.0 mol% or more and 10.0 mol% or less based on the total monomer units from the viewpoint of adjusting the acid value of the amorphous polyester and from the viewpoint of interfacial tension.

  In addition, a long-chain monomer is industrially obtained by alcohol- or acid-modifying the aliphatic hydrocarbon used as a raw material. For example, as for alcohol-modified products, an aliphatic hydrocarbon having 27 to 102 carbon atoms is subjected to liquid phase oxidation with a molecular oxygen-containing gas in the presence of a catalyst such as boric acid, anhydrous boric acid, or metaboric acid. It is known that it can be converted to The catalyst addition amount used is preferably 0.01 mol or more and 0.5 mol or less with respect to 1 mol of the raw material aliphatic hydrocarbon.

  As the molecular oxygen-containing gas blown into the reaction system, oxygen, air, or a wide range of gases diluted with an inert gas can be used, but an oxygen concentration of 3% to 20% is preferable. Moreover, reaction temperature is 100 degreeC or more and 200 degrees C or less.

  In addition, when the long-chain monomer is modified with alcohol or acid, each unmodified component may also be generated. In order to prevent the charge amount from being lowered by the unmodified component, the preferable range of the modification rate of the aliphatic hydrocarbon component is 85% or more, more preferably 90% or more. By carrying out purification work after optimization of reaction conditions and modification reaction, unmodified aliphatic hydrocarbon components can be removed and the modification rate can be controlled.

  If necessary, the toner base particles may contain a charge control agent to improve charging characteristics. Various types of charge control agents can be used, and charge control agents that can quickly maintain a constant charge amount with a high charging speed are particularly preferable. Further, when the toner is produced using a suspension polymerization method as described later, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.

As a charge control agent,
Metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid;
Metal salts or metal complexes of azo dyes or azo pigments;
A polymer compound having a sulfonic acid or carboxylic acid group in the side chain;
Boron compounds;
Urea compounds;
Silicon compounds;
Examples include calix arene.

  When a toner is manufactured by suspension polymerization, a polymer compound having a sulfonic acid or carboxylic acid group in the side chain (hereinafter also referred to as a polar resin) is used as a charge control agent. By adjusting the polarity of toner, it is more preferable because toner mother particles having various structures can be formed. For example, by adjusting the acid value of the polar resin to be higher than the acid value of the amorphous polyester, the amorphous polyester domain is formed near the surface layer while forming a thin shell of the polar resin on the toner base particles. can do. As a result, the toner base particles can be provided with excellent chargeability and melting characteristics with a low heat quantity.

  Further, as described above, in order to make the surface roughness index of the toner base particles within a desired range, the difference between the interfacial tension C of the amorphous polyester and the interfacial tension D measured by changing the amorphous polyester to a polar resin is different. It is preferable to set it to 13 mN / m or more and 25 mN / m or less.

  By adjusting to the above range, generation of fine particles and destabilization of toner droplets during granulation in the suspension polymerization method can be suppressed, and the surface unevenness index can be lowered.

  Further, it is preferable that the polar resin is a vinyl polymer because the surface of the toner base particles can be more uniformly covered and the chargeability tends to be uniform.

  In the vinyl polymer, a styrene copolymer is more preferable. Polymerizable monomers used with styrene monomers to form styrene copolymers include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, acrylic acid-2 A monocarboxylic acid having a double bond such as ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; Dicarboxylic acids having double bonds such as acid, butyl maleate, methyl maleate and dimethyl maleate and their substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene, propylene and butylene Such ethylenic olefin; vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether; a sulfonic acid group-containing monomers such as styrenesulfonic acid.

  It is also possible to add a crosslinking agent to the polar resin. As the crosslinking agent, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; Divinyl ether, divinyl sulfide, divinyl compounds such as divinyl sulfone; compounds having three or more vinyl groups. These crosslinking agents can be used alone or as a mixture.

  The content of the polar resin is preferably 0.10 parts by mass or more and 10.0 parts by mass or less, and more preferably 0.10 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the binder resin.

  Containing 0.10 parts by mass or more makes it easy to control the unevenness of the surface of the toner base particles and gives excellent chargeability, so that excellent charge stability can be obtained through long-term use in various environments. Fine line reproducibility is excellent. Further, by containing 3.0 parts by mass or less, excellent charging stability can be obtained while suppressing charge-up even in a low temperature and low humidity environment.

  Moreover, as mentioned above, it is preferable to prepare the acid value AvB (mgKOH / g) of the polar resin higher than the acid value AvA (mgKOH / g) of the amorphous polyester. For example, in a toner manufactured with an aqueous medium, a polar resin is more easily present on the toner surface, which is preferable. The acid value AvB of the polar resin is preferably 5.0 mgKOH / g or more and 20.0 mgKOH / g or less, more preferably 10.0 mgKOH / g or more and 20.0 mgKOH / g or less. If it is within the above range, the shielding property as a shell is increased, so that the charging property is easily stabilized.

  Next, the release agent will be described. As the release agent, known waxes can be used as long as they are intended to impart release properties and plasticity.

For example, petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof;
Montan wax and its derivatives;
Hydrocarbon wax and its derivatives by Fischer-Tropsch process;
Polyolefin waxes such as polyethylene and derivatives thereof;
Examples thereof include natural waxes such as carnauba wax and candelilla wax, and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, acid amide waxes, ester waxes, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can also be used.

  Among these waxes, paraffin wax is preferably used from the viewpoint of compatibility with the vinyl resin and releasability.

  The content of the release agent is preferably 1.0 part by mass or more and 30.0 parts by mass or less, and 3.0 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the vinyl resin. Is more preferable.

  Next, the colorant will be described. As the black colorant, carbon black, magnetic fine particles, and those toned to black using yellow, magenta and cyan colorants described later are used.

  When magnetic one-component development is adopted in the one-component development method, it is preferable to use magnetic fine particles having high transportability as a black colorant with respect to a toner carrier including a magnet roller. Further, when omitting the supply roller for supplying the toner in the cartridge to the toner carrier, it is preferable to use magnetic fine particles having high transportability as the black colorant.

  In order to obtain uniform adhesion and high adhesion of the external additive, it is more preferable to use a magnetic toner using magnetic fine particles having a large specific gravity. We speculate why this high adhesion is obtained as follows.

  As a method for attaching the external additive to the toner base particles, it is preferable to use a mixing device using a stirring blade or the like from the viewpoint of mixing property and shearing force. In such an external addition step, the part to be mainly processed is in the vicinity of the stirring blade. It is considered that the magnetic toner having a large specific gravity has a larger load at the time of external addition processing near the stirring blade than the non-magnetic toner, and the probability of being further processed is increased. Therefore, it is considered that the magnetic toner can obtain a higher fixing property than the non-magnetic toner.

The magnetic fine particles are mainly composed of magnetic iron oxides such as triiron tetroxide and γ-iron oxide, and may contain elements such as phosphorus, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. These magnetic fine particles is preferably a BET specific surface area by nitrogen adsorption method is 2~30m ² / g, more preferably 3~28m ² / g. Further, those having a Mohs hardness of 5 to 7 are preferred. The shape of the magnetic fine particle includes polyhedron, octahedron, hexahedron, spherical shape, needle shape, scale shape, and the like, but those having low anisotropy such as polyhedron, octahedron, hexahedron, and spherical shape increase the image density. Preferred above.

  The magnetic fine particles preferably have a number average particle diameter of 0.10 μm to 0.40 μm. When the number average particle diameter is 0.10 μm or more, the magnetic fine particles are difficult to aggregate, and the uniform dispersibility of the magnetic fine particles in the toner base particles is improved. Further, when the number average particle size is 0.40 μm or less, the coloring power of the toner is improved.

  The number average particle diameter of the magnetic fine particles can be measured using a transmission electron microscope. Specifically, after sufficiently dispersing the toner to be observed in the epoxy resin, a cured product obtained by curing in an atmosphere at a temperature of 40 ° C. for 2 days is obtained. The obtained cured product is used as a flaky sample by a microtome, and the diameter of 100 magnetic fine particles in the field of view is measured with a transmission electron microscope (TEM) with a photograph with an enlargement magnification of 10,000 to 40,000 times. Then, the number average particle diameter is calculated based on the equivalent diameter of a circle equal to the projected area of the magnetic fine particles. It is also possible to measure the particle size with an image analyzer.

  Magnetic fine particles can be produced, for example, by the following method. An aqueous solution containing ferrous hydroxide is prepared by adding an alkali such as sodium hydroxide in an amount equivalent to or greater than the iron component to the ferrous salt aqueous solution. Air was blown in while maintaining the pH of the prepared aqueous solution at 7 or higher, and ferrous hydroxide was oxidized while the aqueous solution was heated to 70 ° C. or higher. First, seed crystals serving as the core of the magnetic iron oxide powder were formed. Generate.

