JP6849352B2 - toner - Google Patents

Description

The present invention relates to toners used in image forming methods such as electrophotographic methods.

In recent years, image forming devices such as copiers and printers have been diversified in purpose and environment, and there is an increasing demand for higher speed, higher image quality, and higher stability. For example, printers, which were mainly used in offices in the past, are now being used in environments such as high temperature and high humidity, and are stable even in such environments. It is important to provide good image quality.
Especially in the market where high image quality is required, for light printing (print-on-demand use that enables high-mix low-volume printing from document editing to copying and bookbinding with a personal computer) that requires more reliability. It has begun to be used, and stable high image quality is required throughout the product life.
Further, in recent years, the need for outputting a large amount of text images is increasing in the monochrome print market, and it is required to increase the number of prints per toner cartridge and reduce the number of interruptions due to toner cartridge replacement. In order to achieve a long life per toner cartridge, studies are underway for a high-density filling cartridge with an increased toner filling density, but there are still issues to be solved in order to achieve both high image quality and long life. The reality is that there are many.

Considering the image quality of the text image, it is necessary to make the amount of toner on the line image uniform and suppress the fineness of the line image and the scattering of toner. In particular, in contracts and catalogs that require reliability, it is necessary to suppress roughness such as missing or uneven line images. It is a problem called "hollow" in which the amount of toner loaded in the center of the vertical line image is small, and "tailing" in which the amount of toner loaded in the rear end of the horizontal line image is large.
On the other hand, in recent years, a technique of coating silica fine particles with a highly hydrophobic coating agent has been adopted for the purpose of improving the charging characteristics and fluidity of toner in a high temperature and high humidity environment (see Patent Documents 1 and 2). ..
Further, it contains a charge control agent of a pyrazolone monoazo metal complex compound having a high charge amount and a remarkably high charge rise property for the purpose of suppressing a decrease in charge of the toner and improving durability even in a high temperature and high humidity environment. Toners have been proposed (see Patent Document 3). Alternatively, there is also an attempt to optimize the crystal structure of the charge control agent and enhance the affinity with other materials for the purpose of stabilizing the image quality when left in a harsh environment (see Patent Document 4).

Japanese Patent No. 5739223 JP-A-2015-146037 International Publication No. 2005/09552 Japanese Unexamined Patent Publication No. 2014-78003

However, when a high-density filling cartridge that supports a long life is left in a harsh environment, especially in a line image where the line width is small, "hollow" occurs in a high temperature and high humidity environment and "hollow" occurs in a low temperature and low humidity environment. There is a tendency for a problem called "tailing" to become apparent.
An object of the present invention is "hollow" during long-term use in a high-temperature and high-humidity environment, and long-term in a low-temperature and low-humidity environment, even when the toner is placed in a harsh environment with a high density of toner. The purpose is to provide a toner capable of suppressing "tailing" during use.

（式［１］中、Ａ _１ 、Ａ _２ 及びＡ _３ は、それぞれ独立して、水素原子、ニトロ基又はハロゲン原子を示す。Ｂ _１ は水素原子又はアルキル基を示す。Ｍは、Ｆｅ原子、Ｃｒ原子、又はＡｌ原子を示し、Ｘ ^＋ は、水素イオン、アルカリ金属イオン、アンモニウムイオン、アルキルアンモニウムイオン又はこれらの混合イオンを示す。）
該荷電制御剤１５ｍｇを２５℃の動粘度が５０ｍｍ^２／ｓの該シリコーンオイル８．０ｇに分散させた分散液を、静置し、該分散液の経時変化を測定したシリコーンオイル沈降試験において、静置してから４８時間後の該分散液の波長７００ｎｍの吸光度が、１．８５以下である
ことを特徴とするトナーに関する。
Toner particles containing a binder resin, a colorant, and a charge control agent,
And inorganic fine particles,
Toner containing
The inorganic fine particles contain silica fine particles containing a silica base and silicone oil, and the inorganic fine particles contain
The toner contains the silica fine particles in an amount of 0.40 parts by mass or more and 1.50 parts by mass or less per 100 parts by mass of the toner particles.
The content of the silicone oil in the silica fine particles is 5.0 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the silica base material.
The basis of carbon immobilization ratio of the silicone oil in the fine silica particles, not less than 50 wt%,
The charge control agent is a compound represented by the following formula [1].

(In the formula [1], A ₁ , A ₂ and A ₃ independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group. M is an Fe atom. It represents a Cr atom or an Al atom, and X ⁺ indicates a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion or a mixed ion thereof.)
In a silicone oil sedimentation test in which a dispersion liquid in which 15 mg of the charge control agent ^{was dispersed in 8.0 g of the silicone oil having a kinematic viscosity of 50 mm 2} / s at 25 ° C. was allowed to stand and the change over time of the dispersion liquid was measured. The present invention relates to a toner characterized in that the absorbance of the dispersion liquid at a wavelength of 700 nm after 48 hours from standing is 1.85 or less.

According to the present invention, even when the toner is filled in a high density and is allowed to stand in a harsh environment, it is "hollowed out" during long-term use in a high temperature and high humidity environment, and in a low temperature and low humidity environment afterwards. A toner that can suppress "tailing" during long-term use can be obtained.

In the present invention, the description of "○○ or more and XX or less" and "○○ to XX" indicating a numerical range means a numerical range including a lower limit and an upper limit which are end points unless otherwise specified.
The present invention is a toner containing toner particles containing a binder resin, a colorant, and a charge control agent, and inorganic fine particles.
The inorganic fine particles contain silica fine particles containing a silica base and silicone oil, and the inorganic fine particles contain
The toner contains the silica fine particles in an amount of 0.40 parts by mass or more and 1.50 parts by mass or less per 100 parts by mass of the toner particles.
The content of the silicone oil in the silica fine particles is 5.0 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the silica base material.
The carbon content-based immobilization rate of the silicone oil in the silica fine particles is 50% by mass or more.
In a silicone oil sedimentation test in which a dispersion liquid in which 15 mg of the charge control agent ^{was dispersed in 8.0 g of the silicone oil having a kinematic viscosity of 50 mm 2} / s at 25 ° C. was allowed to stand and the change over time of the dispersion liquid was measured. The dispersion liquid has an absorbance of 1.85 or less at a wavelength of 700 nm 48 hours after being allowed to stand.
As a result of studies by the present inventors, by using the above-mentioned toner, even when the toner is left in a harsh environment with a high density of toner, it is "tailed" during long-term use in a low temperature and low humidity environment. , And found that it is possible to suppress "hollow" during long-term use in a high-temperature and high-humidity environment.

The reason for this will be described below.
When the toner is placed in a harsh environment with a high density of toner, the contact area between the toner particles becomes large due to the influence of temperature, humidity, and pressure. As a result, the silica fine particles on the surface of the toner particles are embedded, and the silicone oil not fixed to the silica fine particles plasticizes and coats the surface of the toner particles. The silicone oil plasticizes the surface of the toner particles, so that the adhesive force of the toner layer on the electrostatic latent image carrier increases. Further, the silicone oil coats the charge control agent that serves as a charge-imparting site on the surface of the toner particles, so that triboelectric charging is inhibited and the charge characteristics are deteriorated. In particular, in the market where high image quality of text images is important, a slight increase in the amount of adhesion and a decrease in charging characteristics cause "tailing" in a low temperature and low humidity environment, and "hollowing out" in a high temperature and high humidity environment. It became clear that the deterioration of the image quality of the text image was noticeable.

"Tail pulling" that occurs during long-term use in a low-temperature and low-humidity environment is a phenomenon that occurs when the toner does not fly faithfully to the latent image of the electrostatic latent image carrier due to the broad charging distribution of the toner. .. In particular, in the latter half of use in a low-temperature and low-humidity environment, triboelectric charging is inhibited by coating the charge control agent with unimmobilized silicone oil, and the charge distribution tends to be broadened remarkably. As a result, in a low-temperature and low-humidity environment, the non-uniform charging characteristics make it impossible for the toner to fly faithfully to the line latent image, so that "tailing" is likely to occur.
In particular, in the boundary region between the image portion and the non-image portion, the boundary line on the electrostatic latent image carrier tends to be unclear, and the toner having a non-uniform charge distribution tends to cause tailing. Further, as the diameter of the developing sleeve is reduced due to the miniaturization of the image forming apparatus, the peripheral length of the developing sleeve is shortened, so that the chance of triboelectric charging between the developing sleeve and the toner is reduced, and the charging rise is deteriorated. Therefore, "tailing" tends to occur easily.

"Cut-out" that occurs during long-term use in a high-temperature and high-humidity environment means that the toner is not transferred to the recording medium in the process of transferring the toner image formed on the electrostatic latent image carrier to the recording medium. By remaining on the image, it is an image defect caused by omission or unevenness on the image. In the latter half of use in a high temperature and high humidity environment, embedding of silica fine particles and plasticization with silicone oil tend to be promoted. As a result, the adhesive force of the toner layer on the electrostatic latent image carrier increases and the charge decreases, and "hollowing out" is likely to occur in the transfer process.
In the transfer step, the toner is transferred from the front surface of the electrostatic latent image carrier to the paper by applying a charge having a polarity opposite to that of the toner from the back surface of the paper to the paper. Therefore, when the adhesive force of the toner layer on the electrostatic latent image carrier increases and the charge decreases, the flying force to the paper weakens, and hollowing out easily occurs in the transfer process. In particular, when the speed of the image forming apparatus is increased, the load on the toner increases due to the temperature rise in the machine, which accelerates the deterioration of the toner and tends to cause “hollowing out”.
In the above-mentioned "tailing" during long-term use in a low-temperature and low-humidity environment and "hollow" during long-term use in a high-temperature and high-humidity environment, a small amount of silicone oil that is not adhered to silica fine particles adheres to the toner surface. It is easy to occur.

When silica fine particles containing silicone oil are used, the toner of the present invention suppresses the increase in adhesive force and the decrease in charging characteristics caused by the silicone oil contained in the silica fine particles, thereby suppressing the "tail" in a low temperature and low humidity environment. It suppresses "pulling" and "hollowing out" in a high temperature and high humidity environment.
That is, as a result of diligent studies by the present inventors, regarding the decrease in the charging characteristics of the toner and the increase in the adhesive force, the affinity between the silicone oil and the charge control agent and the fixation of the silicone oil contained in the silica fine particles are fixed. It became clear that it was important to control the amount of unmodified silicone oil. That is, by controlling the affinity between the silicone oil and the charge control agent and the amount of the silicone oil that is not immobilized on the silica fine particles, the silicone oil that is not immobilized is bound to the silicone oil via the charge control agent. It was clarified that the deterioration of the charge performance of the charge control agent and the increase of the adhesive force of the binder resin can be suppressed by permeating into.

