JP6173137B2 - toner - Google Patents

Description

  The present invention relates to a toner used in a recording method using electrophotography or the like.

  Many methods are known as electrophotographic methods. In general, an electrostatic latent image is formed on an electrostatic charge image carrier (hereinafter also referred to as “photoconductor”) by using a photoconductive substance by various means. Next, the latent image is developed with toner to form a visible image, and if necessary, the toner image is transferred to a recording medium such as paper, and then the toner image is fixed on the recording medium by heat or pressure, etc. Is what you get. Examples of such an image forming apparatus using electrophotography include a copying machine and a printer.

  These printers and copiers are moving from analog to digital, and have excellent reproducibility of latent images and high resolution, and at the same time, stable image quality is required even when used for a long period of time. Furthermore, a toner having a good fixing property is required as an energy saving measure, and a binder resin and a wax are improved to improve the fixing property.

  Focusing on the wax here, it is generally known that the use of a large amount of wax reduces the viscosity at the time of melting and improves the fixability. On the other hand, when a large amount of wax is used, durability and storage stability are liable to be inferior. Conventionally, both have been achieved by adjusting the balance between fixing property, durability, and storage stability.

  However, even in a range where both of these are compatible, there is a new image problem that the image density at the end of the image is thin.

  Regarding the density thinness at both ends of the image, this occurs as follows. Many printers use a scanner to form an electrostatic latent image on the surface of the photoreceptor with a laser. Inside the scanner, the polygon mirror rotates at a high speed to form an electrostatic latent image. However, when part of the polygon mirror is soiled, the potential at both ends of the electrostatic latent image drops and the development contrast decreases, so Thin concentration occurs.

  Analysis of this polygon mirror stain reveals that it is a wax component of the toner. It is known that the toner exudes wax at the time of fixing and exhibits a releasability from the fixing member, but part of it volatilizes. On the other hand, since the polygon mirror inside the scanner rotates at high speed, the inside of the scanner becomes negative pressure, and it is easy to suck in the surrounding air. Here, a part of the wax component that has been volatilized and solidified is sucked into the scanner, and a part of the wax component adheres to the polygon mirror, resulting in a thin density at both ends of the image as described above.

  For improving the toner performance by improving the wax, many methods have been proposed in the past, and proposals focusing on the composition of the wax have also been made (see Patent Document 1, Patent Document 2, and Patent Document 3). However, even if these proposed waxes are used, the density thinness at both ends of the image due to the contamination of the polygon mirror is insufficient and improvement is required.

Japanese Patent Laid-Open No. 08-50367 JP 2000-19768 A JP 2007-193253 A

  According to the present invention, it is possible to provide a toner having no thin density at both ends of an image even in long-term use.

The present invention is a toner containing toner particles containing a binder resin, a colorant and an ester wax, and inorganic fine particles present on the surface of the toner particles,
The ester wax is a difunctional to hexafunctional polyfunctional ester wax,
The melting point of the ester wax is 65 ° C. or higher and 85 ° C. or lower,
In the composition distribution of the ester wax, the ratio of the most numerous components is 30% by mass or more and 80% by mass or less,
When the molecular weight of the most numerous component of the ester wax is M1, the component within M1 ± 20% is 90% by mass or more based on the total amount of the ester wax.
The toner contains 0.05 to 0.60 ppm of a total amount of styrene derivative in terms of toluene based on the toner mass in an organic volatile component analysis at a heating temperature of 120 ° C. of the toner by the headspace method. About.

  According to the present invention, it is possible to provide a toner that does not have a thin density at both ends of an image even after long-term use.

FIG. 2 is a schematic cross-sectional view illustrating an example of an image forming apparatus that can suitably use the toner of the present invention.

The present invention is a toner containing toner particles containing a binder resin, a colorant and an ester wax, and inorganic fine particles present on the surface of the toner particles,
The ester wax is a difunctional to hexafunctional polyfunctional ester wax,
The melting point of the ester wax is 65 ° C. or higher and 85 ° C. or lower,
In the composition distribution of the ester wax, the ratio of the most numerous components is 30% by mass or more and 80% by mass or less,
When the molecular weight of the most numerous component of the ester wax is M1, the component within M1 ± 20% is 90% by mass or more based on the total amount of the ester wax.
The toner is characterized in that the total amount of styrene derivatives in terms of toluene based on the toner mass is 0.05 ppm or more and 0.60 ppm or less in an organic volatile component analysis at a toner heating temperature of 120 ° C. by the headspace method. It is.

  As a result of intensive studies by the present inventors, by using a specific ester wax in the toner and adding an appropriate amount of a styrene derivative, the density thinness at both ends of the image can be greatly improved, leading to the present invention.

  First, considering the low density at both ends of the image, as described above, the wax component volatilized at the time of fixing is cooled and solidified as particles move away from the heat source. At this time, considering the particle size of the particles, those having a smaller particle size are more likely to ride on the airflow, so that fine particles mainly reach the scanner portion, causing a decrease in density at both ends of the image. Therefore, it was important to control the particle size of the solidified product. Hereinafter, particles formed by coagulation of the volatilized wax component are simply referred to as a coagulated product.

  Next, the present inventors' idea about coagulation | solidification of the volatilized wax component is described. In the process of solidifying the volatilized wax component, crystal nuclei are first formed, and then crystals grow. When this process is described in detail, it is known from the theory of nucleation that the activation energy (Gt) of nucleation is as shown in the following formula (1).

（ここで、Ｒは臨界核半径、ΔＧは自由エネルギー変化、γは定数。）

(Where R is the critical nucleus radius, ΔG is the free energy change, and γ is a constant)

  When this is differentiated by R, R becomes as shown in the following equation (2).

  Here, the “critical nucleus radius” can be considered as the smallest particle size at which nucleation is promoted. In general, small nuclei that do not reach the critical nucleus radius are said to lose their stable energy level and disappear. Yes.

  Considering the crystal growth process, it is considered that when the crystal nucleus is large and the crystal grows slowly, it becomes a large crystal and the grain size also increases. Therefore, the size of the crystal nucleus and the crystal growth rate have a great influence on the particle size of the solidified product.

Therefore, considering the size of crystal nuclei, since the size of crystal nuclei can be considered as the critical nucleus radius described above, it is important to increase the critical nucleus radius. , ΔG needs to be reduced. ΔG is expressed as follows from the Gibbs equation of free energy.
ΔG = H−TΔS (3)

  Here, ΔG is Gibbs free energy change, T is temperature, and ΔS is entropy change. Therefore, in order to reduce ΔG at a certain temperature, it is necessary to increase ΔS.

  In the ester wax used in the toner of the present invention, it is important that the ratio of the most numerous components is 30% by mass or more and 80% by mass or less. The ratio of the most numerous component of the ester wax being 30% by mass or more and 80% by mass or less means that the ester wax has a composition distribution.

  When the composition of the ester wax is considered here, it is clear that the entropy is larger in the case of having a distribution than in the case of a single one. That is, if there is a composition distribution, ΔG is reduced from the equation (3), and the critical nucleus radius R is considered to be increased from the equation (2). Therefore, it is considered that the particle size of the solidified product is increased.

  From these facts, when the proportion of the largest component of the ester wax is higher than 80% by mass, the entropy is small to approach the state of a single composition, and the particle size of the solidified product is small. As a result, thin density occurs at both ends of the image, which is not preferable. On the other hand, when the ratio of the most numerous component of the ester wax is lower than 30% by mass, the composition distribution becomes too broad, so that the storage stability and developability deteriorate, which is not preferable.

  According to the study by the present inventors, the ratio of the most numerous component is preferably 30% by mass to 65% by mass, and more preferably 30% by mass to 45% by mass.

  Next, focusing on crystal growth, it is generally known that crystals grow large when the crystal growth rate is low. Therefore, it is considered important to keep the crystal growth rate small in order to increase the particle size of the solidified product. Further, when considering the portion where the crystal growth is performed, the surface of the portion where the growth is progressing has a metastable crystal structure, and the crystal growth proceeds at a high speed until reaching a stable energy level. Therefore, in order to suppress the speed, it is necessary to lower the energy level of the metastable crystal structure.

  The toner of the present invention contains a total amount of styrene derivatives in terms of toluene based on the toner mass in the range of 0.05 ppm to 0.60 ppm in an organic volatile component analysis at a toner heating temperature of 120 ° C. by the headspace method. Although details regarding the styrene derivative will be described later, the styrene derivative in the present invention refers to a compound having a structure in which a vinyl group of styrene is substituted with a functional group such as an OH group, an aldehyde group, a carboxyl group, or an ethyl group.

  The content of the styrene derivative of 0.05 ppm or more and 0.60 ppm or less means that the styrene derivative is present in the gas phase part in the process of wax crystal growth. The detailed mechanism is unknown, but if the styrene derivative coexists in the gas phase, it is assumed that the styrene derivative is coordinated or adsorbed to the metastable surface, and the energy level is in a stable direction. . This is considered to suppress the crystal growth rate and increase the crystal diameter, that is, the particle diameter of the solidified product.

  In addition, it is clear that the entropy increases in the presence of a styrene derivative, and the critical nucleus radius increases from formulas (2) and (3), and large crystals tend to be formed.

  From these facts, when the content of the styrene derivative is less than 0.05 ppm, the effects of suppressing the crystal growth rate as described above and increasing the entropy cannot be obtained, and the particle size of the solidified product becomes small. . As a result, thin density occurs at both ends of the image, which is not preferable. When the content exceeds 0.60 ppm, the tendency to stabilize the crystal surface in the crystal growth process is strengthened, and by stopping the crystal growth, the particle size of the solidified product tends to be reduced, and the density at both ends of the image is reduced. It is not preferable.

  Further, in the ester wax used in the toner of the present invention, when the molecular weight of the ester compound having the highest abundance in the ester wax is M1, the component within M1 ± 20% is 90% by mass or more based on the total amount of the ester wax. It is important that This is also presumed to influence the critical nucleus radius. About this reason, the present inventors consider as follows.

