JP2018159864A - Toner for electrostatic charge image development, electrostatic charge image developer, toner cartridge, process cartridge, image forming apparatus, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the occurrence of an image defect at the boundary between an image part and a non-image part in each of the same images, when the same images are continuously formed under a high-temperature and high-humidity environment and subsequently a halftone image different from the same images is formed.SOLUTION: A toner for electrostatic charge image development contains toner particles, silica particles having a volume average primary particle diameter of 80 nm or more and 200 nm or less in an amount of 0.5 mass% or more and 3.0 mass% or less relative to the toner particles, negatively-charged lubricant particles N in an amount of 0.005 mass% or more and 0.5 mass% or less relative to the toner particles, and positively-charged lubricant particles P in an amount of 0.001 mass% or more and 0.5 mass% or less relative to the toner particles. The isolation rate of the silica particles, s mass%, the isolation rate of the lubricant particles N, n mass%, and the isolation rate of the lubricant particles P, p mass% after ultrasonic treatment in an aqueous dispersion satisfy the formulas 1 to 3. Formula 1 5≤s≤50; formula 2 0.10≤p/s≤0.95; formula 3 0.10≤n/s≤0.95.SELECTED DRAWING: None

Description

  The present invention relates to an electrostatic charge image developing toner, an electrostatic charge image developer, a toner cartridge, a process cartridge, an image forming apparatus, and an image forming method.

  In electrophotographic image formation, a toner is used as an image forming material. For example, a toner containing toner particles containing a binder resin and a colorant and an external additive externally added to the toner particles is used. Many are used.

  For example, Patent Document 1 discloses a toner including “a toner base particle containing at least a binder resin and a colorant; and an external additive containing inorganic fine particles and fatty acid metal salt particles, and the inorganic fine particles Includes at least hydrophobic silica particles, the liberation rate Ya of the hydrophobic silica particles from the toner is 1% by mass to 20% by mass, and the liberation rate Yb of the fatty acid metal salt particles from the toner is 30% by mass. The toner is characterized by being -90% by mass. "

  Patent Document 2 states that “a toner formed by coating at least a fatty acid metal compound on the surface, and the toner base particle surface is coated with the fatty acid metal compound, and then an external additive other than the fatty acid metal compound is attached. The toner is characterized by being made up. "

JP2013-156430A JP 2006-227190 A

As toner used in an image forming apparatus having a cleaning means having a cleaning blade, abrasive particles having a function of scraping off deposits on the surface of the image carrier and lubricant particles having a function of suppressing wear on the surface of the image carrier And toner externally added to the toner particles.
Using the toner containing the toner particles, the abrasive particles, and the lubricant particles, the same image is formed after continuously forming the same image in an environment of high temperature and high humidity (for example, temperature 29 ° C., humidity 80% RH). When a halftone image different from the image is formed, an image defect may occur at the boundary between the image portion and the non-image portion in the same image.

  The problem of the present invention is that toner particles and silica particles having a volume average primary particle size of 80 nm or more and 200 nm or less are 0.5 mass% or more and 3.0 mass% or less, and negatively charged lubricant particles N are 0.005 mass% or more and 0.0. In a toner containing 5% by mass or less and positively chargeable lubricant particles P 0.001% by mass to 0.5% by mass and having s of 5 to 50, p / s is 0.10 or more and 0.00. Compared to the case where the range is 95 or less or the case where n / s exceeds the range of 0.10 or more and 0.95 or less, the same image is formed after the same image is continuously formed in a high-temperature and high-humidity environment. An object of the present invention is to provide an electrostatic image developing toner that suppresses the occurrence of image defects that occur at the boundary between an image portion and a non-image portion in the same image when different halftone images are formed.

  The above problem is solved by the following means. That is,

The invention according to claim 1
Toner particles and silica particles having a volume average primary particle size of 80 nm or more and 200 nm or less are 0.5% by mass or more and 3.0% by mass or less based on the toner particles, and negatively chargeable lubricant particles N are used as the toner particles. 0.005% by mass to 0.5% by mass with respect to the toner particles, and positively chargeable lubricant particles P with respect to the toner particles in an amount of 0.001% by mass to 0.5% by mass,
After the ultrasonic treatment in the aqueous dispersion, the free rate s mass% of the silica particles, the free rate n mass% of the lubricant particles N, and the free rate p mass% of the lubricant particles P are represented by the formulas 1 to An electrostatic charge image developing toner satisfying Formula 3.
Formula 1 5 ≦ s ≦ 50
Formula 2 0.10 ≦ p / s ≦ 0.95
Formula 3 0.10 ≦ n / s ≦ 0.95

The invention according to claim 2
The liberation rate s mass% of the silica particles, the liberation rate n mass% of the lubricant particles N, and the liberation rate p mass% of the lubricant particles P satisfy the following formulas 2-1 to 3-1. 2. The toner for developing an electrostatic charge image according to 1.
Formula 2-1 0.10 ≦ p / s ≦ 0.75
Formula 3-1 0.10 ≦ n / s ≦ 0.75

The invention according to claim 3
The electrostatic image developing toner according to claim 1, wherein the silica particles are monodispersed spherical silica particles having an average circularity of 0.75 to 1.0.

The invention according to claim 4
The electrostatic charge image developing toner according to claim 1, wherein the lubricant particles P are fatty acid metal salts.

The invention according to claim 5
The electrostatic charge image developing toner according to claim 1, wherein the lubricant particles N are polytetrafluoroethylene.

The invention according to claim 6
An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1.

The invention according to claim 7 provides:
Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 5,
A toner cartridge to be attached to and detached from the image forming apparatus.

The invention according to claim 8 provides:
A developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus.

The invention according to claim 9 is:
An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Cleaning means having a cleaning blade for cleaning the surface of the image carrier;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising:

The invention according to claim 10 is:
A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 6;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A cleaning step of cleaning the surface of the image carrier with a cleaning blade;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising:

  According to the invention according to claim 1, 4 or 5, the negatively chargeable lubricant having toner particles and silica particles having a volume average primary particle size of 80 nm or more and 200 nm or less and 0.5 mass% or more and 3.0 mass% or less. In a toner containing 0.005% by mass to 0.5% by mass of particles N and 0.001% by mass to 0.5% by mass of positively-charged lubricant particles P and having s of 5 to 50, p Compared to the case where / s exceeds the range of 0.10 to 0.95 or the case where n / s exceeds the range of 0.10 to 0.95, the same image is continuously formed in a high temperature and high humidity environment. Then, an electrostatic charge image developing toner that suppresses the occurrence of image defects at the boundary between the image portion and the non-image portion in the same image when a halftone image different from the same image is formed is provided. The

  According to the invention of claim 2, compared to the case where p / s exceeds the range of 0.10 to 0.75 or the case where n / s exceeds the range of 0.10 to 0.75, When a halftone image different from the same image is formed after continuously forming the same image in an environment, occurrence of an image defect occurring at a boundary between the image portion and the non-image portion in the same image An electrostatic charge image developing toner is provided.

  According to the third aspect of the present invention, the same image is continuously formed in a high-temperature and high-humidity environment as compared with the electrostatic image developing toner in which the average circularity of the silica particles contained is less than 0.75. Then, an electrostatic charge image developing toner that suppresses the occurrence of image defects at the boundary between the image portion and the non-image portion in the same image when a halftone image different from the same image is formed is provided. The

  According to the invention of claim 6, 7, 8, 9, or 10, toner particles and silica particles having a volume average primary particle size of 80 nm to 200 nm are 0.5% by mass to 3.0% by mass and negatively charged. -Containing lubricant particles N 0.005 mass% or more and 0.5 mass% or less and positively chargeable lubricant particles P 0.001 mass% or more and 0.5 mass% or less, and s is 5 or more and 50 or less. Compared to the case where the toner for developing an electrostatic charge image having a p / s exceeding the range of 0.10 to 0.95 or the n / s exceeding the range of 0.10 to 0.95 is applied. When a halftone image different from the same image is formed after continuously forming the same image in a humid environment, image defects occurring at the boundary between the image portion and the non-image portion in the same image Electrostatic image developer that suppresses generation, toner Chromatography cartridges, process cartridges, image forming apparatus, or an image forming method is provided.

1 is a schematic configuration diagram illustrating an image forming apparatus according to an exemplary embodiment. It is a schematic block diagram which shows the process cartridge which concerns on this embodiment.

  Hereinafter, the present invention will be described in detail with reference to an exemplary embodiment.

<Toner for electrostatic image development>
The electrostatic image developing toner according to the exemplary embodiment (also simply referred to as “toner”) includes 0.5% by mass of toner particles and silica particles having a volume average primary particle size of 80 nm or more and 200 nm or less based on the toner particles. More than 3.0% by mass and negatively chargeable lubricant particles N are 0.005% by mass to 0.5% by mass with respect to the toner particles, and positively charged lubricant particles P are used as the toner particles. 0.001% by mass or more and 0.5% by mass or less.
Then, after the ultrasonic treatment in the aqueous dispersion, the release rate s% by mass of the silica particles, the release rate n% by mass of the lubricant particles N, and the release rate p% by mass of the lubricant particles P are expressed by the formula: 1 to Equation 3 are satisfied.
Formula 1 5 ≦ s ≦ 50
Formula 2 0.10 ≦ p / s ≦ 0.95
Formula 3 0.10 ≦ n / s ≦ 0.95

  Here, the “particle release rate” means the toner when an aqueous vibration of toner set at a temperature of 40 ° C. is maintained at 40 ° C. and ultrasonic vibration with an output of 20 W and a frequency of 20 kHz is applied for 1 minute. The ratio (% by mass) of the particles released from the toner particles with respect to the total amount of particles contained in the toner.

The method for measuring the release rate of particles is as follows.
First, 100 ml of ion exchange water and 5.5 ml of 10 mass% Triton X100 aqueous solution (manufactured by Acros Organics) are added to a 200 ml glass bottle, 5 g of toner is added to the mixture, and the mixture is stirred 30 times and allowed to stand for 1 hour or more. Put.
Then, after stirring the mixed solution 20 times, using an ultrasonic homogenizer (manufactured by SONICS & MATERIALS Co., Ltd., product name homogenizer, model VCX750, CV33), a dial was set at an output of 30%, and ultrasonic energy was applied under the following conditions. Apply for 1 minute.
・ Vibration time: 60 seconds continuous ・ Amplitude: 20W (30%) set ・ Vibration start temperature: 40 ± 1.5 ℃
・ Distance between the ultrasonic transducer and the bottom of the container: 10 mm

Next, the mixed liquid to which ultrasonic energy is applied is suction filtered using a filter paper (trade name: qualitative filter paper (No. 2, 110 mm), manufactured by Advantech Toyo Co., Ltd.), washed twice with ion exchange water again, The free particles are removed by filtration, and then the toner is dried.
The amount of particles remaining in the toner after removal of the particles by the above treatment (hereinafter referred to as the amount of particles after dispersion), the amount of toner particles not subjected to the treatment for removing the above particles (hereinafter referred to as the amount of particles before dispersion) Are determined by the fluorescent X-ray method, and the values of the amount of particles before dispersion and the amount of particles after dispersion are substituted into the following formula.
The value calculated by the following formula is defined as the particle liberation rate.
Formula: Particle release rate (% by mass) = [(particle amount before dispersion−particle amount after dispersion) / particle amount before dispersion] × 100

  The toner according to the present embodiment has a halftone different from the same image after the same image is continuously formed in an environment of high temperature and high humidity (for example, a temperature of 29 ° C. and a humidity of 80% RH). When an image is formed, occurrence of an image defect that occurs at the boundary between the image portion and the non-image portion in the same image is suppressed. The reason is estimated as follows.