  Next, an aqueous solution containing about 1 equivalent of ferrous sulfate is added to the slurry-like liquid containing seed crystals based on the amount of alkali added previously. While maintaining the pH of the solution at 5 to 10, the reaction of ferrous hydroxide proceeds while blowing air to grow a magnetic iron oxide powder with the seed crystal as a core. At this time, the shape and magnetic characteristics of the magnetic fine particles can be controlled by selecting an arbitrary pH, reaction temperature, and stirring conditions. As the oxidation reaction proceeds, the pH of the liquid shifts to the acidic side, but the pH of the liquid is preferably not less than 5. The magnetic fine particles can be obtained by filtering, washing, and drying the magnetic fine particles thus obtained by a conventional method.

  Further, when the toner is produced by the suspension polymerization method, it is very preferable that the surface of the magnetic fine particles is hydrophobized because the magnetic fine particles are easily included in the toner. When the surface treatment is performed by a dry method, the coupling agent treatment is performed on the washed, filtered and dried magnetic fine particles. When wet surface treatment is performed, after the oxidation reaction is completed, the dried product is redispersed, or after completion of the oxidation reaction, the iron oxide body obtained by washing and filtering is not dried but in another aqueous medium. The dispersion is redispersed and a coupling treatment is performed. Specifically, a silane coupling agent is added while stirring the redispersion sufficiently, and the temperature is increased after hydrolysis, or the coupling is performed by adjusting the pH of the dispersion to an alkaline region after hydrolysis. . Among these, from the viewpoint of performing a uniform surface treatment, it is preferable to carry out the surface treatment by reslurry as it is without drying after filtration and washing after completion of the oxidation reaction.

  In order to treat the surface of the magnetic fine particles with a wet method, that is, to treat the magnetic fine particles with a coupling agent in an aqueous medium, first, sufficiently disperse the magnetic fine particles in the aqueous medium so as to have a primary particle size so as not to settle or aggregate. Stir with a stirring blade. Next, an arbitrary amount of the coupling agent is added to the dispersion, and the surface treatment is performed while the coupling agent is hydrolyzed. At this time, the agglomeration is sufficiently carried out using a device such as a pin mill or a line mill while stirring. It is more preferable to perform the surface treatment while dispersing.

  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. As the surfactant, nonionic surfactants such as polyvinyl alcohol are preferable. The surfactant is preferably added in an amount of 0.1% by mass to 5.0% by mass with respect to water. Examples of the pH adjuster include inorganic acids such as hydrochloric acid. Examples of the organic solvent include alcohols.

Examples of the coupling agent that can be used in the surface treatment of the magnetic fine particles in the present invention include a silane coupling agent, a silane compound, a titanium coupling agent, and the like. More preferably used are a silane coupling agent and a silane compound, which are represented by the general formula (1).
R _m SiY _n general formula (1)
[Wherein, R represents an alkoxy group, m represents an integer of 1 to 3, Y represents a functional group such as an alkyl group, a phenyl group, a vinyl group, an epoxy group, an acrylic group, or a methacrylic group, and n represents 1 An integer of ~ 3 is shown. However, m + n = 4. ]

  Examples of the silane coupling agent and silane compound represented by the general formula (1) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4 epoxycyclohexyl) ethyltri Methoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltri Methoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane , Diphenyldiethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, n-decyltrimethoxysilane , Hydroxypropyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane and the like.

Among these, from the viewpoint of imparting high hydrophobicity to the magnetic fine particles, it is preferable to use an alkyltrialkoxysilane coupling agent represented by the following general formula (2).
_{C p H 2p + 1 -Si- (} OC q H 2q + 1) 3 Formula (2)
[In formula, p shows the integer of 2-20, q shows the integer of 1-3. ]

  When p in the above formula is 2 or more, it is easy to sufficiently impart hydrophobicity to the magnetic fine particles. Further, when p is 20 or less, the hydrophobicity is sufficient and the coalescence of the magnetic fine particles can be prevented. When q is 3 or less, the reactivity of the silane coupling agent is good, and the hydrophobicity is sufficiently performed. Therefore, p in the formula represents an integer of 2 to 20 (more preferably an integer of 3 to 15), and q represents an integer of 1 to 3 (more preferably an integer of 1 or 2). It is preferable to use a coupling agent.

  When using the said silane coupling agent, it is possible to process independently or to process in combination of several types. When using several types together, you may process separately with each coupling agent, and may process simultaneously.

  In the present invention, other colorants may be used in addition to the magnetic fine particles. Examples of the colorant that can be used in combination include magnetic or nonmagnetic inorganic compounds in addition to the above-described known dyes and pigments. Specifically, ferromagnetic metal particles such as cobalt and nickel, or alloys obtained by adding chromium, manganese, copper, zinc, aluminum, rare earth elements and the like to these. Examples thereof include particles such as hematite, titanium black, nigrosine dye / pigment, carbon black, and phthalocyanine. These are also preferably used by treating the surface.

  The content of the magnetic fine particles in the toner base particles is preferably 20 parts by mass or more and 200 parts by mass or less, more preferably 40 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or vinyl resin. .

  Examples of the yellow colorant include compounds typified by 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.

  Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, 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, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. And CI Pigment Bio Red 19.

  Examples of cyan colorants include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, and basic dye lake compounds. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66.

  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 toner base particles. The addition amount of the colorant is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer or vinyl resin that forms the vinyl resin.

  In the present invention, the toner base particles can be produced by any known method. First, the case where it manufactures by the grinding | pulverization method is demonstrated.

  When the toner base particles are produced by a grinding method, for example, toner components such as vinyl resin, colorant, release agent, amorphous polyester and crystalline polyester, and other additives are mixed with Henschel mixer, ball mill, etc. Mix well by machine. Then, melt and knead using a heat kneader such as a heating roll, kneader, extruder, etc., disperse or dissolve the above materials, cool and solidify, pulverize, classify, and perform surface treatment as necessary Thus, toner mother particles can be obtained. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier from the viewpoint of production efficiency.

  The pulverization step can be performed by a method using various pulverization apparatuses such as a mechanical impact type and a jet type. Further, in order to obtain a toner (toner base particles) having a preferable circularity used in the present invention, it is preferable to further pulverize by applying heat or to perform a process of applying a mechanical impact as an auxiliary. Further, a hot water bath method in which finely pulverized (classified if necessary) toner base particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.

  Examples of the method for applying a mechanical impact force include a method using a mechanical impact type pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry. Further, as a method adopted by a device such as a mechano-fusion system manufactured by Hosokawa Micron, there is a method of applying a mechanical impact force to the toner by pressing the toner against the inside of the casing by a high-speed rotating blade by a centrifugal force. .

  In order to control the dispersion state of the vinyl resin and the amorphous polyester by the pulverization method, it is preferable to perform a treatment such as external addition of the amorphous polyester.

  The toner base particles can also be produced by the pulverization method as described above, but the toner base particles obtained by this pulverization method are generally indeterminate and have low fluidity at the regulating part. There is a tendency. In addition, it is difficult to achieve the above-described control of the presence state of the resin in the toner base particles. For example, when a magnetic material is used, the magnetic material is likely to be exposed on the surface, so that charging stability is lowered and concentration is likely to be lowered. Therefore, in the present invention, it is preferable to produce toner mother particles in an aqueous medium such as a dispersion polymerization method, an association aggregation method, a dissolution suspension method, a suspension polymerization method, etc. Among them, the suspension polymerization method is more preferable. .

  In the suspension polymerization method, a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are dissolved or dispersed in the polymerizable monomer. A composition is obtained. Thereafter, this polymerizable monomer composition is added to a continuous phase (for example, an aqueous medium (which may contain a dispersion stabilizer if necessary)). Then, particles of the polymerizable monomer composition are formed in the continuous phase (in the aqueous medium), and the polymerizable monomer contained in the particles is polymerized. In this way, the toner is obtained. In the toner obtained by the suspension polymerization method (hereinafter also referred to as “polymerized toner”), the shape of each toner base particle is almost spherical, so that the fluidity at the regulating portion is easily improved and uniform friction is obtained. Since charging becomes easier, the image quality is easily improved.

  The following are mentioned as a polymerizable monomer used for manufacture of a polymerization toner.

As a polymerizable monomer,
Styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene;
Methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, Acrylic esters such as phenyl acrylate;
Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid Methacrylic acid esters such as dimethylaminoethyl and diethylaminoethyl methacrylate;
Etc. Other examples include acrylonitrile, methacrylonitrile, and acrylamide. These can be used alone or in combination of two or more.