  Considering R (critical nucleus radius) in the formula (2), as described above, it is generally said that a nucleus smaller than the critical nucleus radius cannot take a stable energy level and disappears alone. However, there are exceptions. If a large nucleus exceeding the critical nucleus radius is present in the vicinity, a nucleus smaller than the critical nucleus radius has a metastable crystal structure and a structure covering a large nucleus exceeding the critical nucleus radius. It is also known. Since such a structure has a low energy level, the crystal growth rate is low. Here, when the component within M1 ± 20% is 90% by mass or more with respect to the total amount of the ester wax, it is considered that the above-described structure is smoothly formed. This is considered to be because the formation of a metastable state is facilitated by the presence of a reasonably approximate substance, and the crystal nucleus becomes large.

  In addition, it is important that the ester wax used in the toner of the present invention is a bifunctional to hexafunctional polyfunctional ester wax. Here, in the present invention, the functional group of the ester wax refers to an ester group. For example, a bifunctional ester wax is one having two ester groups in one molecule.

  The bi- to hexa-functionality means that it has two or more ester bonds as an ester and has a bent shape as a molecular structure. It is obvious that the bent structure has more movable parts than the linear structure or the branched structure, and the entropy is increased. For this reason, it is thought that the density thinness at both ends of the image is improved by increasing the critical nucleus radius and the particle size of the solidified product. From these facts, monofunctionality is not preferable because there is only one ester bond and it is difficult to obtain the effect of increasing entropy. On the other hand, a low molecular polymer having a structure with many branches generally has a high crystallization speed and a small crystal diameter. For this reason, if it exceeds 6 functional groups, a solidified product having a small particle size is likely to be formed, which is not preferable.

  Thus, by using a bi- to hexa-functional ester wax containing an appropriate amount of a styrene derivative and having a composition distribution, the crystal nucleus is enlarged and the crystal growth rate is also suppressed. Thereby, since the diameter of the particle | grains produced | generated when a wax component volatilizes and coagulate | solidifies becomes large, the solidified material of a small particle size reduces significantly.

  The melting point of the ester wax used in the present invention is 65 ° C. or higher and 85 ° C. or lower. When the temperature is lower than 65 ° C., the degree of crystallization in the toner is lowered, so that storage stability and developability are deteriorated. Further, if it exceeds 85 ° C., the fixing temperature of the toner increases, which is not preferable.

  The ester wax used in the present invention has 2 to 6 functional groups, preferably 4 to 6 functional polyfunctional ester waxes, more preferably 6 functional groups. The ester wax is not particularly limited as long as it has a melting point, a ratio of the most numerous components, and a component ratio within M1 ± 20%.

  Below, the component which can contain ester wax is illustrated concretely.

First, as the bifunctional ester wax, a condensate of dicarboxylic acid and alcohol or a condensate of diol and carboxylic acid can be used. Of these, preferred structures are shown.
Formula (4): R ₁ —CO—O— (CH ₂ ) x —O—OC—R ₂
Equation _{(5): R 3 -O-} OC- (CH 2) x-CO-O-R 4

In the formulas (4) and (5), R _{1 to} R ₄ are preferably alkyl groups, and x is preferably an integer of 8 to 10.

Specific examples of the dicarboxylic acid include decanedioic acid and dodecanedioic acid, and examples of the diol include 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol. In addition, although linear fatty acid and linear alcohol were illustrated here, you may have a branched structure. R ₄ is preferably an alkyl group having 14 to 26 carbon atoms.

  Further, the alcohol to be condensed with the dicarboxylic acid is preferably an aliphatic alcohol. Specific examples include tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, octacosanol and the like. .

  The carboxylic acid condensed with the diol is preferably an aliphatic carboxylic acid. Specific examples of the fatty acid include myristic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, lignoceric acid, and serotic acid.

  Examples of the trifunctional ester wax include a condensate of a glycerin compound and a monofunctional aliphatic carboxylic acid. Examples of the tetrafunctional ester wax include a condensate of pentaerythritol and a monofunctional aliphatic carboxylic acid and a condensate of diglycerin and a carboxylic acid. It is a condensate of an aliphatic carboxylic acid. Examples of pentafunctional ester waxes include condensates of triglycerin and monofunctional aliphatic carboxylic acids. Examples of the hexafunctional ester wax include a condensate of dipentaerythritol and a monofunctional aliphatic carboxylic acid, and a condensate of tetraglycerin and a monofunctional aliphatic carboxylic acid.

  As the carboxylic acid described above, it is preferable that any of them is an aliphatic carboxylic acid having 14 to 26 carbon atoms. Specific examples of fatty acids include myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, tricosanoic acid, lignoceric acid, serotic acid, and montanic acid.

  The toner of the present invention preferably contains 3 to 25 parts by mass of ester wax in a total amount with respect to 100 parts by mass of the binder resin. When the content of the ester wax is 3 parts by mass or more and 25 parts by mass or less, it is preferable because the toner production stability is excellent and the density at both ends of the image hardly occurs.

  The toner of the present invention preferably contains a crystalline polyester. Here, the crystalline polyester refers to a polyester that uses a modulated mode in differential scanning calorimetry (DSC) measurement, has an endothermic peak when the temperature is raised, and has an exothermic peak when the temperature is lowered. DSC measurement is performed according to ASTM D 3417-99. For example, it is measured using DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. A measurement sample (polyester) is placed in an aluminum pan for measurement, and an empty pan is set as a control for measurement.

<Measurement conditions using the modulated mode>
• Equilibrate at 20 ° C for 1 minute.
・ Turn the temperature up to 180 ° C. at 2 ° C./min while applying modulation of amplitude 1.5 ° C. and frequency 1 / min.
• Equilibrate at 180 ° C for 10 minutes.
・ The temperature is lowered to 20 ° C. at 2 ° C./min while applying modulation of amplitude 1.5 ° C. and frequency 1 / min.

  In the present invention, in the endothermic curve obtained from the DSC measurement, the crystalline polyester preferably has a peak top of the endothermic peak in the range of 50 to 130 ° C.

  The content of the crystalline polyester is preferably 2 to 50 parts by mass with respect to 100 parts by mass of the toner particles from the viewpoints of production stability and storage stability.

  Further, if the ratio (α / β) of the crystalline polyester content (α) and the ester wax content (β) is 0.3 or more and 3.0 or less, the scanner dirt tends to be improved, preferable. This is presumed that the amount of volatilization at the time of thermal fixing is reduced because the polyester wax having a simple structure such as crystalline polyester and the ester wax are close to each other and partially exist. If it is less than 0.3, the effect of the crystalline polyester is thin, and if it exceeds 3.0, the storage stability tends to decrease, which is not preferable.

  The crystalline polyester may be a known polyester having crystallinity, and the monomer component is not particularly limited, but is preferably a crystalline polyester obtained by polycondensation of an aliphatic diol and an aliphatic dicarboxylic acid.

  As the aliphatic diol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1,4-butadiene glycol, trimethylene glycol, Examples include tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, neopentyl glycol, 1,6-hexanediol, and 1,9-nonanediol. Among these, 1,6-hexanediol and 1,9-nonanediol are particularly preferred.

  On the other hand, the aliphatic dicarboxylic acid is not particularly limited, but is preferably a linear aliphatic dicarboxylic acid. Specific examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid 1,10-dodecanedioic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, and itaconic acid, and their anhydrides. Further, the lower alkyl ester can be hydrolyzed and used as the aliphatic dicarboxylic acid. Among these, sebacic acid and 1,10-dodencandioic acid are particularly preferred.

  The crystalline polyester in the present invention can be produced according to an ordinary polyester synthesis method. For example, the above-mentioned carboxylic acid monomer and alcohol monomer are esterified or transesterified, and then subjected to a polycondensation reaction in accordance with a conventional method under reduced pressure or by introducing nitrogen gas. Crystalline polyester can be obtained.

  The polycondensation reaction can be performed using a conventional polymerization catalyst such as titanium butoxide, dibutyltin oxide, tin acetate, zinc acetate, tin disulfide, antimony trioxide, germanium dioxide and the like. The polymerization temperature and the catalyst amount are not particularly limited, and may be appropriately adjusted so that the reaction rate becomes 99% or more.

  The weight average molecular weight of the crystalline polyester used in the toner of the present invention is preferably 2,000 to 20,000. When the number average molecular weight of the crystalline polyester is less than 2,000, compatibility with other resins contained in the binder resin is likely to occur at the time of toner particle production. When the number average molecular weight is larger than 20,000, the solubility decreases. In addition, the dispersibility in the toner tends to decrease.

  The weight average molecular weight of the crystalline polyester is determined by the GPC method. As a specific measurement procedure, 0.03 g of the polyester to be measured is dispersed in 10 ml of o-dichlorobenzene and dissolved; the obtained solution is shaken at 135 ° C. for 24 hours with a shaker; The solution is filtered through a 0.2 μm filter; the obtained filtrate is used as a sample and measured under the following analysis conditions.

[Analysis conditions]
Separation column: Shodex (TSK GMHHR-H HT20) × 2
Column temperature: 135 ° C
Mobile phase solvent: o-dichlorobenzene mobile phase flow rate: 1.0 ml / min.
Sample concentration: about 0.3%
Injection volume: 300 μl
Detector: Differential refractive index detector Shodex RI-71

  Further, in calculating the molecular weight of the sample, a molecular weight calibration curve prepared with a standard polystyrene resin is used. Examples of the standard polystyrene resin include TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, manufactured by Tosoh Corporation. F-2, F-1, A-5000, A-2500, A-1000, A-500 are included.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 3 μm or more and 12 μm or less, more preferably 4 μm or more and 9 μm or less.

  The glass transition temperature (Tg) of the toner of the present invention is preferably 40 to 70 ° C. When the glass transition temperature is less than 40 ° C., the storage stability is lowered, and the toner is liable to deteriorate during long-term use. When the glass transition temperature is higher than 70 ° C., the fixing property is deteriorated. Therefore, the glass transition temperature of the toner is preferably 40 to 70 ° C. in consideration of the balance between the fixing property, the storage stability, and the developability.