  Conventionally, in electrophotographic image formation, a cleaning means using a cleaning blade has been used for the purpose of removing transfer residual toner on the surface of an image carrier. In addition, lubricant particles are added to the toner from the viewpoint of suppressing wear of the image carrier due to contact with the cleaning blade. Further, deposits such as discharge products may adhere to the surface of the image carrier, and abrasive particles are also added to the toner from the viewpoint of imparting a function of scraping off these deposits. ing.

Examples of the lubricant particles include positive (plus) chargeable particles and negative (minus) chargeable particles.
For example, when toner particles are negative (minus) charged, and positively charged particles such as fatty acid metal salts are used as the lubricant particles, the lubricant particles are supplied to the surface of the image carrier. Is more supplied to the non-image area. If negatively charged particles are used as the lubricant particles, the lubricant particles are supplied more to the image area. In a region where a large amount of lubricant particles is supplied, a lubricant film in which the lubricant particles are stretched in a film shape on the surface of the image carrier is more easily formed than in other regions.

  The lubricant film is scraped off by abrasive particles. Examples of the abrasive particles include silica particles having a volume average primary particle size of 80 nm to 200 nm (hereinafter also referred to as “specific silica particles”). The specific silica particles are used because they easily reduce the amount of wear on the surface of the image carrier as compared with conventionally used large-diameter and irregularly shaped abrasives. In addition, the specific silica particles are moderately liberated from the toner particles and are appropriately supplied to the surface of the image carrier, thereby removing the deposits such as discharge products, and the lubricant particles on the surface of the image carrier. The function of scraping is also exerted on the lubricant film stretched into a film shape. The specific silica particles exhibit a scraping function of the lubricant film while suppressing wear of the image carrier itself with an appropriate polishing force. However, since silica particles are generally negatively charged, when toner particles are negatively charged, more toner particles are supplied to the image area, that is, the lubricant film is scraped off in the image area. Function is demonstrated more.

  Thus, due to the chargeability of the lubricant particles and the abrasive particles, the supply amount of the lubricant particles and the abrasive particles differs between the image area and the non-image area. Therefore, when the same image (a) is output continuously, a difference occurs in the progress of formation and scraping of the lubricant film between the non-image portion and the image portion of the image (a), and the image portion And a non-image part are likely to have a step. If a halftone image (b) different from the image (a) is output after the step is generated, an image defect (for example, white spots or color streaks) due to the step may occur.

In particular, in an environment of high temperature and high humidity (for example, a temperature of 29 ° C. and a humidity of 80% RH), it is caused by a step at the boundary between the image portion and the non-image portion when the same image (a) is output continuously. It is difficult to suppress the occurrence of image defects.
For example, specific silica particles are used as abrasive particles, and positively charged particles and negatively charged particles are used in combination as lubricant particles. It is conceivable to suppress the step generated at the boundary with the part. However, if images are output continuously in a high-temperature and high-humidity environment, the progress of lubricant film formation and scraping even if the amount of each particle added is adjusted so that the step is suppressed. The image balance may be lost, and image defects may occur due to the steps.

As a cause of the occurrence of image defects in the high-temperature and high-humidity environment, it is conceivable that the specific silica particles and the lubricant particles differ in how the adhesive force increases with respect to the toner particles when the environmental temperature becomes high. Specifically, as the environmental temperature increases, the adhesion force of the specific silica particles to the toner particles is relatively higher than the adhesion force of the lubricant particles to the toner particles. That is, the specific silica particles are particularly less likely to be released from the toner particles than the lubricant particles, and the amount of the specific silica particles reaching the contact portion between the image carrier and the cleaning blade is relatively small.
And since the quantity of the specific silica particle which reaches | attains the said contact part is small, the scraping function (polishing power) of a lubricant film falls. In addition, it is difficult to form an aggregate in which the specific silica particles are aggregated due to the pressure from the cleaning blade in the contact portion, and the antiskid effect of the lubricant particles by the specific silica particles is reduced, and the formation of the lubricant film is promoted. . In this way, when the polishing force and the clogging effect of the specific silica particles are lowered, the balance of the progress of the formation of the lubricant film and the scraping is broken, and a step is likely to occur at the boundary between the image portion and the non-image portion. Conceivable.

  Therefore, in the present embodiment, specific silica particles, negatively chargeable lubricant particles N, and positively chargeable lubricant particles P are used, and the amount of each particle added is within the above range, and then in the aqueous dispersion liquid. The free rate s% by mass of the specific silica particles after the ultrasonic treatment, the free rate n% by mass of the lubricant particles N, and the free rate p% by mass of the lubricant particles P are set to satisfy Formulas 1 to 3. That is, the specific silica particles can be obtained by relatively reducing the liberation ratio n mass% of the lubricant particles N and the liberation ratio p mass% of the lubricant particles P and relatively increasing the liberation ratio s mass% of the specific silica particles. The amount of the specific silica particles supplied to the image holding member is increased without increasing the amount of addition itself. Accordingly, the polishing force by the specific silica particles released from the toner particles is ensured while avoiding the deterioration of fluidity and the influence on the charging characteristics due to the addition amount of the specific silica particles being too large. For this reason, it is presumed that image defects due to the steps generated at the boundary between the image portion and the non-image portion are suppressed even in a high temperature and high humidity environment. However, if the liberation rate n% by mass of the lubricant particles N and the liberation rate p% by mass of the lubricant particles P are relatively low relative to the specific silica particles, the lubricating function will not be exhibited.

  Hereinafter, details of the toner according to the exemplary embodiment will be described.

  The toner according to the exemplary embodiment includes toner particles and, if necessary, external additives.

(Toner particles)
The toner particles include, for example, a binder resin and, if necessary, a colorant, a release agent, and other additives.

-Binder resin-
Examples of the binder resin include styrenes (eg, styrene, parachlorostyrene, α-methylstyrene, etc.), (meth) acrylic acid esters (eg, methyl acrylate, ethyl acrylate, n-propyl acrylate, acrylic acid). n-butyl, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (for example, acrylonitrile, Methacrylonitrile, etc.), vinyl ethers (eg, vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), olefins (eg, ethylene, propylene, etc.) Emissions, a homopolymer of a monomer such as butadiene) and the like, or a vinyl-based resin composed of these monomers with two or more combinations copolymer.
As the binder resin, for example, epoxy resin, polyester resin, polyurethane resin, polyamide resin, cellulose resin, polyether resin, non-vinyl resin such as modified rosin, a mixture of these with the vinyl resin, or these Examples also include a graft polymer obtained by polymerizing a vinyl monomer in the coexistence.
These binder resins may be used alone or in combination of two or more.

A polyester resin is suitable as the binder resin.
Examples of the polyester resin include known polyester resins.

  As a polyester resin, the condensation polymer of polyhydric carboxylic acid and polyhydric alcohol is mentioned, for example. In addition, as a polyester resin, a commercial item may be used and what was synthesize | combined may be used.

Examples of the polyvalent carboxylic acid include aliphatic dicarboxylic acids (eg, oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, alkenyl succinic acid, adipic acid, sebacic acid, etc.) Alicyclic dicarboxylic acids (for example, cyclohexanedicarboxylic acid), aromatic dicarboxylic acids (for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or lower (for example, having 1 or more carbon atoms) 5 or less) alkyl esters. Among these, as polyvalent carboxylic acid, aromatic dicarboxylic acid is preferable, for example.
The polyvalent carboxylic acid may be used in combination with a dicarboxylic acid or a trivalent or higher carboxylic acid having a crosslinked structure or a branched structure. Examples of the trivalent or higher carboxylic acid include trimellitic acid, pyromellitic acid, anhydrides thereof, and lower (for example, having 1 to 5 carbon atoms) alkyl esters.
Polyvalent carboxylic acid may be used individually by 1 type, and may use 2 or more types together.

Examples of the polyhydric alcohol include aliphatic diols (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (for example, cyclohexanediol, cyclohexanedimethanol, Hydrogenated bisphenol A, etc.) and aromatic diols (for example, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, as the polyhydric alcohol, for example, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.
As the polyhydric alcohol, a trihydric or higher polyhydric alcohol having a crosslinked structure or a branched structure may be used together with the diol. Examples of the trihydric or higher polyhydric alcohol include glycerin, trimethylolpropane, and pentaerythritol.
A polyhydric alcohol may be used individually by 1 type, and may use 2 or more types together.

The glass transition temperature (Tg) of the polyester resin is preferably 50 ° C. or higher and 80 ° C. or lower, and more preferably 50 ° C. or higher and 65 ° C. or lower.
The glass transition temperature is determined from a DSC curve obtained by differential scanning calorimetry (DSC), and more specifically described in the method for determining the glass transition temperature in JIS K 7121-1987 “Method for Measuring Plastic Transition Temperature”. Of “extrapolated glass transition start temperature”.

The weight average molecular weight (Mw) of the polyester resin is preferably from 5,000 to 1,000,000, and more preferably from 7,000 to 500,000.
The number average molecular weight (Mn) of the polyester resin is preferably from 2,000 to 100,000.
The molecular weight distribution Mw / Mn of the polyester resin is preferably 1.5 or more and 100 or less, and more preferably 2 or more and 60 or less.
The weight average molecular weight and the number average molecular weight are measured by gel permeation chromatography (GPC). The molecular weight measurement by GPC is performed with a THF solvent using a Tosoh GPC / HLC-8120GPC as a measuring device and a Tosoh column / TSKgel SuperHM-M (15 cm). The weight average molecular weight and the number average molecular weight are calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample from this measurement result.

The polyester resin is obtained by a well-known manufacturing method. Specifically, for example, the polymerization temperature is set to 180 ° C. or higher and 230 ° C. or lower, the pressure in the reaction system is reduced as necessary, and the reaction is performed while removing water and alcohol generated during the condensation.
In addition, when the monomer of the raw material is not dissolved or compatible at the reaction temperature, a solvent having a high boiling point may be added and dissolved as a solubilizing agent. In this case, the polycondensation reaction is performed while distilling off the solubilizer. If there is a monomer with poor compatibility, it is recommended to condense the monomer with poor compatibility with the monomer and the acid or alcohol to be polycondensed in advance before polycondensing with the main component. .

  The content of the binder resin is, for example, preferably 40% by weight to 95% by weight, more preferably 50% by weight to 90% by weight, and more preferably 60% by weight to 85% by weight with respect to the entire toner particles. Further preferred.