  Among the polymerizable monomers described above, it is preferable to use styrene or a styrene derivative alone or in combination of a plurality of types from the viewpoints of development characteristics and durability of the toner.

  The polymerization initiator used in the production of the toner used in the present invention by the polymerization method preferably has a half-life of 0.5 hours or more and 30.0 hours or less during the polymerization reaction. In addition, when the polymerization reaction is performed using an addition amount of 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer, the toner can have desirable strength and appropriate melting characteristics. it can.

  Specific examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1 -Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl Peroxide-based polymerization initiators such as peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate Is mentioned.

  When the toner used in the present invention is produced by a polymerization method, a crosslinking agent may be added. A preferable addition amount is 0.01 parts by mass or more and 5.00 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Or less.

Here, as the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used.
Aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene;
Carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, etc .;
Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone;
A compound having three or more vinyl groups is used alone or as a mixture of two or more.

  In the method for producing the toner used in the present invention by the polymerization method, the above-described toner composition or the like is added as necessary, and the resulting solution is uniformly dissolved or dispersed by a disperser to obtain a polymerizable monomer composition. Examples of the disperser include a homogenizer, a ball mill, and an ultrasonic disperser. The obtained polymerizable monomer composition is suspended in an aqueous medium containing a dispersion stabilizer. At this time, the particle size of the toner base particles obtained becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner size all at once. The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Moreover, a polymerization initiator can also be added immediately after granulation and before starting a polymerization reaction.

  After granulation, stirring may be performed using an ordinary stirrer to such an extent that the particle state is maintained and particle floating and sedimentation are prevented.

  When the toner used in the present invention is produced, various surfactants, organic dispersants, and inorganic dispersants can be used as the dispersion stabilizer. Among these, inorganic dispersants can be preferably used because they do not easily generate harmful ultrafine powders and have obtained dispersion stability due to their steric hindrance. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, hydroxyapatite and other phosphate polyvalent metal salts, calcium carbonate, magnesium carbonate and other carbonates, calcium metasilicate, calcium sulfate, sulfuric acid Inorganic salts such as barium, and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide can be used.

  These inorganic dispersants are desirably used in an amount of 0.2 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the polymerizable monomer. Moreover, the said dispersion stabilizer may be used independently and may use multiple types together. Further, a surfactant may be used in combination.

  In the step of polymerizing the polymerizable monomer, the polymerization temperature is set to 40 ° C or higher, and generally 50 ° C to 90 ° C. When the polymerization is carried out in this temperature range, the release agent to be sealed inside precipitates by phase separation, and the encapsulation becomes more complete.

  In order to obtain the toner having the preferred amorphous polyester domain of the present invention by suspension polymerization, the following steps are important.

Moreover, after the polymerization process is completed, it is preferable to carry out a distillation process in order to efficiently remove the remaining unreacted polymerizable monomer and to adjust the surface roughness index to a desired range.
The distillation step is preferably performed at a temperature equal to or higher than the glass transition temperature of the binder resin of the toner, preferably 60 ° C. or higher and 100 ° C. or lower, more preferably 80 ° C. or higher and 100 ° C. or lower. preferable.

  In order to control the surface unevenness index within a desired range, the retention time in the distillation step is preferably maintained within a range where the toner base particles are not coarse. Preferably it is 60 minutes or more, More preferably, it is 120 minutes or more.

  In order to form a domain of amorphous polyester, it is preferable to carry out the following steps.

  After the polymerization of the polymerizable monomer is completed to obtain colored particles, the colored particles are dispersed in an aqueous medium, and the vicinity of the softening point of the amorphous polyester (softening point to softening point + 10 ° C.), specifically In this case, the temperature is preferably raised to about 100 ° C. and kept at that temperature for 30 minutes or more. The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less from the viewpoint of production efficiency.

  In order to achieve the dispersion state of the amorphous polyester as described above, it is preferable to perform the following operation in the subsequent cooling step. Specifically, the aqueous medium is preferably cooled at a cooling rate of 5.00 ° C./min or more, more preferably at a cooling rate of 20 ° C./min or more, and the cooling rate is 100 ° C./min or less to Tg or less of the toner. More preferably, cooling is performed as described above. The upper limit of the cooling rate is not particularly limited, but is preferably 500 ° C./min or less.

  After cooling at the cooling rate, it is preferable to hold at that temperature for 30 minutes or more. The holding time is more preferably 60 minutes or more, and further preferably 120 minutes or more. The upper limit of the holding time is about 24 hours or less from the viewpoint of production efficiency. In addition, Tg or less refers to Tg to about Tg-5 degreeC.

  The obtained polymer particles are filtered, washed and dried to obtain toner base particles.

  The toner base particles may be used as the toner as they are, or a toner having inorganic fine particles attached to the surface of the toner base particles by externally adding inorganic fine particles as described later may be used. It is also possible to insert a classification step in the manufacturing process (before mixing of the inorganic fine particles) to cut coarse powder and fine powder contained in the toner base particles.

  In the toner of the present invention, as a fluidizing agent, inorganic fine particles having a primary particle number average diameter of 4 nm to 80 nm, more preferably 6 nm to 40 nm are added (externally added) to the toner base particles. preferable. Furthermore, it is more preferable to use together inorganic fine particles having a primary particle number average diameter of 80 nm to 200 nm. By externally adding, the fluidity of the toner can be ensured through durability, uniform and stable triboelectric chargeability can be obtained, and the density can be easily improved. Inorganic fine particles are added to improve the fluidity of the toner and make the charge of the toner uniform. Functions such as adjusting the charge amount of the toner and improving environmental stability can be achieved by hydrophobizing the inorganic fine particles. Giving is also a preferred form.

  In the present invention, the number average diameter of the primary particles of the inorganic fine particles is measured by using a photograph of the toner magnified by a scanning electron microscope.

  As the inorganic fine particles used in the present invention, fine particles such as silica, titanium oxide, and alumina can be used. Examples of the silica fine particles include so-called dry silica produced by vapor phase oxidation of silicon halides or dry silica called fumed silica, and so-called wet silica produced from water glass.

However, dry silica with fewer silanol groups on the surface and inside the silica fine particles and less production residue such as Na ₂ O and SO ₃ ²⁻ is preferred. In dry silica, it is also possible to obtain fine particles of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. , Including them.

  The addition amount of the inorganic fine particles is preferably 0.1 parts by mass or more and 3.0 parts by mass or less with respect to 100 parts by mass of the toner base particles. The content of inorganic fine particles can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  In the present invention, it is preferable that the inorganic fine particles have been subjected to a hydrophobic treatment since the environmental stability of the toner can be improved. Examples of the treatment agent used for the hydrophobic treatment of the inorganic fine particles include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, and silane coupling agents. In addition, treatment agents such as other organosilicon compounds and organotitanium compounds are listed. These can be used alone or in combination of two or more.

  Among the above-mentioned treatment agents, those treated with silicone oil are preferred, and those treated with silicone oil are more preferred at the same time as or after hydrophobizing inorganic fine particles with a silane compound. As a method for treating such inorganic fine particles, for example, as a first stage reaction, a silylation reaction is performed with a silane compound, silanol groups are eliminated by chemical bonds, and then a second stage reaction is performed on the surface with silicone oil. A hydrophobic thin film can be formed.

The silicone oil is preferably a viscosity at 25 ° C. is 10 mm ² / s or more 200,000 mm ² / s or less things, more preferably the following 3,000 mm ² / s or more 80,000mm ² / s.

  As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

  As a method of treating inorganic fine particles with silicone oil, for example, a method of directly mixing inorganic fine particles treated with a silane compound and silicone oil using a mixer such as a Henschel mixer, or spraying silicone oil onto inorganic fine particles A method is mentioned. Alternatively, after dissolving or dispersing silicone oil in a suitable solvent, inorganic fine particles may be added and mixed to remove the solvent. A spraying method is more preferable in that the formation of aggregates of inorganic fine particles is relatively small.

  The treatment amount of the silicone oil is 1 to 40 parts by mass, preferably 3 to 35 parts by mass with respect to 100 parts by mass of the inorganic fine particles, and good hydrophobicity is easily obtained.

Inorganic fine particles used in the present invention, in order to impart good fluidity to the toner, the specific surface area measured by the BET method by nitrogen adsorption include: 20 m ² / g or more 350 meters ² / g Preferably, 25 m ² / g to 300 m ² / g or less is more preferable. The specific surface area is calculated using the BET multipoint method by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device “Gemini 2375 Ver. 5.0” (manufactured by Shimadzu Corporation) according to the BET method. .