  Examples of the binder resin used in the toner of the present invention include styrene such as polystyrene and polyvinyltoluene, and homopolymers of substitution products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer. Polymer, 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-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene -Vinyl ethyl ether copolymer, Styrene copolymers such as lene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate , Polybutyl methacrylate, polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin can be used, and these can be used alone or in combination. Can do. Of these, styrene copolymers and polyester resins are particularly preferred from the standpoints of development characteristics and fixability.

  In the toner of the present invention, a charge control agent may be blended as necessary to improve charging characteristics. As the charge control agent, a known one can be used, but a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced using a 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. Among the charge control agents, specific compounds as negative charge control agents include metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid; metal salts of azo dyes or azo pigments Or a metal complex; a polymer compound having a sulfonic acid or carboxylic acid group in the side chain; a boron compound; a urea compound; a silicon compound; and a calixarene. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  As a method for adding a charge control agent to the toner, a method of adding the charge control agent to the inside of the toner particles, and in the case of producing the toner by suspension polymerization, the charge control agent is added to the polymerizable monomer composition before granulation. A method of adding is generally used. Also, during the polymerization by forming oil droplets in water, or after polymerization, seed polymerization is carried out by adding a polymerizable monomer in which the charge control agent is dissolved and suspended, and the toner surface is made uniform. It is also possible to cover. In the case where an organometallic compound is used as the charge control agent, it is also possible to introduce the compound by adding these compounds to the toner particles, and applying a shear and mixing and stirring.

  The amount of these charge control agents used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. However, when added internally to the toner particles, it is preferably used in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin. Further, when externally added to the toner particles, the amount is preferably 0.005 to 1.0 part by mass with respect to 100 parts by mass of the toner.

  The toner of the present invention contains a colorant that matches the target color. As the colorant used in the toner of the present invention, any of known organic pigments or dyes, carbon black, magnetic powder, and the like can be used.

  The toner of the present invention preferably uses magnetic powder as a colorant. The magnetic powder is preferably used in an amount of 50 to 130 parts by mass with respect to 100 parts by mass of the binder resin. Since the magnetic powder is hydrophilic to the ester wax, it is difficult to mix with each other. Therefore, for example, when the toner is produced in an aqueous medium, the inclusion of the wax is promoted, and when the toner is produced, for example, by a pulverization method, the fine dispersion of the wax is promoted. When encapsulated, the amount of wax volatilization at the time of heat fixing is suppressed. On the other hand, when finely dispersed, the rate of compatibility with the binder resin increases, so that the amount of wax volatilization tends to be suppressed. If the addition amount of the magnetic powder is less than 50 parts by mass, the above effect is poor, and if it exceeds 130 parts by mass, it becomes difficult to disperse all the magnetic powder in the toner together with the concern that the fixability is deteriorated.

  Note that the content of the magnetic powder in the toner can be measured using a thermal analyzer manufactured by PerkinElmer, TGA7. The measuring method is as follows. The toner is heated from room temperature to 900 ° C. at a temperature rising rate of 25 ° C./min in a nitrogen atmosphere. The weight loss mass% between 100 ° C. and 750 ° C. is defined as the binder resin amount, and the remaining mass is approximately defined as the magnetic powder amount.

When magnetic powder is used in the toner of the present invention, the magnetic powder is mainly composed of magnetic iron oxide such as triiron tetroxide and γ-iron oxide, and phosphorus, cobalt, nickel, copper, magnesium, Elements such as manganese, aluminum, and silicon may be included. These magnetic powders preferably have a BET specific surface area of 2 to 30 m ² / g by nitrogen adsorption method, and more preferably 3 to 28 m ² / g. A Mohs hardness of 5 to 7 is preferred. The shape of the magnetic powder includes polyhedron, octahedron, hexahedron, spherical shape, needle shape, scale shape, etc., but those having low anisotropy such as polyhedron, octahedron, hexahedron, spherical shape, etc. It is preferable in terms of enhancement.

  The magnetic powder preferably has a volume average particle size of 0.10 to 0.40 μm. In general, the smaller the particle size of the magnetic powder, the higher the coloring power, but the magnetic powder tends to aggregate, and the uniform dispersibility of the magnetic powder in the toner is inferior. In addition, when the volume average particle size is 0.10 μm or less, the magnetic powder itself becomes reddish black, so that the image becomes particularly reddish in a halftone image, which is not preferable because it is not a high-quality image. . On the other hand, when the volume average particle size is 0.40 μm or more, the coloring power of the toner is insufficient, and in the suspension polymerization method (described later) which is a preferable method for producing the toner of the present invention, uniform dispersion becomes difficult.

  The volume average particle size of the magnetic powder can be measured using a transmission electron microscope. Specifically, after sufficiently dispersing the toner particles 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 powder particles in the field of view is measured with a transmission electron microscope (TEM) at a magnification of 10,000 to 40,000 times. Then, the volume average particle diameter is calculated based on the equivalent diameter of a circle equal to the projected area of the magnetic powder. It is also possible to measure the particle size with an image analyzer.

  The magnetic powder used for the toner of the present invention 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 pH 7 or higher, and ferrous hydroxide was oxidized while heating the aqueous solution 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 magnetic iron oxide powder with the seed crystal as the core. At this time, it is possible to control the shape and magnetic properties of the magnetic powder 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. A magnetic powder can be obtained by filtering, washing, and drying the magnetic material thus obtained by a conventional method.

  In the present invention, when the toner is produced by a polymerization method, it is very preferable to subject the surface of the magnetic powder to a hydrophobic treatment. When the surface treatment is performed by a dry method, the coupling agent treatment is performed on the magnetic powder that has been washed, filtered, and dried. 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. In the present invention, both a dry method and a wet method can be selected as appropriate.

Examples of the coupling agent that can be used in the surface treatment of the magnetic powder in the present invention include a silane coupling agent and a titanium coupling agent. More preferably used is a silane coupling agent, which is represented by the general formula (I).
R _m SiY _n (I)
[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 vinyl group, an epoxy group, or a (meth) acryl group, and n represents 1 to 3] Indicates an integer. However, m + n = 4. ]

  Examples of the silane coupling agent represented by the general formula (I) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, Vinyltriacetoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyl Diethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, trimethylmethoxysilane, n-hexyltrimethoxysilane, n-octyltrimethoxysilane, n-octyltri Examples include ethoxysilane, n-decyltrimethoxysilane, hydroxypropyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane. In the present invention, those in which Y in formula (I) is an alkyl group can be preferably used. Among them, an alkyl group having 3 to 6 carbon atoms is preferable, and 3 or 4 is particularly preferable. If the number of carbon atoms is 3 or 4, the degree of hydrophobicity on the surface of the magnetic powder will be moderately low. Therefore, when produced in an aqueous medium, it tends to be distributed near the outside of the toner particles. Furthermore, it is considered that it is difficult to be compatible with the ester wax of the present invention due to the low degree of hydrophobicity, and that the volatilization amount of the wax is easily suppressed by being sufficiently encapsulated inside the toner.

  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.

  The total amount of the coupling agent used is preferably 0.9 to 3.0 parts by mass with respect to 100 parts by mass of the magnetic powder, and the treatment is performed according to the surface area of the magnetic powder, the reactivity of the coupling agent, and the like. It is important to adjust the amount of agent.

  In the present invention, other colorants may be used in combination with the magnetic powder. 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 toner of the present invention preferably has a core-shell structure, the core layer contains a styrene acrylic resin, and the shell layer preferably contains an amorphous polyester resin. In the present invention, having a core-shell structure means a structure in which the shell layer covers the surface of the core layer. Here, “coating” means covering the surface of the core layer with a shell layer.

  The toner of the present invention is preferably produced in an aqueous medium. This is because when considering the ester wax necessary for the toner of the present invention, the resin component and the ester wax can have sufficient opportunities to be compatible. Further, in the production in an aqueous medium, it is possible to form a shell layer by attaching ultrafine particles for shells to core particles and drying them.

  In the toner of the present invention, the styrene acrylic resin constituting the core layer is a resin obtained by copolymerizing styrene and (meth) acrylic acid or a derivative thereof, and means a known styrene acrylic resin. To do.

  The following can be illustrated as a polymerizable monomer which forms the said styrene acrylic resin.

  Examples of the styrene polymerizable monomer include styrene; styrene polymerizable monomers such as α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, and p-methoxy styrene.

  Acrylic polymerizable monomers include methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate And acrylic polymerizable monomers such as n-octyl acrylate and cyclohexyl acrylate.

  Methacrylic polymerizable monomers include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate. And methacrylic polymerizable monomers such as n-octyl methacrylate.

  In addition, the manufacturing method of a styrene acrylic resin is not specifically limited, A well-known method can be used. The content of the styrene acrylic resin with respect to the total amount of the binder resin is preferably 70% by mass or more, and more preferably 80% by mass or more.

  In addition to the amorphous polyester resin and the styrene acrylic resin, the binder resin may contain a known resin used for the toner binder resin to the extent that the effect of the present invention is not affected.

  The toner of the present invention can be produced by any known method. First, when manufacturing by a pulverization method, for example, binder resin, colorant, ester wax, low melting point substance, charge control agent and other necessary components and other additives are mixed in a Henschel mixer, ball mill, etc. Mix thoroughly with a vessel. Thereafter, the toner material is dispersed or dissolved by using a heat kneader such as a heating roll, a kneader, or an extruder to disperse or dissolve the toner material, and after cooling and solidification, pulverization, and surface treatment as necessary to obtain toner particles. be able to. Either the classification or the surface treatment may be performed first. In the classification step, it is preferable to use a multi-division classifier in terms of production efficiency.

  The pulverization step can be performed by a method using a known pulverizer such as a mechanical impact type or a jet type. Further, it is preferable to further pulverize by applying heat or to add a mechanical impact to the auxiliary. Further, a hot water bath method in which finely pulverized (classified as necessary) toner particles are dispersed in hot water, a method of passing in a hot air stream, or the like may be used.