-Colorant-
Examples of the colorant include carbon black, chrome yellow, hansa yellow, benzidine yellow, sren yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, vulcan orange, watch young red, permanent red, brilliant carmine 3B, and brilliant. Carmine 6B, Dupont Oil Red, Pyrazolone Red, Resol Red, Rhodamine B Lake, Lake Red C, Pigment Red, Rose Bengal, Aniline Blue, Ultramarine Blue, Calco Oil Blue, Methylene Blue Chloride, Phthalocyanine Blue, Pigment Blue, Phthalocyanine Green, Various pigments such as malachite green oxalate, or acridine, xanthene, , Benzoquinone, azine, anthraquinone, thioindico, dioxazine, thiazine, azomethine, indico, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, thiazole, and other dyes Etc.
A colorant may be used individually by 1 type and may use 2 or more types together.

  As the colorant, a surface-treated colorant may be used as necessary, or it may be used in combination with a dispersant. A plurality of colorants may be used in combination.

  The content of the colorant is, for example, preferably 1% by mass or more and 30% by mass or less, and more preferably 3% by mass or more and 15% by mass or less with respect to the entire toner particles.

-Release agent-
Examples of mold release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. And so on. The release agent is not limited to this.

The melting temperature of the release agent is preferably 50 ° C. or higher and 110 ° C. or lower, and more preferably 60 ° C. or higher and 100 ° C. or lower.
Note that the melting temperature is obtained from the DSC curve obtained by differential scanning calorimetry (DSC) according to “melting peak temperature” described in JIS K 7121-1987 “Method for measuring the melting temperature of plastics”. .

  The content of the release agent is, for example, preferably 1% by mass to 20% by mass and more preferably 5% by mass to 15% by mass with respect to the entire toner particles.

-Other additives-
Examples of other additives include known additives such as a magnetic material, a charge control agent, and inorganic powder. These additives are contained in the toner particles as internal additives.

-Toner particle characteristics-
The toner particles may be toner particles having a single layer structure, or toner particles having a so-called core / shell structure composed of a core (core particle) and a coating layer (shell layer) covering the core. May be.
Here, the core / shell structure toner particles include, for example, a core portion including a binder resin and, if necessary, other additives such as a colorant and a release agent, and a binder resin. It is good to be comprised with the comprised coating layer.

  The volume average particle diameter (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.

In addition, various average particle diameters and various particle size distribution indexes of toner particles are measured using Coulter Multisizer II (manufactured by Beckman Coulter, Inc.), and the electrolyte is measured using ISOTON-II (manufactured by Beckman Coulter, Inc.). The
In the measurement, 0.5 mg to 50 mg of a measurement sample is added as a dispersant to 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate). This is added to 100 ml or more and 150 ml or less of the electrolytic solution.
The electrolyte in which the sample is suspended is dispersed for 1 minute with an ultrasonic disperser, and the particle size distribution of particles having a particle size in the range of 2 μm to 60 μm is measured using a 100 μm aperture with a Coulter Multisizer II. taking measurement. The number of particles to be sampled is 50,000.
For the particle size range (channel) divided based on the measured particle size distribution, the cumulative distribution is drawn from the smaller diameter side to the volume and number, respectively, and the particle size to be 16% is the volume particle size D16v, the number particle size D16p, a particle size that is 50% cumulative is defined as a volume average particle size D50v, a cumulative number average particle size D50p, and a particle size that is 84% cumulative is defined as a volume particle size D84v and a number particle size D84p.
Using these, the volume particle size distribution index (GSDv) is calculated as (D84v / D16v) ^1/2 and the number particle size distribution index (GSDp) is calculated as (D84p / D16p) ^1/2 .

  The average circularity of the toner particles is preferably from 0.94 to 1.00, more preferably from 0.95 to 0.98.

The average circularity of the toner particles is obtained by (circle equivalent perimeter) / (perimeter) [(perimeter of a circle having the same projection area as the particle image) / (perimeter of the particle projected image)]. Specifically, it is a value measured by the following method.
First, the toner particles to be measured are collected by suction, a flat flow is formed, a flash image is instantaneously emitted, a particle image is captured as a still image, and the particle image is analyzed (Sysmex). FPIA-3000 manufactured by the company). The number of samplings for obtaining the average circularity is 3500.
When the toner has an external additive, the toner (developer) to be measured is dispersed in water containing a surfactant and then subjected to ultrasonic treatment to obtain toner particles from which the external additive has been removed. .

(External additive)
-Specific silica particles-
The specific silica particles may be silica, that is, particles containing SiO ₂ as a main component, and may be crystalline or amorphous. In addition, the specific silica particles may be particles produced from a silicon compound such as water glass or alkoxysilane, or may be particles obtained by pulverizing quartz. Examples of the silica particles include sol-gel silica particles, aqueous colloidal silica particles, alcoholic silica particles, fumed silica particles obtained by a gas phase method, and fused silica particles. Among them, the specific silica particles are preferably sol-gel silica particles from the viewpoint of satisfying the following characteristics.

The specific silica particles are preferably monodispersed and spherical. The monodispersed spherical silica particles are dispersed in a nearly uniform state on the toner particle surface, and a stable spacer effect can be obtained.
Here, the definition of monodispersion is discussed in terms of standard deviation with respect to the average particle diameter including aggregates, and the standard deviation is preferably volume average particle diameter D50 × 0.22 or less. Further, the definition of the spherical shape is discussed in terms of the average circularity described later.

-Volume average primary particle size The volume average primary particle size of the specific silica particles is 80 nm or more and 200 nm or less. More preferably, it is 100 nm or more and 150 nm or less, More preferably, it is 110 nm or more and 130 nm or less.
When the volume average primary particle size of the specific silica particles is in the above range, the release of the silica particles from the toner particles is appropriately controlled as compared with the case where the volume average primary particle size is smaller than the above range, and the silica particles on the surface of the image carrier are controlled. The required amount is also adjusted to an appropriate range. As a result, the scraping ability of the lubricant film is obtained, and the difference in film thickness between the lubricant film formed on the image portion and the lubricant film formed on the non-image portion on the surface of the image carrier is suppressed.
In addition, since the volume average primary particle size of the specific silica particles is in the above range, the silica particles are not excessively released from the toner particles as compared with the case where the volume average primary particle size is larger than the above range. The scraping ability is moderately controlled, and image defects generated at the boundary between the image portion and the non-image portion are suppressed.

The average particle diameter of the silica particles is measured by the following method.
The primary particles of the silica particles are observed with a scanning electron microscope SEM (Scanning Electron Microscope) device (manufactured by Hitachi, Ltd .: S-4100) to take an image, and this image is taken as an image analysis device (LUZEXIII, (stock) ) (Manufactured by Nireco), the area of each particle is measured by image analysis of primary particles, and the equivalent circle diameter is calculated from the area value. The calculation of the equivalent circle diameter is performed for 100 silica particles. The 50% diameter (D50) in the volume-based cumulative frequency of the obtained equivalent circle diameter is defined as the average primary particle diameter (average equivalent circle diameter D50) of the silica particles. Note that the magnification of the electron microscope is adjusted so that about 10 to 50 silica particles are captured in one field of view, and the equivalent circle diameter of the primary particles is obtained by observing a plurality of fields of view.

-Average circularity The average circularity of the specific silica particles is preferably from 0.75 to 1.0, more preferably from 0.9 to 1.0, and even more preferably from 0.92 to 0.98.
By setting the average circularity of the specific silica particles to 0.75 or more, the silica particles become more spherical, and the scraping ability of the lubricant film is not too strong and is controlled within an appropriate range. As a result, even when the same image (a) is continuously formed and a halftone image (b) different from the image (a) is output, the image portion and non-image of the image (a) are output. Image defects at the boundary with the part are suppressed. In addition, the contamination of the lubricant is suppressed, the adhesion of deposits such as discharge products to the surface of the image carrier is suppressed, and the occurrence of image defects due to the deposits is also suppressed.

Here, the average circularity of the silica particles is measured by the following method.
First, the circularity of the silica particles is obtained as “100 / SF2” calculated by the following formula from the planar image analysis of the primary particles obtained by observing the primary particles of the silica particles with an SEM apparatus.
Formula: Circularity (100 / SF2) = 4π × (A / I ² )
[In the formula, I represents the perimeter of the primary particles on the image, and A represents the projected area of the primary particles. ]
The average circularity of the silica particles is obtained as 50% circularity in the cumulative frequency of 100 primary particles obtained by the planar image analysis.

-Surface treatment The surface of the specific silica particles is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of silica particles, for example.

-Lubricant particles-
In the toner according to the exemplary embodiment, negatively chargeable lubricant particles N and positively chargeable lubricant particles P are used in combination. Here, “negative chargeability” and “positive chargeability” mean whether the toner is charged negatively (−) or positively (+) when the toner is charged in the developing device.

Examples of the positively chargeable lubricant particles P include fatty acid metal salt particles. The fatty acid metal salt particle is a salt particle composed of a fatty acid and a metal.
The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. Examples of the fatty acid include fatty acids having 10 to 25 (preferably 12 to 22) carbon atoms. In addition, carbon number of a fatty acid contains carbon of a carboxy group.
Examples of the fatty acid include saturated fatty acids such as behenic acid, stearic acid, palmitic acid, myristic acid and lauric acid; and unsaturated fatty acids such as oleic acid, linoleic acid and ricinoleic acid. Among these fatty acids, stearic acid and lauric acid are preferable, and stearic acid is more preferable.
As the metal, a divalent metal is preferable. Examples of the metal include magnesium, calcium, aluminum, barium, and zinc. Among these, the metal is preferably zinc.

Examples of the fatty acid metal salt particles include aluminum stearate, calcium stearate, potassium stearate, magnesium stearate, barium stearate, lithium stearate, zinc stearate, copper stearate, lead stearate, nickel stearate, stearic acid. Metal salts of stearic acid such as strontium, cobalt stearate, sodium stearate; metal salts of palmitic acid such as zinc palmitate, cobalt palmitate, copper palmitate, magnesium palmitate, aluminum palmitate, calcium palmitate; lauric acid Metal salts of lauric acid such as zinc, manganese laurate, calcium laurate, iron laurate, magnesium laurate, aluminum laurate; zinc oleate, olei Metal salts of oleic acid such as manganese acid, iron oleate, aluminum oleate, copper oleate, magnesium oleate, calcium oleate; metal salts of linoleic acid such as zinc linoleate, cobalt linoleate, calcium linoleate; ricinol Examples of such particles include metal salts of ricinoleic acid such as zinc acid and aluminum ricinoleate.
Among the fatty acid metal salt particles, metal particles of stearic acid or metal salts of lauric acid are preferable, zinc stearate or zinc laurate particles are more preferable, and zinc stearate particles are more preferable.

Examples of the negatively chargeable lubricant particles N include fluorine resin particles, silicon resin, inorganic particles, and wax resin particles.
Examples of the fluororesin particles include polytetrafluoroethylene (PTFE, “tetrafluoroethylene resin”), perfluoroalkoxy fluororesin, polychlorotrifluoroethylene, polyvinylidene fluoride, polydichlorodifluoroethylene, tetrafluoroethylene-per Fluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-perfluoroalkoxy Examples thereof include particles such as an ethylene copolymer.
Among these, polytetrafluoroethylene (PTFE) is preferable.

-Particle size The average particle size of the lubricant particles P is preferably from 0.1 µm to 50 µm, more preferably from 1 µm to 20 µm, and even more preferably from 1 µm to 10 µm.
The average particle diameter of the lubricant particles N is preferably 100 nm to 1000 nm, more preferably 100 nm to 400 nm, and still more preferably 200 nm to 400 nm.