In the toner of the present invention, other additives such as, for example,
Lubricant particles such as fluororesin particles, zinc stearate particles, polyvinylidene fluoride particles;
Abrasives such as cerium oxide particles, silicon carbide particles, strontium titanate particles;
Fluidity-imparting agents such as titanium oxide particles and aluminum oxide particles;
Anti-caking agent;
A small amount of reverse polarity organic fine particles and inorganic fine particles can also be used as a developability improver. It is also possible to use the surface of these additives after hydrophobizing them.

  A developing device to which the toner of the present invention can be preferably applied will be described in detail with reference to the drawings.

  FIG. 1 is a schematic cross-sectional view illustrating an example of a developing device. FIG. 2 is a schematic cross-sectional view showing an example of an image forming apparatus in which a developing device is incorporated.

  In FIG. 1 or FIG. 2, an electrostatic latent image carrier 45, which is an image carrier on which an electrostatic latent image is formed, is rotated in the direction of arrow R1. The toner carrier 47 rotates in the direction of the arrow R2 to convey the toner 57 to the development area where the toner carrier 47 and the electrostatic latent image carrier 45 are opposed to each other. Further, a toner supply member 48 is in contact with the toner carrier, and the toner 57 is supplied to the surface of the toner carrier by rotating in the direction of arrow R3.

  Around the electrostatic latent image carrier 45, a charging roller 46, a transfer member (transfer roller) 50, a fixing device 51, a pickup roller 52, and the like are provided. The electrostatic latent image carrier 45 is charged by the charging roller 46. Then, exposure is performed by irradiating the electrostatic latent image carrier 45 with laser light by the laser generator 54, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the electrostatic latent image carrier 45 is developed with toner in the developing device 49 to obtain a toner image. The toner image is transferred onto a transfer material (paper) 53 by a transfer member (transfer roller) 50 in contact with the electrostatic latent image carrier 45 via the transfer material. The transfer material (paper) 53 on which the toner image is placed is conveyed to the fixing device 51 and fixed on the transfer material (paper) 53.

<Measuring method of softening point (Tm) of toner and amorphous polyester>
The softening point of the toner and the amorphous polyester is measured using a constant load extrusion type capillary rheometer “Flow Characteristic Evaluation Apparatus Flow Tester CFT-500D” (manufactured by Shimadzu Corporation) according to the manual attached to the apparatus. In this device, while applying a constant load from the top of the measurement sample with the piston, the measurement sample filled in the cylinder is heated and melted, and the melted measurement sample is pushed out from the die at the bottom of the cylinder, and the piston drop amount at this time A flow curve showing the relationship between temperature and temperature can be obtained.

  In the present invention, the “melting temperature in the 1/2 method” described in the manual attached to the “flow characteristic evaluation apparatus Flow Tester CFT-500D” is the softening point. The melting temperature in the 1/2 method is calculated as follows. First, ½ of the difference between the piston lowering amount Smax at the time when the outflow ends and the piston lowering amount Smin at the time when the outflow starts is obtained (this is X. X = (Smax−Smin) / 2). The temperature of the flow curve when the piston descending amount is the sum of X and Smin in the flow curve is the melting temperature in the ½ method (a schematic diagram of the flow curve is shown in FIG. 3).

  The measurement sample was about 1.0 g of toner or amorphous polyester in an environment of 25 ° C. using a tablet molding compressor (for example, NT-100H, manufactured by NP System Co., Ltd.) at about 10 MPa, about 60 A cylinder having a diameter of about 8 mm and compression-molded for 2 seconds is used.

The measurement conditions of CFT-500D are as follows.
Test mode: Temperature rising start temperature: 50 ° C
Achieving temperature: 200 ° C
Measurement interval: 1.0 ° C
Temperature increase rate: 4.0 ° C./min
Piston cross-sectional area: 1.000 cm ²
Test load (piston load): 10.0 kgf (0.9807 MPa)
Preheating time: 300 seconds Die hole diameter: 1.0 mm
Die length: 1.0mm

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1) of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman Measurement and analysis were carried out using a dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) for measurement condition setting and measurement data analysis. .

  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 part by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up 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 aqueous solution is put in a glass 250 ml round bottom beaker exclusively for ultisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated 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 placed in a water tank of an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkiki Bios) with an electrical output of 120 W. A fixed amount of ion-exchanged water is added, 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 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 (1) round bottom beaker installed in the sample stand, the (5) electrolytic aqueous solution in which the toner is dispersed is dropped using a pipette, and the measured concentration is adjusted to about 5%. The 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 / number% and graph / volume% are set in the dedicated software, the “arithmetic diameter” on the analysis / number statistics (arithmetic average) and analysis / volume statistics (arithmetic average) screens is the number average. The particle diameter (D1) and the weight average particle diameter (D4).

<Measurement method of true density of toner base particles>
When measuring the true density of toner base particles in a toner in which an external additive is externally added to the toner base particles, it is necessary to remove the external additive, and a specific method is described below. As described in B / A calculation method>.

The true density of the toner base particles was measured by a dry automatic densimeter autopycnometer (manufactured by Yuasa Ionics). The conditions are as follows.
Cell: SM cell (10 ml)
Sample amount: About 2.0g

  This measurement method measures the true density of a solid / liquid based on a gas phase substitution method. Similar to the liquid phase replacement method, it is based on Archimedes' principle, but uses a gas (argon gas) as a replacement medium, and therefore has high accuracy for micropores.

<Calculation method of surface roughness index B / A>
The surface roughness index is obtained from the theoretical specific surface area A and BET specific surface area B of the toner base particles (= B / A). In addition, when measuring the surface roughness index of the toner base particles in a toner in which an external additive is externally added to the toner base particles, it is necessary to remove the external additive. As a specific method, for example, A method is mentioned.

When the toner is a magnetic toner (1) 45 mg of magnetic toner is put in a sample bottle, and 10 mL of methanol is added.
(2) Disperse the sample for 1 minute with an ultrasonic cleaner to separate the external additive.
(3) The magnetic toner base particles and the external additive are separated by suction filtration (10 μm membrane filter). Alternatively, only the supernatant liquid may be separated by applying a magnet to the bottom of the sample bottle to fix the magnetic toner mother particles.
(4) The above (2) and (3) are carried out three times in total, and the obtained magnetic toner mother particles are sufficiently dried in a vacuum dryer at room temperature. The magnetic toner base particles from which the external additive has been removed can be observed with a scanning electron microscope to confirm the absence of the external additive. If the external additive is not sufficiently removed, (2) and (3) are repeated until the external additive is sufficiently removed. As another method for removing the external additive in place of the above (2) and (3), there is a method of dissolving the external additive with an alkaline solution. As the alkali, an aqueous sodium hydroxide solution is preferred.

In the case of non-magnetic toner: 160 g of sucrose (manufactured by Kishida Chemical) is added to 100 mL of ion-exchanged water, and dissolved with a water bath to prepare a sucrose concentrate. A sucrose concentrate 31 g and 6 mL of Contaminone N are put into a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion and the mass of toner is loosened with a spatula or the like.

  The centrifuge tube is shaken with the above shaker at 350 reciprocations per minute for 20 minutes. After shaking, the solution is replaced with a glass tube (50 mL) for a swing rotor, and centrifuged with a centrifuge at 3500 rpm for 30 minutes. In the glass tube after centrifugation, toner base particles are present in the uppermost layer and silica fine particles are present in the lower aqueous solution side, so that only the toner base particles in the uppermost layer are collected.

  If the external additive has not been sufficiently removed, centrifugation is repeated as necessary, and after sufficient separation, the toner liquid is dried and toner base particles are collected.

  Each calculation method is as follows.

<< Calculation Method of Theoretical Specific Surface Area A of Toner Base Particles >>
In the same manner as the measurement of the number average particle diameter (D1), the number-based particle size distribution of the toner base particles was measured. However, in the analysis using “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.), the measurement target is 2.0 μm to 32.0 μm, and 12 channels (2.00 to 2.520 μm, 2.520 to 3.175 μm, 3.175 to 4.0000 μm, 4.000 to 5.040 μm, 5.040 to 6.350 μm, 6.350 to 8.000 μm, 8.000 to 10.079 μm, 10. 079 to 12.699 μm, 12.699 to 16.000 μm, 16.000 to 20.159 μm, 20.159 to 25.398 μm, 25.398 to 32.000 μm) to obtain the number-based particle size distribution. It was.

Thereafter, using the median value of each channel (for example, if it is 2.00 to 2.520 μm, the median value is 2.260 μm), the toner base particles of the median value of each channel are true spheres. The assumed theoretical surface area (= 4 × π × (median value of each channel) ² ) is obtained. By multiplying the theoretical surface area by the number ratio of the particles belonging to each channel obtained previously, the average theoretical surface area (a) of one particle when the measured toner base particle is assumed to be a true sphere is obtained.