  Examples of means for applying a mechanical impact force include a method using a mechanical impact pulverizer such as a kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industry. In addition, like the Hosokawa Micron Mechano-Fusion System and the Nara Machinery Co., Ltd. Hybridization System, the toner is pressed against the inside of the casing by centrifugal force using high-speed rotating blades. There is a method of applying a mechanical impact force to the toner.

  The toner of the present invention can also be produced by a pulverization method as described above. However, the toner of the present invention can be produced in an aqueous medium such as a dispersion polymerization method, an emulsion aggregation method, a dissolution suspension method, or a suspension polymerization method. It is preferable to produce a toner. In particular, the suspension polymerization method is very preferable because it easily satisfies the suitable physical properties of the present invention.

  The suspension polymerization method is a polymerizable monomer in which a polymerizable monomer and a colorant (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) are uniformly dissolved or dispersed. A composition is obtained. Thereafter, this polymerizable monomer composition is dispersed in a continuous layer containing a dispersant (for example, an aqueous phase) using a suitable stirrer and simultaneously subjected to a polymerization reaction to obtain a toner having a desired particle size. Is. The toner obtained by this suspension polymerization method (hereinafter also referred to as “polymerized toner”) has an almost uniform spherical toner particle shape, and the charge amount distribution is relatively uniform, improving the image quality. I can expect.

  In the production of the polymerized toner according to the present invention, examples of the polymerizable monomer constituting the polymerizable monomer composition include the following.

  Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate, Acrylate esters such as n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and 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 dimethyl aminoethyl, methacrylic acid esters such as diethylaminoethyl methacrylate; and other acrylonitrile, methacrylonitrile, and the like monomers acrylamide. These monomers can be used alone or in combination. Among the above-mentioned monomers, styrene is preferably used alone or mixed with other monomers from the viewpoint of toner development characteristics and durability.

  The polymerization initiator used in the production of the toner according to the present invention by polymerization is preferably one having a half-life of 0.5 to 30 hours during the polymerization reaction. Further, when a polymerization reaction is carried out using an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 5,000 and 50,000 is obtained. The toner can be provided with desirable strength and suitable melting characteristics.

  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, azobisisobutyronitrile and other azo or diazo polymerization initiators; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxide Peroxide polymerization initiators such as oxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, t-butylperoxy 2-ethylhexanoate, t-butylperoxypivalate, etc. Can be mentioned.

  When the toner of the present invention is produced by a polymerization method, a crosslinking agent may be added, and a preferable addition amount is 0.001 to 15 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

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

  In the method for producing the toner of the present invention by a polymerization method, generally, the above-described toner composition or the like is added as appropriate, and the polymerizable single particle is uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, or an ultrasonic disperser. The meter composition is suspended in an aqueous medium containing a dispersant. At this time, the particle size of the obtained toner particles becomes sharper by using a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser to obtain a desired toner particle size at a stretch. 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. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

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

  When the toner of the present invention is produced, known surfactants, organic dispersants and inorganic dispersants can be used as the dispersant. In particular, inorganic dispersants are less likely to produce harmful ultrafine powders, and because of their steric hindrance, dispersion stability is obtained, so even if the reaction temperature is changed, stability is not easily lost, and washing is easy and does not adversely affect the toner. Therefore, it can be preferably used. Examples of such inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, phosphate polyvalent metal salts such as hydroxyapatite, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate, Examples thereof include inorganic salts such as barium sulfate and inorganic compounds such as calcium hydroxide, magnesium hydroxide, and aluminum hydroxide.

  These inorganic dispersants are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. Moreover, the said dispersing agent may be used independently and may use multiple types together. Furthermore, you may use 0.001 to 0.1 mass part surfactant together.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles can be generated and used in an aqueous medium. For example, in the case of tricalcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution can be mixed under high-speed stirring to produce water-insoluble calcium phosphate, which enables more uniform and fine dispersion. At the same time, water-soluble sodium chloride salt is produced as a by-product. However, if water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and ultrafine toner is generated by emulsion polymerization. This is more convenient.

  Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

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

  This is because the toner of the present invention contains 0.05 ppm or more and 0.60 ppm or less of a styrene derivative. The styrene derivative in the present invention refers to a compound having a structure in which a vinyl group of styrene is substituted with a functional group such as an OH group, an aldehyde group, a carboxyl group, or an ethyl group. Specific examples include styrene, ethylbenzene, benzaldehyde, phenol, acetophenone, benzyl acetate, and the like, but any compound having a similar skeleton may be used, and the present invention is not limited thereto. The amount of the styrene derivative is preferably adjusted by polymerizing at least a polymerizable monomer containing styrene or a styrene derivative and further adding a distillation step. As a distillation method, a known method can be used. Examples thereof include a vacuum distillation method in which heating is performed under reduced pressure and a steam distillation method in which pure saturated steam is blown. From the viewpoint of easy adjustment of the amount of styrene derivative, the steam distillation method is preferred.

  Toner particles are obtained by filtering, washing and drying the obtained polymer particles by a known method. The toner of the present invention can be obtained by mixing the toner particles with inorganic fine powder as will be described later, if necessary, and adhering them to the surface of the toner particles. It is also possible to insert a classification step in the manufacturing process (before mixing the inorganic fine powder) to cut coarse powder and fine powder contained in the toner particles.

  In the present invention, the toner is preferably added with inorganic fine powder having a number average primary particle size of 4 to 80 nm, more preferably 6 to 40 nm, as a fluidizing agent. The inorganic fine powder is added to improve the fluidity of the toner and to make the charge of the toner particles uniform. However, adjustment of the charge amount of the toner, improvement of environmental stability, etc. by treatment such as hydrophobizing the inorganic fine powder. It is also a preferable form to provide the function. The method for measuring the number average primary particle size of the inorganic fine powder is performed using a photograph of the toner magnified by a scanning electron microscope.

Silica, titanium oxide, alumina, etc. can be used as the inorganic fine powder used in the present invention. As the fine silica powder, for example, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. is there. However, dry silica having fewer silanol groups on the surface and in the silica fine powder and less production residue such as Na ₂ O and SO ₃ ²⁻ is more preferable. In dry silica, it is also possible to obtain a composite fine powder 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, They are also included.

  The addition amount of the inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably 0.1 to 3.0% by mass with respect to the toner particles. The effect is not sufficient, and if it is 3.0% by mass or more, the fixing property is deteriorated. The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  In the present invention, the inorganic fine powder is preferably a hydrophobized product because the environmental stability of the toner can be improved. When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner particles is remarkably reduced, the charge amount is likely to be non-uniform, and toner scattering is likely to occur. Treatment agents used for hydrophobizing inorganic fine powders include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. May 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 the hydrophobic treatment of the inorganic fine powder with the silane compound. As a method for treating such inorganic fine powder, for example, as a first-stage reaction, a silanization reaction is performed with a silane compound and silanol groups are eliminated by chemical bonds, and then a hydrophobic reaction is performed on the surface with silicone oil as a second-stage reaction. The thin film can be formed.

  Examples of the method of treating the inorganic fine powder with silicone oil include a method of directly mixing the inorganic fine powder treated with the silane compound and the silicone oil using a mixer such as a Henschel mixer, or a method of treating the inorganic fine powder with the silicone oil. The method of spraying is mentioned. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, an inorganic fine powder may be added and mixed to remove the solvent. A spraying method is more preferred in that the formation of inorganic fine powder aggregates 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 powder. If the amount of silicone oil is too small, good hydrophobicity cannot be obtained, and if it is too large, problems such as fogging tend to occur.

The inorganic fine powder used in the present invention preferably has a specific surface area measured by the BET method by nitrogen adsorption in the range of 20 to 350 m ² / g in order to impart good fluidity to the toner, and 25 to 300 m ^2. / G is more preferable. The specific surface area is calculated using the BET multipoint method by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method.

  In the toner of the present invention, for the purpose of improving the cleaning property and the like, an inorganic or organic spherical fine particle having a primary particle size of more than 30 nm, more preferably a primary particle size of 50 nm or more, may be further added to the toner particles. One of the preferred forms. For example, spherical silica particles, spherical polymethylsilsesquioxane particles, spherical resin particles and the like are preferably used.

  In the toner of the present invention, other additives within a range that does not have a substantial adverse effect, for example, a lubricant powder such as fluororesin powder, zinc stearate powder, polyvinylidene fluoride powder; cerium oxide powder, silicon carbide powder, A small amount of an abrasive such as strontium titanate powder; a fluidity-imparting agent such as titanium oxide powder or aluminum oxide powder; an anti-caking agent; or organic fine particles and inorganic fine particles having opposite polarity can be used in small amounts. It is also possible to use the surface of these additives after hydrophobizing them.

  Next, an example of an image forming apparatus that can suitably use the toner of the present invention will be specifically described with reference to FIG. In FIG. 1, reference numeral 100 denotes a photosensitive drum, which is provided with a primary charging roller 117, a developing device 140 having a developing sleeve 102, a transfer charging roller 114, a cleaner 116, a register roller 124, and the like. The photosensitive drum 100 is charged to, for example, −600 V by the primary charging roller 117 (applied voltages are, for example, an AC voltage of 1.85 kVpp and a DC voltage of −620 Vdc). Then, exposure is performed by irradiating the photoreceptor 100 with the laser beam 123 by the laser generator 121, and an electrostatic latent image corresponding to the target image is formed. The electrostatic latent image on the photosensitive drum 100 is developed with a one-component toner by the developing device 140 to obtain a toner image, and the toner image is transferred onto the transfer material by the transfer roller 114 in contact with the photoreceptor via the transfer material. Is done. The transfer material on which the toner image is placed is conveyed to the fixing device 126 by the conveying belt 125 or the like and fixed on the transfer material. In addition, toner remaining on a part of the photoconductor is cleaned by a cleaner 116.

  Although an image forming apparatus for magnetic one-component jumping development is shown here, the toner of the present invention may be toner or non-toner and is used for either one-component development method or two-component development development method. The toner may be used. Furthermore, it may be used for any method of jumping development or contact development.