Here, the average particle diameters of the lubricant particles P and the lubricant particles N are measured by the following method.
The primary particles of the lubricant particles P and the lubricant particles N are observed with a scanning electron microscope SEM (Scanning Electron Microscope) device (manufactured by Hitachi, Ltd .: S-4100), and images are taken. The image is taken into an image analyzer (LUZEXIII, manufactured by Nireco Co., Ltd.), the area of each particle is measured by image analysis of primary particles, and the equivalent circle diameter is calculated from the area value. The calculation of the equivalent circle diameter is performed for 100 pieces. Then, the 50% diameter (D50) in the volume-based cumulative frequency of the obtained equivalent circle diameter is defined as the average primary particle diameter (average equivalent circle diameter D50) of the lubricant particles P and the lubricant particles N. In the electron microscope, the magnification is adjusted so that about 10 or more and 50 or less lubricant particles P and lubricant particles N appear in one field of view, and the equivalent circle diameter of the primary particles is determined by observing multiple fields of view. .

-Content of each particle with respect to toner particles-
The content of the specific silica particles with respect to the toner particles (hereinafter also referred to as “specific silica content”) is 0.5% by mass or more and 3.0% by mass or less, and 1.0% by mass or more and 2.5% by mass or less. Is preferable, and 1.5 mass% or more and 2.0 mass% or less are more preferable.
When the content of the specific silica particles is 0.5% by mass or more, the supply amount of the silica particles to the tip of the cleaning unit is easily secured. When the content of the silica particles is 3.0% by mass or less, excessive release of the silica particles from the toner particles is suppressed, and the lubricant film is hardly scraped off on the surface of the image carrier.

The content of the lubricant particles P with respect to the toner particles (hereinafter also referred to as “lubricant particle P content”) is 0.001% by mass to 0.5% by mass, and 0.005% by mass to 0.05%. % By mass or less is preferable, and 0.01% by mass or more and 0.03% by mass or less is more preferable.
By setting the content of the lubricant particles P to be equal to or higher than the above lower limit value, it becomes easy to secure the supply amount of the lubricant particles P to the non-image area when the negatively charged toner particles are used. By setting the content of the lubricant particles P to the above upper limit or less, the supply amount of the lubricant particles P to the non-image area is not excessive, and the film thickness of the lubricant film between the image area and the non-image area. The difference is suppressed, and only a part of the thickness (lubricant contamination) is also suppressed.

The content of the lubricant particles N with respect to the toner particles (hereinafter also referred to as “lubricant particle N content”) is 0.005% by mass or more and 0.5% by mass or less, and 0.05% by mass or more and 0.5% by mass or less. It is preferable that it is mass% or less, 0.10 mass% or more and 0.40 mass% or less are more preferable, and 0.15 mass% or more and 0.30 mass% or less are still more preferable.
By setting the content of the lubricant particles N to be equal to or higher than the lower limit, when the negatively charged toner particles are used, the supply amount of the lubricant particles N to the image portion is easily secured. By setting the content of the lubricant particles N to be equal to or less than the above upper limit value, the supply amount of the lubricant particles N to the image portion is not excessive, and the film thickness difference of the lubricant film between the image portion and the non-image portion. In addition, the thickness of only a part (lubricant contamination) is also suppressed.

The specific silica content, the lubricant particle P content, and the lubricant particle N content in the toner are measured by the following methods, respectively.
The specific silica content is quantified by fluorescent X-ray measurement. In addition, when silica particles other than the average particle diameter of 80 nm or more and 200 nm or less are included, the silica particles are identified by SEM-EDX (energy dispersive X-ray spectroscopy), and the identified silica particles are subjected to image processing. The particle size distribution is obtained, and the fluorescent X-ray dose is corrected by the particle size difference of the silica particles from the ratio of 80 nm to 200 nm obtained from the particle size distribution and the content of all silica particles quantified by fluorescent X-ray measurement. That is what is required.
For example, in the case of a fatty acid metal salt, the lubricant particle P content is quantified by fluorescent X-ray measurement. In the case of zinc stearate, Zn will be measured.
For example, in the case of fluororesin particles, the content of the lubricant particles N is quantified by fluorescent X-ray measurement.

The specific silica content, the lubricant particle N content, and the lubricant particle P content preferably satisfy the relationship of the following formulas 4 and 5.
Formula 4 0.002 ≦ Lubricant Particle P Content / Specific Silica Content ≦ 0.2
Formula 5 0.02 ≦ Lubricant particle N content / specific silica content ≦ 0.5
By satisfying both Equation 4 and Equation 5, even when the same image (a) is output continuously, the image carrier thickness at the boundary between the image portion and the non-image portion of the image (a) As a result, even when the halftone image (b) is output after the image (a) is continuously formed, the boundary between the image portion and the non-image portion of the image (a) is reduced. Image defects in the portion are suppressed.

The relationship among the specific silica content, the lubricant particle N content, and the lubricant particle P content more preferably satisfies the relationship of the following formula 4-1 and formula 5-1, and the following formula 4-2 and formula 5 -2 is more preferably satisfied.
Formula 4-1 0.005 ≦ Lubricant Particle P Content / Specific Silica Content ≦ 0.050
Formula 5-1 0.02 ≦ Lubricant particle N content / specific silica content ≦ 0.40

Formula 4-2 0.005 ≦ Lubricant Particle P Content / Specific Silica Content ≦ 0.020
Formula 5-2 0.05 ≦ N content of lubricant particles / specific silica content ≦ 0.30

-Free rate of each particle after ultrasonic treatment in aqueous dispersion-
The liberation rate s% by mass of the specific silica particles after ultrasonic treatment in the aqueous dispersion is 5% by mass to 50% by mass, preferably 10% by mass to 30% by mass, and more preferably 15% by mass or more. More preferably, it is 25 mass% or less.
When the release rate of the silica particles is in the above range, scraping of the lubricant film by the silica particles is appropriately controlled, and the occurrence of a difference in film thickness of the image carrier between the image area and the non-image area is suppressed. Moreover, adhesion of deposits such as discharge products is easily suppressed.

The liberation rate p% by mass of the lubricant particles P after ultrasonication in the aqueous dispersion is preferably 0.5% by mass or more and 47.5% by mass or less, and more preferably 0.5% by mass or more and 37.5% by mass. % Or less, more preferably 1.0% by mass or more and 25% by mass or less.
When the liberation rate of the lubricant particles P is in the above range, formation of the lubricant film on the surface of the image carrier by the lubricant particles P is appropriately controlled, and the image carrier in the image portion and the non-image portion is controlled. Occurrence of a film thickness difference is suppressed, and adhesion of deposits such as discharge products is easily suppressed.

The liberation ratio n% by mass of the lubricant particles N after ultrasonication in the aqueous dispersion is preferably 0.5% by mass to 47.5%, and more preferably 0.5% to 37.5%. More preferably, it is 1.0% or more and 25% or less.
When the liberation rate of the lubricant particles N is in the above range, formation of the lubricant film on the surface of the image carrier by the lubricant particles N is appropriately controlled, and the image carrier and the non-image part are formed in the image carrier. Occurrence of a film thickness difference is suppressed, and adhesion of deposits such as discharge products is easily suppressed.

  As described above, the relationship between the liberation rate s% by mass of the specific silica particles, the liberation rate n% by mass of the lubricant particles N, and the liberation rate p% by mass of the lubricant particles P satisfies Equations 1 to 3, and It is preferable to satisfy 2-1 and Formula 3-1, and it is more preferable to satisfy Formula 2-2 and Formula 3-2.

Formula 1 5 ≦ s ≦ 50
Formula 2 0.10 ≦ p / s ≦ 0.95
Formula 3 0.10 ≦ n / s ≦ 0.95

Formula 2-1 0.10 ≦ p / s ≦ 0.75
Formula 3-1 0.10 ≦ n / s ≦ 0.75

Formula 2-2 0.20 ≦ p / s ≦ 0.50
Formula 3-2 0.20 ≦ n / s ≦ 0.50

The release rate of each particle from the toner particles is adjusted, for example, by the material and particle size of the toner particles, the material and particle size of each particle, the external addition conditions when each particle is externally added to the toner particle surface, and the like. It is controlled by. In particular, each particle (specific silica particles, lubricant particles N, and lubricant particles P) is added to the toner particles, the stirring speed and the stirring time are adjusted, and the temperature of the mixture is controlled during the stirring. Thus, the liberation rates of the silica particles, the lubricant particles N, and the lubricant particles P can be controlled within the above ranges, respectively. Also, when you want to change only the amount of the desired external additive, multi-stage mixing or the method of externally adding the external additive to the toner particles together with other external additives after previously pulverizing the external additive alone and so on.
For example, as described above, a method in which the liberation rate n mass% of the lubricant particles N and the liberation rate p mass% of the lubricant particles P are relatively low, and the liberation rate s mass% of the specific silica particles is relatively high. Examples of the method include two-stage mixing in which the mixing is performed in two stages. Specifically, for example, the toner particles, the lubricant particles N, and the lubricant particles P are mixed and stirred for a long time at a high stirring speed. Of stirring. Note that three-stage mixing in which the lubricant particles P, the lubricant particles N, and the specific silica particles are sequentially added to the toner particles may be performed.

-Charged row of each particle in toner-
In the present embodiment, the toner particles, the specific silica particles, the lubricant particles P, and the lubricant particles N included in the toner are charged based on the relationship between positive and negative charges and the magnitude of the charge. It is preferable to satisfy the following relationship.
(Plus charge) “Lubricant particles P”> “Toner particles”
>"Specific silica particles and lubricant particles N" (negative charge)

In this embodiment, the measurement of the charge train of toner particles, specific silica particles, lubricant particles P, and lubricant particles N is performed using four standard carriers distributed by the Japan Imaging Society Technical Committee, using the Japan Imaging Society standard toner. It is performed by a method based on the charge amount measurement method (blow-off measurement method). Specifically, it is as follows.
Two carriers, P-01 and P-02, coated with a resin containing a fluorine atom-containing resin as a positively chargeable carrier were set, and N-01 coated with an acrylic resin as a negatively chargeable carrier. Two types of carriers N-02 are set. 10 g of each carrier and 0.5 g of each particle (that is, one particle of toner particles, specific silica particles, lubricant particles P and lubricant particles N) are mixed to measure the charge amount, and the zero point Using the charge method, the value on the Y-axis when X = 0 is defined as a charge train (standard chargeability).

-Other external additives-
Examples of other external additives include silica particles having a volume average primary particle size of 80 nm to 200 nm and inorganic particles other than the lubricant particles.
As other inorganic particles, SiO ₂ (however, the volume average primary particle size is less than 80 nm or more than 200 nm), TiO ₂ , CuO, SnO ₂ , Fe ₂ O ₃ , BaO, CaO, K ₂ O, Na ₂ O, CaO.SiO ₂ , K ₂ O. (TiO ₂ ) n, Al ₂ O ₃ .2SiO ₂ , MgCO ₃ , BaSO ₄ , MgSO _{4 and the} like.