Next, in the same way, the theoretical mass (= 4/3 × π) assuming that the toner base particles of each channel median are true spheres from the median value of each channel and the true density of the measured toner base particles. X (median value of each channel) ³ x true density). The average theoretical mass (b) of one particle is determined from the theoretical mass and the ratio of the number of particles belonging to each channel determined previously.

  The theoretical specific surface area A (= a / b) of the toner base particles is calculated from the average theoretical surface area and average theoretical mass of one particle.

<< Measurement Method of BET Specific Surface Area B of Toner Base Particles >>
The specific surface area BET of the toner base particles can be determined by a low temperature gas adsorption method by a dynamic constant pressure method according to a BET method (preferably a BET multipoint method). For example, by using a specific surface area measuring device “Gemini 2375 Ver. 5.0” (manufactured by Shimadzu Corporation), nitrogen gas is adsorbed on the sample surface, and measurement is performed using the BET multipoint method. m ² / g) was calculated. Specifically, the measurement is performed according to the following procedure.

  After measuring the mass of the empty sample cell, 1.0 g of the measurement sample is filled in the sample cell. Further, the sample cell filled with the sample is set in the degassing apparatus, and degassing is performed at room temperature for 7 hours. After completion of degassing, the mass of the entire sample cell is measured, and the accurate mass of the sample is calculated from the difference from the empty sample cell. Next, empty sample cells are set in the balance port and analysis port of the BET measuring apparatus. A dewar bottle containing liquid nitrogen is set at a predetermined position, and P0 is measured by a saturated vapor pressure (P0) measurement command. After the P0 measurement is completed, the sample cell prepared for degassing is set in the analysis port, and after inputting the sample mass and P0, the measurement is started by the BET measurement command. After that, the BET specific surface area is automatically calculated.

<25% area ratio, 50% area ratio measurement method>
(25% area ratio)
The toner is sufficiently dispersed in a visible light curable resin (trade name, Aronix LCR series D-800; manufactured by Toagosei Co., Ltd.), and then cured by irradiation with short wavelength light. The obtained cured product is cut out with an ultramicrotome equipped with a diamond knife to produce a 250-nm flaky sample. Next, the cut out sample was magnified at a magnification of 40000 to 50000 times using a transmission electron microscope (Electron Microscope JEM-2800 manufactured by JEOL Ltd.) (TEM-EDX), the cross section of the particle was observed, and EDX was used. Perform element mapping.

  The cross section of the toner to be observed is selected as follows. First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. Only a toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm is observed.

  The mapping conditions are a storage rate of 9000 to 13000 and an integration count of 120. Among the domains derived from the resin confirmed from the observed image, the spectrum intensity derived from the C element and the spectrum intensity derived from the O element are measured. It is a domain of amorphous polyester. After specifying the amorphous polyester domain, a binarization process is performed to determine the distance between the contour and the center point of the cross section from the contour of the cross section of the toner to the total area of the amorphous polyester domains existing in the cross section of the toner. The area ratio (area%) of the amorphous polyester domain existing within% is calculated. For the binarization process, Image Pro PLUS (manufactured by Nippon Roper Co., Ltd.) is used.

  The calculation method is as follows. In the TEM image, the contour and center point of the toner cross section are obtained. The outline of the toner cross section is assumed to be along the surface of the toner observed in the TEM image. The center point of the toner cross section is the center of gravity of the toner cross section.

  A line is drawn from the obtained center point to a point on the contour of the toner cross section. On the line, the position of 25% of the distance between the outline and the center point of the cross section is specified from the outline.

  Then, this operation is performed once for the contour of the toner cross section, and a boundary line of 25% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section.

  Based on the TEM image in which the 25% boundary line is clearly defined, the area of the amorphous polyester domain existing in the region surrounded by the outline of the toner cross section and the 25% boundary line is measured. . Then, the total area of the amorphous polyester domains present in the toner cross section is measured, and the area% based on the total area is calculated.

(50% area ratio)
Similarly to the measurement of the 25% area ratio described above, a boundary line of 50% of the distance between the contour and the center point of the cross section is clearly shown from the contour of the toner cross section. The area of the amorphous polyester domain existing in the region surrounded by the outline of the cross section of the toner and the boundary line of 50% is measured, and area% based on the total domain area is calculated.

<Measuring method of number average diameter of domains of amorphous polyester>
Elemental mapping is performed using EDX in the same manner as described above to specify an amorphous polyester domain. The domain diameter is obtained by obtaining the equivalent circle diameter from the area of the domain. The number of measurements is 100, and the arithmetic average value of the equivalent circle diameters of 100 domains is the number average diameter of the domains. The domain for calculating the domain diameter is determined as follows.

  First, the cross-sectional area of the toner is obtained from the cross-sectional image of the toner, and the diameter (equivalent circle diameter) of a circle having an area equal to the cross-sectional area is obtained. The domain diameter is calculated only for the toner cross-sectional image in which the absolute value of the difference between the equivalent circle diameter and the weight average particle diameter (D4) of the toner is within 1.0 μm. Since the domain diameter may vary depending on the particle diameter of the toner, the average domain diameter can be calculated in this way.

<Method for Measuring Acid Value Av of Amorphous Polyester and Polar Resin>
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 a sample 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 that 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 sample is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a mixed solution of toluene / ethanol (2: 1) is added and dissolved over 5 hours. Next, a few drops of the phenolphthalein solution is added as an indicator and titrated 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 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).

<Measuring method of hydroxyl value OHv of amorphous polyester and long chain monomer>
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 sample is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.

(1) 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 that 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.

(2) Operation (A) Main test 1.0 g of the pulverized sample is precisely weighed into a 200 ml round bottom flask, and 5.0 ml of the acetylating reagent is accurately added thereto 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 a few 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 sample is used.

(3) Substituting the obtained results into the following formula 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 Solution factor, S: sample (g), D: acid value of sample (mgKOH / g).

<Measured by the hanging drop method by changing the interfacial tension C of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) to pH 6.0 in tricalcium phosphate aqueous solution and polar resin. Of measured interfacial tension D>
(1) Preparation of aqueous phase After adding 450 parts of 0.1 mol / L-Na ₃ PO ₄ aqueous solution to 720 parts of ion-exchanged water and heating to 60 ° C., 1.0 mol / L-CaCl ₂ aqueous solution 67 .7 parts are added to obtain an aqueous medium containing a dispersion stabilizer. Measure pH (hereinafter also referred to as water phase) and confirm that it is 6.0 ± 0.2.

(2) Preparation of oil phase 1 g of sample is added and dissolved in 8 g of styrene and 2 g of n-butyl acrylate to prepare a styrene / butyl acrylate dispersion (hereinafter also referred to as an oil phase).

(2) Interfacial tension measurement Interfacial tension was measured by the hanging drop method described below. Specifically, using a FACE solid-liquid interface analyzer Drop Master 700 manufactured by Kyowa Interface Science Co., Ltd. in an environment at a temperature of 25 ° C., measurement was performed with WIDE 1 as the field of view of the lens portion. First, the tip portion of a thin tube having an inner diameter of 0.4 mm is placed in the aqueous phase downward in the vertical direction. Next, the thin tube is connected to the syringe part. An oil phase prepared in advance is placed in the syringe part. Next, a syringe part is connected to Kyowa Interface Science Co., Ltd. AUTO DISPENSER AD-31, and an oil phase is extruded from a thin tube, A droplet can be created in a capillary tube front-end | tip part in an aqueous phase. Then, the interfacial tension is calculated from the shape of the droplet. The control and calculation method for creating droplets was performed using a measurement analysis system manufactured by Kyowa Interface Science Co., Ltd. Note that the density difference between the water phase and the oil phase necessary for the calculation was 0.10 g / cm ³ , which is the density difference between water and styrene. The final measurement result of the interfacial tension was the average value of 10 measurements.

  Although the basic configuration and features of the present invention have been described above, the present invention will be specifically described below based on examples. However, this does not limit the embodiment of the present invention. The number of parts and% in the examples are based on mass unless otherwise specified.

<Preparation of Toner Carrier 1>
(Preparation of substrate 1)
A substrate 1 is prepared by applying a primer (trade name, DY35-051; manufactured by Toray Dow Corning) on a 6 mm diameter cored bar made of SUS304 and baking it.

(Production of elastic roller)
The substrate 1 prepared as described above is placed in a mold, and an addition type silicone rubber composition in which the following materials are mixed is injected into a cavity formed in the mold.
・ Liquid silicone rubber material (trade name, SE6724A / B; manufactured by Toray Dow Corning)
100 parts carbon black (trade name, Toka Black # 4300; manufactured by Tokai Carbon Co., Ltd.)
15 parts / silica particles as heat resistance imparting agent 0.2 parts / platinum catalyst 0.1 part Subsequently, the mold is heated to cure and cure the silicone rubber at a temperature of 150 ° C. for 15 minutes. After the base body 1 having the silicone rubber layer cured on the peripheral surface is removed from the mold, the base body 1 is further heated at a temperature of 180 ° C. for 1 hour to complete the curing reaction of the silicone rubber layer. In this way, an elastic roller having a silicone rubber elastic layer having a diameter of 12 mm so as to cover the outer peripheral surface of the substrate is produced.