  Next, a method for measuring each physical property related to the toner of the present invention will be described.

(1) Melting | fusing point of ester wax Melting | fusing point of ester wax can be calculated | required as the peak top temperature of an endothermic peak when it measures by DSC. The measurement is performed according to ASTM D 3417-99. For these measurements, for example, DSC-7 manufactured by PerkinElmer, DSC2920 manufactured by TA Instruments, and Q1000 manufactured by TA Instruments can be used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, and an empty pan is set for control and measured.

(2) Average particle size and particle size distribution of toner The weight average particle size and particle size distribution of the toner of the present invention can be measured by various methods using a Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter). It is. In the present invention, a Coulter Multisizer (manufactured by Coulter Inc.) is used, and an interface (manufactured by Nikkiki) and a PC9801 personal computer (manufactured by NEC) for outputting the number distribution and volume distribution are connected thereto. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride is used. As such an electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.

  The measurement procedure is as follows. In 100 to 150 ml of the electrolyte solution, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the number distribution of the toner particles of 2 μm or more is measured using the 100 μm aperture as the aperture by the Coulter Multisizer. calculate. Based on this, the weight average particle diameter is determined.

(3) Measurement of molecular weight and composition distribution of ester wax The composition distribution of ester wax is obtained by first measuring the molecular weight distribution by GPC and measuring the region by GC (gas chromatography) or MARDI TOF MASS. GPC of ester wax is measured under the following conditions.

(GPC measurement conditions)
Column: GMH-HT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 m1 / min
Sample: A 0.15% sample is measured under the condition of injection of 0.4 ml, and a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

  The peak obtained by GPC is analyzed, and the maximum value and the minimum value of the molecular weight distribution of the ester wax are calculated. When analyzed by GC or MARDI TOFF MASS as described below, the region sandwiched between the maximum value and the minimum value obtained by GPC is regarded as the “range of molecular weight distribution of ester wax”. The ester wax of the present invention can be measured by either GC or MARDI TOF MASS, but is appropriately selected such as MARDI when gasification is difficult and GC when the matrix and peaks overlap. Both measurement methods are described.

(GC measurement conditions)
Specific conditions when the composition distribution of the ester wax is measured by gas chromatography (GC) will be described. As gas chromatography (GC), GC-17A (manufactured by Shimadzu Corporation) is used. 10 mg of a sample is added to 1 ml of toluene, and heated and dissolved in a constant temperature layer at 80 ° C. for 20 minutes. Next, 1 μl of the lysate is injected into a GC apparatus equipped with an on-column injector. As the column, 0.5 mm diameter × 10 m long Ultra Alloy-1 (HT) is used. The column is first heated from 40 ° C. to 200 ° C. at a rate of 40 ° C./min, further raised to 350 ° C. at 15 ° C./min, and then raised to 450 ° C. at a rate of 7 ° C./min. Let warm. As the carrier gas, He gas is allowed to flow under a pressure condition of 50 kPa.

  Here, by introducing the gasification component into a mass spectrometer (mass spectrometer) and obtaining the molecular weight of a plurality of peaks obtained by GC, the peak group that falls within the above-mentioned “range of molecular weight distribution of ester wax” is obtained. Find out. These peak groups are analyzed, and the sum total of peak areas is calculated. Further, among the peaks obtained by GC, the peak with the largest peak area is defined as the peak derived from the most numerous component of the ester wax, and by taking the ratio of the peak area of the most numerous component to the sum of all peak areas, The ratio of the most numerous component in the composition distribution is obtained.

  The compound can be identified by injecting an ester wax having a known structure separately and comparing the same outflow times, or introducing a gasification component into a mass spectrometer and analyzing the spectrum.

  The molecular weight M1 of the most numerous component in the present invention can be determined by introducing a peak derived from the most numerous component into a mass spectrometer and analyzing it. Multiply M1 by 1.2 to calculate M1 + 20% molecular weight, and multiply by 0.8 to calculate M1-20% molecular weight. A plurality of peaks obtained from a spectrum obtained by GC are analyzed by a mass spectrometer, a peak that falls within the region of M1 ± 20% is searched, analyzed, and a total peak area is calculated. By determining the ratio of this area value to the sum of the peak areas falling within the above-mentioned “range of molecular weight distribution of ester wax”, a component ratio within M1 ± 20% can be obtained.

(MARDI TOF MASS measurement conditions)
The case where the composition distribution of the ester wax is measured by MARDI TOF MASS will be described. The optimum matrix was selected according to the material type, and consideration was given so that the matrix peak and the peak derived from the material did not overlap.

  Among the peaks obtained by MARDI TOF MASS, a peak that falls within the above-mentioned “range of molecular weight distribution of ester wax” is found, and the sum of the peak intensities is calculated. Among these peaks, the peak having the maximum intensity is defined as the peak derived from the most numerous components. The ratio of the most numerous component in the composition distribution of the ester wax is calculated by the ratio of the peak intensity derived from the most numerous component to the sum of the peak intensities.

  The compound can be identified by analyzing a spectrum obtained by MARDI TOF MASS from an ester wax having a known structure.

  The molecular weight M1 of the most numerous component is obtained by spectral analysis of the molecular weight of the peak derived from the most numerous component. Moreover, M1 + 20% molecular weight is calculated by multiplying M1 by 1.2, and M1-20% molecular weight is calculated by multiplying M1 by 0.8, and the sum of the intensities of peaks entering the region of M1 ± 20% is calculated. By obtaining the ratio of the sum of the intensities to the sum of the peak intensities falling within the above-mentioned “range of molecular weight distribution of ester wax”, a component ratio within M1 ± 20% can be obtained.

(4) Method for measuring the total amount of styrene derivative The total amount of the styrene derivative of the present invention is analyzed by organic volatile components at a heating temperature of 120 ° C. of the toner by the headspace method, and the concentration in terms of toluene based on the toner mass is calculated. Get it. The measurement conditions are shown below.

For the measurement, a multiple headspace extraction method was used. The multiple headspace extraction method is a method in which a sample is accommodated in an airtight container having a predetermined volume, the airtight container is heated as necessary, and the gas phase in the airtight container is extracted (extracted). The headspace sampler is manufactured by Perkin Elmer Japan Co., Ltd., HS40XL, and GC / MS is manufactured by ThermoQuest Co., Ltd., TRACE GC, TRACE MS. The sample vial is connected to gas chromatography.
(I) Headspace sampler conditions and sample amount: 500 mg
Sample temperature: 120 ° C
・ Needle temperature: 150 ℃
・ Transfer line temperature: 180 ℃
・ Retention time: 60 min
・ Pressurization time: 0.25 min
・ Injection time: 0.08 min
(Ii) GC conditions / column: HP5-MS (0.25 mm, 60 m)
Column temperature: held at 40 ° C. for 3 minutes, heated at 40 ° C. to 70 ° C. at 2.0 ° C./min, heated at 70 to 150 ° C. at 5.0 ° C./min, 150 to 300 ° C. The temperature is 10.0 ° C / min and the temperature rise / split ratio is 50: 1
(Iii) Apparatus As a sealed container, a glass vial for headspace analysis manufactured by PerkinElmer Japan Co., Ltd. is used.
(Iv) Method 1) Preparation of Standard Sample First, as a standard sample for styrene derivative determination, an acetone solution having a toluene concentration of 1000 ppm is prepared, and 5 μl of this solution is put into a glass vial using a 10 μl volume microsyringe. Put it in and seal it quickly with a high temperature analysis septum.
2) Preparation of toner sample 500 mg of toner is put in a glass vial and sealed with a high-temperature analysis septum to prepare a sample.
(V) Analysis A standard sample of the toluene solution is measured using a quantitative multiple headspace extraction method, and the total peak area per 0.005 μl of toluene is obtained (Note that since the sensitivity of GC varies from day to day, The peak area per 0.005 μl of compound needs to be examined for each measurement). In addition, a gasification component is introduce | transduced into a mass spectrometer (mass spectrometer), and it confirms that the obtained peak is a peak derived from toluene. Next, the toner is measured in the same manner as toluene, and introduced into a mass spectrometer, and a styrene derivative (a compound having a structure in which the vinyl group of styrene is substituted with a functional group such as an OH group, an aldehyde group, a carboxyl group, or an ethyl group). The peak of origin is specified, and the total peak area is obtained. The amount of styrene derivative in the measurement sample is calculated from the peak area of the toluene standard sample by proportional calculation to obtain the amount of styrene derivative in the toner.

  Hereinafter, the present invention will be described more specifically with reference to production examples and examples, but these do not limit the present invention in any way. In addition, all the parts in the following mixing | blending show a mass part.

  Hereinafter, production examples of ester wax will be described. In this invention, ester wax was obtained by manufacturing ester compounds and melt-mixing them at a predetermined blending ratio.

<Production of ester compounds D-22, 12, 14, 16, 17, 18, 19, 20, 24, 26>
To the reactor equipped with Dimroth, Dean-Stark water separator and thermometer, 210 mol parts of benzene, 180 mol parts of docosanoic acid (behenic acid), 30 mol parts of dipentaerythritol and 7 mol parts of p-toluenesulfonic acid were added. After sufficiently stirring and dissolving, the mixture was refluxed for 6 hours, and then the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound D-22.

  Similarly, docosanoic acid was changed to a different monocarboxylic acid to obtain an ester compound. The docosanoic acid is changed to dodecanoic acid (lauric acid), the ester compound D-12 is changed to tetradecanoic acid (myristic acid), and the ester compound D-14 is changed to hexadecanoic acid (palmitic acid) to obtain D-16. Was changed to heptadecanoic acid to obtain D-17. Furthermore, docosanoic acid is changed to octadecanoic acid (stearic acid), D-18 is changed to nonadecanoic acid, D-19 is changed to eicosanoic acid (arachidic acid), and D-20 is changed to tetracosanoic acid. Then, D-24 was changed to hexacosanoic acid (serotic acid) to obtain D-26.