The surface of other inorganic particles is preferably subjected to a hydrophobic treatment. The hydrophobic treatment is performed, for example, by immersing inorganic particles in a hydrophobic treatment agent. The hydrophobizing agent is not particularly limited, and examples thereof include silane coupling agents, silicone oils, titanate coupling agents, aluminum coupling agents and the like. These may be used individually by 1 type and may use 2 or more types together.
The amount of the hydrophobizing agent is usually 1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of other inorganic particles, for example.

  The external addition amount (content) of other external additives is preferably 0.5% by mass or more and 5.0% by mass or less, and preferably 2.0% by mass or more and 3.0% by mass with respect to the toner particles. The following is more preferable.

(Toner production method)
Next, a toner manufacturing method according to this embodiment will be described.
The toner according to the exemplary embodiment can be obtained by externally adding an external additive to the toner particles after the toner particles are manufactured.

The toner particles may be produced by any of a dry production method (for example, a kneading and pulverizing method) and a wet production method (for example, an aggregation coalescence method, a suspension polymerization method, a dissolution suspension method, etc.). The production method of the toner particles is not particularly limited, and a known production method is adopted.
Among these, it is preferable to obtain toner particles by an aggregation and coalescence method.

Specifically, for example, when toner particles are produced by an aggregation coalescence method,
A step of preparing a resin particle dispersion in which resin particles to be a binder resin are dispersed (resin particle dispersion preparation step), and a resin particle dispersion (after mixing other particle dispersions as necessary) In the dispersion), the resin particles (other particles as necessary) are aggregated to form aggregated particles (aggregated particle formation step), and the aggregated particle dispersion in which the aggregated particles are dispersed is heated. Then, toner particles are manufactured through a process of fusing and coalescing the aggregated particles to form toner particles (fusing and coalescing process).

Details of each step will be described below.
In the following description, a method of obtaining toner particles containing a colorant and a release agent will be described. However, the colorant and the release agent are used as necessary. Of course, you may use other additives other than a coloring agent and a mold release agent.

-Preparation step of resin particle dispersion-
First, together with a resin particle dispersion in which resin particles serving as a binder resin are dispersed, for example, a colorant particle dispersion in which colorant particles are dispersed and a release agent particle dispersion in which release agent particles are dispersed are prepared. To do.

  Here, the resin particle dispersion is prepared, for example, by dispersing resin particles in a dispersion medium using a surfactant.

Examples of the dispersion medium used for the resin particle dispersion include an aqueous medium.
Examples of the aqueous medium include water such as distilled water and ion exchange water, and alcohols. These may be used individually by 1 type and may use 2 or more types together.

Examples of the surfactant include anionic surfactants such as sulfate ester, sulfonate, phosphate, and soap; cationic surfactants such as amine salt type and quaternary ammonium salt type; polyethylene glycol And nonionic surfactants such as polyphenols, alkylphenol ethylene oxide adducts, and polyhydric alcohols. Among these, an anionic surfactant and a cationic surfactant are particularly mentioned. The nonionic surfactant may be used in combination with an anionic surfactant or a cationic surfactant.
Surfactant may be used individually by 1 type and may use 2 or more types together.

Examples of the method for dispersing the resin particles in the dispersion medium in the resin particle dispersion include a general dispersion method such as a rotary shear homogenizer, a ball mill having media, a sand mill, and a dyno mill. Depending on the type of resin particles, the resin particles may be dispersed in the resin particle dispersion using, for example, a phase inversion emulsification method.
The phase inversion emulsification method is a method in which a resin to be dispersed is dissolved in a hydrophobic organic solvent in which the resin is soluble, and a base is added to the organic continuous phase (O phase) to neutralize the aqueous medium. (W phase) is added to convert the resin from W / O to O / W (so-called phase inversion) to form a discontinuous phase and disperse the resin in an aqueous medium in the form of particles. It is.

The volume average particle size of the resin particles dispersed in the resin particle dispersion is, for example, preferably 0.01 μm to 1 μm, more preferably 0.08 μm to 0.8 μm, and further preferably 0.1 μm to 0.6 μm. preferable.
In addition, the volume average particle diameter of the resin particles is based on the particle size range (channel) divided by using the particle size distribution obtained by measurement with a laser diffraction particle size distribution measuring apparatus (for example, LA-700 manufactured by Horiba, Ltd.). The cumulative distribution is subtracted from the small particle diameter side with respect to the volume, and the particle diameter that becomes 50% cumulative with respect to all the particles is measured as the volume average particle diameter D50v. The volume average particle size of particles in other dispersions is also measured in the same manner.

  As content of the resin particle contained in a resin particle dispersion liquid, 5 to 50 mass% is preferable, for example, and 10 to 40 mass% is more preferable.

  For example, a colorant particle dispersion and a release agent particle dispersion are also prepared in the same manner as the resin particle dispersion. In other words, regarding the volume average particle diameter of the particles in the resin particle dispersion, the dispersion medium, the dispersion method, and the content of the particles, the colorant particles dispersed in the colorant particle dispersion and the release agent particle dispersion The same applies to the release agent particles to be dispersed.

-Aggregated particle formation process-
Next, the colorant particle dispersion and the release agent particle dispersion are mixed together with the resin particle dispersion.
Then, in the mixed dispersion, resin particles, colorant particles, and release agent particles are hetero-aggregated to have resin particles, colorant particles, and release agent particles having a diameter close to the diameter of the target toner particles. Aggregated particles are formed.

Specifically, for example, the flocculant is added to the mixed dispersion, and the pH of the mixed dispersion is adjusted to acidic (for example, the pH is 2 or more and 5 or less), and a dispersion stabilizer is added as necessary. The resin particles are heated to a glass transition temperature (specifically, for example, the glass transition temperature of the resin particles −30 ° C. or more and the glass transition temperature −10 ° C. or less), and the particles dispersed in the mixed dispersion liquid are aggregated. , Forming aggregated particles.
In the agglomerated particle forming step, for example, the aggregating agent is added at room temperature (for example, 25 ° C.) while stirring the mixed dispersion with a rotary shearing homogenizer, and the pH of the mixed dispersion is acidic (for example, the pH is 2 or more and 5 or less). ), And after adding a dispersion stabilizer as necessary, the heating may be performed.

Examples of the flocculant include a surfactant having a polarity opposite to that of the surfactant used as the dispersant added to the mixed dispersion, an inorganic metal salt, and a divalent or higher-valent metal complex. In particular, when a metal complex is used as the flocculant, the amount of the surfactant used is reduced, and the charging characteristics are improved.
If necessary, an additive that forms a complex or a similar bond with the metal ion of the flocculant may be used. As this additive, a chelating agent is preferably used.

Examples of inorganic metal salts include metal salts such as calcium chloride, calcium nitrate, barium chloride, magnesium chloride, zinc chloride, aluminum chloride, and aluminum sulfate, and inorganic substances such as polyaluminum chloride, polyaluminum hydroxide, and calcium polysulfide. Examples thereof include metal salt polymers.
A water-soluble chelating agent may be used as the chelating agent. Examples of the chelating agent include oxycarboxylic acids such as tartaric acid, citric acid, and gluconic acid, iminodiacid (IDA), nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), and the like.
As addition amount of a chelating agent, 0.01 mass part or more and 5.0 mass part or less are preferable with respect to 100 mass parts of resin particles, for example, and 0.1 mass part or more and less than 3.0 mass parts are more preferable.

-Fusion / unification process-
Next, the aggregated particle dispersion in which the aggregated particles are dispersed is heated to, for example, a glass transition temperature or higher of the resin particles (for example, a temperature of 10 to 30 ° C. higher than the glass transition temperature of the resin particles). Are fused and united to form toner particles.

Through the above steps, toner particles are obtained.
In addition, after obtaining the aggregated particle dispersion liquid in which the aggregated particles are dispersed, the aggregated particle dispersion liquid and the resin particle dispersion liquid in which the resin particles are dispersed are further mixed, and the resin particles are further added to the surface of the aggregated particles. A process of aggregating to adhere to form second aggregated particles, and heating the second aggregated particle dispersion in which the second aggregated particles are dispersed to fuse and coalesce the second aggregated particles. The toner particles may be manufactured through a step of forming toner particles having a core / shell structure.

Here, after completion of the fusion / unification process, toner particles formed in the solution are dried through a known washing process, solid-liquid separation process, and drying process to obtain toner particles.
In the washing step, it is preferable to sufficiently carry out substitution washing with ion-exchanged water from the viewpoint of chargeability. The solid-liquid separation step is not particularly limited, but suction filtration, pressure filtration, etc. are preferably performed from the viewpoint of productivity. In addition, the drying process is not particularly limited, but from the viewpoint of productivity, freeze drying, airflow drying, fluidized drying, vibration fluidized drying, or the like is preferably performed.

  The toner according to the exemplary embodiment is manufactured, for example, by adding an external additive to the obtained dry toner particles and mixing them. Mixing may be performed by, for example, a V blender, a Henschel mixer, a Laedige mixer, or the like. Further, if necessary, coarse toner particles may be removed using a vibration sieving machine, a wind sieving machine, or the like.

<Electrostatic image developer>
The electrostatic charge image developer according to the exemplary embodiment includes at least the toner according to the exemplary embodiment.
The electrostatic image developer according to this embodiment may be a one-component developer including only the toner according to this embodiment, or may be a two-component developer mixed with the toner and a carrier.

There is no restriction | limiting in particular as a carrier, A well-known carrier is mentioned. As a carrier, for example, a coated carrier in which the surface of a core made of magnetic powder is coated with a coating resin; a magnetic powder dispersion type carrier in which magnetic powder is dispersed and mixed in a matrix resin; a porous magnetic powder is impregnated with a resin Resin impregnated type carriers; and the like.
Note that the magnetic powder-dispersed carrier and the resin-impregnated carrier may be a carrier in which the constituent particles of the carrier are used as a core material and coated with a coating resin.

  Examples of the magnetic powder include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite.

Examples of the coating resin and matrix resin include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester. Examples thereof include a straight silicone resin comprising a copolymer, an organosiloxane bond, or a modified product thereof, a fluororesin, a polyester, a polycarbonate, a phenol resin, and an epoxy resin.
The coating resin and matrix resin may contain other additives such as conductive particles.
Examples of the conductive particles include particles of metals such as gold, silver, and copper, carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate.

Here, in order to coat the surface of the core material with the coating resin, a method of coating with a coating layer forming solution obtained by dissolving the coating resin and, if necessary, various additives in an appropriate solvent may be mentioned. The solvent is not particularly limited, and may be selected in consideration of the coating resin to be used, coating suitability, and the like.
Specific resin coating methods include a dipping method in which the core material is immersed in the coating layer forming solution, a spray method in which the coating layer forming solution is sprayed on the surface of the core material, and a state in which the core material is suspended by flowing air. Examples thereof include a fluidized bed method in which a coating layer forming solution is sprayed, a kneader coater method in which a carrier core material and a coating layer forming solution are mixed in a kneader coater, and the solvent is removed.

  The mixing ratio (mass ratio) of the toner and the carrier in the two-component developer is preferably toner: carrier = 1: 100 to 30: 100, and more preferably 3: 100 to 20: 100.