(Preparation of surface layer 1)
(Synthesis of isocyanate group-terminated prepolymer 1)
Polypropylene glycol polyol (trade name: Exenol 4030; manufactured by Asahi Glass Co., Ltd.) 100 with respect to 17.7 parts of tolylene diisocyanate (TDI) (trade name: Cosmonate T80; manufactured by Mitsui Chemicals) in a reaction vessel under a nitrogen atmosphere 0.0 part is gradually added dropwise while maintaining the temperature in the reaction vessel at 65 ° C. After completion of the dropwise addition, the reaction is carried out at 65 ° C. for 2 hours. The obtained reaction mixture is cooled to room temperature to obtain an isocyanate group-terminated prepolymer 1 having an isocyanate group content of 3.8% by mass.

(Synthesis of amino compound 1)
While stirring, 100.0 parts (1.67 mol) of ethylenediamine and 100 parts of pure water are heated to 40 ° C. while stirring in a reaction vessel equipped with a stirrer, a thermometer, a reflux tube, a dropping device, and a temperature controller. Next, 425.3 parts (7.35 mol) of propylene oxide is gradually added dropwise over 30 minutes while maintaining the reaction temperature at 40 ° C. or lower. The reaction is further stirred for 1 hour to obtain a reaction mixture. The obtained reaction mixture is heated under reduced pressure to distill off water, and 426 g of amino compound 1 is obtained.

As a material for the surface layer,
-Isocyanate-terminated prepolymer 1 617.9 parts-Amino compound 1 34.2 parts-Carbon black (trade name, MA230; manufactured by Mitsubishi Chemical Corporation) 117.4 parts-Urethane resin fine particles (trade name, Art Pearl C-400 ; Negami Kogyo Co., Ltd.)
130.4 parts are stirred and mixed.

  Next, methyl ethyl ketone (hereinafter also referred to as “MEK”) is added so that the total solid content ratio is 30% by mass, and then mixed in a sand mill. Next, the viscosity is further adjusted to 10 cps or more and 13 cps or less with MEK to prepare a coating material for forming a surface layer.

  The elastic roller 1 produced previously is immersed in the coating material for surface layer formation, the coating film of the said coating material is formed on the surface of the elastic layer of the elastic roller 1, and it is made to dry. Further, a surface layer having a thickness of 15 μm is provided on the outer periphery of the elastic layer by heat treatment at a temperature of 150 ° C. for 1 hour, whereby the toner carrier 1 is manufactured.

<Example of production of long-chain monomer 1>
1200 g of aliphatic hydrocarbon having a peak value of 35 carbon atoms is placed in a glass cylindrical reaction vessel, 38.5 g of boric acid is added at a temperature of 140 ° C., and immediately an oxygen concentration of 50% by volume of air and 50% by volume of nitrogen is added. After blowing 10% by volume of mixed gas at a rate of 20 liters per minute and reacting at 200 ° C. for 3.0 hours, warm water was added to the reaction solution, followed by hydrolysis at 95 ° C. for 2 hours. The reaction was taken. 20 parts of the modified product was added to 100 parts of n-hexane to obtain a long-chain monomer 1 in which unmodified components were dissolved and removed. The resulting long-chain monomer 1 had a modification rate of 93.5% and a hydroxyl value of 92.4 mgKOH / g.

<Example of production of amorphous polyester 1>
After adjusting the amount of raw material monomers shown in Table 1 as shown in Table 1 into the reaction vessel equipped with a nitrogen introduction tube, dehydration tube, stirrer and thermocouple, the carboxylic acid component and the alcohol component are shown in Table 1. As a catalyst, 1.5 parts of dibutyltin is added to 100 parts of the total amount of monomers. Next, the temperature is rapidly raised to 180 ° C. at normal pressure in a nitrogen atmosphere, and then polycondensation is performed by distilling off water while heating from 180 ° C. to 210 ° C. at a rate of 10 ° C./hour. After reaching 210 ° C., the pressure in the reaction vessel is reduced to 5 kPa or less, and polycondensation is performed under the conditions of 210 ° C. and 5 kPa or less to obtain amorphous polyester 1. At that time, the polymerization time is adjusted so that the peak molecular weight of the obtained amorphous polyester 1 becomes the value shown in Table 1. The physical properties of the amorphous polyester 1 are shown in Table 1.

<Production Example of Amorphous Polyester 2 to 13>
Amorphous polyesters 2 to 13 are obtained in the same manner as amorphous polyester 1, except that the raw material monomers and the amounts used are changed as shown in Table 1. Table 1 shows the physical properties of these amorphous polyesters.

<Example of production of amorphous polyester 14>
In a four-necked flask equipped with a nitrogen introduction tube, a dehydration tube, a stirrer and a thermocouple, 100 mol parts of bisphenol A ethylene oxide 2 mol adduct, 173.6 mol parts of bisphenol A propylene oxide 2 mol adduct, 97.1 mol terephthalic acid Part, 166.2 mol part of fumaric acid, 54.1 mol part of adipic acid and 100 parts of bisphenol A ethylene oxide 2 mol adduct, 2 parts of esterification catalyst (tin octylate) are added, and polycondensation reaction is carried out at 230 ° C. for 8 hours. The mixture was further reacted at 8 kPa for 1 hour and cooled to 160 ° C., and then a mixture of 6 parts of acrylic acid, 70 parts of styrene, 31 parts of n-butyl acrylate and 20 parts of a polymerization initiator (di-t-butyl peroxide). Was dropped with a dropping funnel over 1 hour, and kept at 160 ° C. after dropping. After the addition polymerization reaction is continued for 1 hour, the temperature is raised to 200 ° C. and held at 10 kPa for 1 hour, and then the unreacted acrylic acid, styrene, and butyl acrylate are removed, whereby the vinyl polymerized segment and the polyester polymerized segment are obtained. Amorphous polyester 14 which is a composite resin formed by bonding is obtained.

<Production example of treated magnetic material>
During an aqueous ferrous sulfate solution, 1.10 eq of sodium hydroxide solution from 1.00 relative to iron element, the amount of P ₂ O ₅ to an iron element to be 0.15 parts by terms of phosphorus, to an iron element An aqueous solution containing ferrous hydroxide is prepared by mixing SiO ₂ in an amount of 0.50 parts in terms of silicon element. The pH of the aqueous solution is set to 8.0, and an oxidation reaction is performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Subsequently, ferrous sulfate aqueous solution is added to this slurry liquid so that it may become 0.90 to 1.20 equivalent with respect to the initial alkali amount (sodium component of caustic soda), and the slurry liquid is maintained at pH 7.6, and air is supplied. The oxidation reaction is promoted while blowing to obtain a slurry liquid containing magnetic iron oxide. After filtration and washing, the water-containing slurry is once taken out. At this time, take a small amount of water sample and measure the water content. Next, this water-containing sample is put into another aqueous medium without being dried, stirred and redispersed with a pin mill while circulating the slurry, and the pH of the redispersed liquid is adjusted to about 4.8. Then, 1.6 parts of n-hexyltrimethoxysilane coupling agent was added to 100 parts of magnetic iron oxide with stirring (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample), and water was added. Disassemble. Thereafter, the surface treatment is carried out by sufficiently stirring and adjusting the pH of the dispersion to 8.6. The produced hydrophobic magnetic material is filtered with a filter press, washed with a large amount of water, dried at 100 ° C. for 15 minutes, and then at 90 ° C. for 30 minutes. The resulting particles are crushed to have a volume average particle size of 0. A 21 μm treated magnetic material is obtained.

<Production Example of Toner Base Particle 1>
After adding 473 parts of a 0.1 mol / L-Na ₃ PO ₄ aqueous solution to 720 parts of ion-exchanged water and heating to 60 ° C., 71.1 parts of a 1.0 mol / L-CaCl ₂ aqueous solution was added. An aqueous medium containing a dispersion stabilizer is obtained.

-Styrene 74.0 parts-n-Butyl acrylate 26.0 parts-Amorphous polyester 1 10.0 parts-Divinylbenzene 0.6 parts-Iron complex of monoazo dye (T-77: Hodogaya Chemical Co., Ltd.) 5 parts, treated magnetic material 65.0 parts, polar resin 1
(Styrene-2-ethylhexyl acrylate copolymer containing 3% of 2-acrylamido-2-methylpropanesulfonic acid, Tg = 78 ° C.) 2.0 parts Attritor (Mitsui Miike Chemical Co., Ltd.) Was uniformly dispersed and mixed to obtain a monomer composition. This monomer composition is heated to 63 ° C., and 15 parts of paraffin wax (melting point: 78 ° C.) is added and mixed therein and dissolved. Thereafter, 5.0 parts of a polymerization initiator tert-butyl peroxypivalate is dissolved.