The affinity between the silicone oil and the charge control agent can be controlled by setting the sedimentation property of the charge control agent to a certain value or less in the sedimentation test of the charge control agent in the silicone oil. The amount of non-immobilized silicone oil among the silicone oils contained in the silica fine particles should be controlled by the amount of the added silica fine particles, the amount of silicone oil contained in the silica fine particles, and the immobilization rate of the silicone oil. Can be done.
The reason why controlling the affinity between silicone oil and the charge control agent and the amount of unfixed silicone oil among the silicone oils contained in the silica fine particles leads to a decrease in charge characteristics and an increase in adhesive force. , The present inventors think as follows.
By controlling the amount of unfixed silicone oil among the silicone oils contained in the silica fine particles, the amount of silicone oil that migrates to the toner surface is suppressed, and the plasticization of the binder resin on the toner surface is suppressed. Further, by controlling the affinity between the silicone oil and the charge control agent, it is possible to prevent the silicone oil transferred to the toner surface from coating the charge control agent on the toner surface. As a result, it is considered that the silicone oil on which the silica fine particles are not immobilized is suppressed from coating the charge control agent on the surface of the toner particles, and further, the plasticizing of the binder resin on the toner surface is suppressed. ..
From the above, even if toner that has been left in a harsh environment with a high density of toner filled in is used, it is possible to suppress hollowing out in the latter half of use in a high-temperature and high-humidity environment, and to tail in the latter half of use in a low-temperature and low-humidity environment. It is considered that it is possible to achieve both at a high level.

In the present invention, a dispersion in which 15.0 mg of a charge control agent ^{is dispersed in 8.0 g of silicone oil having a kinematic viscosity of 50 mm 2} / s at 25 ° C. is allowed to stand, and the change over time of the dispersion is measured. In the sedimentation test, it is necessary that the absorbance of the dispersion liquid at a wavelength of 700 nm is 1.85 or less 48 hours after being allowed to stand.
In the above-mentioned sedimentation test of the charge control agent in silicone oil, when the absorbance of the dispersion at a wavelength of 700 nm exceeds 1.85 48 hours after being allowed to stand, the affinity between the silicone oil and the charge control agent becomes high. Increase. As a result, when the toner is stored in a harsh environment with a high density of toner, the contact area between the toner particles increases, and the silicone oil that is not immobilized on the silica fine particles increases the charge control agent on the toner surface. Is easily covered.
As a result, triboelectric charging by the charge control agent on the surface of the toner particles is inhibited, the charging characteristics of the toner are deteriorated, and tailing in a low temperature and low humidity environment is likely to occur. Furthermore, by increasing the affinity between the silicone oil and the charge control agent, the silicone oil permeates the binding resin from the charge control agent, plasticizing the surface of the toner particles and increasing the adhesive force of the toner, resulting in high temperature and high temperature. It is easy for hollows out of the moist environment to occur.
The absorbance is preferably 1.80 or less. The lower limit is not particularly limited, but is preferably 1.70 or more, and more preferably 1.72 or more. The absorbance can be controlled by changing the chemical structure of the charge control agent.

In the present invention, the content of the silica fine particles needs to be 0.40 parts by mass or more and 1.50 parts by mass or less per 100 parts by mass of the toner particles. When the content of the silica fine particles is less than 0.40 parts by mass, the adhesive force of the toner increases and hollowing out easily occurs. Hollow-out is likely to occur when silica fine particles are embedded in the latter half of use in a high-temperature and high-humidity environment after being allowed to stand in a harsh environment. On the other hand, if it exceeds 1.50 parts by mass, the silica fine particles contaminate the members, so that the charging characteristics deteriorate in the latter half of use and tailing is likely to occur.
Further, it is necessary that the content of the silicone oil in the silica fine particles is 5.0 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the silica base material. Further, the carbon content-based immobilization rate of the silicone oil in the silica fine particles is 50% by mass or more.
When the amount of the silica fine particles added, the amount of silicone oil contained in the silica fine particles, and the immobilization rate of the silicone oil are within the above ranges, the amount of silicone oil not immobilized on the silica fine particles becomes appropriate. If the amount of unfixed silicone oil is large, the adhesive force of the toner increases and hollowing out is likely to occur.

The content of the silica fine particles is preferably 0.80 parts by mass or more and 1.40 parts by mass or less per 100 parts by mass of the toner particles. The content of the silicone oil in the silica fine particles is preferably 5.0 parts by mass or more and 20.0 parts by mass or less with respect to 100 parts by mass of the silica base material.
Further, the immobilization rate of the silicone oil based on the carbon content is preferably 70% by mass or more. The upper limit is not particularly limited, but the immobilization rate is preferably 98% by mass or less, and more preferably 95% by mass or less. The immobilization rate is the type of silicone oil contained in the silica fine particles, the content of silicone oil, the reaction temperature during silicone oil treatment, and silicone oil when a surface treatment agent other than silicone oil such as a silane compound is used. It can be controlled by the treatment order of the surface treatment agents other than the above and the silicone oil.

In the present invention, the amount of unimmobilized silicone oil contained in the silica fine particles is preferably 0.30 parts by mass or less per 100 parts by mass of the toner particles. It is more preferably 0.085 parts by mass or less, and further preferably 0.072 parts by mass or less. As described above, by controlling the amount of non-fixed silicone oil contained in the toner within a certain range, the toner adhesion force increases due to the non-fixed silicone oil and the toner charge distribution is broadened. This is because it is possible to suppress the conversion.

Preferably the kinematic viscosity of 25 ° C. of the silicone oil is less than 50 mm ² / s or more 200 mm ² / s, more preferably at most 50 mm ² / s or more 100 mm ² / s. This is because the kinematic viscosity of the silicone oil at 25 ° C. is within the above range, so that the increase in toner adhesion due to the silicone oil can be suppressed. The kinematic viscosity can be controlled by mixing standard viscosity silicone oils of different viscosities.
Examples of the device for measuring the kinematic viscosity of silicone oil include a fully automatic microkinematic viscometer (manufactured by Viscotec Co., Ltd.).

As the inorganic fine particles, silica fine particles are contained. The following can be used as the silica fine particles. Silica fine particles include a silica base and silicone oil.
Fine particles produced by vapor phase oxidation of a silicon halogen compound, so-called dry silica or fumed silica, can be used as the silica base. For example, it utilizes the pyrolysis oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame, and the basic reaction formula is as follows.
SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl
In this manufacturing process, it is also possible to obtain a composite fine powder of silica and other metal oxides by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound, and these are used as silica raw materials. Also includes.
The silica fine particles contain silicone oil for the purpose of hydrophobization and triboelectricity control. In addition, an organosilicon compound, a long-chain fatty acid, or the like may be used in combination for treatment.

Examples of the silicone oil include dimethyl silicone oil, methyl phenyl silicone oil, α-methylstyrene modified silicone oil, chlorphenyl silicone oil, and fluorine-modified silicone oil.
Examples of the organosilicon compound include hexamethyldisilazane, trimethylsilane, trimethylethoxysilane, isobutyltrimethoxysilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, and hexa. Examples thereof include methyldisiloxane. These organosilicon compounds may be used alone or as a mixture of two or more kinds.

As the long-chain fatty acid, a fatty acid having 10 to 22 carbon atoms can be preferably used, but it may be a linear fatty acid or a branched fatty acid. Further, both saturated fatty acids and unsaturated fatty acids can be used.
Among these, linear saturated fatty acids having 10 to 22 carbon atoms are more preferable because they can easily treat the surface of silica fine particles uniformly.
Examples of linear saturated fatty acids include capric acid, lauric acid, myrstinic acid, palmitic acid, stearic acid, arachidic acid, behenic acid and the like.

Examples of the method of treating the silica base with silicone oil include a method of directly mixing the silica base treated with an organosilicon compound and silicone oil using a mixer such as a Henshell mixer, or a method of directly mixing the silica base with silicone. A method of spraying oil can be mentioned. Alternatively, a method may be used in which the silicone oil is dissolved or dispersed in an appropriate solvent, and then the silica base is added and mixed to remove the solvent.

The silica fine particles preferably contain two types of silica fine particles A and silica fine particles B having different number average particle diameters (D1) of the primary particles. It is preferable that the number average particle size of the primary particles of the silica fine particles A is 5 nm or more and 20 nm or less, and the number average particle size of the primary particles of the silica fine particles B is 25 nm or more and 150 nm or less.
By containing two types of silica fine particles with different numbers and average particle sizes of the primary particles, the toner surface of the silica fine particles is even when the silica fine particles are allowed to stand in a high temperature and high humidity environment in a state of being filled with toner at high density. Since embedding in the silica can be suppressed, an increase in toner adhesion can be suppressed. That is, by coating the surface of the toner with silica fine particles B having a large particle size, the contact area between the toners can be reduced even when the toner is placed in the high density state, so that the silica fine particles can be applied to the toner surface. Embedding can be suppressed.
Further, by coating the surface of the toner with silica fine particles A having a small particle size, high chargeability and fluidity can be obtained as the toner. As a result, even when the toner is placed in a high-temperature and high-humidity environment with a high density of toner, hollowing out in the high-temperature and high-humidity environment and tailing in the low-temperature and low-humidity environment are further suppressed. The carbon content-based immobilization rate of the silicone oil when the two types of silica fine particles A and the silica fine particles B are added is the average value of the immobilization rate of the silica fine particles A and the immobilization rate of the silica fine particles B. To do.

In a chromatogram in which the tetrahydrofuran (THF) soluble content of the toner particles is measured by gel permeation chromatography (GPC), the amount of the component having a molecular weight of 1000 or less is preferably 15.0% by mass or less. More preferably, the amount of the component having a molecular weight of 1000 or less is 10.0% by mass or less. The amount of the component having a molecular weight of 1000 or less can be controlled by the type of the binder resin used.
By controlling the amount of the component having a molecular weight of 1000 or less to 15.0% by mass or less, it is possible to prevent the unimmobilized silicone oil from plasticizing the binder resin on the surface of the toner particles. Since the low molecular weight component having a molecular weight of 1000 or less is plasticized by the silicone oil, the developability and transferability in the latter half of use in a high temperature and high humidity environment are further improved by suppressing the amount of the low molecular weight component.

In the toner of the present invention, it is preferable that the binder resin contains a polyester resin. It is preferable that the binder resin contains a polyester resin in terms of both developability and fixability. The present inventors consider that this is because the binder resin contains polyester, so that the low temperature fixability can be extended by utilizing the melting characteristics of polyester without deteriorating the developability.

The composition of polyester is as follows, for example.
Examples of the alcohol component include the following. Ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol , 2-Ethyl-1,3-hexanediol, hydride bisphenol A, aromatic diols include bisphenol represented by the following formula (A) and derivatives thereof, and diols represented by the following formula (B).

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ及びｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

Examples of the acid component include the following. Benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as oxalic acid, adipic acid, sebacic acid, azelaic acid or anhydrides thereof; 6 or more carbon atoms 18 A humic acid or an anhydride thereof substituted with the following alkyl group or alkenyl group; an unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, and itaconic acid or an anhydride thereof.
Examples of trihydric or higher polyhydric alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. , 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene. Be done.
Examples of the trivalent or higher polyvalent carboxylic acid component include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid. 1,2,4-naphthalentricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxy-2-methyl-2-methylenecarboxypropane, tetra (methylene) Examples include carboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, and anhydrides thereof.
The polyester is usually obtained by a generally known polycondensation.

The glass transition temperature (Tg) of the resin used as the binder resin is preferably 50 ° C. or higher and 75 ° C. or lower from the viewpoint of toner storage stability.
From the same viewpoint, the softening point is preferably 80 ° C. or higher and 150 ° C. or lower.
The weight average molecular weight of the resin used as the binder resin is 8,000 or more and 1,200,000 or less, preferably 40,000 or more and 300,000 or less, from the viewpoint of toner durability and fixability. preferable.
The acid value of the resin used as the binder resin is preferably 2 mgKOH / g or more and 40 mgKOH / g or less from the viewpoint of toner durability and charge rising property.
The resin used as the binder resin may be one type, or a plurality of types may be used in combination.

A vinyl-based resin may be used as the binder resin, and examples of the constituent vinyl-based monomers include the following compounds.
Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene, 2,4-dimethyl Styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene Styrene and its derivatives such as; styrene unsaturated monoolefins such as ethylene, propylene, butylene, isobutylene; unsaturated polyenes such as butadiene, isoprene; vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride Vinyl halides such as vinyl acetate, vinyl propionate, vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate. Α-Methylene aliphatic monocarboxylic acid esters such as octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, acrylic acid Acrylic acids such as ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Esters; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinylpyrrole, N-vinylcarbazole, N- N-vinyl compounds such as vinyl indol, N-vinylpyrrolidone; vinyl naphthalines; acrylic acids or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide.
In addition, acrylic acids or methacrylic esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1-hydroxy-). Examples thereof include monomers having a hydroxy group such as 1-methylhexyl) styrene.

The vinyl-based resin used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the cross-linking agent used in this case include the following.
Aromatic divinyl compounds (divinylbenzene, divinylnaphthalene); diacrylate compounds linked by an alkyl chain (ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5- Pentandiol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylate of the above compounds replaced with methacrylate); Diacrylate compounds linked by an alkyl chain containing an ether bond (for example). , Diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and the above compounds replaced with methacrylate. ); Diacrylate compounds enclosed in chains containing aromatic groups and ether bonds [polyoxyethylene (2) -2,2-bis (4 hydroxyphenyl) propandiacrylate, polyoxyethylene (4) -2, 2-Bis (4 hydroxyphenyl) propandiacrylate and the acrylate of the above compound replaced with methacrylate]; polyester type diacrylate compounds.

Examples of the polyfunctional cross-linking agent include the following. Pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds replaced with methacrylate; triallyl cyanurate, triallyl trimerite. ..
These cross-linking agents are preferably used in an amount of 0.01 parts by mass or more and 10.00 parts by mass or less, and more preferably 0.03 parts by mass or more and 5.00 parts by mass or less with respect to 100 parts by mass of other monomer components. it can.
Among these cross-linking agents, those preferably used for the binder resin from the viewpoint of fixability and offset resistance are bonded with a chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. Diacrylate compounds can be mentioned.

Examples of the polymerization initiator used for the polymerization of the vinyl resin include the following.
2,2'-Azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2, 2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisobutyrate, 1,1'-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile , 2,2'-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2-azobis (2-methylpropane), methylethylketone peroxide, Ketone peroxides such as acetylacetone peroxide, cyclohexanone peroxide, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumenehydroperoxide, 1,1,3,3- Tetramethylbutylhydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (tert-butylperoxyisopropyl) benzene, isobutyl peroxide, octanoylper Oxide, decanoyyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioil peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydi Carbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxycarbonate, dimethoxyisopropylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, tert-butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxyneodecanoate, tert-butylperoxy2-ethylhexanoate, tert-butylperoxylaurate, tert-butylper Oxybenzoate, tert-butylperoxyisopropyl carbonate, di-tert-butylperoxyisobutyrate, tert-butylperoxyallyl carbonate, tert-amylperoxy2-ethylhexanoate, di-tert-ptylpa -Oxyhexahydroterephthalate, di-tert-butylperoxyazelate.

The charge control agent preferably has a number average particle diameter (D1) of primary particles of 0.80 μm or more and 2.00 μm or less, and more preferably 0.90 μm or more and 1.50 μm or less.
When the number average particle size of the primary particles of the charge control agent is within the above range, an appropriate amount can be exposed on the surface of the toner particles when the charge control agent is dispersed in the toner particles. It is possible to enhance the effect as. That is, it is possible to suppress variations in the charging characteristics between the toner particles, and even if the toner is placed in a harsh environment with a high density of toner, it is hollowed out in a high-temperature and high-humidity environment and tailed in a low-temperature and low-humidity environment. It becomes easier to suppress. The average particle size of the number of primary particles of the charge control agent can be controlled by the production conditions of the charge control agent such as the complexing reaction time.

The charge control agent is preferably a compound represented by the formula [1]. Among various charge control agents, the pyrazolone monoazometal complex compound represented by the formula [1] has a high charge amount and a high charge rise property. For this reason, it is possible to suppress variations in the charging characteristics per toner grain, and even if the toner is placed in a harsh environment with a high density of toner, it can be used in a high-temperature, high-humidity environment and in a low-temperature, low-humidity environment. It is easy to suppress tailing.

(In the formula, A ₁ , A ₂ and A ₃ independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group. M is an Fe atom, a Cr atom and Or, it indicates an Al atom, and X ⁺ indicates a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.)
The charge control agent is more preferably a compound represented by the following formula [2]. The charge control agent represented by the formula [2] can control the affinity with silicone oil by using the coordination metal as an iron atom and adding a chlorine atom to the ligand. The present inventors consider the reason for this as follows.
The compound represented by the following formula [2] has a plurality of pyrazolone skeletons, so that a plurality of electrons can be stably retained, and the present invention has an affinity for silicone oil (preferably non-polar dimethyl silicone oil). Easy to control within the range of. That is, even when the surface of the toner particles is covered with silicone oil, it becomes difficult to cover the charge control agent and the deterioration of the charge characteristics can be suppressed. Easy to suppress.

(In the formula, X ⁺ indicates a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.)
The charge control agent represented by the formula [2] can be produced by using a known method. A typical manufacturing method is described below. First, mineral acids such as hydrochloric acid and sulfuric acid are added to 4-chloro-2-aminophenol, and when the liquid temperature drops to 5 ° C or lower, sodium nitrite dissolved in water is maintained at a liquid temperature of 10 ° C or lower. While dripping. 4-Chloro-2-aminophenol is diazotized by stirring and reacting at 10 ° C. or lower for 30 minutes to 3 hours or shorter. Add sulfamic acid and check with potassium iodide starch paper that no excess nitrite remains.

Next, 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone, an aqueous solution of sodium hydroxide, sodium carbonate, and an organic solvent, which are coupling components, are added and dissolved by stirring at room temperature. The diazo compound is added thereto, and the mixture is stirred at room temperature for several hours to perform coupling. After stirring, it is confirmed that there is no reaction between the diazo compound and resorcin, and the reaction is terminated. After adding water, stir well and let stand before separating. Further, an aqueous sodium hydroxide solution is added, and the mixture is stirred and washed to separate the liquids. This gives a solution of the monoazo compound.
As the organic solvent used in the above coupling, a monohydric alcohol, a dihydric alcohol, and a ketone-based organic solvent are preferable. Examples of monohydric alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, and ethylene glycol monoalkyl (1 to 4 carbon atoms). Ethanol can be mentioned. Examples of the divalent alcohol include ethylene glycol and propylene glycol. Examples of the ketone system include methyl ethyl ketone and methyl isobutyl ketone.

Next, a metallization reaction is carried out. Water, salicylic acid, n-butanol, and sodium carbonate are added to the solution of the monoazo compound and stirred. When iron is used as the coordination metal, ferric chloride aqueous solution and sodium carbonate are added.
The liquid temperature is raised to 30 ° C. to 40 ° C. and the reaction is followed by TLC. After 5 to 10 hours have passed, it is confirmed that the spots of the raw material have disappeared, and the reaction is terminated. After the stirring is stopped, the mixture is stopped and the liquid is separated. Further, water, n-butanol, and an aqueous sodium hydroxide solution are added, and alkaline cleaning is performed. Filter, remove the cake and wash with water.

Further, in order to sharpen the particle size distribution of the charge control agent, the following processing may be performed. The cake washed with water above is dissolved in an organic solvent. As the organic solvent used at this time, dimethyl sulfoxide, N, N-dimethylformamide, monohydric alcohol and dihydric alcohol are preferable. Examples of monohydric alcohols include methanol, ethanol, n-propanol, 2-propanol, n-butanol, isobutyl alcohol, sec-butyl alcohol, n-amyl alcohol, isoamyl alcohol, and ethylene glycol monoalkyl (1 to 4 carbon atoms). Ethanol can be mentioned. Examples of the divalent alcohol include ethylene glycol and propylene glycol.
The charge control agent is gradually precipitated by raising the temperature of this solution to 50 ° C. and adding water while stirring. It is more preferable to add an antifoaming agent to water in advance to remove bubbles generated in the system. After chill filtration, the cake is washed with water and then vacuum dried to obtain a charge control agent. By performing this treatment, the particle size distribution of the charge control agent becomes sharp, and the effect of the present invention can be more easily obtained.
The content of the charge control agent is preferably 0.1 part by mass or more and 10.0 parts by mass or less, and more preferably 0.3 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the binder resin. More preferably, it is 0.3 parts by mass or more and 3.0 parts by mass or less.

The toner may contain a magnetic material and may be used as a magnetic toner. In this case, the magnetic material can also serve as a colorant.
Magnetic materials contained in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, and zinc. , Antimony, bismuth, calcium, manganese, titanium, tungsten, vanadium and other metal alloys and mixtures thereof.
These magnetic materials have an average particle size of preferably 2 μm or less, more preferably 0.05 μm or more and 0.5 μm or less. The amount contained in the toner is preferably 20 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the resin component.

As the colorant, carbon black, grafted carbon, or a yellow / magenta / cyan colorant shown below is used as the black colorant and the colorant is toned to black.
Examples of the yellow colorant include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds.
Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinone compounds, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds and the like.
Examples of the cyan colorant include a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound. These colorants can be used alone or in the form of a solid solution.
The colorant is selected in terms of hue angle, saturation, lightness, weather resistance, transparency, and dispersibility in toner. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.

The toner may contain a mold release agent in order to impart releasability at the time of fixing.
Examples thereof include aliphatic hydrocarbon waxes such as polyolefin copolymers, polyolefin waxes, microcrystalline waxes, paraffin waxes and Fishertropsh waxes.
Further, these release agents have a molecular weight distribution sharpened by using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a fusion liquid crystal analysis method.
Specific examples of the release agent include the following.

Viscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Kasei Kogyo Co., Ltd.), High Wax 400P, 200P, 100P, 410P, 420P, 320P, 220P, 210P, 110P (Mitsui Chemicals Co., Ltd.) ), Sazole H1, H2, C80, C105, C77 (Schumann Sazol), HNP-1, HNP-3, HNP-9, HNP-10, HNP-11, HNP-12 (Nippon Seikan Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unisid (registered trademark), Unisid (registered trademark) 350, 425, 550, 700 (Toyo Adre Co., Ltd.), wood wax, beeswax, rice wax, candelilla wax , Carnauba Wax (Cerarica NODA Co., Ltd.).
The content of the release agent is preferably 0.5 parts by mass or more and 20.0 parts by mass or less with respect to 100.0 parts by mass of the binder resin.
The melting point peak temperature of the release agent is preferably 60 ° C. or higher and 180 ° C. or lower, and more preferably 70 ° C. or higher and 110 ° C. or lower, from the viewpoint of toner durability and low-temperature fixability.

From the viewpoint of the balance between developability and fixability, the toner of the present invention preferably has a weight average particle diameter (D4) of 5.0 μm or more and 10.0 μm or less, more preferably 5.5 μm or more and 9.5 μm or less. Is.

The method for producing the toner particles is not particularly limited, and for example, a pulverization method, an emulsion polymerization method, a suspension polymerization method, a dissolution suspension method, or the like can be used.
In the pulverization method, first, the binder resin, the colorant, the charge control agent, and if necessary, wax and the like constituting the toner particles are sufficiently mixed by a mixer such as a Henschel mixer or a ball mill. Next, the obtained mixture is melt-kneaded using a heat kneader such as a twin-screw kneading extruder, a heating roll, a kneader, and an extruder, cooled and solidified, and then pulverized and classified. As a result, toner particles can be obtained.
Further, if necessary, the desired external additive can be sufficiently mixed with a mixer such as a Henschel mixer to obtain toner.

Examples of the mixer include the following. FM mixer (manufactured by Nippon Coke Industries Co., Ltd.); Super mixer (manufactured by Kawata); Ribocorn (manufactured by Okawara Seisakusho); Nower mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Pacific Kiko) Made by); Lady Gemixer (manufactured by Matsubo).
Examples of the kneading machine include the following. KRC Kneader (manufactured by Kurimoto Iron Works); Bus Co Kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Japan Steel Works) Iron Works); Three roll mill, mixing roll mill, kneader (Inoue Mfg. Co., Ltd.); Kneedex (Mitsui Miike Kakoki Co., Ltd.); MS type pressurized kneader, Nider Ruder (Moriyama Mfg. Co., Ltd.); Banbury mixer (Moriyama Seisakusho) Made by Kobe Steel Works).

Examples of the crusher include the following. Counter jet mill, micron jet, innomizer (manufactured by Hosokawa Micron); IDS type mill, PJM jet crusher (manufactured by Nippon Pneumatic Industries); cross jet mill (manufactured by Kurimoto Iron Works); Ulmax (manufactured by Nisso Engineering Co., Ltd.) ); SK Jet O Mill (manufactured by Seishin Enterprise); Cryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turbo Industries); Super Rotor (manufactured by Nisshin Engineering Co., Ltd.).
Examples of the classifier include the following. Classy Classy, Micron Classifier, Spedic Classifier (manufactured by Seishin Enterprise); Turbo Classy Fire (manufactured by Nisshin Engineering Co., Ltd.); Micron Separator, Turboplex (ATP), TSP Separator (manufactured by Hosokawa Micron); Iron Mining Co., Ltd.), Dispersion Separator (manufactured by Nippon Pneumatic Industries Co., Ltd.); YM Microcut (manufactured by Yasukawa Shoji Co., Ltd.).

Next, a method for measuring each physical property according to the present invention will be described.
<Silicone oil sedimentation test of charge control agent>
The sedimentation test method of the charge control agent in silicone oil will be described below.
(1) Weigh 8.0 g of silicone oil having a charge control agent of 15 mg and a kinematic viscosity of 50 mm at 25 ° C. of ^{2 / s in a 15 ml vial.} As the silicone oil, the same type of silicone oil as that used for the surface treatment of the silica fine particles is used after adjusting the kinematic viscosity. For example, since the silica fine particles are treated with dimethyl silicone oil in the examples described later, dimethyl silicone oil is used in the test.
(2) Using an ultrasonic homogenizer VP-050 (manufactured by TIETECH Co., Ltd.), the charge control agent is dispersed in the silicone oil under the following ultrasonic dispersion conditions.
[Ultrasonic Disperser / Conditions]
Equipment: Ultrasonic homogenizer VP-050 (manufactured by TIETECH Co., Ltd.)
Microchip: Step type microchip, tip diameter φ2 mm
Tip position of microchip: height of 5 mm from the center of the glass vial and the bottom of the vial Ultrasonic conditions: Intensity 30% (intensity 15 W, 120 W / cm ² ), 3 minutes. At this time, ultrasonic waves are applied while cooling the vial with ice water so that the dispersion liquid does not rise in temperature.
(3) Leave the 15 ml vial in a place where vibration is not applied for 48 hours, and collect 4 ml of the upper layer silicone oil after standing.
(4) Using the collected silicone oil, measure the absorbance according to the following procedure.
The collected silicone oil is placed in a quartz cell, and the absorbance is measured using a spectrophotometer (UV-3100PC, manufactured by Shimadzu Corporation). The value of absorbance at a wavelength of 700 nm is measured as the concentration of the charge control agent. At this time, a single silicone oil having a kinematic viscosity of 50 mm ² / s at 25 ° C. is placed in the control cell. In the examples described later, dimethyl silicone oil is used as the silicone oil.
Measurement conditions: Scan speed (medium speed), slit width (0.5 nm), sampling pitch (2 nm), measurement range (800 nm to 350 nm)
The principle of measuring absorbance is as follows.
A = log ₁₀ (I0 / I)
A: Absorbance I0: Incident light intensity I: Transmitted light intensity

<Separation method of silica fine particles>
It is also possible to separate silica fine particles from the toner and measure their physical characteristics by the following method.
(1) In the case of magnetic toner First, in 100 mL of ion-exchanged water, a 10% by mass aqueous solution of Contaminone N (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder). , Wako Pure Chemical Industries, Ltd.) is added in 6 mL to prepare a dispersion medium. To this dispersion medium, 5 g of toner is added and dispersed with an ultrasonic disperser for 5 minutes. After that, it is set in "KM Shaker" (model: V.SX) manufactured by Iwaki Sangyo Co., Ltd., and shaken for 20 minutes under the condition of 350 round trips per minute.
Then, the toner particles are restrained using a neodymium magnet, and the supernatant is collected. By drying the supernatant, the silica fine particles and the toner particles are separated, and the silica fine particles are collected. If a sufficient amount of silica fine particles cannot be collected, this operation is repeated.
In this method, when an external agent other than the silica fine particles is added, the external agent other than the silica fine particles is also collected. In such a case, silica fine particles may be selected from the collected external additives by using a centrifugation method or the like.
(2) In the case of non-magnetic toner Add 160 g of sucrose (manufactured by Kishida Chemical Co., Ltd.) to 100 mL of ion-exchanged water and dissolve it while boiling to prepare a sucrose concentrate. 31 g of the sucrose concentrate and 6 mL of Contaminone N are placed in a centrifuge tube to prepare a dispersion. 1 g of toner is added to this dispersion, and the toner lumps are loosened with a spatula or the like.
The centrifuge tube is shaken with the above shaker for 20 minutes under the condition of 350 reciprocations per minute. After shaking, the solution is replaced with a glass tube for a swing rotor (50 mL), and centrifugation is performed at 3500 rpm for 30 minutes with a centrifuge. In the glass tube after centrifugation, toner is present in the uppermost layer, and silica fine particles are present on the aqueous solution side of the lower layer. The aqueous solution of the lower layer is collected and centrifuged to separate sucrose and silica fine particles, and the silica fine particles are collected. If necessary, centrifugation is repeated, and after sufficient separation, the dispersion is dried and silica fine particles are collected.
As in the case of the magnetic toner, when an external additive other than the silica fine particles is added, the external additive other than the silica fine particles is also collected. Therefore, silica fine particles are selected from the collected external additives by using a centrifugation method or the like.

<Measuring method of carbon content of silica fine particles>
The amount of carbon derived from the hydrophobizing agent for silica fine particles is measured using a carbon / sulfur analyzer (trade name: EMIA-320) manufactured by HORIBA. 0.3 g of silica fine particles as a sample are precisely weighed and placed in the crucible for the carbon / sulfur analyzer. To this, 0.3 g ± 0.05 g of tin (supplementary part number 9052012500) and 1.5 g ± 0.1 g of tungsten (supplementary part number 9051104100) are added as combustion improvers. Then, according to the description in the instruction manual attached to the carbon / sulfur analyzer, the silica fine particles are heated at 1100 ° C. in an oxygen atmosphere. As a result, the hydrophobic group derived from the hydrophobizing agent on the surface of the silica fine particles _{is thermally decomposed into CO 2} , and the amount thereof is measured. The amount of carbon contained in the silica fine particles (mass%) is determined from the amount of CO ₂ obtained, and this is defined as the amount of carbon derived from the hydrophobizing agent (hereinafter, also simply referred to as "carbon amount").

<Measurement method of carbon content-based immobilization rate of silicone oil in silica fine particles>
(Extraction of non-immobilized silicone oil)
Put 0.50 g of silica fine particles and 40 mL of chloroform in an Erlenmeyer flask, cover and stir for 2 hours. Then, the stirring is stopped and the mixture is allowed to stand for 12 hours. Then centrifuge to remove all supernatant. Centrifugation is performed using a centrifuge (trade name: H-9R) manufactured by KOKUSAN, using a Bn1 rotor and a polycentrifuge tube for the Bn1 rotor at 20 ° C., 10000 rpm, and 5 minutes.
The centrifuged silica fine particles are placed in the Erlenmeyer flask again, 40 mL of chloroform is added, the lid is closed, and the mixture is stirred for 2 hours. Then, the stirring is stopped and the mixture is allowed to stand for 12 hours. Then centrifuge to remove all supernatant. This operation is repeated two more times. Then, the obtained sample is dried at 50 ° C. for 2 hours using a constant temperature bath. Further, the pressure is reduced to 0.07 MPa and the mixture is dried at 50 ° C. for 24 hours to sufficiently volatilize chloroform.
(Carbon content measurement)
The carbon amount of the silica fine particles treated with chloroform as described above and the carbon amount of the silica fine particles before the treatment with chloroform are measured in the same manner as in the above-mentioned "Measuring method of carbon amount of silica fine particles". The carbon content-based immobilization rate of silicone oil in silica fine particles can be calculated by the following formula.
Immobilization rate (%) based on the carbon content of silicone oil in silica fine particles = (carbon content of silica fine particles treated with chloroform / carbon content of silica fine particles) × 100
When surface treatment with silicone oil is performed after hydrophobic treatment with a silane compound or the like, the carbon content in the silica fine particles is measured according to the "method for measuring the carbon content of silica fine particles" after the hydrophobic treatment with a silane compound or the like, and silicone is used. After the oil treatment, the carbon content before and after the extraction of the silicone oil is compared, and the immobilization rate based on the carbon content derived from the silicone oil is calculated as follows.
(Carbon amount of silica fine particles treated with chloroform) / [(Carbon amount of silica fine particles-Carbon amount of silica fine particles after hydrophobic treatment with silane compound etc.)] × 100, as the immobilization rate based on the carbon amount of silicone oil To do.
On the other hand, when the surface treatment with silicone oil is followed by the hydrophobic treatment with a silane compound or the like, the immobilization rate based on the carbon content derived from the silicone oil is calculated as follows.
(Carbon amount of silica fine particles treated with chloroform) / [(Carbon amount of silica fine particles)-(Carbon amount of silica fine particles before hydrophobic treatment with silane compound etc.)] × 100, Immobilization based on carbon amount of silicone oil Let it be a rate.
As the silica fine particles, the silica fine particles used as the raw material may be used, but the silica fine particles isolated according to the above-mentioned method for isolating the silica fine particles from the toner may be used.

<Method of measuring the content of silicone oil in silica fine particles>
(1) Preparation of calibration line for silicone oil content in silica fine particles Silicone oil with a kinematic viscosity of 50 mm ² / s at 25 ° C. of 5 parts by mass with respect to 100 parts by mass of silica base (for surface treatment of silica fine particles) Similar to the above-mentioned "Method for measuring carbon content of silica fine particles" using a standard product of silica fine particles hydrophobized with the same type of silicone oil as the one used. For example, dimethyl silicone oil is used in the examples described later). And measure the amount of carbon. Similarly, the carbon content is measured using a standard product of silica fine particles hydrophobized with 10 parts by mass, 20 parts by mass, and 40 parts by mass of silicone oil. A calibration curve of a linear function is obtained with the amount of carbon (mass%) derived from the obtained silicone oil on the vertical axis and the amount of dimethyl silicone oil added on the horizontal axis.
(2) Quantification of Silicone Oil Content in Silica Fine Particles Next, the carbon content of the silica fine particles is measured in the same manner as the above-mentioned "Method for measuring the carbon content of silica fine particles". Then, the content of silicone oil in the silica fine particles is determined from the carbon content of the silica fine particles and the above calibration curve.

<Method for quantifying silica fine particles in toner>
As the measuring device, the wavelength dispersive fluorescent X-ray analyzer "Axios" (manufactured by PANalytical) and the attached dedicated software "SuperQ ver.4.0F" (manufactured by PANalytical) for setting measurement conditions and analyzing measurement data ) Is used. Rh is used as the anode of the X-ray tube, the measurement atmosphere is vacuum, the measurement diameter (collimator mask diameter) is 27 mm, and the measurement time is 10 seconds. Further, when measuring a light element, it is detected by a proportional counter (PC), and when measuring a heavy element, it is detected by a scintillation counter (SC).
As a measurement sample, put about 4 g of toner in a dedicated press aluminum ring, flatten it, and use a tablet molding compressor "BRE-32" (manufactured by Maekawa Testing Machine Mfg. Co., Ltd.) at 20 MPa for 60. Pressurize for seconds and use pellets molded to a thickness of about 2 mm and a diameter of about 39 mm.
The measurement is performed under the above conditions, the element is identified based on the obtained peak position of X-rays, and the concentration is calculated from the counting rate (unit: cps) which is the number of X-ray photons per unit time.
(1) Separation of Silica Fine Particles from Toner Toner particles obtained by separating silica fine particles are obtained by the same method as the above-mentioned method for separating silica fine particles.
_{(2) Quantification of Silica Fine Particles Silica (SiO 2} ) fine particles are added so as to be 0.10 parts by mass with respect to 100 parts by mass of the toner particles, and sufficiently mixed using a coffee mill. Similarly, the silica fine powder is mixed with the toner particles so as to be 0.20 parts by mass and 0.50 parts by mass, respectively, and these are used as a sample for the calibration curve.
For each sample, pellets of the sample for the calibration curve were prepared as described above using a tablet molding compressor, and when PET was used for the spectroscopic crystal, the diffraction angle (2θ) = 109.08 ° was observed. The count rate (unit: cps) of Si-Kα rays is measured. At this time, the acceleration voltage and current value of the X-ray generator are set to 24 kV and 100 mA, respectively. A calibration curve of a linear function is obtained with the obtained X-ray count rate on the vertical axis and the _{amount of SiO 2 added in each calibration curve sample on the horizontal axis.}
Next, the toner to be analyzed is pelletized as described above using a tablet molding compressor, and the count rate of Si—Kα rays is measured. Then, the content of silica fine particles in the toner is determined from the above calibration curve.

<Calculation method of the amount of silicone oil not immobilized on the silica fine particles derived from the silica fine particles contained in the toner>
The amount of non-immobilized silicone oil is obtained from the above-mentioned "method for quantifying silica fine particles in toner" and the above-mentioned "method for measuring the content of silicone oil in silica fine particles". The content of silicone oil in the silica fine particles contained in the toner to be obtained, and the immobilization of the silicone oil in the silica fine particles obtained from the above-mentioned "Method for measuring the immobilization rate of silicone oil based on the carbon content of the silicone oil". From the rate, calculate as follows.
(Unimmobilized silicone oil content) = (Content of silica fine particles in toner with respect to 100 parts by mass of toner particles) × (Content of silicone oil in silica fine particles with respect to 100 parts by mass of silica base material) × [100 -(Immobilization rate of silicone oil based on carbon content in silica fine particles)] / 100

<Measuring method of number average particle size (D1) of primary particles of silica fine particles>
The number average particle size (D1) of the primary particles of the silica fine particles is calculated from the silica fine particle image of the toner surface taken by Hitachi ultra-high resolution field emission scanning electron microscope S-4800 (Hitachi High-Technologies Corporation). To. The image capturing conditions of S-4800 are as follows.
(1) Sample preparation A thin layer of conductive paste is applied to a sample table (aluminum sample table 15 mm x 6 mm), and toner is sprayed onto the sample table. Further air blow to remove excess toner from the sample table and allow it to dry sufficiently. Set the sample table in the sample holder and adjust the sample table height to 36 mm with the sample height gauge.
(2) Setting of observation conditions for S-4800 The number average particle size of the primary particles of the silica fine particles is calculated using the image obtained by observing the reflected electron image of S-4800. Since the backscattered electron image has less charge-up of the silica fine particles than the secondary electron image, the particle size of the silica fine particles can be measured with high accuracy.
Inject liquid nitrogen into the anti-contamination trap attached to the housing of S-4800 until it overflows, and leave it for 30 minutes. Start up "PC-SEM" of S-4800 and perform flushing (cleaning of FE chip which is an electron source). Click the acceleration voltage display part of the control panel on the screen and press the [Flushing] button to open the flushing execution dialog. Confirm that the flushing intensity is 2, and execute. Confirm that the emission current due to flushing is 20 to 40 μA. Insert the sample holder into the sample chamber of the S-4800 housing. Press [Origin] on the control panel to move the sample holder to the observation position.
Click the acceleration voltage display to open the HV setting dialog, and set the acceleration voltage to [0.8 kV] and the emission current to [20 μA]. In the [Basic] tab of the operation panel, set the signal selection to [SE], select [Up (U)] and [+ BSE] for the SE detector, and select [+ BSE] in the selection box to the right of [+ BSE]. L. A. 100] is selected to set the mode for observing with a reflected electron image. Similarly, in the [Basic] tab of the operation panel, set the probe current of the electro-optical system condition block to [Normal], the focus mode to [UHR], and the WD to [3.0 mm]. Press the [ON] button on the acceleration voltage display of the control panel to apply the acceleration voltage.
(3) Calculation of Number Average Particle Size (D1) of Silica Fine Particles Drag the inside of the magnification display section of the control panel to set the magnification to 100,000 (100k) times. Rotate the focus knob [COARSE] on the operation panel to adjust the aperture alignment when the focus is adjusted to some extent. Click [Align] on the control panel to display the alignment dialog, and select [Beam]. Rotate the STIGMA / ALIGNMENT knobs (X, Y) on the operation panel to move the displayed beam to the center of the concentric circles. Next, select [Aperture] and turn the STIGMA / ALIGNMENT knobs (X, Y) one by one to stop the movement of the image or adjust it to the minimum movement. Close the aperture dialog and focus with autofocus. This operation is repeated twice more to focus.
Then, the particle size of at least 300 silica fine particles on the surface of the toner is measured to obtain the average particle size. Here, since some silica fine particles exist as agglomerates, the maximum diameter of what can be confirmed as the primary particles is obtained, and the obtained maximum diameter is arithmetically averaged to obtain the average particle size of the number of primary particles of the silica fine particles ( D1) is obtained.

<Measuring method of number average particle size (D1) of primary particles of charge control agent>
The number average particle size (D1) of the primary particles of the charge control agent is measured by using a flow type particle image measuring device "FPIA-3000" (manufactured by Sysmex Corporation) under the measurement and analysis conditions after the calibration work. The specific measurement method is as follows.
First, about 20 ml of ion-exchanged water from which impure solids and the like have been removed in advance is placed in a glass container. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument with a pH of 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.2 ml of the diluted solution is added. Further, about 0.02 g of the measurement sample is added, and the dispersion treatment is performed for 2 minutes using an ultrasonic disperser to prepare a dispersion liquid for measurement. At that time, the dispersion is appropriately cooled so that the temperature of the dispersion is 10 ° C. or higher and 40 ° C. or lower. As the ultrasonic disperser, a desktop ultrasonic cleaner disperser (for example, "VS-150" (manufactured by Vervocrea)) having an oscillation frequency of 50 kHz and an electrical output of 150 W is used, and a predetermined amount is contained in the water tank. Ion-exchanged water is added, and about 2 ml of the contaminanton N is added into the water tank.
The flow type particle image measuring device equipped with a standard objective lens (10 times) is used for the measurement, and the particle sheath "PSE-900A" (manufactured by Sysmex Corporation) is used as the sheath liquid. The dispersion prepared according to the above procedure is introduced into the flow type particle image measuring device, and 3000 charge control agents are measured in the total count mode in the HPF measurement mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the diameter of the analyzed particle is limited to 0.50 μm or more and less than 39.69 μm, and the average particle size (D1) of the number of primary particles of the charge control agent is obtained. ..
In the measurement, automatic focus adjustment is performed using standard latex particles (for example, "RESAARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A" manufactured by Duke Scientific Co., Ltd. diluted with ion-exchanged water) before the start of the measurement. After that, it is preferable to perform focus adjustment every 2 hours from the start of measurement.
In the present invention, a flow-type particle image measuring device that has been calibrated by Sysmex and has been issued with a calibration certificate issued by Sysmex is used. The measurement is performed under the measurement and analysis conditions when the calibration certificate is obtained, except that the particle size to be analyzed is limited to the equivalent circle diameter of 0.50 μm or more and less than 39.69 μm.
The measurement principle of the flow-type particle image measuring device "FPIA-3000" (manufactured by Sysmex Corporation) is that the flowing particles are imaged as a still image and image analysis is performed. The sample added to the sample chamber is sent to the flat sheath flow cell by the sample suction syringe. The sample sent into the flat sheath flow is sandwiched between the sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Moreover, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, the captured image is image-processed at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), the outline of each particle image is extracted, and the particle image is obtained. The projected area S, the peripheral length L, and the like are measured. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and can be calculated from the projected area S. The number average particle diameter (D1) of the primary particles of the charge control agent of the present invention refers to the diameter equivalent to the circle.

<Measurement method of toner molecular weight>
In the present invention, the molecular weight of the toner is measured by GPC as follows using the tetrahydrofuran (THF) soluble content of the toner particles obtained by the method for separating silica fine particles.
First, the toner particles are dissolved in THF over 24 hours at room temperature. Then, the obtained solution is filtered through a solvent-resistant membrane filter "Myshori Disc" (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. This sample solution is used for measurement under the following conditions.
Equipment: HLC8120 GPC (Detector: RI) (manufactured by Tosoh Corporation)
Column: 7 stations of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: tetrahydrofuran (THF)
Flow velocity: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade name "TSK standard polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10," A molecular weight calibration curve prepared using F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) is used. (Amount of components having a molecular weight of 1000 or less in the THF-soluble content of toner particles)
In the above GPC measurement, the elution time at which the molecular weight became 1000 was calculated using the calibration curve prepared from the standard polystyrene sample. Then, the solutions before and after the elution time of the molecular weight 1000 are separated. The sample is allowed to stand at room temperature for 48 hours, and then sufficiently dried in a vacuum dryer at 50 ° C. for 24 hours. The weight of the dried sample was measured, and the amount of the component having a molecular weight of 1000 or less was calculated by the following formula.
Amount of component having a molecular weight of 1000 or less (mass%) = (mass with a molecular weight of 1000 or less) / {(mass with a molecular weight of 1000 or more) + (mass with a molecular weight of 1000 or less)} × 100

<Measuring method of toner weight average particle size (D4)>
The weight average particle size (D4) of the toner is calculated as follows. As the measuring device, a precision particle size distribution measuring device "Coulter Counter Multisizer 3" (registered trademark, manufactured by Beckman Coulter Co., Ltd.) equipped with a 100 μm aperture tube by the pore electrical resistance method is used. For the setting of measurement conditions and the analysis of measurement data, the attached dedicated software "Beckman Coulter Multisizer 3 Version 3.51" (manufactured by Beckman Coulter) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, a special grade sodium chloride dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, "ISOTON II" (manufactured by Beckman Coulter) can be used.
Before the measurement and analysis, the dedicated software was set as follows.
On the "Change standard measurement method (SOM)" screen of the dedicated software, set the total count number in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to "standard particles 10.0 μm" (Beckman Coulter). Set the value obtained using (manufactured by the company). By pressing the "threshold / noise level measurement button", the threshold and noise level are automatically set. Also, set the current to 1600 μA, the gain to 2, and the electrolyte to ISOTON II, and check “Flash of aperture tube after measurement”.
On the "Pulse to particle size conversion setting" screen of the dedicated software, the bin spacing is set to logarithmic particle size, the particle size bin is set to 256 particle size bins, and the particle size range is set from 2 μm to 60 μm.
The specific measurement method is as follows.
(1) Put about 200 mL of the electrolytic aqueous solution in a glass 250 mL round bottom beaker dedicated to Multisizer 3, set it on a sample stand, and stir the stirrer rod counterclockwise at 24 rpm. Then, the dirt and air bubbles in the aperture tube are removed by the "aperture flash" function of the dedicated software.
(2) Put about 30 mL of the electrolytic aqueous solution in a 100 mL flat-bottomed beaker made of glass. Among them, as a dispersant, "Contaminone N" (a 10% by mass aqueous solution of a neutral detergent for cleaning a precision measuring instrument at pH 7 consisting of a nonionic surfactant, an anionic surfactant, and an organic builder, manufactured by Wako Pure Chemical Industries, Ltd. ) Is diluted about 3 times by mass with ion-exchanged water, and about 0.3 mL of the diluted solution is added.
(3) Two oscillators having an oscillation frequency of 50 kHz are built in with their phases shifted by 180 degrees, and an ultrasonic disperser "Ultrasonic Dispersion System Tetora 150" (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. Approximately 3.3 L of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 mL of contaminationon N is added into the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. Then, the height position of the beaker is adjusted so that the resonance state of the liquid level of the electrolytic aqueous solution in the beaker is maximized.
(5) With the electrolytic aqueous solution in the beaker of (4) being irradiated with ultrasonic waves, about 10 mg of toner is added little by little to the electrolytic aqueous solution and dispersed. Then, the ultrasonic dispersion processing is continued for another 60 seconds. In ultrasonic dispersion, the water temperature in the water tank is appropriately adjusted to be 10 ° C. or higher and 40 ° C. or lower.
(6) Using a pipette, the electrolytic aqueous solution of (5) in which toner is dispersed is dropped onto the round bottom beaker of (1) installed in the sample stand, and the measured concentration is adjusted to about 5%. .. Then, the measurement is performed until the number of measurement particles reaches 50,000.
(7) The measurement data is analyzed by the dedicated software attached to the device, and the weight average particle size (D4) is calculated. The "average diameter" of the "analysis / volume statistical value (arithmetic mean)" screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measurement of kinematic viscosity of silicone oil>
As a device for measuring the kinematic viscosity of silicone oil, a fully automatic microkinematic viscometer (manufactured by Viscotech Co., Ltd.) was used to measure the viscosity at 25 ° C.

Hereinafter, the present invention will be described in more detail with reference to Examples, but these Examples do not limit the present invention in any way. The number of copies or% in the following formulations are all based on mass unless otherwise specified.

<Manufacturing of magnetic material 1>
Using ferrous sulfate, 50 liters of an iron sulfate aqueous solution containing 2.0 mol / liter of ^{Fe 2+ was prepared.} Further, using sodium silicate, 10 liters of a sodium silicate aqueous solution containing 0.23 mol / liter of ^{Si 4+ was prepared, and this was added to the iron sulfate aqueous solution.} Next, 42 liters of a 5.0 mol / liter NaOH aqueous solution was stirred and mixed with the mixed aqueous solution to obtain a ferrous hydroxide slurry. The ferrous hydroxide slurry was adjusted to pH 12.0 and a temperature of 90 ° C., 30 liters / min of air was blown into the slurry, and an oxidation reaction was carried out until 50% of the ferrous hydroxide became magnetic iron oxide particles. Then, 20 liters / min of air was blown until 75% of the magnetic iron oxide particles were produced, and then 10 liters / min of air was blown until 90% of the magnetic iron oxide particles were produced. Further, when the ratio of the magnetic iron oxide particles exceeded 90%, air was blown at 5 liters / min to complete the oxidation reaction, and a slurry containing octahedral core particles was obtained.
To the obtained slurry containing core particles, 94 ml of an aqueous solution of sodium silicate (containing 13.4% by mass of Si) and 288 ml of an aqueous solution of aluminum sulfate (containing 4.2% by mass of Al) were simultaneously added. Then, the temperature of the slurry was adjusted to 80 ° C. and the pH was adjusted to 5 or more and 9 or less with dilute sulfuric acid to form a coating layer containing silicon and aluminum on the surface of the core particles. The obtained magnetic material was filtered by a conventional method, dried and pulverized to obtain a magnetic material 1. The number average particle size (D1) of the magnetic material 1 is 0.12 nm, the coercive force (Hc) is 11.5 kA / m, the saturation magnetization (σs) is 85.0 Am ² / kg, and the residual magnetization (σr) is 14.0 Am. ^{It was 2} / kg.

<Production example of charge control agent (C-1)>
To a mixed solution of 76.5 parts of water and 15.2 parts of 35% hydrochloric acid, 10 parts of 4-chloro-2-aminophenol was added, and the mixture was stirred under cooling. It was ice-cooled, the temperature of the solution was maintained at 0 ° C. to 5 ° C., 13.6 parts of sodium nitrite dissolved in 24.6 parts of water was added dropwise to an aqueous hydrochloric acid solution, and the mixture was stirred for 2 hours to diazotize. .. After eliminating excess nitrite with sulfamic acid, filtration was performed to obtain a diazo solution.
Next, 12.0 parts of 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone was added to 87 parts of water, 12.1 parts of 25% sodium hydroxide, 4.9 parts of sodium carbonate, and n-. It was added to a mixed solution of 104.6 parts of butanol and dissolved. The diazo solution was added thereto, and the mixture was stirred at a temperature of 20 ° C. to 22 ° C. for 4 hours to carry out a coupling reaction. After that, 92.8 parts of water,
43.5 parts of a 25% aqueous sodium hydroxide solution was added, and the mixture was stirred and washed to separate and remove the lower aqueous layer.
Next, 42.2 parts of water, 5.9 parts of salicylic acid, 24.6 parts of butanol, and 48.5 parts of 15% sodium carbonate were added to the above reaction solution and stirred. Further, 15.1 part of a 38% ferric chloride aqueous solution and 18.0 part of 15% sodium carbonate were added, and the pH of the reaction solution was adjusted to 4.5 with acetic acid. After raising the liquid temperature to a temperature of 30 ° C., the mixture was stirred for 8 hours to carry out a complexing reaction. After the stirring was stopped, the mixture was allowed to stand to separate the lower aqueous layer. Further, 189.9 parts of water was added, and the mixture was stirred and washed to separate the lower aqueous layer. After filtration, the cake was washed with 253 parts of water. After vacuum drying at a temperature of 60 ° C. for 24 hours, a charge control agent (C-1) which is a monoazo metal complex compound was obtained.
When the structure of the charge control agent (C-1) was identified from the infrared absorption spectrum, the visible absorption spectrum, the elemental analysis (C, H, N), the atomic absorption spectroscopy, and the mass spectrum, the structure of the above formula [2] was identified. It was confirmed that (X ⁺ is H ^+). The number average particle size (D1) of the primary particles of the charge control agent (C-1) is 1.41 μm, and the absorbance at a wavelength of 700 nm 48 hours after being allowed to stand in the dispersion test of the charge control agent in dimethyl silicone oil. Was 1.75

<Production examples of charge control agents (C-2) to (C-5)>
In the production example of the charge control agent (C-1), the charge control agents (C-2) to (C-5) were obtained by changing the time of the complexing reaction. Charge control agent When the structures of the charge control agents (C-2) to (C-5) were identified, it was confirmed that the structure was of the formula [2] (X ⁺ is H ⁺ ). The physical characteristics are shown in Table 1.

<Production example of charge control agent (C-6)>
In the production example of the charge control agent (C-1), 3-methyl-1- (3,4-dichlorophenyl) -5-pyrazolone was changed to 3-methyl-1-phenyl-5-pyrazolone. A charge control agent (C-6) was obtained in the same manner as in the production example of the charge control agent (C-1) except for the above.
Charge control agent When the structure of the charge control agent (C-6) was identified, it was confirmed that the structure was as follows. Table 1 shows the physical characteristics of the charge control agent (C-6).

<Charge control agent (C-7)>
As the charge control agent (C-7), T-77 manufactured by Hodogaya Chemical Co., Ltd. was used. Structure of charge control agent (C-7) The structure is shown below. In addition, a + b + c is 1. The physical characteristics are shown in Table 1.

<Production example of binder resin (B-1)>
・ Bisphenol A propylene oxide adduct (2.2 mol addition) 60.0 parts ・ Bisphenol A ethylene oxide adduct (2.2 mol addition) 40.0 parts ・ Telephthalic acid 77.0 parts The above polyester monomer mixture was added to the total amount of monomers. Te, were charged to a 5 liter autoclave together with 0.2 wt% of dibutyl tin oxide, reflux condenser, water separator, denoted N ² gas inlet tube, a thermometer and a stirrer, N ² gas was introduced into the autoclave However, the autoclave reaction was carried out at 230 ° C. The reaction time was adjusted so as to reach a desired softening point, and after the reaction was completed, the mixture was taken out of the container, cooled and pulverized to obtain a binder resin (B-1). The glass transition temperature (Tg) of the binder resin (B-1) was 56 ° C., the softening point (Tm) was 126 ° C., and the ratio of the molecular weight of 1000 or less was 8.4% by mass.

<Production examples of binder resins (B-2) to (B-4)>
In the production example of the binder resin (B-1), the binder resins (B-2) to (B-4) were obtained by adjusting the reaction time of the polycondensation reaction. The physical characteristics are shown in Table 2.

<Production example of binder resin (B-5)>
・ Styrene 75.3 parts ・ n-butyl acrylate 20.0 parts ・ Acrylic acid 4.7 parts ・ Divinylbenzene 0.05 parts 2,2-bis (4,5-di-tert-butylperoxycyclohexyl) propane (Half-life 10 hours temperature; 92 ° C.) 0.08 parts 180 parts of degassed water and 20 parts of a 2% aqueous solution of polyvinyl alcohol are put into a four-necked flask, and then the above mixed solution is added and stirred to form a suspension. did. After sufficiently replacing the inside of the flask with nitrogen, the temperature was raised to 80 ° C. for polymerization, and after holding for 24 hours, 0.1 part of benzoyl peroxide (half-life 10 hours temperature; 72 ° C.) was additionally added, and further. , 12 hours was held to complete the polymerization. Then, after sufficiently mixing under reflux, the organic solvent was distilled off to obtain a binder resin (B-5). Table 2 shows the physical characteristics of the binder resin (B-5).

<Production example of silica fine particles (S-1)>
Fumed silica (silica base; spherical, BET specific surface area: 300 m ² / g) 100 in a solution of 10 parts of dimethyl silicone oil (kinematic viscosity at temperature 25 ° C.: 50 mm ^{2 / s) diluted with 10,000 parts of hexane.} Parts were gradually added, and the solvent was removed after reacting at a temperature of 130 ° C. Then, it was crushed using a pin type crusher to obtain silica fine particles (S-1). The number average particle size of the primary particles of the obtained silica fine particles (S-1) was 14 nm. Table 3 shows the physical characteristics of the silica fine particles (S-1). The content of the silicone oil with respect to 100 parts of the silica base of the silica fine particles (S-1) was 10 parts by mass as measured based on the above-mentioned "quantification of the content of the silicone oil in the silica fine particles".

<Production example of silica fine particles (S-2)>
^{100 parts of fumed silica (silica base; spherical, BET specific surface area: 90 m 2} / g) in a solution prepared by dissolving 10 parts of 90% methanol water and 10 parts of hexamethyldisilazane in 10,000 parts of hexane. Was put in and reacted. Then, the solvent and by-products were removed, and the product was crushed using a pin-type crusher, and ^{10 parts of dimethyl silicone oil (kinematic viscosity at a temperature of 25 ° C.: 100 mm 2} / s) was added to 10,000 parts of hexane. The mixture was gradually added to the solution diluted with (S-2) and reacted at a temperature of 130 ° C. to obtain silica fine particles (S-2). The number average particle size of the primary particles of the obtained silica fine particles (S-2) was 26 nm. Table 3 shows the physical characteristics of the silica fine particles (S-2). The content of the silicone oil with respect to 100 parts of the silica base of the silica fine particles (S-2) was 10 parts by mass as measured based on the above-mentioned "quantification of the content of the silicone oil in the silica fine particles".

<Production Examples of Silica Fine Particles (S-3) to (S-7)>
In the production example of the silica fine particles (S-1), Table 3 shows in the same manner except that the BET specific surface area of the silica base, the number of copies of the dimethyl silicone oil added, and the kinematic viscosity of the dimethyl silicone oil at 25 ° C. are changed. Silica fine particles (S-3) to (S-7) were produced as described above. The physical characteristics are shown in Table 3. The content of silicone oil with respect to 100 parts of the silica base of the silica fine particles (S-3) to (S-7) was measured based on the above-mentioned "quantification of the content of silicone oil in the silica fine particles". It was the same value as the amount of silicone oil added (parts by mass) to 100 parts of the silica base of 3.

<Production example of silica fine particles (S-8)>
In the production example of the silica fine particles (S-2), the same applies except that the BET specific surface area of the silica base, the number of copies of the silane compound added, the number of copies of the dimethyl silicone oil added, and the kinematic viscosity of the dimethyl silicone oil at 25 ° C. are changed. As shown in Table 3, silica fine particles (S-8) were produced. The physical characteristics of the obtained silica fine particles (S-8) are shown in Table 3. The content of the silicone oil with respect to 100 parts of the silica base of the silica fine particles (S-8) was 23 parts by mass as measured based on the above-mentioned "quantification of the content of the silicone oil in the silica fine particles".

<Production example of toner particles 1>
-Bound resin (B-1): 100.0 parts-Magnetic material 1:40 parts-Fishertro push wax: 2.0 parts (Sazole C105, melting point: 105 ° C)
-Charge control agent (C-1): 1.0 part After premixing the above materials with an FM mixer (manufactured by Nippon Coke Industries Co., Ltd.), a twin-screw extruder (trade name: PCM-30, Ikegai Iron Works Co., Ltd.) The temperature was set so that the temperature of the melt at the discharge port was 150 ° C., and the mixture was melt-kneaded. The obtained kneaded product was cooled, roughly pulverized with a hammer mill, and then finely pulverized using a crusher (trade name: Turbo Mill T250, manufactured by Turbo Industries, Ltd.). Toner particles 1 were obtained by classifying the obtained finely pulverized powder using a multi-division classifier utilizing the Coanda effect.

<Production example of toner particles 2 to 13>
Toner particles 2 to 13 were obtained in the same manner as in the production example of the toner particles 1 except that the types and addition amounts of the charge control agent and the binder resin used were changed from the production example of the toner particles 1 as shown in Table 4. It was.

<Manufacturing example of toner 1>
As shown in Table 5, 1.0 part of silica fine particles (S-1) and 0.3 parts of silica fine particles (S-2) are added to toner particles 1 (100 parts) by FM mixer (manufactured by Nippon Coke Industries Co., Ltd.). Toner 1 was obtained by mixing with an external particle and sieving with a mesh having a mesh size of 100 μm. The physical characteristics of the toner 1 are shown in Table 6.

<Manufacturing example of toners 2 to 21>
Toners 2 to 21 were obtained in the same manner as in the production example of toner 1 except that the type and the amount of added silica fine particles used were changed from the production example of toner 1 as shown in Table 5. The physical characteristics are shown in Table 6.

<Example 1>
As the machine used for the evaluation in this example, a commercially available magnetic one-component printer HP LaserJet Enterprise600 M603dn (manufactured by Hewlett-Packard Co., Ltd .: process speed 350 mm / s) was used. Further, a modified cartridge in which a developing sleeve having a diameter of 14 mm was changed to a developing sleeve having a diameter of 10 mm was used. The developing apparatus modified in this way was filled with 900 g of toner 1 and the following evaluation was carried out. The evaluation results are shown in Table 7.

<Examples 2 to 17>
The evaluation was carried out in the same manner as in Example 1 except that toners 2 to 17 were used. The evaluation results are shown in Table 7.

<Comparative Examples 1 to 4>
The evaluation was carried out in the same manner as in Example 1 except that the toners 18 to 21 were used. The evaluation results are shown in Table 7.

<Evaluation 1: Hollow out when used for a long time in a high temperature and high humidity environment>
The evaluation of the hollow was carried out in a high temperature and high humidity environment (32 ° C., 80% RH). A total of 20000 sheets were printed in a mode in which the horizontal line pattern with a print rate of 2% was set as 2 sheets / job and the machine was temporarily stopped between jobs before the next job started. .. An 8 mm grid-shaped grid chart composed of repeating line widths of 200 μm, 500 μm, 1 mm, and 2 mm ^{was printed out on both sides of 250 g / m 2} (A4) paper for both the vertical and horizontal lines. Arbitrary 10 points of the second side print were visually observed and loupe (× 30), and the evaluation was made as a hollow. The evaluation criteria for hollows are as follows.
A: No hollow B: Observation with a 30x loupe confirms hollow in a part of the field of view C: Visually confirms a small part of hollow D: Visually, overall You can see the hollow

<Evaluation 2: Image density and hollow when used in a high-temperature and high-humidity environment after being left in a harsh environment in a high-density state>
The toner-filled cartridge was tapped 300 times and allowed to stand in a harsh environment (40 ° C., 95% RH) for 30 days. Then, after allowing to stand in a high temperature and high humidity environment (32 ° C., 80% RH) for 1 day, one solid black image was printed out on ^{thick paper (105 g / m 2).} The image density of the solid black image printed out was measured.
The solid black density image was measured by measuring the reflection density of the solid image using a Macbeth densitometer (manufactured by Macbeth), which is a reflection densitometer, using an SPI filter. The average value of the reflection densities of the five solid black images (upper left corner, upper right corner, center, lower left corner, and lower right corner) was taken as the image density. The larger the number, the better.
The evaluation criteria for reflection density are as follows.
A: 1.30 or more B: 1.20 or more and less than 1.30 C: 1.10 or more and less than 1.20 D: less than 1.10 After that, a horizontal line pattern with a printing rate of 2% is used as 2 sheets / 1 job. In the mode set so that the machine stops once between jobs and then the next job starts, a total of 20000 images are ^{printed and one solid image is printed on 105 g / m 2} (A4) paper. Out. The image density of the solid black image printed out was measured. Further, an 8 mm grid-shaped grid chart composed of repeating line widths of 200 μm, 500 μm, 1 mm, and 2 mm for both vertical and horizontal lines was printed out on both sides ^{of 250 g / m 2 (A4) paper.} Arbitrary 10 points of the second side print were visually observed and loupe (× 30), and the evaluation was made as a hollow.
The evaluation criteria for hollows are as follows.
A: No hollow B: Observation with a 30x loupe confirms hollow in a part of the field of view C: Visually confirms a small part of hollow D: Visually, overall You can see the hollow

<Evaluation 3: Image density and tailing when used in a low-temperature and low-humidity environment after being left in a harsh environment in a high-density state>
The evaluation of tailing was carried out in a low temperature and low humidity environment (15 ° C, 10% RH) where tailing is likely to occur. The toner-filled cartridge was tapped 300 times and allowed to stand in a harsh environment (40 ° C., 95% RH) for 30 days. Then, it was allowed to stand in a low temperature and low humidity environment (15 ° C., 10% RH) for 1 day. After that, a horizontal line pattern with a print rate of 2% is set as 2 sheets / job, and a total of 20000 sheets are printed in a mode in which the machine is temporarily stopped between jobs and then the next job is started. Did. One solid image was ^{printed out on 105 g / m 2} (A4) paper. The image density of the solid black image printed out was measured.
The solid black density image was measured by measuring the reflection density of the solid image using a Macbeth densitometer (manufactured by Macbeth), which is a reflection densitometer, using an SPI filter. The average value of the reflection densities of the five solid black images (upper left corner, upper right corner, center, lower left corner, and lower right corner) was taken as the image density. The larger the number, the better.
The evaluation criteria for reflection density are as follows.
A: 1.30 or more B: 1.20 or more and less than 1.30 C: 1.10 or more and less than 1.20 D: less than 1.10 After that, the surface of the electrophotographic photosensitive member is exposed to laser to obtain 600 dpi of 10 dots vertical and horizontal lines. An image in which a pattern latent image (the line width of the electrostatic latent image is 420 μm) was written at 1 cm intervals was printed out on a PET OHP to obtain a tailing image. The line width of the printed line image was measured.
For the evaluation of tail pulling, use the obtained vertical and horizontal line pattern images with a surface roughness meter (trade name: Surfcoder SE-30H) manufactured by Kosaka Laboratory Co., Ltd. to determine how to apply toner on the vertical and horizontal line lines. Obtained as a profile of surface roughness. Then, each line width was obtained from the width of this profile, and the vertical / horizontal line ratio was calculated.
Since the tailing occurs along the rotation direction of the electrostatic latent image carrier, the width of the horizontal line is more susceptible to the tailing than the vertical line, and the line width becomes thicker. Therefore, it is considered that the vertical / horizontal line ratio is usually 1 or less, and the closer the value is to 1, the more the tailing is suppressed. The evaluation criteria for tailing are as follows.
A: Vertical / horizontal line ratio is 0.95 or more and 1.00 or less B: Vertical / horizontal line ratio is 0.90 or more and less than 0.95 C: Vertical / horizontal line ratio is 0.80 or more and less than 0.90 D: Vertical / horizontal line ratio less than 0.80

<Evaluation 4: Tail when used in a low temperature and low humidity environment>
After standing in a low temperature and low humidity environment (15 ° C, 10% RH) for 1 day, the horizontal line pattern with a printing rate of 2% is set as 2 sheets / job, and after the machine is stopped between jobs, the next In the mode set to start the job, a total of 20000 images were printed. After that, one image on the surface of the electrophotographic photosensitive member was written with a laser exposure of 600 dpi of 10 dot vertical and horizontal line pattern latent images (the line width of the electrostatic latent image is 420 μm) at 1 cm intervals on one PET OHP. It was printed out and used as a tailing image. The line width of the printed line image was measured.
The evaluation of tailing was performed in the same manner as above.

Claims (6)

Toner particles containing a binder resin, a colorant, and a charge control agent,
And inorganic fine particles,
Toner containing
The inorganic fine particles contain silica fine particles containing a silica base and silicone oil, and the inorganic fine particles contain
The toner contains the silica fine particles in an amount of 0.40 parts by mass or more and 1.50 parts by mass or less per 100 parts by mass of the toner particles.
The content of the silicone oil in the silica fine particles is 5.0 parts by mass or more and 40.0 parts by mass or less with respect to 100 parts by mass of the silica base material.
The basis of carbon immobilization ratio of the silicone oil in the fine silica particles, not less than 50 wt%,
The charge control agent is a compound represented by the following formula [1].

(In the formula [1], A ₁ , A ₂ and A ₃ independently represent a hydrogen atom, a nitro group or a halogen atom. B ₁ represents a hydrogen atom or an alkyl group. M is an Fe atom. It represents a Cr atom or an Al atom, and X ⁺ indicates a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion or a mixed ion thereof.)
In a silicone oil sedimentation test in which a dispersion liquid in which 15 mg of the charge control agent ^{was dispersed in 8.0 g of the silicone oil having a kinematic viscosity of 50 mm 2} / s at 25 ° C. was allowed to stand and the change over time of the dispersion liquid was measured. The absorbance of the dispersion at a wavelength of 700 nm 48 hours after being allowed to stand is 1.8.
A toner characterized by being 5 or less. The toner according to claim 1, wherein the silicone oil has a kinematic viscosity of 25 ° C. of 50 mm ² / s or more and 200 mm ^{2 / s or less.} The toner according to claim 1 or 2, wherein the binder resin contains a polyester resin. Toner of the number average particle diameter of primary particles of the charge control agent (D1) is, according to any one of claims 1 to 3 or less than 0.80 .mu.m 2.00 .mu.m. The charge control agent, the toner according to any one of claims 1 to 4 which is a compound represented by the following formula [2].

(In the formula [2] , X ⁺ represents a hydrogen ion, an alkali metal ion, an ammonium ion, an alkylammonium ion, or a mixed ion thereof.) In the chromatogram of tetrahydrofuran-soluble matter as measured by gel permeation chromatography of the toner particles, the amount of molecular weight of 1,000 or less components, according to any one of claims 1 to 5, 15.0 wt% or less Toner.