<Image Forming Apparatus / Image Forming Method>
The image forming apparatus / image forming method according to the present embodiment will be described.
The image forming apparatus according to the present embodiment includes an image carrier, a charging unit that charges the surface of the image carrier, an electrostatic image forming unit that forms an electrostatic image on the surface of the charged image carrier, and an electrostatic charge. Development means for containing an image developer and developing the electrostatic image formed on the surface of the image carrier as a toner image with the electrostatic image developer, and the toner image formed on the surface of the image carrier as a recording medium A transfer unit that transfers the toner image transferred onto the surface of the recording medium, and a fixing unit that fixes the toner image transferred onto the surface of the recording medium. The electrostatic charge image developer according to this embodiment is applied as the electrostatic charge image developer.

  In the image forming apparatus according to this embodiment, a charging process for charging the surface of the image carrier, an electrostatic charge image forming process for forming an electrostatic image on the surface of the charged image carrier, and an electrostatic charge according to this embodiment. A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with an image developer; a transfer step of transferring the toner image formed on the surface of the image carrier to the surface of the recording medium; An image forming method (an image forming method according to this embodiment) including a cleaning process for cleaning the surface of the image carrier with a cleaning blade and a fixing process for fixing the toner image transferred to the surface of the recording medium is performed. The

The image forming apparatus according to the present embodiment is a direct transfer type apparatus that directly transfers a toner image formed on the surface of an image carrier to a recording medium; the toner image formed on the surface of the image carrier is transferred to an intermediate transfer member Intermediate transfer system device that primarily transfers the toner image transferred to the surface of the intermediate transfer body to the surface of the intermediate transfer body; then neutralizes the image on the surface of the image carrier after the toner image is transferred and before charging. A well-known image forming apparatus such as an apparatus provided with a neutralizing unit that performs neutralization by irradiating is applied.
In the case of an intermediate transfer type apparatus, the transfer means includes, for example, an intermediate transfer body on which a toner image is transferred to the surface, and a primary transfer that primarily transfers the toner image formed on the surface of the image holding body to the surface of the intermediate transfer body. And a secondary transfer unit that secondarily transfers the toner image transferred onto the surface of the intermediate transfer member onto the surface of the recording medium.

  In the image forming apparatus according to the present embodiment, for example, the part including the developing unit may have a cartridge structure (process cartridge) that is detachable from the image forming apparatus. As the process cartridge, for example, a process cartridge including a developing unit containing the electrostatic charge image developer according to the present embodiment is preferably used.

  Hereinafter, an example of the image forming apparatus according to the present embodiment will be described, but the present invention is not limited thereto. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 1 is a schematic configuration diagram illustrating an image forming apparatus according to the present embodiment.
The image forming apparatus shown in FIG. 1 is a first to first electrophotographic method that outputs yellow (Y), magenta (M), cyan (C), and black (K) images based on color-separated image data. Fourth image forming units 10Y, 10M, 10C, and 10K (image forming means) are provided. These image forming units (hereinafter sometimes simply referred to as “units”) 10Y, 10M, 10C, and 10K are arranged in parallel at a predetermined distance from each other in the horizontal direction. The units 10Y, 10M, 10C, and 10K may be process cartridges that are detachable from the image forming apparatus.

Above each of the units 10Y, 10M, 10C, and 10K, an intermediate transfer belt 20 as an intermediate transfer member is extended through each unit. The intermediate transfer belt 20 is provided by being wound around a drive roll 22 and a support roll 24 that are in contact with the inner surface of the intermediate transfer belt 20 that are spaced apart from each other in the left to right direction in the drawing. The vehicle travels in the direction toward the unit 10K. The support roll 24 is applied with a force in a direction away from the drive roll 22 by a spring or the like (not shown), and tension is applied to the intermediate transfer belt 20 wound around the support roll 24. An intermediate transfer member cleaning device 30 is provided on the side of the image carrier of the intermediate transfer belt 20 so as to face the drive roll 22.
Further, each of the developing devices (developing means) 4Y, 4M, 4C, and 4K of the units 10Y, 10M, 10C, and 10K has yellow, magenta, cyan, and black contained in the toner cartridges 8Y, 8M, 8C, and 8K. The toner including the four color toners is supplied.

  Since the first to fourth units 10Y, 10M, 10C, and 10K have the same configuration, here, the first unit that forms a yellow image disposed on the upstream side in the intermediate transfer belt traveling direction. 10Y will be described as a representative. It should be noted that reference numerals with magenta (M), cyan (C), and black (K) are attached to the same parts as those of the first unit 10Y instead of yellow (Y). Description of the units 10M, 10C, and 10K will be omitted.

The first unit 10Y includes a photoreceptor 1Y that functions as an image holding member. Around the photoreceptor 1Y, a charging roll (an example of a charging unit) 2Y that charges the surface of the photoreceptor 1Y to a predetermined potential, and the charged surface is exposed by a laser beam 3Y based on the color-separated image signal. Then, an exposure device (an example of an electrostatic image forming unit) 3 that forms an electrostatic image, and a developing device (an example of a developing unit) 4Y that develops the electrostatic image by supplying toner charged to the electrostatic image, developed A photoreceptor cleaning device having a primary transfer roll 5Y (an example of a primary transfer unit) that transfers a toner image onto the intermediate transfer belt 20, and a cleaning blade 6Y-1 that removes toner remaining on the surface of the photoreceptor 1Y after the primary transfer. (Example of cleaning means) 6Y are arranged in order.
The primary transfer roll 5Y is disposed inside the intermediate transfer belt 20, and is provided at a position facing the photoreceptor 1Y. Further, a bias power source (not shown) for applying a primary transfer bias is connected to each of the primary transfer rolls 5Y, 5M, 5C, and 5K. Each bias power source varies the transfer bias applied to each primary transfer roll under the control of a control unit (not shown).

Hereinafter, an operation of forming a yellow image in the first unit 10Y will be described.
First, prior to operation, the surface of the photoreceptor 1Y is charged to a potential of −600V to −800V by the charging roll 2Y.
The photoreceptor 1Y is formed by laminating a photosensitive layer on a conductive substrate (for example, volume resistivity at 20 ° C .: 1 × 10 ⁻⁶ Ωcm or less). This photosensitive layer usually has a high resistance (general resin resistance), but has a property that the specific resistance of the portion irradiated with the laser beam changes when irradiated with the laser beam 3Y. Therefore, a laser beam 3Y is output to the surface of the charged photoreceptor 1Y via the exposure device 3 in accordance with yellow image data sent from a control unit (not shown). The laser beam 3Y is applied to the photosensitive layer on the surface of the photoreceptor 1Y, whereby an electrostatic charge image having a yellow image pattern is formed on the surface of the photoreceptor 1Y.

The electrostatic charge image is an image formed on the surface of the photoreceptor 1Y by charging, and the specific resistance of the irradiated portion of the photosensitive layer is lowered by the laser beam 3Y, and the charged charge on the surface of the photoreceptor 1Y flows. On the other hand, this is a so-called negative latent image formed by the charge remaining in the portion not irradiated with the laser beam 3Y.
The electrostatic charge image formed on the photoreceptor 1Y is rotated to a predetermined development position as the photoreceptor 1Y travels. At this development position, the electrostatic charge image on the photoreceptor 1Y is visualized (developed image) as a toner image by the developing device 4Y.

  In the developing device 4Y, for example, an electrostatic charge image developer containing at least yellow toner and a carrier is accommodated. The yellow toner is triboelectrically charged by being agitated inside the developing device 4Y, and has a charge of the same polarity (negative polarity) as the charged electric charge on the photoreceptor 1Y, and has a developer roll (a developer holding member). Example) is held on. As the surface of the photoreceptor 1Y passes through the developing device 4Y, the yellow toner is electrostatically attached to the latent image portion on the surface of the photoreceptor 1Y, and the latent image is developed with the yellow toner. . The photoreceptor 1Y on which the yellow toner image is formed continues to run at a predetermined speed, and the toner image developed on the photoreceptor 1Y is conveyed to a predetermined primary transfer position.

When the yellow toner image on the photoreceptor 1Y is conveyed to the primary transfer, a primary transfer bias is applied to the primary transfer roll 5Y, and an electrostatic force from the photoreceptor 1Y toward the primary transfer roll 5Y is applied to the toner image, so that the photoreceptor is exposed. The toner image on 1Y is transferred onto the intermediate transfer belt 20. The transfer bias applied at this time has a (+) polarity opposite to the polarity (−) of the toner, and is controlled to +10 μA by the control unit (not shown) in the first unit 10Y, for example.
On the other hand, the toner remaining on the photoreceptor 1Y is removed and collected by the photoreceptor cleaning device 6Y.

Further, the primary transfer bias applied to the primary transfer rolls 5M, 5C, and 5K after the second unit 10M is also controlled in accordance with the first unit.
Thus, the intermediate transfer belt 20 onto which the yellow toner image has been transferred by the first unit 10Y is sequentially conveyed through the second to fourth units 10M, 10C, and 10K, and the toner images of the respective colors are superimposed and transferred in a multiple manner. The

  The intermediate transfer belt 20 on which the four color toner images are transferred in multiple ways through the first to fourth units is disposed on the image transfer surface side of the intermediate transfer belt 20, the support roll 24 in contact with the inner surface of the intermediate transfer belt 20. The secondary transfer roll (an example of a secondary transfer unit) 26 is formed to a secondary transfer portion configured. On the other hand, recording paper (an example of a recording medium) P is fed at a predetermined timing into a gap where the secondary transfer roll 26 and the intermediate transfer belt 20 are in contact with each other via a supply mechanism, and the secondary transfer bias is supplied to the support roll. 24. The transfer bias applied at this time is a (−) polarity that is the same polarity as the polarity (−) of the toner, and an electrostatic force from the intermediate transfer belt 20 toward the recording paper P is applied to the toner image, so The toner image is transferred onto the recording paper P. The secondary transfer bias at this time is determined according to the resistance detected by a resistance detection means (not shown) for detecting the resistance of the secondary transfer portion, and is voltage-controlled.

  Thereafter, the recording paper P is fed into the pressure contact portions (nip portions) of a pair of fixing rolls in a fixing device (an example of a fixing unit) 28, and the toner image is fixed on the recording paper P to form a fixed image.

Examples of the recording paper P to which the toner image is transferred include plain paper used in electrophotographic copying machines, printers, and the like. In addition to the recording paper P, the recording medium may be an OHP sheet.
In order to further improve the smoothness of the image surface after fixing, the surface of the recording paper P is also preferably smooth. For example, coated paper with the surface of plain paper coated with resin, art paper for printing, etc. are preferably used. Is done.

  The recording paper P on which the color image has been fixed is carried out toward the discharge unit, and a series of color image forming operations is completed.

<Process cartridge / toner cartridge>
The process cartridge according to this embodiment will be described.
The process cartridge according to the present embodiment accommodates the electrostatic image developer according to the present embodiment, and develops the electrostatic image formed on the surface of the image carrier as a toner image by the electrostatic image developer. And a process cartridge that can be attached to and detached from the image forming apparatus.

  Note that the process cartridge according to the present embodiment is not limited to the above-described configuration, and other means such as a developing device and other units such as an image carrier, a charging unit, an electrostatic charge image forming unit, and a transfer unit, if necessary. And at least one selected from the above.

  Hereinafter, an example of the process cartridge according to the present embodiment will be shown, but the present invention is not limited to this. In addition, the main part shown to a figure is demonstrated and the description is abbreviate | omitted about others.