The aqueous medium of the above monomer composition was charged in, 60 ° C., T. under N ₂ atmosphere K. The mixture is stirred at 12000 rpm for 10 minutes with a homomixer (Special Machine Industries Co., Ltd.) and granulated. Thereafter, the mixture is reacted at 70 ° C. for 4 hours while stirring with a paddle stirring blade. After completion of the reaction, it is confirmed that colored particles are dispersed in the aqueous medium obtained here, and calcium phosphate is adhered to the surface of the colored particles as an inorganic dispersant.

  At this point, hydrochloric acid was added to the aqueous medium to remove calcium phosphate by washing, followed by filtration and drying to analyze the colored particles. As a result, the glass transition temperature Tg of the binder resin was 55 ° C.

  Subsequently, the aqueous medium in which the colored particles are dispersed is heated to 100 ° C. and held for 240 minutes. Then, 5 degreeC water is thrown into an aqueous medium and it cools from 100 degreeC to 50 degreeC with the cooling rate of 100 degreeC / min. Subsequently, the aqueous medium was held at 50 ° C. for 120 minutes.

  Thereafter, hydrochloric acid is added to the aqueous medium to wash away calcium phosphate, followed by filtration and drying to obtain toner base particles 1. Table 2 shows the production conditions of the toner base particles 1.

<Production Example of Toner Base Particles 2 to 26>
In the production of the toner base particles 1, the toner base particles 2 to 2 are similarly produced except that the amorphous polyester, the polar resin, the colorant, the number of parts of the Na ₃ PO ₄ aqueous solution, the number of parts of the CaCl ₂ aqueous solution, and the production conditions are changed. 26 is manufactured. Table 2 shows the production conditions of the toner base particles obtained.

<Production Example of Toner Base Particles 27>
<< Preparation of each dispersion liquid >>
-Resin particle dispersion (1)-
-Styrene (Wako Pure Chemical Industries): 325 parts-n-butyl acrylate (Wako Pure Chemical Industries): 100 parts-Acrylic acid (Rhodia Nikka Co., Ltd.): 13 parts-1,10-decanediol diacrylate (new) Nakamura Chemical Co., Ltd.): 1.5 parts · Dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.): 3.0 parts The above components are mixed in advance and dissolved to prepare a solution. An anionic surfactant (Dow Chemical) A surfactant solution prepared by dissolving 9 parts of Dowfax A211) in 580 parts of ion-exchanged water is placed in a flask, and 400 parts of the above solution is added, dispersed and emulsified, and slowly stirred for 10 minutes. While mixing, 50 parts of ion-exchanged water in which 6 parts of ammonium persulfate was dissolved was added.

  Next, after sufficiently replacing the inside of the flask with nitrogen, the flask was heated with an oil bath while stirring the flask until it reached 75 ° C., and emulsion polymerization was continued for 5 hours to obtain a resin particle dispersion (1). It was.

  When the resin particles were separated from the resin particle dispersion (1) and examined for physical properties, the number average particle diameter was 195 nm, the solid content in the dispersion was 42%, the glass transition point was 51.5 ° C., and the weight average molecular weight Mw. Was 32,000.

-Resin particle dispersion (2)-
The amorphous polyester 14 was dispersed using a disperser modified to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) high temperature and high pressure type. Specifically, the composition ratio is 79% ion-exchanged water, 1% anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen RK) (active ingredient), and 20% solid content, By adjusting the pH to 8.5, operating the Cavitron under the conditions of a rotor rotation speed of 60 Hz, a pressure of 5 kg / cm ² and heating by a heat exchanger at 140 ° C., resin fine particles having a number average particle diameter of 200 nm A dispersion (2) was obtained.

-Colorant dispersion-
・ Carbon black 20 parts ・ Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen R) 2 parts ・ Ion-exchanged water 78 parts The above components were used at 3000 rpm using a homogenizer (IKA, Ultra Turrax T50). After 2 minutes of blending the pigment in water and dispersing at 5000 rpm for 10 minutes, the mixture was stirred for one day with a normal stirrer and defoamed, and then a high-pressure impact disperser Ultimateizer (manufactured by Sugino Machine Co., Ltd.) HJP30006) was used and dispersed at a pressure of 240 MPa for about 1 hour to obtain a colorant dispersion. Further, the pH of the dispersion was adjusted to 6.5.

-Release agent dispersion-
・ 45 parts of hydrocarbon wax (Fischer-Tropsch wax, maximum endothermic peak = 78 ° C., Mw = 750)
・ Cationic surfactant (Neogen RK, Daiichi Kogyo Seiyaku) 5 parts ・ Ion-exchanged water 200 parts The above components were heated to 95 ° C. and sufficiently dispersed with a homogenizer (manufactured by IKA, Ultra Tarax T50). Dispersion treatment was performed with a pressure-discharge type gorin homogenizer to obtain a release agent dispersion having a number average diameter of 190 nm and a solid content of 25%.

<Production example of toner base particles>
・ Ion-exchanged water 400 parts ・ Resin particle dispersion (1) 620 parts (resin particle concentration: 42%)
Resin particle dispersion (2) 279 parts (resin particle concentration: 20%)
Anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd., Neogen RK, active ingredient amount: 60%)
1.5 parts (0.9 parts as an active ingredient)
The above components were put into a 3 liter reaction vessel equipped with a thermometer, pH meter, and stirrer, and maintained at a temperature of 30 ° C. and a stirring rotation speed of 150 rpm for 30 minutes while controlling the temperature with a mantle heater from the outside. Thereafter, 88 parts of the colorant dispersion and 60 parts of the release agent dispersion were added and held for 5 minutes. As it was, a 1.0% nitric acid aqueous solution was added to adjust the pH to 3.0. Next, the stirrer and the mantle heater were removed, and 0.33 parts of polyaluminum chloride and 37.5 parts of 0.1% nitric acid aqueous solution were dispersed while being dispersed at 3000 rpm with a homogenizer (manufactured by IKA Japan: Ultratarax T50). After adding 1/2 of the mixed solution, the dispersion speed was set to 5000 rpm, the remaining 1/2 was added over 1 minute, and the dispersion speed was set to 6500 rpm, and dispersed for 6 minutes.

  A reactor is equipped with a stirrer and a mantle heater, and the temperature is increased to 42 ° C. at 0.5 ° C./min while appropriately adjusting the rotation speed of the stirrer so that the slurry is sufficiently stirred. After maintaining for 15 minutes, the particle size was measured with a Coulter Multisizer every 10 minutes while raising the temperature at 0.05 ° C./min. When the weight average particle size became 7.4 μm, 5% water The pH was adjusted to 9.0 using an aqueous sodium oxide solution. Thereafter, while adjusting the pH to 9.0 every 5 ° C., the temperature was raised to 96 ° C. at a temperature rising rate of 1 ° C./min and maintained at 96 ° C. When the particle shape and surface properties were observed every 30 minutes with an optical microscope and a scanning electron microscope (FE-SEM), the particles were almost spherical in the second hour. Solidified.

  Thereafter, the reaction product is filtered and washed with ion-exchanged water. When the filtrate has a conductivity of 50 mS or less, cake-like particles are taken out, and ion-exchanged water having an amount 10 times the particle weight is taken out. When the particles were sufficiently loosened by stirring with a three-one motor, the pH was adjusted to 3.8 with a 1.0% nitric acid aqueous solution and held for 10 minutes. Thereafter, filtration and washing with water were performed again, and when the conductivity of the filtrate became 10 mS or less, water flow was stopped and solid-liquid separation was performed. The obtained cake-like particles were pulverized by a sample mill and dried in an oven at 40 ° C. for 24 hours. Further, the obtained powder was pulverized by a sample mill and then further vacuum-dried in an oven at 40 ° C. for 5 hours to obtain toner mother particles 27.

<Production Example of Toner Base Particle 28>
Toner mother particles were produced according to Example 1 of JP-A-2006-184746, and toner mother particles 28 were obtained.

<Production of toner>
<Production Example of Toner 1>
To 100 parts of toner base particle 1, 0.3 part of sol-gel silica fine particles having a primary particle number average diameter of 115 nm was added and mixed using a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Thereafter, silica having a number average diameter of 12 nm of primary particles was further treated with hexamethyldisilazane and then with silicone oil, and 0.9 parts of hydrophobic silica fine particles having a BET specific surface area value of 120 m ² / g after treatment were obtained. Toner 1 was prepared by adding and mixing in the same manner using a Mitsui Henschel mixer (Mitsui Miike Chemical Co., Ltd.). Table 3 shows the physical properties of Toner 1 thus obtained.