<Production of ester compounds P-22, 16, 20, 24>
A reactor equipped with Dimroth, Dean-Stark water separator and thermometer was added with 210 mol parts of benzene, 168 mol parts of docosanoic acid (behenic acid), 42 mol parts of pentaerythritol, and 7 mol parts of p-toluenesulfonic acid. After stirring and dissolving, the mixture was refluxed for 6 hours, and then the water separator valve was opened to perform azeotropic distillation. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound P-22.

  Similarly, docosanoic acid was changed to a different monocarboxylic acid to obtain an ester compound. The docosanoic acid was changed to hexadecanoic acid (palmitic acid), P-16 was changed to eicosanoic acid (arachidic acid), P-20 was changed to tetracosanoic acid, and P-24 was obtained.

<Production of ester compounds S-22, 20, 24>
Dimroth, Dean-Stark water separator, reactor equipped with a thermometer, 300 mol parts of benzene, 200 mol parts of docosanol (behenyl alcohol), 100 mol parts of decanedioic acid (sebacic acid), and 10 mol parts of p-toluenesulfonic acid After stirring and dissolving, the mixture was refluxed for 6 hours, and then the valve of the water separator was opened to perform azeotropic distillation. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound S-22.

  Similarly, docosanol was changed to a different kind of alcohol to obtain an ester compound. Docosanol was changed to eicosanol and S-20 was changed to tetracosanol to obtain S-24.

<Production of ester compounds N-22, 20, 24>
Dimroth, Dean-Stark water separator, reactor equipped with a thermometer, 300 mol parts of benzene, 200 mol parts of docosanoic acid (behenic acid), 100 mol parts of 1,9-nonanediol, and 10 mol of p-toluenesulfonic acid After stirring and dissolving, the mixture was refluxed for 6 hours, and then the water separator valve was opened to perform azeotropic distillation. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound N-22.

  Similarly, docosanoic acid was changed to a different monocarboxylic acid to obtain an ester compound. N-20 was changed to eicosanoic acid by changing docosanoic acid, and N-24 was obtained by changing to tetracosanoic acid.

<Production of ester compounds B-22, 20, 24>
A reaction apparatus equipped with a Dimroth, Dean-Stark water separator and thermometer was equipped with 200 mol parts of benzene, 100 mol parts of docosanoic acid (behenic acid), 100 mol parts of docosanol (behenyl alcohol), and 7 mol parts of p-toluenesulfonic acid. After sufficiently stirring and dissolving, the mixture was refluxed for 6 hours, and then the water separator valve was opened to carry out azeotropic distillation. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound B-22.

  Similarly, docosanoic acid was changed to a different monocarboxylic acid to obtain an ester compound. The docosanoic acid was changed to eicosanoic acid and B-20 was changed to tetracosanoic acid to obtain B-24.

<Production of ester compounds DD-22, 20, 24>
A reactor equipped with Dimroth, Dean-Stark water separator and thermometer was added with 300 mol parts of benzene, 200 mol parts of docosanol (behenyl alcohol), 100 mol parts of dodecanedioic acid, and 10 mol parts of p-toluenesulfonic acid, and stirred well. After dissolution, the mixture was refluxed for 6 hours, and then the valve of the water separator was opened and azeotropic distillation was performed. After azeotropic distillation, the residue was thoroughly washed with sodium hydrogen carbonate and dried to remove benzene. The obtained product was recrystallized, washed and purified to obtain ester compound DD-22.

  Similarly, docosanol was changed to a different kind of alcohol to obtain an ester compound. The docosanol was changed to eicosanol, and DD-20 was changed to tetracosanol to obtain DD-24.

<Manufacture of ester wax 1>
D-20, D-22, and D-24 were melted and mixed at the ratios shown in Table 1, cooled, and crushed to obtain ester wax 1. Table 1 also shows the composition ratio measured by GS-MASS, the ratio satisfying M1 ± 20%, and the melting point of the ester wax.

<Production of ester waxes 2 to 17>
The ester compound was melted and mixed at the ratio shown in Table 1, cooled, and crushed to obtain an ester wax 1. Table 1 also shows the composition ratio measured by GS-MASS, the ratio satisfying M1 ± 20%, and the melting point of the ester wax.

<Manufacture of amorphous polyester resin>
Bisphenol A-PO2 molar adduct, bisphenol A-EO2 molar adduct, and terephthalic acid are put in a molar ratio of 50 moles, 50 moles, and 100 moles in a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen introduction tube. The reaction was carried out for 10 hours at 230 ° C. while distilling off the water produced under a nitrogen stream. At this time, as a catalyst, 0.25 part of a titanium-based catalyst (titanium dihydroxybis (triethanolamate)) was added to 100 parts of the total monomer of acid and alcohol.

  Next, the reaction was carried out under a reduced pressure of 20 mmHg, and when the acid value became 0.5 (mgKOH / g) or less, the mixture was cooled to 180 ° C. 0.0 part by mass was added, taken out after reaction for 2 hours under sealed at normal pressure, cooled to room temperature, and then pulverized to obtain amorphous polyester resin 1. The resulting amorphous polyester resin had a glass transition temperature of 68 ° C. and a peak molecular weight of 10,000.

<Manufacture of crystalline polyester resin 1>
To a heat-dried three-necked flask, 250 parts of 1,10-dodecanedioic acid, 150 parts of 1,9-nonanediol and 0.4 part of dibutyltin oxide as a catalyst were added. By reducing the pressure, the air in the three-necked flask was replaced with nitrogen to create an inert atmosphere, followed by mechanical stirring at 180 ° C. for 5 hours and refluxing to proceed the reaction. During the reaction, water produced in the reaction system was distilled off. Thereafter, the temperature was gradually raised to 230 ° C. under reduced pressure, and the reaction was stopped by stirring for 3 hours to obtain a crystalline polyester resin 1. When the molecular weight was confirmed by GPC, the weight average molecular weight was 25000, and the melting point by DSC was 73.6 ° C.

<Production of crystalline polyester resin 2>
To a heat-dried three-necked flask, 200 parts of sebacic acid, 120 parts of 1,6-hexanediol, and 0.045 part of tetrabutoxytitanium as a catalyst were added. The air in the three-necked flask was replaced with nitrogen to create an inert atmosphere, and the reaction was allowed to proceed with mechanical stirring at 180 ° C. for 5 hours and refluxed. During the reaction, water produced in the reaction system was distilled off. Thereafter, the temperature was gradually raised to 200 ° C. under reduced pressure, and the reaction was stopped by stirring for 3 hours to obtain a crystalline polyester resin 2. When the molecular weight was confirmed by GPC, the weight average molecular weight was 15000, and the melting point by DSC was 88 ° C.

<Manufacture of magnetic powder 1>
(Manufacture of untreated magnetic material)
In a ferrous sulfate aqueous solution, 1.0 equivalent of caustic soda solution with respect to iron element, 1.5 mass% sodium silicate in terms of silicon element with respect to iron element are mixed, and contain ferrous hydroxide An aqueous solution was prepared. While maintaining the aqueous solution at pH 9.0, air was blown in, and an oxidation reaction was performed at 80 ° C. or higher and 90 ° C. or lower to prepare a slurry liquid for generating seed crystals. Subsequently, ferrous sulfate aqueous solution was added to this slurry liquid so that it might become 1.0 equivalent with respect to alkali amount (sodium component of caustic soda). Thereafter, the slurry liquid was maintained at pH 8.0, and an oxidation reaction was promoted while air was blown to obtain a slurry liquid containing magnetic iron oxide. The slurry was filtered and washed, and then filtered again. Thereafter, crushing and drying were performed to obtain an untreated magnetic material.

(Preparation of Silane Compound 1)
20 parts by mass of isobutyltrimethoxysilane was added dropwise with stirring to 80 parts by mass of ion-exchanged water. Thereafter, this aqueous solution is maintained at pH 5.5 and a temperature of 40 ° C., and dispersed by using a disper blade at 0.46 m / s for 2 hours for hydrolysis, and silane compound 1 which is an aqueous solution containing a hydrolyzate is obtained. Obtained.

(Manufacture of magnetic powder 1)
100 parts by mass of the untreated magnetic material was put into a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), and 3.8 parts by mass of silane compound 1 was added while being dispersed at 34.5 m / s. After dispersing for 10 minutes, the magnetic material adsorbed with the silane compound 1 was taken out, allowed to stand at 160 ° C. for 2 hours and dried, and the condensation reaction of the silane compound was advanced. Then, the magnetic powder 1 was obtained by passing through a sieve having an opening of 100 μm.

<Manufacture of magnetic powder 2>
(Manufacture of untreated magnetic material)
It was manufactured in the same manner as magnetic powder 1.

(Preparation of Silane Compound 2)
20 parts by mass of n-propyltrimethoxysilane was added dropwise with stirring to 80 parts by mass of ion-exchanged water. Thereafter, this aqueous solution is maintained at pH 4.2 and at a temperature of 60 ° C., and dispersed using a disper blade at 0.46 m / s for 1 hour for hydrolysis, and silane compound 2 which is an aqueous solution containing a hydrolyzate Obtained.

(Manufacture of magnetic powder 2)
A magnetic powder 2 was obtained in the same manner except that the silane compound used was changed from silane compound 1 to 2 and the addition amount was 4.5 parts by mass.

<Manufacture of magnetic powder 3>
In a ferrous sulfate aqueous solution, 1.1 equivalent of a caustic soda solution with respect to iron element, P ₂ O _{5 in} an amount of 0.12% by mass in terms of phosphorus element with respect to iron element, and silicon element with respect to iron element An aqueous solution containing ferrous hydroxide was prepared by mixing SiO ₂ in an amount of 0.55% by mass in terms of conversion. The pH of the aqueous solution was set to 7.5, and an oxidation reaction was performed at 85 ° C. while blowing air to prepare a slurry liquid having seed crystals.

  Next, after adding an aqueous ferrous sulfate solution to this slurry liquid so as to be 1.1 equivalent to the initial alkali amount (sodium component of caustic soda), the slurry liquid is maintained at pH 7.6 and air is blown into it. Then, the oxidation reaction was promoted to obtain a slurry liquid containing magnetic iron oxide. After filtration and washing, the water-containing slurry was once taken out. At this time, a small amount of water-containing sample was collected and the water content was measured. 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. While stirring, 1.5 parts of n-hexyltrimethoxysilane is added to 100 parts of magnetic iron oxide (the amount of magnetic iron oxide is calculated as a value obtained by subtracting the water content from the water-containing sample), and hydrolysis is performed. It was. Thereafter, the mixture was sufficiently stirred and dispersed with a pin mill while circulating the slurry, and the pH of the dispersion was adjusted to 8.6 to perform a hydrophobic treatment. The obtained hydrophobic magnetic powder is filtered with a filter press, washed with a large amount of water and then dried at 100 ° C. for 15 minutes and at 90 ° C. for 30 minutes. A magnetic powder 3 having a diameter of 0.21 μm was obtained.

<Manufacture of toner 1>
After warming the 0.1M-Na ₃ PO ₄ aqueous solution 450 parts turned to 60 ° C. to 720 parts of deionized water, with the addition of 1.0 M-CaCl ₂ aqueous solution 67.7 parts water containing a dispersant A medium was obtained.
-Styrene 78.0 parts-N-butyl acrylate 22.0 parts-Divinylbenzene 0.48 parts-Iron complex of monoazo dye (T-77: manufactured by Hodogaya Chemical Co., Ltd.) 1.5 parts-Magnetic powder 1 90.0 Parts / amorphous polyester resin 5.0 parts / crystalline polyester resin 1 5.0 parts The above composition is uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. Obtained. This monomer composition was heated to 60 ° C., and 15 parts of ester wax 1 was added and mixed there. After dissolution, the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 4.5 Part was dissolved.

The monomer composition was charged into the aqueous medium, and granulated by stirring at 12,000 rpm for 10 minutes in a TK homomixer (Special Machine Industries Co., Ltd.) in an N ₂ atmosphere at 60 ° C. Then, a polymer dispersion was obtained by reacting at 70 ° C. for 5 hours while stirring with a paddle stirring blade. After that, the stirring was stopped, and the polymer dispersion was put into a distillation vessel equipped with a carrier gas introduction pipe, a vent pipe and a condenser for cooling and condensing the gas discharged from the vent pipe. When 100 parts / hr (steam pressure: 120 kPa) of pure saturated water vapor was introduced into the polymer dispersion, 10 minutes after the start of the introduction of saturated water vapor, a fraction began to come out from the vent pipe via the condenser. Steam distillation was performed starting from the time when the fraction started to come out. Then, after continuing distillation for 5 hours, the introduction of pure saturated water vapor was stopped and cooled. Thereafter, hydrochloric acid was added for washing, followed by filtration, crushing and drying to obtain toner particles 1.

  100 parts of this toner particle 1 and 0.8 part of hydrophobic silica having a number average primary particle size of 12 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), and the weight average particle size (D4) was 7. Toner 1 having a thickness of 8 μm was obtained. When toner 1 was analyzed for organic volatile components by the headspace method, the total amount of styrene derivatives was 0.25 ppm. Table 2 shows the physical properties of Toner 1.

<Manufacture of toner 2>
Toner 2 was obtained in the same manner as in the manufacture of toner 1 except that the preparation of toner 1 was changed to the blend of ester wax and crystalline polyester as shown in Table 2. Table 2 shows the composition and physical properties of Toner 2.

<Manufacture of toner 3>
In the production of the toner 1, the toner 3 was prepared in the same manner as in the production of the toner 1 except that the blend of ester wax and crystalline polyester shown in Table 2 was used and the magnetic powder used was changed to the magnetic powder 2. Obtained. Table 2 shows the composition and physical properties of Toner 3.

<Manufacture of toner 4>
In the production of the toner 1, a toner 4 was obtained in the same manner as in the production of the toner 1 except that the crystalline polyester was not used. Table 2 shows the composition and physical properties of Toner 4.

<Manufacture of toner 5>
In the production of the toner 4, a toner 5 was obtained in the same manner as in the production of the toner 4 except that the ester wax composition shown in Table 2 was changed and the distillation time was 12 hours. Table 2 shows the composition and physical properties of Toner 5.

<Manufacture of toner 6>
In the production of the toner 4, the toner 6 was obtained in the same manner as in the production of the toner 4 except that the ester wax composition shown in Table 2 was changed and the distillation time was 2.5 hours. Table 2 shows the composition and physical properties of Toner 6.

<Manufacture of toner 7>
In the production of the toner 6, a toner 7 was obtained in the same manner as the production of the toner 6 except that the magnetic powder used was changed from the magnetic powder 1 to the magnetic powder 3. Table 2 shows the composition and physical properties of Toner 7.

<Manufacture of toner 8>
In the production of the toner 7, a toner 8 was obtained in the same manner as in the production of the toner 7 except that the ester wax composition shown in Table 2 was changed and the distillation time was changed to 5 hours. Table 2 shows the composition and physical properties of Toner 8.

<Production of toners 9 to 12>
In the production of the toner 8, toners 9 to 12 were obtained in the same manner as in the production of the toner 8, except that the blending of the ester wax as shown in Table 2 was changed. Table 2 shows the compositions and physical properties of the toners 9 to 12.

<Manufacture of toner 13>
In the production of the toner 8, the toner 13 was obtained in the same manner as in the production of the toner 8 except that the ester wax composition shown in Table 2 was changed and the distillation time was changed to 12 hours. Table 2 shows the composition and physical properties of Toner 13.

<Production of Toners 14 and 15>
In the production of the toner 8, toners 14 and 15 were obtained in the same manner as in the production of the toner 8 except that the ester wax composition shown in Table 2 was changed and the distillation time was 2.5 hours. The composition and physical properties of the toners 14 and 15 are shown in Table 2.

<Manufacture of Toner 16>
In the production of the toner 15, the toner 16 was obtained in the same manner as in the production of the toner 15 except that the amount of the magnetic powder used was changed from 90.0 parts by mass to 50.0 parts by mass. The composition and physical properties of Toner 16 are shown in Table 2.

<Manufacture of toner 17>
In the production of the toner 15, the toner 17 was obtained in the same manner as in the production of the toner 15 except that the amount of the magnetic powder used was changed from 90.0 parts by mass to 130.0 parts by mass. Table 2 shows the composition and physical properties of Toner 17.

<Manufacture of Toner 18>
In the production of the toner 15, the toner 18 was obtained in the same manner as in the production of the toner 15 except that the amount of the magnetic powder used was changed from 90.0 parts by mass to 30.0 parts by mass. Table 2 shows the composition and physical properties of Toner 18.

<Production of Comparative Toners 1 to 4>
In the production of the toner 4, the composition of the toner wax shown in Table 2 was changed, the distillation time was changed to 18 hours, and vacuum drying was performed for 24 hours while keeping the temperature at 40 ° C. after drying. Comparative toners 1 to 4 were obtained in the same manner as in the production. Table 2 shows the compositions and physical properties of Comparative Toners 1 to 4.

<Production of Comparative Toner 5>
In the production of the toner 11, a comparative toner 5 was obtained in the same manner as in the production of the toner 11 except that the distillation time was 1 hour. Table 2 shows the composition and physical properties of the comparative toner 5.

<Production of Comparative Toner 6>
In the production of the toner 11, a comparative toner 6 was obtained in the same manner as in the production of the toner 11 except that the distillation time was 1.5 hours. Table 2 shows the composition and physical properties of the comparative toner 6.

<Production of Comparative Toner 7>
A comparative toner 7 was obtained in the same manner as in the production of the toner 11 except that the ester wax used was changed to 7.5 parts for the ester wax and 7.5 parts for the ester wax 8 in the production of the toner 11. Table 2 shows the composition and physical properties of Comparative Toner 7. The ratio of the most ester wax component in the comparative toner 7 was 30%, and the component within M1 ± 20% was 50%.

<Production of Comparative Toners 8 to 11>
Comparative toners 8 to 11 were obtained in the same manner as in the production of the toner 11 except that the formulation of the toner 11 was changed to the ester wax composition shown in Table 2. Table 2 shows the compositions and physical properties of Comparative Toners 8 to 11.

<Manufacture of Comparative Toner 12>
After adding 500 parts of a 0.1M Na ₃ PO ₄ aqueous solution to 600 parts of ion-exchanged water and heating to 60 ° C., 70 parts of a 1.0M CaCl ₂ aqueous solution is added to prepare an aqueous medium containing a dispersant. Obtained.
・ Styrene 78.0 parts ・ 2-ethylhexyl acrylate 22.0 parts ・ Divinylbenzene 0.10 parts ・ Monoazo dye iron complex (T-77: Hodogaya Chemical Co., Ltd.) 1.5 parts ・ Carbon black 7.0 parts ・Amorphous polyester resin 2.0 parts The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.) to obtain a monomer composition. This monomer composition was heated to 60 ° C., 10 parts of ester wax 12 was added and mixed there, dissolved, and then the polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) 8.0. Part was dissolved.

The monomer composition was charged into the aqueous medium, and granulated by stirring at 12,000 rpm for 10 minutes in a TK homomixer (Special Machine Industries Co., Ltd.) in an N ₂ atmosphere at 60 ° C. Then, a polymer dispersion was obtained by reacting at 70 ° C. for 10 hours while stirring with a paddle stirring blade. Thereafter, the stirring was stopped, and the polymer dispersion was charged into a carrier gas charging pipe, a vent pipe, and a distillation vessel equipped with a condenser for cooling and condensing gas discharged from the vent pipe. When 100 parts / hr (steam pressure: 120 kPa) of pure saturated water vapor was introduced into the polymer dispersion, 10 minutes after the start of the introduction of saturated water vapor, a fraction began to come out from the vent pipe via the condenser. One hour after starting the fraction, pure saturated water vapor was stopped and cooled. The mixture was cooled to 40 ° C., washed with hydrochloric acid, filtered, crushed and dried to obtain comparative toner particles 12. 100 parts of the toner particles 12 and 0.8 part of hydrophobic silica having a number average primary particle size of 12 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.), and the weight average particle size (D4) was 6. A comparative toner 12 having a thickness of 5 μm was obtained. Table 2 shows the physical properties of the comparative toner 12.