FIG. 2 is a schematic configuration diagram showing a process cartridge according to the present embodiment.
The process cartridge 200 shown in FIG. 2 is provided around the photoconductor 107 and the photoconductor 107 by, for example, a housing 117 provided with an attachment rail 116 and an opening 118 for exposure. A charged roll 108 (an example of a charging unit), a developing device 111 (an example of a developing unit), and a photosensitive member cleaning device 113 (an example of a cleaning unit) having a cleaning blade 113-1 are held in an integrated combination. It is configured and made into a cartridge.
In FIG. 2, 109 is an exposure device (an example of an electrostatic charge image forming unit), 112 is a transfer device (an example of a transfer unit), 115 is a fixing device (an example of a fixing unit), and 300 is a recording paper (a recording medium). An example).

Next, the toner cartridge according to this embodiment will be described.
The toner cartridge according to the present exemplary embodiment is a toner cartridge that accommodates the toner according to the present exemplary embodiment and is detachable from the image forming apparatus. The toner cartridge contains toner for replenishment to be supplied to the developing means provided in the image forming apparatus.

  The image forming apparatus shown in FIG. 1 is an image forming apparatus having a configuration in which toner cartridges 8Y, 8M, 8C, and 8K are attached and detached, and the developing devices 4Y, 4M, 4C, and 4K are each developing devices (colors). And a toner supply pipe (not shown). Further, when the amount of toner stored in the toner cartridge becomes low, the toner cartridge is replaced.

  Hereinafter, although an Example and a comparative example are given and this embodiment is described in detail in detail, this embodiment is not limited to these Examples at all. “Parts” and “%” are based on mass unless otherwise specified.

[Production of toner particles]
(Toner particles (1))
-Preparation of polyester resin dispersion-
・ Ethylene glycol [Wako Pure Chemical Industries, Ltd.] 37 parts ・ Neopentyl glycol [Wako Pure Chemical Industries, Ltd.] 65 parts ・ 1,9 Nonanediol [Wako Pure Chemical Industries, Ltd.] 32 parts ・96 parts of terephthalic acid [manufactured by Wako Pure Chemical Industries, Ltd.] The above monomer was charged into a flask, and the temperature was raised to 200 ° C. over 1 hour. After confirming that the reaction system was stirred, dibutyltin oxide was added. 1.2 parts were added. Further, while distilling off the generated water, the temperature was increased from the same temperature to 240 ° C. over 6 hours, and the dehydration condensation reaction was continued at 240 ° C. for another 4 hours. The acid value was 9.4 mgKOH / g, and the weight average molecular weight. A polyester resin A having a glass transition temperature of 13,000 and 62 ° C. was obtained.

Subsequently, the polyester resin A was transferred in a molten state to Cavitron CD1010 (manufactured by Eurotech Co., Ltd.) at a rate of 100 parts per minute. A 0.37% diluted aqueous ammonia solution obtained by diluting reagent ammonia water with ion-exchanged water is put into a separately prepared aqueous medium tank, and the polyester is heated at 120 ° C. with a heat exchanger at a rate of 0.1 liter per minute. Simultaneously with the resin melt, it was transferred to the Cavitron. The Cavitron is operated under the conditions of a rotor rotation speed of 60 Hz and a pressure of 5 kg / cm ² .
An amorphous polyester resin dispersion in which resin particles having a volume average particle size of 160 nm, a solid content of 30%, a glass transition temperature of 62 ° C., and a weight average molecular weight Mw of 13,000 was obtained was obtained.

-Preparation of colorant particle dispersion-
-Cyan pigment (Pigment Blue 15: 3, manufactured by Dainichi Seika Kogyo Co., Ltd.) 10 parts-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 80 parts The mixture was mixed and dispersed for 1 hour with a high-pressure impact type disperser [HJP30006, manufactured by Sugino Machine Co., Ltd.] to obtain a colorant particle dispersion having a volume average particle size of 180 nm and a solid content of 20%.

-Preparation of release agent particle dispersion-
-Paraffin wax (HNP 9, manufactured by Nippon Seiki Co., Ltd.) 50 parts-Anionic surfactant (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 2 parts-Ion-exchanged water 200 parts After sufficiently mixing and dispersing with Ultra Turrax T50, manufactured by the company, the mixture was dispersed with a pressure discharge homogenizer to obtain a release agent particle dispersion having a volume average particle size of 200 nm and a solid content of 20%.

-Production of toner particles (1)-
・ Polyester resin particle dispersion 200 parts ・ Colorant particle water dispersion 25 parts ・ Releasing agent particle dispersion 30 parts ・ Polyaluminum chloride 0.4 part ・ Ion-exchanged water 100 parts The above ingredients were put into a stainless steel flask. After thoroughly mixing and dispersing using IKA Ultra Turrax, the flask was heated to 45 ° C. with stirring in an oil bath for heating. After maintaining at 45 ° C. for 15 minutes, 70 parts of the same polyester resin dispersion as above was gently added thereto.

Then, after adjusting the pH of the system to 8.0 using a 0.5 mol / L sodium hydroxide aqueous solution, the stainless steel flask was sealed, and the stirring shaft seal was magnetically sealed while stirring was continued. Heat to 90 ° C. and hold for 3 hours. After completion of the reaction, the temperature lowering rate was cooled at 2 ° C./min, filtered, sufficiently washed with ion exchange water, and then subjected to solid-liquid separation by Nutsche suction filtration. This was further redispersed with 3 L of ion exchange water at 30 ° C., and stirred and washed at 300 rpm for 15 minutes. This washing operation was further repeated 6 times, and when the pH of the filtrate became 7.54 and the electric conductivity was 6.5 μS / cm, No. was obtained by Nutsche suction filtration. Solid-liquid separation was performed using 5A filter paper. Next, vacuum drying was continued for 12 hours to obtain toner particles (1).
The volume average particle diameter (D50v) of the toner particles (1) is 5.8 μm, and SF1 is 130.

[Preparation of external additives]
(Preparation of silica particles)
-Production of silica particles (S1)-
To a 1.5 L glass reaction vessel equipped with a stirrer, a dropping nozzle and a thermometer, 320 parts of methanol and 72 parts of 10% ammonia water were added and mixed to obtain an alkali catalyst solution.
After adjusting the alkali catalyst solution to 30 ° C., 185 parts of tetramethoxysilane (TMOS) and 50 parts of 8.0% aqueous ammonia are simultaneously added dropwise with stirring to obtain a hydrophilic silica particle dispersion (solid content). Concentration 12.0%). Here, the dropping time was 30 minutes.
Then, the obtained silica particle dispersion was concentrated to a solid content concentration of 40% with a rotary filter R-Fine (manufactured by Kotobuki Industries). This concentrated product was used as a silica particle dispersion (S1).
To 250 parts of the silica particle dispersion (S1), trimethylsilane as a hydrophobizing agent is added in an amount of 20% by mass based on the solid content of the silica particles, reacted at 150 ° C. for 2 hours, cooled, and sprayed. It dried by drying (spray drying) and obtained the hydrophobic silica particle (S1) by which the surface of the silica particle was hydrophobized.

-Preparation of silica particles (S2-S7)-
Silica particles (S2 to S7) were prepared under the same conditions as in the method for preparing silica particles S1, except that the amount of methanol charged, 10% ammonia water, tetramethoxysilane (TMOS), 8% ammonia water, and the dropping time were adjusted. Produced.
The production conditions of the silica particles (S1 to S7), the average particle diameter of the obtained silica particles, and the average circularity are shown in Table 1 below.

(Lubricant particles N and lubricant particles P)
As the lubricant particles N, PTFE particles (trade name “Lublon L2 (manufactured by Daikin Industries, Ltd.), average particle size = 300 nm) were prepared.
As lubricant particles P, fatty acid metal salt particles (zinc stearate particles, trade name “SZ-2000 (manufactured by Sakai Chemical Co., Ltd.), average particle size = 3 μm) were prepared.

(Charged column of silica particles, PTFE particles, fatty acid metal salt particles)
It was measured by a method based on the standard method for measuring the charge amount of toner (blow-off measurement method) of the Japanese Society of Imaging Science, using the above-mentioned four types of standard carriers distributed by the Technical Committee of the Japan Imaging Society. That is, 0.5 g of silica particles, PTFE particles, or fatty acid metal salt particles was added to 10 g of the carrier and measured.
Silica particles were −100 to −150 (μC / g), PTFE particles were −50 (μC / g), and fatty acid metal salt particles were +80 (μC / g) with respect to the toner particles.

<Example 1>
[Production of toner]
To 100 parts of toner particles (1), 0.02 part of lubricant particles P (fatty acid metal salt particles) and 0.2 parts of lubricant particles N (PTFE particles) are added, and the stirring peripheral speed is 30 m / sec using a Henschel mixer. For 10 minutes to obtain a mixture. Thereafter, 2.0 parts of silica particles (S1) were further added to the obtained mixture, and mixed with a Henschel mixer at a stirring peripheral speed of 30 m / sec for 15 minutes to obtain a toner.

[Production of developer]
The obtained toner and carrier were put in a V blender at a ratio of toner: carrier = 5: 95 (mass ratio) and stirred for 20 minutes to obtain a developer.

In addition, the carrier produced as follows was used.
Ferrite particles (volume average particle diameter: 50 μm) 100 parts ・ Toluene 14 parts ・ Styrene-methyl methacrylate copolymer 2 parts (component ratio: 90/10, Mw = 80000)
Carbon black (R330: manufactured by Cabot Corporation) 0.2 part First, the above components excluding ferrite particles are stirred with a stirrer for 10 minutes to prepare a dispersed coating solution, and then the coating solution and ferrite particles are combined. After putting in a vacuum degassing type kneader and stirring at 60 ° C. for 30 minutes, the carrier was obtained by further depressurizing while heating and degassing and drying.

<Example 2>
In the preparation of the toner, the stirring speed and stirring time of the Henschel mixer after adding the lubricant particles P and the lubricant particles N were 30 m / sec and 10 minutes, respectively, and the stirring speed of the Henschel mixer after adding the silica particles and A toner and a developer were obtained in the same manner as in Example 1 except that the stirring time was 30 m / sec and 15 minutes, respectively.

<Example 3>
In the preparation of the toner, the stirring speed and stirring time of the Henschel mixer after adding the lubricant particles P and the lubricant particles N were 30 m / sec and 5 minutes, respectively, and the stirring speed of the Henschel mixer after adding the silica particles and A toner and a developer were obtained in the same manner as in Example 1 except that the stirring time was 30 m / sec and 20 minutes, respectively.

<Example 4>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S2) shown in Table 2 were changed.

<Example 5>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S3) shown in Table 2 below were changed.

<Example 6>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S4) shown in Table 2 were changed.

<Example 7>
Toner and developer in the same manner as in Example 1 except that the lubricant particles P of Example 1 were changed to zinc laurate particles (C ₂₄ H ₄₆ O ₄ Zn, manufactured by Wako Pure Chemical Industries, Ltd.). Got.

<Example 8>
A toner and a developer were obtained in the same manner as in Example 1 except that the lubricant particles N of Example 1 were changed to calcium fluoride particles (CaF ₂ ) (manufactured by Stella Chemifa Corporation).