<Production Examples of Toners 2 to 23 and Comparative Toners 1 to 5>
In the production of the toner 1, the toner base particles were changed as shown in Table 3 to obtain toners 2 to 23 and comparative toners 1 to 5. Table 3 shows the physical properties of the obtained toners 2 to 23 and comparative toners 1 to 5.

[Example 1]
A printer LBP7700C (manufactured by Canon Inc.) whose fixing method is an on-demand fixing method by film fixing was modified and used for image output evaluation. As a modification point, the toner carrier 1 was changed, the toner supply member (toner supply roller 48 shown in FIG. 1) of the developing device was removed, and the voltage application to the toner supply member was turned off. The contact pressure was adjusted so that the width of the contact portion between the toner carrier and the photosensitive drum was 1.0 mm.

  As described above, by removing the supply roller, the toner can be transported to the carrier more strictly, and the area of the contact portion between the toner carrier and the electrostatic latent image carrier can be reduced. Therefore, it is possible to strictly evaluate changes in fine line reproducibility and fine line reproducibility due to durability.

  The developing device modified as described above was charged with 100 g of toner 1 to be evaluated, and a developing device was produced using the toner carrier 1. The produced developing apparatus was set in a cyan station and / or a black station, and image evaluation was performed. In addition, the horizontal line which makes a printing rate 1% was used as a durable printed image, and the test was conducted by using two sheets of intermittent paper as a durable condition. The evaluation results are shown in Table 4.

[Evaluation of Fine Line Reproducibility] In (1) to (3), the check image is FOX River Bond (manufactured by FOX River Paper) having a basis weight of 90 g / m ² , and the 3000 printed images have a basis weight of 75 g / m ^2. This is performed using m ² business 4200 (manufactured by Xerox).

(1) Evaluation of fine line reproducibility of initial image in normal temperature and humidity environment and image after printing 3000 sheets The developing device filled with toner is left in a normal temperature and humidity environment (23 ° C / 50% RH) for 48 hours. .

  Using the modified machine, fine line reproducibility was evaluated for the check image after printing the initial check image and 3000 horizontal lines.

A lattice pattern (1 cm interval) on a 100 μm (latent image) line was drawn, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and hardly splattered. B: The line is comparatively sharp with a slight splattering. C: Slightly splattering makes the line feel dull. D: Less than C level

(2) Evaluation of fine line reproducibility of initial image in normal temperature and high humidity environment A developing device filled with toner is left in a normal temperature and high humidity environment (23 ° C./85% RH) for 48 hours.

Fine line reproducibility was evaluated for the initial check image with the modified machine. A lattice pattern (1 cm interval) on a 100 μm (latent image) line was drawn, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and hardly splattered. B: The line is comparatively sharp with a slight splattering. C: Slightly splattering makes the line feel dull. D: Less than C level

(3) Evaluation of fine line reproducibility of check images after printing 3000 sheets in a low temperature and low humidity environment Under a room temperature and normal humidity environment with the above-mentioned remodeling machine, a developing device that printed 3000 sheets was placed in a low temperature and low humidity environment (15 ° C., 10% RH). ) For 48 hours, a check image was printed, and fine line reproducibility was evaluated. A lattice pattern (1 cm interval) on a 100 μm (latent image) line was drawn, and the scattering was visually evaluated using an optical microscope.
A: The line is very sharp and hardly splattered. B: The line is comparatively sharp with a slight splattering. C: Slightly splattering makes the line feel dull. D: Less than C level

[Low temperature fixability (tape peeling)]
The developing device filled with the toner is left for 48 hours in a normal temperature and normal humidity environment (23 ° C./50% RH). Thereafter, the developing device is set in the cyan station and / or the black station, the fixing device is temporarily removed from the image forming apparatus, and the image forming apparatus is remodeled so that an unfixed image can flow. As for the image, a solid image with a tip margin of 10 mm and 50 mm × 50 mm is output on GF-104 (basis weight 104 g / m ² , Canon A4 size) evaluation paper so that the applied toner amount becomes 0.90 mg / cm ^2. A solid black unfixed image was adjusted.

  An “external fixing device” was set in the cyan station and / or black station, the fixing device was removed from the evaluation machine, and the fixing temperature of the fixing device could be arbitrarily set.

  Under the above environment, the fixing performance was evaluated while changing the set temperature control every 5 ° C. in the temperature range from 170 ° C. to 220 ° C. of the sleeve surface of the external fixing device.

  The image density of the solid black image portion of the obtained unfixed image was measured at five points and averaged to obtain an “initial density”. Thereafter, a polyester tape (No. 5515, manufactured by Nichiban Co., Ltd.) was attached to the solid black image portion, and a 100 g load was reciprocated three times on the polyester tape to adhere the polyester tape to the image. Thereafter, the polyester tape was peeled off, and the image density of the fixed image was measured at five points and averaged to obtain a “density after tape peeling”. The image density was measured using X-Rite (manufactured by X-Rite, 500 series, density measurement mode).

And the density maintenance rate (%) after tape peeling was calculated | required by remove | dividing the difference of initial density and density after tape peeling by initial density, and multiplying by 100. The temperature at which the concentration maintenance rate after tape peeling was less than 10% was regarded as the temperature at which the fixing property was excellent, and was ranked A to D according to the following criteria.
A: Even at 180 ° C., the concentration retention rate (%) after tape peeling is less than 10.0%.
B: Even at 190 ° C., the concentration maintenance ratio (%) after tape peeling is less than 10.0%.
C: Even at 200 ° C., the concentration maintenance ratio (%) after tape peeling is less than 10.0%.
D: Concentration maintenance ratio (%) after tape peeling is less than 10.0% even at 210 ° C.

[Examples 2 to 23]
The toner was changed in accordance with Table 4, and image output evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.

[Comparative Examples 1-5]
The toner was changed in accordance with Table 4, and image output evaluation was performed in the same manner as in Example 1. The evaluation results are shown in Table 4.

  45: electrostatic latent image carrier, 46: charging roller, 47: toner carrier, 48: toner supply member, 49: developing device, 50: transfer member (transfer roller), 51: fixing device, 52: pickup roller, 53: Transfer material (paper), 54: Laser generator, 55: Toner regulating member, 56: Metal plate, 57: Toner, 58: Stirring member

Claims (6)

A toner having toner base particles containing a vinyl resin, a colorant, and amorphous polyester,
In the toner cross section observed with a transmission electron microscope (TEM) of the toner, a matrix-domain structure is observed, the vinyl resin forms a matrix, and the amorphous polyester forms a plurality of domains,
The domain is within a range of 30% to 70% by area with respect to the total area of the domains of the amorphous polyester within 25% of the distance between the outline and the center point of the toner cross section from the outline of the toner cross section. And the softening point (Tm) of the amorphous polyester is 85 ° C. or higher and 105 ° C. or lower,
The theoretical specific surface area A (m ² / g) obtained from the number-based particle size distribution and true density of the toner base particles and the specific surface area B (m ² / g) measured by the BET method are expressed by the following formula (1): And a toner satisfying (2).
0.450 ≦ B ≦ 1.500 (1)
1.00 ≦ B / A ≦ 1.26 (2) The toner according to claim 1, wherein a theoretical specific surface area A of the toner base particles and a specific surface area B measured by a BET method satisfy the following formula (3).
1.00 ≦ B / A ≦ 1.19 (3) The toner contains a polar resin, the polar resin is a vinyl polymer;
Interfacial tension C (mN / m) of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) in an aqueous tricalcium phosphate solution at pH 6 and the polar resin Claim that the interfacial tension D (mN / m) of the amorphous polyester dissolved in styrene / butyl acrylate = 80/20 (mass ratio) in a tricalcium phosphate aqueous solution at pH 6 satisfies the following formula (4): Item 3. The toner according to Item 1 or 2.
13 ≦ C−D ≦ 25 (4)   The toner according to claim 1, wherein the toner has 5.0 to 30.0 parts by mass of the amorphous polyester with respect to 100 parts by mass of the vinyl resin.   The toner according to claim 1, wherein an acid value of the amorphous polyester is 1.0 mgKOH / g or more and 10.0 mgKOH / g or less. The amorphous polyester resin has a monomer unit derived from a linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms and a monomer unit derived from a dialcohol.
The content ratio of the monomer unit derived from the linear aliphatic dicarboxylic acid having 8 to 14 carbon atoms is 10 mol% or more and 50 mol% or less with respect to all monomer units derived from the carboxylic acid of the amorphous polyester. The toner according to any one of 1 to 5.

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