<Production of Comparative Toners 13 to 15>
(Method for producing polymer fine particle A)
A mixture of the following monomers / aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[Monomers]
Styrene 80.0 parts n-Butyl acrylate 20.0 parts Acrylic acid 3.0 parts Bromotrichloromethane 0.5 part 2-Mercaptoethanol 0.01 part Divinylbenzene 0.15 part [Emulsifier aqueous solution]
10% sodium dodecylbenzenesulfonate 4.0 parts demineralized water 100.0 parts [initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9.0 parts 8% ascorbic acid aqueous solution 9.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare a polymer fine particle dispersion A.

(Method for producing polymer fine particle B)
A mixture of the following monomers / aqueous emulsifier solution was added over 5 hours from the start of polymerization, and an aqueous initiator solution was added over 6 hours from the start of polymerization, and the mixture was further maintained for 30 minutes.
[Monomers]
Styrene 80.0 parts n-butyl acrylate 20.0 parts Acrylic acid 3.0 parts Bromotrichloromethane 0.5 parts 2-mercaptoethanol 0.01 parts Divinylbenzene 0.80 parts [Emulsifier aqueous solution]
10% sodium dodecylbenzenesulfonate 4.0 parts demineralized water 100.0 parts [initiator aqueous solution]
8% hydrogen peroxide aqueous solution 9.0 parts 8% ascorbic acid aqueous solution 9.0 parts

  After completion of the polymerization reaction, the mixture was cooled to prepare polymer fine particles B.

(Method for producing wax dispersion 1)
25.0 parts of ester wax 13, 2.5 parts of an anionic surfactant (Neogen SC Daiichi Kogyo Seiyaku Co., Ltd.) and 100.0 parts of demineralized water were heated to 90 ° C. and stirred with a disper for 15 minutes. Next, this dispersion was emulsified using a homogenizer (15-M-8PA type Gorin Co., Ltd.) under conditions of high-pressure shear of 95 ° C. and 4900 kPa (50 kg / cm ² ) to obtain wax dispersion 1.

(Method for producing wax dispersions 2 and 3)
A wax dispersion 2 was produced in the same manner as the wax dispersion 1 except that the ester wax used was changed to the ester wax 14 in the production of the wax dispersion 1. Moreover, the wax dispersion 3 was manufactured by using the ester wax 15 as the ester wax to be used.

(Method for producing colorant dispersion)
To 100.0 parts of demineralized water, 25.0 parts of carbon black and 6.0 parts of polyoxyethylene nonylphenyl ether were added and dispersed with a ball mill to obtain a magnetic powder dispersion.

(Method for producing charge control agent fine particle dispersion)
To 100.0 parts of demineralized water, 25.0 parts of a charge control agent 4,4′-methylenebis [2- [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene], and an alkylnaphthalene sulfonate 5.0 Was dispersed by a ball mill in the presence of a part to obtain a charge control agent fine particle dispersion.

(Production Method of Comparative Toner 13)
-Polymer fine particle A dispersion 410.0 parts (as solid content)
Colorant dispersion 40.0 parts (as solids)
・ 1.0 parts of charge control agent fine particle dispersion (as solid content)
The above was put into a reaction vessel for coagulation aging equipped with a stirrer, a cooling tube and a thermometer and stirred.

  The mixture was adjusted to pH = 5.1 using 1.0N aqueous potassium hydroxide solution.

  As a flocculant, 180.0 parts of a 20.0% sodium chloride aqueous solution is dropped into the above mixed solution over 20 minutes, and the reaction vessel is heated to 50 ° C. with stirring in an oil bath for heating, and then at 50 ° C. for 1 hour. Then, the temperature was raised to 55 ° C. and held for 1 hour to prepare an aggregate of (polymer fine particles + colorant + charge control agent fine particles).

In the aggregate dispersion,
-Wax dispersion 1 76.5 parts (as solids)
As a flocculant, 500.0 parts of a 20.0% sodium chloride aqueous solution was dropped, and an aggregate was produced by the same production method as described above.

Furthermore, in the aggregate dispersion liquid,
-Polymer fine particle B dispersion 50.0 parts (as solid content)
As a flocculant, 500.0 parts of a 20.0% sodium chloride aqueous solution was dropped, and an aggregate was produced by the same production method as described above.

Finally in the aggregate dispersion,
-Polymer fine particle B dispersion 35.0 parts (as solid content)
Was added dropwise as a flocculant, and 500.0 parts of a 20.0% sodium chloride aqueous solution was added thereto, and an aggregate was produced by the same production method as described above. After adding 5.0 parts of an anionic surfactant (Daiichi Kogyo Seiyaku: Neogen SC), the reaction vessel was sealed and heated to 95 ° C. while continuing to stir using a magnetic seal for 5 hours. Retained. The slurry was cooled and washed with a water amount 10 times that of the slurry, and then the slurry was put into a distillation vessel equipped with a carrier gas inlet pipe, a vent pipe, and a condenser for cooling and condensing the gas discharged from the vent pipe. When 100 parts / hr (steam pressure: 120 kPa) of pure saturated water vapor was introduced into the polymer dispersion, 10 minutes after the start of the introduction of saturated water vapor, a fraction began to come out from the vent pipe via the condenser. One hour after starting the fraction, the introduction of pure saturated water vapor was stopped, and the mixture was cooled and dried to obtain comparative toner particles 13.

  100 parts of this comparative toner particle 13 and 0.8 part of hydrophobic silica having a number average primary particle size of 12 nm were mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain comparative toner 13. Table 2 shows the physical properties of the comparative toner 13.

(Method for producing comparative toner 14)
A comparative toner 14 was obtained in the same manner as the comparative toner 13 except that the wax dispersion 1 was changed to the wax dispersion 2. Table 2 shows the physical properties of the comparative toner 14.

(Method for producing comparative toner 15)
A comparative toner 15 was obtained in the same manner as the comparative toner 13 except that the wax dispersion 1 was changed to the wax dispersion 3. Table 2 shows the physical properties of the comparative toner 15.

  The number of added parts of the ester wax or crystalline polyester indicates the amount with respect to 100 parts of the binder resin.

<Example 1>
(Image forming device)
LaserJET P2055dn was used as an image forming apparatus, toner 1 was used, and a horizontal line with a printing rate of 4% was tested in a continuous mode under normal temperature and humidity conditions (23 ° C./60% RH). . The intermittent mode is an evaluation mode in which the temperature of the fixing device is always kept high because the idle rotation is performed every time one image is printed, and the wax component is volatilized. As the recording medium, A4 75 g / m ² paper was used. The same image drawing test was further repeated, and the image drawing test was performed twice in total.

  After completion of the image output test, a solid image portion was formed, and the density of this solid image was measured. Further, it was confirmed with a halftone image whether there was a decrease in density at both ends of the image. The development bias was set so that the reflection density at the center of the image was 0.60 to 0.65, and the image was printed, and the density difference between the center and the edge of the image was confirmed. Further, a solid black image was drawn under the same conditions, and the image density was measured. The image density was measured with a Macbeth reflection densitometer (manufactured by Macbeth).

  The same test was also performed in a low temperature and low humidity environment (15 ° C./10% RH). In a low-temperature and low-humidity environment, the coagulation of the volatilized wax component is promoted, which is a severe evaluation mode.

  As a result, in any of the evaluations, there was no decrease in density at both ends of the image, and a high density image could be obtained. The evaluation results are shown in Table 3.

<Examples 2 to 18>
In Example 1, an image output test was performed in the same manner as in Example 1 except that the toner 1 was changed from the toner 2 to 18. As a result, in any toner, the image density was high before and after the durability test, and the density reduction at both ends of the image was small. The evaluation results are shown in Table 3.

<Comparative Examples 1 to 15>
An image printing test was performed in the same manner as in Example 1 except that the toner 1 was changed from the comparative toner 1 to 15 in Example 1. As a result, in any toner, the image density was high before and after the durability test, but the density decrease at both ends of the image was increased. The evaluation results are shown in Table 3.

  DESCRIPTION OF SYMBOLS 100 Photosensitive drum (image carrier, to-be-charged body), 102 Developing sleeve (toner carrier), 114 Transfer charging roller (transfer member), 116 Cleaner, 117 Primary charging roller (contact charging member), 121 Laser generator (latent (Image forming means, exposure apparatus), 124 register roller, 125 transport belt, 126 fixing device, 140 developing device, 141 stirring member

Claims (5)

A toner containing toner particles containing a binder resin, a colorant and an ester wax, and inorganic fine particles present on the surface of the toner particles,
The ester wax is a difunctional to hexafunctional polyfunctional ester wax,
The melting point of the ester wax is 65 ° C. or higher and 85 ° C. or lower,
In the composition distribution of the ester wax, the ratio of the most numerous components is 30% by mass or more and 80% by mass or less,
When the molecular weight of the most numerous component of the ester wax is M1, the component within M1 ± 20% is 90% by mass or more based on the total amount of the ester wax.
The toner contains 0.05 to 0.60 ppm of a total amount of styrene derivative in terms of toluene based on the toner mass in an organic volatile component analysis at a heating temperature of 120 ° C. of the toner by the headspace method. .   The toner contains crystalline polyester, and a ratio (α / β) of the content (α) of the crystalline polyester and the content (β) of the ester wax is 0.3 or more and 3.0 or less. The toner according to claim 1.   The toner according to claim 1, wherein the ester wax has 4 to 6 functionalities.   4. The toner according to claim 1, wherein in the composition distribution of the ester wax, a ratio of the most numerous component is 30% by mass or more and 65% by mass or less. The toner according to claim 1, wherein the binder resin is a styrene copolymer.

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