<Example 9>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the addition amount of the lubricant particles P was changed to 0.005 part (0.005% by mass with respect to the toner particles).

<Example 10>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the addition amount of the lubricant particles P was changed to 0.4 part (0.4% by mass with respect to the toner particles).

<Example 11>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the addition amount of the lubricant particles N was changed to 0.05 part (0.05% by mass with respect to the toner particles).

<Example 12>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the addition amount of the lubricant particles N was changed to 0.5 part (0.5% by mass with respect to the toner particles).

<Example 13>
In Example 1, the content of silica particles is 0.5 parts (0.5% by mass based on toner particles), and the content of lubricant particles P is 0.001 parts (0.001% by mass based on toner particles). The toner and the developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.01 part (0.01% by mass with respect to the toner particles).

<Example 14>
In Example 1, the content of silica particles was 0.5 parts (0.5% by mass with respect to toner particles), and the content of lubricant particles P was 0.1 parts (0.1% by mass with respect to toner particles). The toner and developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.25 parts (0.25% by mass with respect to the toner particles).

<Example 15>
In Example 1, the content of the silica particles is 3.0 parts (3.0% by mass with respect to the toner particles), and the content of the lubricant particles P is 0.006 parts (0.006% by mass with respect to the toner particles). The toner and the developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.06 parts (0.06% by mass with respect to the toner particles).

<Example 16>
In Example 1, the content of silica particles was 3.0 parts (3.0% by mass with respect to toner particles), and the content of lubricant particles P was 0.5 parts (0.5% by mass with respect to toner particles). The toner and the developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.5 part (0.5% by mass with respect to the toner particles).

<Comparative Example 1>
In the preparation of the toner, 100 parts of toner particles (1), 2.0 parts of silica particles (S1), 0.02 parts of lubricant particles P (fatty acid metal salt particles), and lubricant particles N (PTFE particles) 0. A toner and a developer were obtained in the same manner as in Example 1 except that 2 parts were added and mixed with a Henschel mixer at a stirring peripheral speed of 30 m / sec for 15 minutes to obtain a toner.

<Comparative example 2>
In the preparation of the toner, 100 parts of toner particles (1), 2.0 parts of silica particles (S1), 0.02 parts of lubricant particles P (fatty acid metal salt particles), and lubricant particles N (PTFE particles) 0. Toner and developer were obtained in the same manner as in Example 1 except that 2 parts were added and mixed with a Henschel mixer at a stirring peripheral speed of 30 m / sec for 30 minutes to obtain a toner.

<Comparative Example 3>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S5) shown in Table 3 were changed.

<Comparative example 4>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S6) having an average particle size shown in Table 3 below were changed.

<Comparative Example 5>
A toner and a developer were obtained in the same manner as in Example 1 except that the silica particles (S7) having an average particle size shown in Table 3 below were changed.

<Comparative Example 6>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles P was changed to 0.0005 part (0.0005% by mass with respect to the toner particles).

<Comparative Example 7>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles P was changed to 0.6 parts (0.6% by mass with respect to the toner particles).

<Comparative Example 8>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.002 part (0.002% by mass with respect to the toner particles).

<Comparative Example 9>
In Example 1, a toner and a developer were obtained in the same manner as in Example 1 except that the content of the lubricant particles N was changed to 0.6 parts (0.6% by mass with respect to the toner particles).

<Comparative Example 10>
A toner and a developer were obtained in the same manner as in Comparative Example 9, except that the content of silica particles in Comparative Example 9 was changed to 0.3 part (0.3% by mass with respect to the toner particles).

<Comparative Example 11>
A toner and a developer were obtained in the same manner as in Comparative Example 9, except that the content of silica particles in Comparative Example 9 was changed to 4.0 parts (4.0% by mass with respect to the toner particles).

In Table 2 above, “* 1” indicates that “zinc laurate particles (C ₂₄ H ₄₆ O ₄ Zn, manufactured by Wako Pure Chemical Industries, Ltd.)” was used as the lubricant particles P.
“* 2” indicates that “calcium fluoride (CaF ₂ , manufactured by Stella Chemifa Co., Ltd.)” was used as the lubricant particle N.

<Evaluation>
The developer of each example was accommodated in a developing device of an image forming apparatus “Apeos Port IV C5575 (produced by Fuji Xerox Co., Ltd.)”. Using this image forming apparatus, in an environment of high temperature and high humidity (temperature 29 ° C., humidity 80% RH), an image (a) having an image density of 1% is output continuously to 20,000 sheets of A4 paper, and then the image density is 40%. One halftone image (b) was output on A4 paper. Thereafter, the following evaluation was performed. The evaluation results are shown in Table 4.

(Evaluation of filming on the photoreceptor surface)
The filming of the lubricant or toner formed on the surface of the photoreceptor was judged by sensory evaluation by visual observation for image portions and non-image portions in the continuously formed image (a). Judgment criteria are as follows.
The allowable range is up to G2.
-Evaluation criteria-
G1: No filming at all.
G2: Level at which filming is observed even thinly and does not affect image quality.
G3: The filming level is between G2 and G4, and the image quality starts to be affected.
G4: Filming is clearly present on the surface, and appears as color streaks and white streaks in the image quality.

(Image Defect: Evaluation of Image Defect Generated at Boundary between Image Part and Non-Image Part in Image (a))
The last output halftone image (b) was visually observed, and the occurrence state of image defects (striated image defects) generated at the boundary between the image portion and the non-image portion in the image (a) was evaluated.
The allowable range is up to G2.
-Evaluation criteria-
G1: A streak-like image defect generated at the boundary between the image portion and the non-image portion is not observed, and there is no problem in image quality.
G2: Although a streak-like image defect generated at the boundary between the image portion and the non-image portion is observed slightly, there is no problem in image quality.
G3: A streak-like image defect generated at the boundary between the image portion and the non-image portion is observed, and there is a concern in actual use.
G4: A streak-like image defect generated at the boundary between the image portion and the non-image portion is clearly observed, and there is a problem in image quality.

(Image defect: Defect evaluation due to defective cleaning)
The occurrence of image defects such as color streaks due to slipping through the cleaning blade was evaluated.
The allowable range is up to G2.
-Evaluation criteria-
G1: No problem in image quality.
G2: Color streaks are slightly observed on the image, but there is no problem with the image quality.
G3: Color streaks and image flow are slightly observed on the image, but are within an allowable range.
G4: Color streaks and image flow are clearly observed on the image, and there is clearly a problem with image quality.

From the above results, compared to the comparative example, this example shows that the same image is formed when a halftone image different from the same image is formed after the same image is continuously formed in a high temperature and high humidity environment. It can be seen that the occurrence of image defects occurring at the boundary between the image portion and the non-image portion is suppressed.
In addition, from the above results, compared to the comparative example, the present example has the suppression of the occurrence of an image defect that occurs at the boundary between the image portion and the non-image portion in the same image, and the suppression of the image defect due to poor cleaning. You can see that both are compatible.

1Y, 1M, 1C, 1K photoconductor (an example of an image carrier)
2Y, 2M, 2C, 2K charging roll (an example of charging means)
3. Exposure device (an example of electrostatic charge image forming means)
3Y, 3M, 3C, 3K Laser beams 4Y, 4M, 4C, 4K Developing device (an example of developing means)
5Y, 5M, 5C, 5K primary transfer roll (an example of primary transfer means)
6Y, 6M, 6C, 6K Photoconductor cleaning device (an example of cleaning means)
6Y-1, 6M-1, 6C-1, 6K-1 Cleaning blades 8Y, 8M, 8C, 8K Toner cartridges 10Y, 10M, 10C, 10K Image forming unit 20 Intermediate transfer belt (an example of an intermediate transfer member)
22 Drive roll 26 Secondary transfer roll (an example of secondary transfer means)
30 Intermediate transfer member cleaning device 107 Photosensitive member (an example of an image holding member)
108 Charging roll (an example of charging means)
109 Exposure apparatus (an example of electrostatic charge image forming means)
111 Developing device (an example of developing means)
112 Transfer device (an example of transfer means)
113 photoconductor cleaning device (an example of cleaning means)
113-1 Cleaning blade 115 Fixing device (an example of fixing means)
116 Attachment rail 118 Opening 117 for exposure 117 Case 200 Process cartridge 300 Recording paper (an example of recording medium)
P Recording paper (an example of a recording medium)

Claims (10)

Toner particles and silica particles having a volume average primary particle size of 80 nm or more and 200 nm or less are 0.5% by mass or more and 3.0% by mass or less based on the toner particles, and negatively chargeable lubricant particles N are used as the toner particles. 0.005% by mass to 0.5% by mass with respect to the toner particles, and positively chargeable lubricant particles P with respect to the toner particles in an amount of 0.001% by mass to 0.5% by mass,
After the ultrasonic treatment in the aqueous dispersion, the free rate s mass% of the silica particles, the free rate n mass% of the lubricant particles N, and the free rate p mass% of the lubricant particles P are represented by the formulas 1 to An electrostatic charge image developing toner satisfying Formula 3.
Formula 1 5 ≦ s ≦ 50
Formula 2 0.10 ≦ p / s ≦ 0.95
Formula 3 0.10 ≦ n / s ≦ 0.95 The liberation rate s mass% of the silica particles, the liberation rate n mass% of the lubricant particles N, and the liberation rate p mass% of the lubricant particles P satisfy the following formulas 2-1 to 3-1. 2. The toner for developing an electrostatic charge image according to 1.
Formula 2-1 0.10 ≦ p / s ≦ 0.75
Formula 3-1 0.10 ≦ n / s ≦ 0.75   The electrostatic image developing toner according to claim 1, wherein the silica particles are monodispersed spherical silica particles having an average circularity of 0.75 to 1.0.   The electrostatic charge image developing toner according to claim 1, wherein the lubricant particles P are fatty acid metal salts.   The electrostatic charge image developing toner according to claim 1, wherein the lubricant particles N are polytetrafluoroethylene.   An electrostatic charge image developer comprising the electrostatic charge image developing toner according to claim 1. Containing the toner for developing an electrostatic charge image according to any one of claims 1 to 5,
A toner cartridge to be attached to and detached from the image forming apparatus. A developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer,
A process cartridge attached to and detached from the image forming apparatus. An image carrier,
Charging means for charging the surface of the image carrier;
An electrostatic charge image forming means for forming an electrostatic charge image on the surface of the charged image carrier;
Developing means for containing the electrostatic charge image developer according to claim 6 and developing the electrostatic charge image formed on the surface of the image carrier as a toner image by the electrostatic charge image developer;
Transfer means for transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
Cleaning means having a cleaning blade for cleaning the surface of the image carrier;
Fixing means for fixing the toner image transferred to the surface of the recording medium;
An image forming apparatus comprising: A charging step for charging the surface of the image carrier;
An electrostatic charge image forming step of forming an electrostatic charge image on the surface of the charged image carrier;
A developing step of developing an electrostatic charge image formed on the surface of the image carrier as a toner image with the electrostatic charge image developer according to claim 6;
A transfer step of transferring a toner image formed on the surface of the image carrier to the surface of a recording medium;
A cleaning step of cleaning the surface of the image carrier with a cleaning blade;
A fixing step of fixing the toner image transferred to the surface of the recording medium;
An image forming method comprising: