JP5305927B2 - Toner cartridge - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner cartridge capable of stably obtaining high-resolution and a high-definition image over a long period of time irrespectively of the environment even in an electrophotographic main unit reduced in size. <P>SOLUTION: The toner cartridge can be set in and detached from an image forming apparatus and comprises a toner and a toner container housing the toner, wherein the toner container is obtained by stretch blow molding of a molding resin 103 containing a polyester prepared by polymerizing at least an aromatic dicarboxylic acid and an alkylene glycol and carbon black, and the toner comprises toner particles containing at least a binder resin and a colorant and an inorganic fine powder having a number average particle diameter of 80-400 nm and a volume resistivity of 1.0&times;10<SP>3</SP>-1.0&times;10<SP>9</SP>&Omega;/cm<SP>3</SP>. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a toner cartridge for supplying toner to an electrophotographic method, an electrostatic recording method, and a magnetic recording method.

  Conventionally, as a method of supplying toner to the electrophotographic main body, a so-called replenishment type container in which the toner contained in the container is supplied all at once to the toner receiving portion in the copying machine main body, and a toner container is attached to the electrophotographic main body. Thereafter, the container is roughly classified into a so-called stationary toner container in which the container is left in the copying machine body until the built-in toner is used up, and the toner is gradually discharged according to the required amount.

  In these stationary toner containers, as a method for discharging the toner, when the toner container is cylindrical, a stirring member using a combination of a stirring shaft and a stirring blade is used, and the rotation speed and rotation amount of the stirring member are controlled. Thus, a method of regulating the toner discharge amount, or a method of forming a spiral rib on the side wall of the toner container, rotating the container itself, and controlling the discharge amount of the built-in toner by the rotation amount has been proposed. In either case, friction between the toner and the inner surface of the container, the stirring member, and the like occurs in the toner container due to stirring for discharging control, and the toner is charged while being minute.

  Conventionally, a toner receiving space is provided in the electrophotographic main body for the purpose of supplying a fixed amount of toner to the developing unit, and toner is stored in advance in the buffer space from a toner container, and then the fixed amount is supplied to the developing unit as necessary. In order to cope with the recent downsizing of the main body, a method of eliminating this buffer space and supplying the toner cartridge directly to the developing unit is desired.

  On the other hand, the development unit itself is becoming more compact and simpler, and multifunctional and high-speed printing is progressing so that a wide variety of images can be printed out at a high speed. It is necessary.

  As materials for these toner containers, polyolefin resin, polystyrene resin, acrylic resin, polyester resin, etc. are selected from the viewpoint of strength, moldability, cost, etc., and these materials are transferred to the toner cartridge by a technique such as injection molding or blow molding. Molded. For example, in Patent Document 1, polystyrene raw materials are divided and injection molded and then bonded together, or in Patent Document 2, biaxial stretch blow molding using a mixture of polyethylene terephthalate and polyethylene as a material Etc. have been proposed.

  These are effective in terms of manufacturing stability, strength, flame retardancy, light-shielding properties, etc., but are not considered from the viewpoint of assisting charging stability for stored toner.

  In recent years, a toner container is required not only as a container for storing toner, but also as a preliminary process for reinforcing electrophotographic characteristics, particularly in the development process.

On the other hand, various proposals have been made to add a charging aid to toner as a developer. For example, as in Patent Document 3, a method of adding two kinds of silica and titanium oxide has been proposed. However, it is insufficient in terms of both charging stability and mechanical stress resistance. Patent Document 4 proposes a method of adding strontium titanate particles having a small particle size to toner particles. The particles used in these methods are sufficiently effective as an abrasive to prevent filming and fusing by the toner on the electrostatic latent image bearing member, but at the same time impair the fluidity of the toner, In order to supply the toner stably and to supply the toner uniformly to the developing process, mechanical assistance in the electrophotographic main body is required.

  As described above, in the miniaturized and simplified electrophotographic configuration, in order to stably obtain a high-resolution and high-definition image over a long period of time, it is not sufficient to control toner charging in the development process. Therefore, there is a demand for a toner cartridge that supplies toner having stable charging ability to the developing process.

  In particular, in recent years, it has been required to have the same performance even in severe environments such as high temperature and high humidity environment or low temperature and low humidity environment, and efforts to solve the problem by countermeasures from the toner side have been repeated. However, the current situation is that no fundamental measures have been taken.

JP 2004-004792 A Japanese Patent Laid-Open No. 2002-221858 JP 2002-372800 A Japanese Patent Laid-Open No. 10-10770

  An object of the present invention is to provide a toner cartridge in which the above problems are solved.

  That is, the object of the present invention is to achieve extremely quantitative discharge performance and to achieve uniform toner charging in the developing section.

In order to achieve the above object, the present inventors have developed a resin composition for molding a toner container in a toner cartridge, and the toner contains a special inorganic fine powder according to the present invention, so that the toner can be discharged in a fixed amount and in the developing section. It has been found that uniform chargeability of the toner can be achieved to a high degree. That is, the present invention is as follows.
(1) In a toner cartridge composed of at least toner and a toner container for containing the toner and detachable from the image forming apparatus,
The toner container is a toner container obtained by molding a molding resin containing at least a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and carbon black by a stretch blow method,
The toner has toner particles containing at least a binder resin and a colorant, a number average particle diameter of 80 nm to 400 nm, and a volume resistivity value of 1.0 × 10 ³ Ω · m to 1.0 × 10 ^9. have a fine inorganic particles is less than or equal to Ω · m,
The molding resin has a dielectric constant ε (C) of 2.8 pF / m or more and less than 3.8 pF / m at 40 ° C. and 2 kHz, and the dielectric constant ε (A) of the inorganic fine particles at 40 ° C. and 2 kHz. The following formula (1)
30.0 <ε (A) / ε (C) <150.0 (1)
A toner cartridge characterized by satisfying
(2) A toner wherein the shape of the inorganic fine powder particles is an octahedron that is a convex polyhedron surrounded by eight triangles and / or a hexahedron that is a convex polyhedron surrounded by six quadrangles. cartridge.
(3) The toner cartridge, wherein the inorganic fine particles are hydrophobized.
(4) The toner cartridge , wherein the inorganic fine particles are hydrophobized with a fatty acid .
(5) A toner cartridge wherein the toner has a dielectric constant ε (T) at 40 ° C. and 2 kHz of 30.0 pF / m or more and 80.0 pF / m or less.
(6) The toner cartridge, wherein the inorganic fine particles are strontium titanate.
(7) A toner cartridge, wherein the colorant is magnetic iron oxide.

  According to the present invention, there is no toner storage space in the electrophotographic main body, and there is no reduction in image density or fogging, and high resolution and high definition images can be produced over a long period of time regardless of the environment and print images. It can be obtained stably.

The toner cartridge of the present invention is detachable from the image forming apparatus, and includes at least a toner container that contains toner. Further, the toner container is formed by molding a specific molding resin by the stretch blow method, and the toner incorporated therein is a toner particle containing a binder resin and a colorant, and a number average particle diameter of 80 nm to 400 nm, which is specific to the volume. It has inorganic fine particles having a resistance value of 1.0 × 10 ³ Ω · m or more and 1.0 × 10 ⁹ Ω · m or less. As a result, excessive frictional charging consisting of the toner container and the toner does not occur during toner storage and replenishment operation, toner electrostatic aggregation does not occur, and toner quantitative discharge performance can be extremely achieved. Can suppress problems in the developing process without causing uneven charging of the toner when it reaches the developing portion.

That is, the present invention is a toner container in which a molding resin containing at least a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and carbon black is molded by a stretch blow method. The toner has toner particles containing at least a binder resin and a colorant, a number average particle diameter of 80 nm to 400 nm, and a volume resistivity of 1.0 × 10 ³ Ω · m to 1.0 × 10 ⁹ Ω. The present invention relates to a toner cartridge having inorganic fine powder (inorganic fine particles) having a size of m or less.

By having a molded resin having the above structure, it suppresses suppresses the excessive charging of the local toner during storage and at the time of discharge of an electrophotographic machine, the moisture absorption of the built toner by suppressing water vapor permeability of the container material toner Therefore, it is possible to suppress the charging failure.

The toner has toner particles containing at least a binder resin and a colorant, a number average particle diameter of 80 nm to 400 nm (preferably 90 nm to 250 nm), and a volume resistivity of 1.0 × 10 ³ Ω. -It has the inorganic fine powder which is m or more and 1.0 * 10 < ⁹ > (omega | ohm) * m or less.

  When the number average particle diameter is less than 80 nm, an embedding phenomenon occurs on the surface of the toner base during toner conveyance and stirring, and the charge adjustment effect of the inorganic fine powder does not appear. If the particle diameter is 400 nm or more, the particle diameter is too large, and the effect of scraping off the toner material adhering to the minute irregularities on the inner surface of the container is hardly exhibited, and the photosensitive drum surface is scratched in the development process. Causes image damage.

On the other hand, when the volume resistivity is less than 1.0 × 10 ³ Ω · m , the charge inherent to the toner base leaks, and the charge amount of the toner base becomes insufficient, so that sufficient developability cannot be obtained. When the density is 1.0 × 10 ⁹ Ω · m or more, local charge-up phenomenon of toner occurs in the stirring and conveying process in the toner container, and development unevenness occurs.

  In the toner cartridge of the present invention, the particle shape of the inorganic fine powder includes an octahedron that is a convex polyhedron surrounded by eight triangles, and a hexahedron that is a convex polyhedron surrounded by six squares. It is preferable that at least one of them is based.

  Since the inorganic fine powder has an apex, it is possible to scrape off the toner composition that has entered the minute irregularities on the inner surface during stirring in the toner container, and minimizes changes in the toner composition when discharged from the toner container. Can be suppressed.

  In the toner cartridge of the present invention, the inorganic fine powder is preferably subjected to a hydrophobic treatment.

  Similarly, by coating the inner surface of the toner container with the surface hydrophobizing agent of the inorganic fine powder, it becomes possible to achieve highly uniform chargeability and suppress charge reduction due to moisture absorption even in a high temperature and high humidity environment. be able to.

  The hydrophobization treatment in the present invention indicates that the degree of hydrophobicity of the inorganic fine powder of the present invention is 70% or more. The method is not limited, but it is preferable to coat the surface of the inorganic fine powder of the present invention with a hydrophobizing agent.

  Examples of the hydrophobizing agent for the inorganic fine powder include silicone oils and titanate-based, aluminum-based, silane-based coupling agents, and fatty acid metal salts as coupling agents.

  Examples of the fatty acid metal salt include zinc stearate, sodium stearate, calcium stearate, zinc laurate, aluminum stearate, magnesium stearate and the like.

  The same effect can be obtained with stearic acid, which is a fatty acid.

  The surface treatment agent to be treated is dissolved and dispersed in a solvent, the inorganic fine powder is added to the solution, the solvent is removed while stirring, the wet treatment method, the coupling agent, and the fatty acid metal salt. And a dry method in which the inorganic fine powder is directly mixed and treated with stirring.

The toner cartridge of the present invention has a dielectric constant ε (C) at 40 ° C. and 2 kHz of a resin for molding a toner container of 2.8 pF / m or more and less than 3.8 pF / m. The dielectric constant ε (A) at 40 ° C. and 2 kHz is expressed by the following formula (1)
30.0 <ε (A) / ε (C) <150.0 (1)
Is preferably satisfied.

  When the dielectric constant (ε) of the molding resin is less than 2.8 pF / m, the electrophotographic main body has no toner buffer space and the toner cartridge and the developing device are directly connected. During continuous output at high printing in a wet environment, the preliminary charging effect cannot be obtained, and the density stability becomes difficult to obtain. In addition, when the dielectric constant (ε) is 3.8 pF / m or more, excessively charged toner is generated during continuous output in a low-humidity environment. Fog is likely to occur. When the ratio ε (A) / ε (C) between the dielectric constant ε (C) of the resin for molding the toner container and the dielectric constant ε (A) of the inorganic fine powder is 30.0 or less, the toner at the time of high print output When replenishment is required, the frictional charge balance between the toner and the toner container due to agitation and conveyance is lost, and non-uniform toner charging is likely to occur. Similarly, when ε (A) / ε (C) is 150.0 or more, charge leakage on the toner container side becomes active, and the toner tends to cause non-uniform charging.

  In the toner cartridge of the present invention, it is preferable that the dielectric constant ε (T) of the toner at 40 ° C. and 2 kHz is 30.0 pF / m or more and 80.0 pF / m or less.

  When the dielectric constant ε (T) of the toner is less than 30.0 pF / m, the toner is likely to be insufficient in charge, particularly in a high humidity environment, and the toner is replenished when replenishing the developer and in the developer. It tends to cause band-like density unevenness due to unevenness. On the other hand, when ε (T) is more than 80.0 pF / m, the toner easily retains an excessive charge, and similarly, toner unevenness in the toner supply due to electrostatic aggregation is likely to occur. Uneven images are likely to occur.

<Method for measuring particle size of inorganic fine powder>
About the number average particle diameter of the inorganic fine powder in the present invention, 100 average particle diameters were measured from photographs taken at a magnification of 50,000 times with an electron microscope, and the average was determined.

<Method for measuring dielectric constant of toner and inorganic fine powder>
The dielectric constant of the toner of the present invention is measured by the following method.

1 g of the toner is weighed and molded into a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm) over a period of 2 minutes under a load of 19600 kPa (200 kg / cm ² ). This measurement sample is mounted on an ARES (Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm, heated to a temperature of 80 ° C. and melt-fixed. Thereafter, the toner is cooled to a temperature of 40 ° C., and a dielectric constant of the toner is measured by measuring a frequency range of 500 to 5 × 10 ⁵ Hz under a load of 1.47 N (150 g).

  The dielectric constant of the inorganic fine powder according to the present invention is measured by the following method.

1 g of inorganic fine powder is weighed and molded into a disk-shaped measurement sample having a diameter of 25 mm and a thickness of 1 mm or less (preferably 0.5 to 0.9 mm) over a period of 2 minutes under a load of 19600 kPa (200 kg / cm ² ). . This measurement sample is mounted on ARES (manufactured by Rheometric Scientific F.E.) equipped with a dielectric constant measuring jig (electrode) having a diameter of 25 mm. The dielectric constant of the inorganic fine powder is measured by measuring a frequency range of 500 to 5 × 10 ⁵ Hz with a temperature of 40 ° C. and a load of 1.47 N (150 g) applied.

  Examples of the inorganic fine powder of the present invention include various metal oxides (aluminum oxide, titanium oxide, cerium oxide, magnesium oxide, chromium oxide, tin oxide, zinc oxide, etc.), metal acid salts (strontium titanate, calcium titanate, titanium). Titanates such as magnesium oxide, aluminates, zirconates, etc., nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (Zinc stearate, calcium stearate, etc.), carbon black, silica and the like. Preferred are titanate and cerium oxide.

  As the binder resin for the toner particles contained in the toner of the present invention, a polyester resin, a vinyl copolymer resin, an epoxy resin, or a binder resin including a hybrid resin having a vinyl polymer unit and a polyester unit. Is preferred.

  A release agent can be added to the toner particles contained in the toner of the present invention as necessary.

  Examples of release agents that can be used in the present invention include aliphatic hydrocarbon waxes and oxides thereof; block copolymers of the oxides; waxes based on fatty acid esters; Or what deoxidized all is mentioned. Among these release agents, one or more release agents may be contained in the toner particles as necessary.

  A preferable addition amount of the release agent is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass per 100 parts by mass of the binder resin.

  In addition, these release agents can usually be contained in the toner particles by dissolving the resin in a solvent, increasing the temperature of the resin solution, adding and mixing with stirring, or mixing at the time of kneading.

  In the toner of the present invention, a charge control agent can be used as necessary in order to further stabilize the chargeability. Examples of the negative charge control agent for controlling the toner to be negative charge include an organometallic complex or a chelate compound. Examples of positive charge control agents that control the toner to be positively charged include modified products of nigrosine and fatty acid metal salts, quaternary ammonium salt compounds, triphenylmethane dyes and their lake pigments, metal salts of higher fatty acids, etc. Is effective.

  A preferable content of the charge control agent is 0.5 to 10 parts by mass per 100 parts by mass of the binder resin. When the amount of the charge control agent is less than 0.5 parts by mass, sufficient charging characteristics may not be obtained, which is not preferable. When the amount exceeds 10 parts by mass, the compatibility with other materials may be deteriorated, or charging may be excessively performed under low humidity, which is not preferable.

  The toner particles contained in the toner of the present invention are preferably made into a magnetic toner by adding a magnetic material as necessary. As the magnetic material, magnetic oxides such as magnetite, maghematite, ferrite and mixtures thereof are preferably used. Examples of the magnetic material include at least one element selected from the group consisting of magnesium, aluminum, silicon, phosphorus, titanium, zirconium, tin, calcium, manganese, cobalt, copper, nickel, strontium, and zinc. Containing magnetic iron oxide.

  By containing the magnetic iron oxide, the dielectric constant ε (T) of the toner which is a preferable embodiment of the present invention is adjusted to 30.0 pF / m to 80.0 pF / m, and the scattering of the toner from the developing roller is suppressed. In addition, the toner surface charge is made uniform and an image excellent in dot reproduction is easily obtained.

  The number average particle diameter of these magnetic materials is preferably 0.05 μm or more and less than 1.0 μm, more preferably 0.1 or more and less than 0.5 μm.

The BET specific surface area by nitrogen adsorption of the magnetic material is preferably 2 to 40 m ² / g, more preferably 4 to 20 m ² / g.

A preferable magnetic property of the magnetic material is that the saturation magnetization measured with a magnetic field of 795.8 kA / m is 10 to 200 Am ² / kg, and more preferably 70 to 100 Am ² / kg. A preferable residual magnetization is 1 to 100 Am ² / kg, and more preferably 2 to 20 Am ² / kg. A preferable coercive force is 1 to 30 kA / m, and more preferably 2 to 15 kA / m.

  A preferable content of the magnetic body is 20 to 200 parts by mass with respect to 100 parts by mass of the binder resin.

  To the toner particles contained in the toner of the present invention, a colorant can be added as necessary. Any appropriate pigment or dye can be used as the colorant.

  Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine yellow, alizarin yellow, bengara, phthalocyanine blue and the like. A preferable addition amount of the pigment is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes, and the like. A preferable addition amount of the dye is 0.1 to 20 parts by mass, more preferably 0.3 to 10 parts by mass with respect to 100 parts by mass of the binder resin.

  In addition to the inorganic fine powder contained in the toner of the present invention, specific examples in which other external additives may be used in combination include inorganic oxides such as silica, alumina, titanium oxide, carbon black, carbon fluoride, etc. Inorganic fine powder having a fine particle diameter of

  If the silica fine powder, alumina fine powder or titanium oxide fine powder is fine particles, these fine powders have a high fluidity-imparting effect on the toner, and therefore it is preferable that these fine powders are fine particles.

  These fine powders preferably have a number average particle diameter of 5 to 100 nm, more preferably 5 to 50 nm.

  A preferable addition amount of these inorganic fine powders is 0.03 parts by mass or more and less than 5 parts by mass with respect to 100 parts by mass of the toner particles. When the added amount of the inorganic fine powder is less than 0.03 parts by mass, sufficient fluidity imparting effect cannot often be obtained. On the other hand, when the amount is 5 parts by mass or more, the compression index of the toner becomes high, the toner is easily tightened, and an excessive external additive is liberated, which tends to have an adverse effect.

  In the toner of the present invention, the binder resin and other additives are sufficiently mixed by a mixer such as a Henschel mixer and a ball mill and then melt-kneaded using a heat kneader such as a heating roll, a kneader, and an extruder. .

  Further, after cooling and solidification, pulverization and classification are performed, and further, the composite inorganic fine powder and, if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer.

  Examples of the mixer include a Henschel mixer (manufactured by Mitsui Mining); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); a nauter mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); Pin mixer one (manufactured by Taiheiyo Kiko Co., Ltd.);

  Examples of the kneader include: KRC kneader (manufactured by Kurimoto Iron Works); bus co-kneader (manufactured by Buss); TEM type extruder (manufactured by Toshiba Machine); TEX twin-screw kneader (manufactured by Nippon Steel Works) PCM kneading machine (Ikegai Iron Works Co., Ltd.); three roll mill, mixing roll mill, kneader (Inoue Seisakusho Co., Ltd.); kneedex (Mitsui Mining Co., Ltd.); MS pressure kneader, Nider Ruder (Moriyama Seisakusho Co., Ltd.) Manufactured); Banbury mixer (manufactured by Kobe Steel).

  Examples of the pulverizer include counter jet mill, micron jet, inomizer (manufactured by Hosokawa Micron Corporation); IDS type mill, PJM jet pulverizer (manufactured by Nippon Pneumatic Industry Co., Ltd.); cross jet mill (manufactured by Kurimoto Iron Works Co., Ltd.); ULMAX (manufactured by Nisso Engineering Co., Ltd.); SK Jet O Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.);

  Examples of the classifier include a class seal, a micron classifier, a speck classifier (manufactured by Seishin Enterprise Co., Ltd.); a turbo classifier (manufactured by Nissin Engineering Co., Ltd.); a micron separator, a turboplex (ATP), and a TSP separator (Hosokawa Micron). Elbow Jet (manufactured by Nippon Steel & Mining Co., Ltd.), dispersion separator (manufactured by Nippon Pneumatic Engineering Co., Ltd.); YM Microcut (manufactured by Yaskawa Shoji Co., Ltd.).

  Examples of sieving devices used for sieving coarse particles include Ultrasonic (manufactured by Sakae Sangyo Co., Ltd.); Resonator Sheave, Gyroshifter (Tokusu Kosakusha Co., Ltd.); Vibrasonic System (manufactured by Dalton Co., Ltd.); Shinto Kogyo Co., Ltd.); turbo screener (Turboe Co., Ltd.); micro shifter (Ogino Sangyo Co., Ltd.); circular vibrating screen, etc.

  The toner container molding resin according to the present invention is characterized by a molding resin containing at least a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and carbon black.

  By having the above-described configuration, in combination with the toner of the present invention, local excessive charging of the toner during storage and discharge of the toner is alleviated, and stable supply without impairing quantitative discharge performance and electrostatic characteristics of the toner after discharge. Is possible. On the other hand, it becomes possible to satisfy the moldability and strength of the container at the same time.

  Hereinafter, the molding resin will be described more specifically.

  Specific examples of the structural unit derived from an aromatic dicarboxylic acid include terephthalic acid, phthalic acid, isophthalic acid, dibromoisophthalic acid, sodium sulfoisophthalate, 4,4′-diphenyldicarboxylic acid, and 4,4′-diphenylether dicarboxylic acid. Acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2 , 5-naphthalenedicarboxylic acid, dibromoterephthalic acid and the like. If desired, other polycarboxylic acids may be used in combination with aromatic dicarboxylic acids. Examples of polycarboxylic acids used in combination with aromatic dicarboxylic acids include fatty acids such as hexahydroterephthalic acid and hexahydroisophthalic acid. Cyclic dicarboxylic acids; α, ω-aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadicarboxylic acid and dodecadicarboxylic acid.

  As the polyalkylene glycol which is the main component of the diol component, ethylene glycol is preferable. Usually, ethylene glycol is mainly used, and a diol having a cyclic structure such as isosorbide which has an effect of increasing the glass transition temperature of the polyester resin formed therein is used in combination.

  The diol component according to the present invention is usually composed of the above-mentioned ethylene glycol, isosorbide and diethylene glycol, but other diols can be used instead of or in combination with these if desired. Such diols include polymethylene glycols such as trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, decamethylene glycol; 1,2-propylene glycol, neopentyl glycol, 2-ethyl Aliphatic diols such as 2-butyl-1,3-propanediol, polyethylene glycol, polytetramethylene ether glycol; 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1, Cycloaliphatic diols such as 4-cyclohexanedimethylol, 2,5-norbornane dimethylol; xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4′-hydroxyl) Nyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid and the like; Examples thereof include ethylene oxide adducts and propylene oxide adducts of 2,2-bis (4′-hydroxyphenyl) propane.

  The molding resin according to the present invention can be produced by a conventional resin production method through esterification or transesterification and melt polycondensation. The esterification or transesterification can be carried out without a catalyst, but a conventional esterification catalyst or transesterification catalyst may be used if desired.

  As the catalyst for the polycondensation reaction, any one known as a polycondensation catalyst such as a germanium compound, an antimony compound, a titanium compound, a manganese compound, a zinc compound, a cobalt compound, an aluminum compound, or a tungsten compound can be used. Usually, a metal compound selected from the group consisting of germanium compounds, antimony compounds, cobalt compounds and titanium compounds is used.

  The molding resin according to the present invention consists essentially of a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and carbon black, but contains a small amount of other copolymerization components in a small amount. Also good. Examples of such a copolymer component include polystyrene, polycarbonate, polyethylene, and polypropylene.

  The present invention is characterized by containing carbon black as a molding resin.

  By containing carbon black, accumulation of electric charges on the inner surface of the container can be suppressed, local excessive charging of the toner can be suppressed at the time of toner storage and at the time of stirring during conveyance, and uniformly charged toner can be supplied to the developing process.

  The carbon black content can be changed according to the purpose, but is preferably 0.5% by mass or more and less than 25.0% by mass (more preferably 2.5% by mass or more and less than 10.0% by mass). It is preferable. When the amount is less than 0.5% by mass, the toner is likely to be poorly charged due to frictional charging with the toner. Moreover, when it is 25.0 mass% or more, a reinforcement effect becomes strong and it becomes easy to cause a malfunction in a moldability.

  Further, the toner container of the present invention may contain a conductive substance or the like in addition to carbon black. For example, graphite, aluminum-doped zinc oxide, tin oxide, tin oxide-coated barium sulfate, potassium titanate, aluminum metal powder, nickel metal powder and the like are used.

  In addition, as a method of dispersing carbon black in the molding resin of the present invention, a method of dispersing using various extruders such as a twin screw extruder and a single screw extruder, various mixers such as a kneader and a Banbury mixer, There is a method of dispersing using various roll mills such as a main roll and a three-roll mill, but a twin screw extruder is preferable for controlling dispersion. This is because the screw configuration is easy to change in the twin-screw extruder, the conditions of the appropriate dispersion state can be easily found by changing the screw configuration, and the discharge amount and shaft rotation speed can be controlled individually, making it thermoplastic. This is because the residence time of the resin can be changed, the dispersion state can be changed without changing the screw, and the optimum conditions for dispersion can be easily found.

  Next, an example of a method for manufacturing a toner container (bottle) according to the present invention will be described more specifically with reference to FIGS.

  First, a preform is manufactured from the molding resin as described above. The preform can be manufactured by a conventionally known method, for example, an injection molding apparatus 101 as shown in FIG. As shown in FIG. 1, the molding material 103 containing the molding resin charged into the hopper 102 is heated by the heating cylinder 104 to become a molten state, and is injected into the mold 106 by the extrusion screw 105 to mold the preform 107.

  Next, as shown in FIGS. 2 and 3, the preform 107 is placed in a heating furnace 108 and heated to the stretching temperature. After heating, the preform 107 is placed in the blow mold 109 in FIG. 3 and the preform is further heated. While the preform is stretched in the vertical direction by the stretching rod 110, the gas 112 is caused to flow from the preform mouth portion 111 and blown. A molded product 113 is obtained. The gas to be blown can be selected from nitrogen, carbon dioxide, argon and the like in addition to air. Since these blow molded products 113 are stretched in both the vertical and horizontal directions, they become high strength molded products.

  The present invention will be described more specifically with reference to the following examples.

(Inorganic fine powder production example 1)
The hydrous titanium oxide slurry obtained by hydrolyzing the aqueous titanyl sulfate solution was washed with an alkaline aqueous solution. Next, hydrochloric acid was added to the hydrous titanium oxide slurry to adjust the pH to 0.7 to obtain a titania sol dispersion. NaOH was added to the titania sol dispersion, the pH of the dispersion was adjusted to 4.0, and washing was repeated until the electrical conductivity of the supernatant reached 70 μS / cm. 0.98-fold molar amount of Sr (OH) 2 .8H ₂ O was added to the hydrous titanium oxide, and the mixture was placed in a SUS reaction vessel and purged with nitrogen gas. Further, distilled water was added so as to be 0.5 mol / L in terms of SrTiO ₃ . The slurry was heated to 83 ° C. at 6.0 ° C./hour in a nitrogen atmosphere, and reacted for 6 hours after reaching 80 ° C. After the reaction, cool to room temperature, remove the supernatant, and repeat washing with pure water.

  Furthermore, in a nitrogen atmosphere, the slurry was placed in an aqueous solution in which 7.0% by mass of sodium stearate was dissolved with respect to the solid content of the slurry, and surface treatment was performed while stirring. The slurry was washed repeatedly with pure water and then filtered with Nutsche, and the resulting cake was dried to obtain strontium titanate surface-treated with stearic acid.

  The obtained strontium titanate had a hexahedral shape in which the particle shape was approximately cubic or cuboid. This hydrophobized inorganic fine powder 1 having a number average particle diameter of 100 nm and hexahedral strontium titanate particles was obtained. The physical properties of the obtained inorganic fine powder 1 are shown in Table 1.

(Inorganic fine powder production example 2)
A hydrous titanium oxide slurry obtained by hydrolyzing a titanyl sulfate aqueous solution is neutralized to pH 7 with aqueous ammonia, filtered and washed with water. The cake obtained by flocculating titanium oxide with hydrochloric acid is used to prepare anatase titania sol. Obtained. The average primary particle size of this sol was 7 nm.

In addition, an ilmenite ore containing 50% by mass of TiO ₂ equivalent as a starting material was used, and after the raw material was dried at 150 ° C. for 2 hours, sulfuric acid was added to dissolve the TiOSO ₄ aqueous solution. Obtained. This was concentrated, and 4.0 parts by mass of the anatase titania sol was added as a seed, followed by hydrolysis at 120 ° C. to obtain a slurry of TiO (OH) ₂ containing impurities. This slurry was repeatedly washed with water at pH 5 to 6 to sufficiently remove sulfuric acid, FeSO ₄ , and impurities. Then, a slurry of high purity metatitanic acid [TiO (OH) ₂ ] was obtained.

The metatitanic acid was heat-treated at 300 ° C. for 5 hours, and then sufficiently pulverized to obtain a hydrophilic anatase crystal hydrophilic titanium oxide fine powder having a BET specific surface area of 120 m ² / g and a number average particle size of 100 nm. Obtained.

Next, 20 parts by mass of i-C ₄ H ₉ —Si— (OCH ₃ ) ₃ as a hydrophobizing agent is sufficiently dispersed in 100 parts by mass of the hydrophilic titanium oxide in water. While being added dropwise, the mixture was hydrophobized. Then, after filtering and drying at 120 ° C. for 5 hours, heat treatment is performed at 170 ° C. for 5 hours, and pulverization is performed by a jet mill until aggregates of the hydrophobic titanium oxide fine particles disappear, thereby obtaining hydrophobic titanium oxide fine particles. It was. The hydrophobized number average particle diameter of 150 nm and spherical titanium oxide are used as the inorganic fine powder 2. The physical property values of the obtained inorganic fine powder 2 are shown in Table 1.

(Inorganic fine powder production example 3)
Using slaked lime powder obtained by dehydrating quicklime, the concentration was adjusted to 120 g / L. Carbonation reaction was performed by blowing CO ₂ gas into lime milk while stirring. In the carbonation reaction, a CO ₂ -containing gas is blown until the carbonation rate reaches 6.0% at a feed rate of 20 m ³ / m ² · hr as the first stage, and then the feed rate is set to 1.2 m ³ / Reduce to m ² · hr and blow in CO ₂ -containing gas until the carbonation rate reaches 13.0%. Further, as the third stage, increase the feed rate to 18 m ³ / m ² · hr and increase the carbonation rate to 45.0%. The reaction was carried out by blowing a gas containing CO ₂ until the reaction product was obtained.

1 mol of aqueous calcium hydroxide suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L was mixed with 1 mol of the obtained reaction product. The obtained mixture was blown with a CO ₂ -containing gas at a reaction start temperature of 25 ° C. at a supply rate of 8.0 m ³ / m ² · hr to be carbonated to a carbonation rate of 50.5%. Aqueous suspension A was prepared by coarsening to a thickness of 0.4 μm at 8 μm. On the other hand, a calcium hydroxide aqueous suspension having a viscosity of 2500 cp at 25 ° C. and a concentration of 400 g / L is adjusted to a concentration of 50 g / L, and a CO ₂ -containing gas is supplied at a reaction start temperature of 13 ° C. at a feed rate of 10.0 m ³ / m. Aqueous suspension B was prepared by blowing to a carbonation rate of 32.3% at ² · hr.

Next, liquid A and liquid B are mixed so that the molar ratio of the Ca-based compound in liquid A and the Ca-based compound in liquid B is 100: 8, and then the CO ₂ gas supply rate at a reaction start temperature of 15 ° C. The mixture was blown at 15 m ³ / m ² · hr and reacted to obtain uniform cubic calcium carbonate having a number average particle size of 150 nm.

  After washing the suspension containing calcium carbonate, it was adjusted to a slurry having a solid content of 10% by mass. While the slurry was stirred with a disperser at 65 ° C., a sodium stearate content of 20% by mass was added and stirred, followed by press dehydration. The obtained filter cake was dried with a box-type dryer and then crushed to obtain inorganic fine powder 3 which is calcium carbonate particles treated with stearic acid. The physical property values of the obtained inorganic fine powder 3 are shown in Table 1.

(Inorganic fine powder production example 4)
To a reaction vessel containing 20 L of 3.0 mol / L sodium hydroxide aqueous solution, 20 L of ferrous sulfate aqueous solution with Fe ²⁺ of 1.5 mol / L is added, and the temperature is set to 95 ° C. A ferrous salt suspension containing was produced. The mixture was stirred for 90 minutes while aeration of 100 L / min air was conducted to obtain a ferrous suspension containing magnetite. A 6.0 mol / L aqueous sodium hydroxide solution was added thereto to adjust the pH to 10.0. Furthermore, it stirred for 60 minutes, ventilating 100 L / min air, and the magnetite particle | grains were produced | generated. After stirring sufficiently, the magnetite was filtered off. The magnetite was washed with water; dried, and then crushed to obtain octahedral magnetite particles.

  An inorganic fine powder 4 that is octahedral magnetite particles having a number average particle diameter of 240 nm was obtained. Table 1 shows the physical properties of the obtained inorganic fine powder.

(Inorganic fine powder production example 5)
Surface treatment was performed with 10.0 parts by mass of dimethyl silicon oil (100 cps) with respect to 100 parts by mass of the 4 particles of the inorganic fine powder, whereby an inorganic fine powder 5 was obtained. The physical properties of the obtained inorganic fine powder 5 are shown in Table 1.

(Inorganic fine powder production example 6)
Hydrogen peroxide water was added to an aqueous cerium chloride (CeCl ₃ ) solution, and then aqueous ammonia was added dropwise with stirring to precipitate a cerium oxide-containing cerium gel. Next, this precipitated gel was heat-treated at 150 ° C. for 24 hours in an autoclave to obtain a slurry, which was filtered and washed 5 times with pure water, stirred, filtered and dried under reduced pressure to obtain a number average particle size of 250 nm. Inorganic fine powder 6 which is a cerium oxide powder having a hexahedral shape was obtained. The physical property values of the obtained inorganic fine powder 6 are shown in Table 1.

(Inorganic fine powder production example 7)
Aqueous ammonia was added to ethanol and stirred, and tetraethoxysilane was added dropwise to the solution maintained at 25 ° C. for 60 minutes to react. After completion of the dropping, stirring was further continued at 25 ° C. for 3 hours to obtain a silica sol suspension. Next, the silica sol suspension was heated to remove ethanol, dried with a fluid bed dryer, and then pulverized with a pin mill. Then, after drying at 110 degreeC using the fluidized bed dryer, it fully pulverized again with the pin mill, and the silica particle was obtained. This silica having an irregular shape with a number average particle diameter of 85 nm is used as the inorganic fine powder 7.

(Inorganic fine powder production example 8)
A ferrous sulfate solution containing 0.95 equivalents of sodium hydroxide aqueous solution was mixed with Fe ^{2+ in a} ferrous sulfate solution, and then a ferrous salt aqueous solution containing Fe (OH) ₂ was produced. Next, air was passed through the aqueous ferrous salt solution containing Fe (OH) ₂ at a temperature of 90 ° C. to cause an oxidation reaction under the condition of pH 7. Further, 1.05 equivalent of an aqueous sodium hydroxide solution was added to this suspension with respect to the remaining Fe ²⁺ , and the mixture was further oxidized at a temperature of 8 to 11.5 while being heated at 90 ° C. To produce magnetite. The produced magnetite was washed, filtered and dried by a conventional method. Thereafter, the mixture was crushed by a mix muller to obtain inorganic fine powder 8 which was spherical magnetite particles having a number average particle diameter of 380 nm. The physical properties of the obtained inorganic fine powder 8 are shown in Table 1.

(Inorganic fine powder production example 9)
Aluminum hydroxide was molded at a pressure of 1000 kg / cm ² (98000 kPa) and sintered at a temperature of 1600 ° C. for 2 hours. Thereafter, it was mechanically pulverized to obtain inorganic fine powder 9 which is aluminum oxide particles having a number average particle diameter of 85 μm. The physical properties of the obtained inorganic fine powder 9 are shown in Table 1.

(Inorganic fine powder production example 10)
Cerium oxalate was molded at a pressure of 1200 kg / cm ² (117600 kPa) and sintered at a temperature of 1800 ° C. for 5 hours. Thereafter, the mixture was mechanically pulverized to obtain inorganic fine powder 10 which is cerium oxide particles having an average particle diameter of 390 nm. The physical properties of the obtained inorganic fine powder 10 are shown in Table 1.

(Inorganic fine powder production example 11)
Trimethyl borate was synthesized from 1 mol of boron oxide and 7.5 mol of methanol. The obtained trimethyl borate was introduced into a quartz tube attached to a tubular furnace using nitrogen gas, and white powder generated by heating to 700 ° C. in an argon gas and ammonia gas stream was converted into an ammonia gas stream. Heated to 1100 ° C. for 5 hours.

  The boron nitride particles that are spherical particles having an average particle diameter of 70 nm thus obtained are further heated at 1100 ° C. and grown for 5 hours until reaching 430 nm to obtain inorganic fine powder 11 that is boron nitride particles having a number average particle diameter of 430 nm. . Table 1 shows the physical properties of the obtained inorganic fine powder.

  Next, an example of manufacturing a preform for molding a toner container is shown.

[Preform production example 1]
Polyethylene terephthalate resin (TR-8550T manufactured by Teijin Limited) 100 parts by mass Carbon black (average particle size 30 μm, oil absorption 50 g / 100 g) 2 parts by mass The above materials are mixed well and melt kneaded with a twin-screw kneader. Then, a test tubular preform 1 was molded from the melt using an injection molding machine (“PE-80S” manufactured by Nissei Plastic Industry Co., Ltd.).

[Preform production example 2]
Preform 2 was produced in the same manner as in Preform Production Example 1 except that the amount of carbon black added was changed to 5.0 parts by mass.

[Preform production example 3]
-Polyethylene naphthalate resin (TR-8550T manufactured by Teijin Ltd.) 100 parts by mass-Carbon black 7.0 parts by mass The above materials are thoroughly mixed and melt-kneaded with a twin-screw kneader, and then the melt is injection molded. A test tubular preform 3 was molded using a machine (“PE-80S” manufactured by Nissei Plastic Industry Co., Ltd.).

[Preform Production Example 4]
Preform 4 was produced in the same manner as in Preform Production Example 3 except that the amount of carbon black added was changed to 0.2 parts by mass.

[Preform Production Example 5]
-Polyethylene terephthalate resin (TR-8550T manufactured by Teijin Ltd.) 50 parts by mass-Polycarbonate resin (L1225Y manufactured by Teijin Ltd.) 50 parts by mass-Carbon black 10 parts by mass After melt-kneading, a test tubular preform 5 was molded from the melt using an injection molding machine ("PE-80S" manufactured by Nissei Plastic Industry Co., Ltd.).

[Preform Production Example 6]
・ Polybutylene terephthalate resin
(BT-2535, manufactured by Dainippon Ink & Chemicals, Inc.) 40 parts by mass, polystyrene resin (VS142, manufactured by Nippon Polystyrene Co., Ltd.) 60 parts by mass, carbon black 10 parts by mass After melt-kneading, a test tubular preform 6 was molded from this melt using an injection molding machine (“PE-80S” manufactured by Nissei Plastic Industry Co., Ltd.).

[Preform Production Example 7]
A preform 7 was molded in the same manner as in Preform Production Example 5 except that carbon black was not added.

[Preform production example 8]
-Polypropylene resin (J-2003GP, manufactured by Idemitsu Petrochemical Co., Ltd.) 100 parts by mass-Carbon black 10 parts by mass The above materials are sufficiently mixed and melt-kneaded by a twin-screw kneader. A test tubular preform 8 was molded using “PE-80S” manufactured by Nissei Plastic Industrial Co., Ltd.

[Manufacture example 1 of container]
<Stretch blow molding>
Prepare a blow mold for a toner container of a commercially available copying machine imageRUNNER iR5075N (manufactured by Canon Inc.) so that the preform obtained above has an optimum heating time in an infrared irradiation furnace equipped with a quartz heater. Held on. This was held at room temperature for 25 seconds, then charged into the blow mold set at 98 ° C., and blow-molded while being stretched in the height direction with a stretch rod to obtain a toner container 1.

[Container Production Examples 2 to 8]
A blow mold for a cyan toner container of a commercially available copying machine imageRUNNER iRC5180 (manufactured by Canon Inc.) is prepared, blow-molded using preforms 2 to 8, and then subjected to secondary processing to toner container 2 Thru 8 were obtained.

[Manufacturing Example 9 of Container]
A mold for an injection molding machine for a cyan toner container of a commercially available copying machine imageRUNNER iRC5180 (manufactured by Canon Inc.) was prepared, and a toner container 9 was obtained using the preform 7.

[Example 1]
(Toner Production Example 1)
Polyester resin 100 parts by mass (Av. = 25 mgKOH / g, OHv. = 35 mgKOH / g, Tg = 60 ° C.,
Mn = 2,700, Mw = 83,000, THF insoluble content 15 wt%)
Low molecular weight ethylene-propylene copolymer (melting point: 102 ° C.) 6 parts by mass Charge control agent (azo-based iron complex compound) 2 parts by mass Magnetic iron oxide 90 parts by mass (average particle size 0.19 μm, coercive force 11. 2KA / m, residual magnetization 10.8Am ² / kg, saturation magnetization 82.3Am ² / kg)
The above mixture was melt-kneaded with a twin-screw kneader heated to 130 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. Further, finely pulverized by a collision type pulverizer, and the finely pulverized product obtained is classified by an air classifier, and toner particles (toner base material) having a weight average diameter of 7.6 μm, 10.1 μm or more particles of 6.8% by volume. 1) was obtained.

To 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobic dry silica (BET specific surface area: 300 m ² / g) and 1.0 part by mass of inorganic fine powder 1 were added, and a Henschel mixer FM500 (Mitsui Miike Co., Ltd.) was added. The toner 1 of the present invention was obtained by rotating and stirring for 3 minutes at a stirring blade rotational speed of 1100 rpm to disperse and adhere to the toner surface.

  Using the toner 1, the following evaluation was performed.

<Image evaluation test>
A commercially available copying machine, imageRUNNER iR5075N (made by Canon Inc.) is modified so that the toner discharged from the toner cartridge is directly supplied to the developing machine by eliminating the sub hopper between the toner cartridge mounting part and the developing machine. Furthermore, the printing speed was modified from 75 cpm to 100 cpm.

  100,000 sheets were copied using a test chart with a printing ratio of 20% in a low-temperature and low-humidity environment (7.5 ° C / 5% RH) and a high-temperature and high-humidity environment (40 ° C / 90% RH). The image density, in-plane uniformity, fog, and dot reproducibility were evaluated as shown below. The results are shown in Tables 2 and 3.

1) Image Density With a “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.), an SPI filter was used to measure the reflection density of an image having a 5 mm diameter circle, and the average value was evaluated.
Rank 5: Reflection density 1.45 or higher Rank 4: Reflection density 1.40 to 1.44
Rank 3: reflection density 1.35 to 1.39
Rank 2: Reflection density 1.30 to 1.34
Rank 1: Reflection density less than 1.29

2) In-plane density uniformity “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.) uses an SPI filter to measure the reflection density of a solid black image, the maximum value (Dmax) of the reflection density and the lowest In-plane density uniformity was evaluated based on the difference (Dmax−Dmin) of the value (Dmin).
Rank 5: In-plane density uniformity Less than 0.05 Rank 4: In-plane density uniformity 0.06 to 0.10
Rank 3: In-plane density uniformity 0.11 to 0.15
Rank 2: In-plane density uniformity 0.16 to 0.20
Rank 1: In-plane density uniformity 0.21 or more

3) Fog Using a “reflection densitometer” (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), the reflection density (Dr) of the transfer paper before image formation and the reflection density after copying the solid white image The worst value was measured as (Ds), and the difference (Ds−Dr) was evaluated as the fog value.
Rank 5: Fog less than 0.1 Rank 4: Fog 0.1 to 0.5
Rank 3: fog 0.5 to 1.5
Rank 2: fog 1.5 to 2.0
Rank 1: fog 2.0 or higher

4) Evaluation of dot reproducibility A checkered electrostatic latent image composed of 1 dot, 2 dots, 3 dots, and 4 dots shown in FIG. 5 is formed on the photoreceptor, and a developer is supplied to the surface of the photoreceptor. The obtained visible image was used as a sample. This sample was observed with an optical microscope to evaluate dot reproducibility.
Rank 5: An image faithful to the latent image.
Rank 4: When enlarged with an optical microscope, some scattering is observed.
Rank 3: When enlarged with an optical microscope, scattering and disturbance are observed.
Rank 2: Scattering and image distortion are observed by visual inspection.
Rank 1: The original is not reproduced.

[Example 2]
(Toner Production Example 2)
Polyester resin (Av. = 25 mgKOH / g, OHv. = 35 mgKOH / g, Tg = 60 ° C., Mn = 2,700, Mw = 83,000, THF insoluble content 15% by mass)
60 parts by mass / Cyan pigment (Pigment Blue 15: 3) 40 parts by mass The above formulation was melt-kneaded with a kneader mixer to prepare a cyan master batch.

-100.0 parts by mass of the above polyester resin-Refined paraffin wax (maximum endothermic peak: 72 ° C, Mw = 450, Mn = 32)
4.0 parts by mass · Cyan masterbatch (colorant content 40% by mass) 15.0 parts by mass · Aluminum compound of di-tert-butylsalicylic acid (charge control agent) 1.0 part by mass Heat the above mixture to 150 ° C The resulting mixture was melt-kneaded with the twin-screw kneader and the cooled mixture was coarsely pulverized with a hammer mill. Further, finely pulverized by a collision type pulverizer, and the finely pulverized product obtained was classified by an air classifier, and toner particles (toner base material) having a weight average diameter of 7.4 μm, 10.1 μm or more of particles of 6.8% by volume. 2) was obtained.

With respect to 100 parts by mass of the toner particles, 0.5 part by mass of hydrophobic silica (BET specific surface area: 300 m ² / g), hydrophobic titanium oxide (BET specific surface area: 150 m ² / g), and inorganic fine powder 1 1.0 part by mass was added and externally added by a Henschel mixer FM500 (manufactured by Mitsui Miike) at a stirring blade rotational speed of 1100 rpm for 5 minutes to obtain toner 2 of the present invention.

<Image evaluation test>
In the cyan toner cartridge section and developing section of a commercially available color copying machine imageRUNNER iRC5180 (manufactured by Canon Inc.), the sub hopper between the toner cartridge mounting section and the developing machine is eliminated, and the toner discharged from the toner cartridge is directly Modified to be supplied to the developing machine.

  Further, as shown in FIG. 6, the developing machine is modified to have a developing roller 114 having a urethane resin layer 115 and a sponge roller 116 for applying toner to the developing roller 114, and further, the developing roller and the photosensitive roller are arranged. The drum 117 was installed so that it contacted. Further, the potentials of the photosensitive member and the developing roller were set to a non-image portion photosensitive drum potential of −650 V, an image portion photosensitive drum potential of −250 V, a developing bias of −500 V, and an image potential contrast of 250 V.

  In the above-described evaluation machine, using a test chart with a cyan single color mode and a printing ratio of 20%, each of a low temperature and low humidity environment (7.5 ° C / 5% RH) and a high temperature and high humidity environment (40 ° C / 90% RH) In the above, 100,000 copies were made, and image density, in-plane uniformity, fog, and dot reproducibility were evaluated as shown below. The evaluation results are shown in Tables 2 and 3.

1) Image density Using an X-Rite 500 type (manufactured by X-rite), the reflection density of an image having a 5 mm diameter circle was measured at five points, and the average value was evaluated.
Rank 5: Reflection density 1.50 or higher Rank 4: Reflection density 1.40 to 1.49
Rank 3: Reflection density 1.30 to 1.39
Rank 2: Reflection density 1.20 to 1.30
Rank 1: Reflection density less than 1.19

2) In-plane density uniformity “Macbeth reflection densitometer” (manufactured by Macbeth Co., Ltd.) uses an SPI filter to measure the reflection density of a solid black image, the maximum value (Dmax) of the reflection density and the lowest In-plane density uniformity was evaluated based on the difference (Dmax−Dmin) of the value (Dmin).
Rank 5: In-plane density uniformity Less than 0.05 Rank 4: In-plane density uniformity 0.06 to 0.10
Rank 3: In-plane density uniformity 0.11 to 0.15
Rank 2: In-plane density uniformity 0.16 to 0.20
Rank 1: In-plane density uniformity 0.21 or more

3) Fog Using a “reflection densitometer” (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), the reflection density (Dr) of the transfer paper before image formation and the reflection density after copying the solid white image The worst value was measured as (Ds), and the difference (Ds−Dr) was evaluated as the fog value.
Rank 5: Fog less than 0.1 Rank 4: Fog 0.1 to 0.5
Rank 3: fog 0.5 to 1.5
Rank 2: fog 1.5 to 2.0
Rank 1: fog 2.0 or higher

4) Evaluation of dot reproducibility A checkered electrostatic latent image composed of 1 dot, 2 dots, 3 dots, and 4 dots shown in FIG. 5 is formed on the photoreceptor, and a developer is supplied to the surface of the photoreceptor. The obtained visible image was used as a sample. This sample was observed with an optical microscope to evaluate dot reproducibility.
Rank 5: An image faithful to the latent image.
Rank 4: When enlarged with an optical microscope, some scattering is observed.
Rank 3: When enlarged with an optical microscope, scattering and disturbance are observed.
Rank 2: Scattering and image distortion are observed by visual inspection.
Rank 1: The original is not reproduced.

[ Reference Examples 1 to 9 and Comparative Examples 1 to 3]
In Example 2, the toner cartridge was changed in the same manner as in Example 2 except that the inorganic fine powder added to the toner and the amount added were changed as shown in Table 2, and the container was changed as shown in Table 2. Were prepared and evaluated in the same manner. The evaluation results are shown in Tables 2 and 3.

It is explanatory drawing of the blow molding method of the toner container of this invention. It is explanatory drawing of the blow molding method of the toner container of this invention. It is explanatory drawing of the blow molding method of the toner container of this invention. It is explanatory drawing of the blow molding method of the toner container of this invention. It is explanatory drawing of the checker pattern for testing the development characteristic of the toner of this invention. FIG. 3 is an explanatory diagram of a developing device for testing the toner of the present invention.

DESCRIPTION OF SYMBOLS 101: Injection molding apparatus 102: Hopper 103: Molding material 104: Heating cylinder 105: Extrusion screw 106: Mold 107: Preform 108: Heating furnace 109: Blow mold 110: Drawing rod 111: Preform mouth part 112: Gas 113: Blow molded product 114: Developing roller 115: Urethane resin layer 116: Sponge roller 117: Photosensitive drum

Claims (7)

In a toner cartridge which is constituted by at least a toner container containing toner and detachable from an image forming apparatus,
The toner container is a toner container obtained by molding a molding resin containing at least a polyester obtained by polymerizing an aromatic dicarboxylic acid and an alkylene glycol and carbon black by a stretch blow method,
The toner has toner particles containing at least a binder resin and a colorant, a number average particle diameter of 80 nm to 400 nm, and a volume resistivity value of 1.0 × 10 ³ Ω · m to 1.0 × 10 ^9. have a fine inorganic particles is less than or equal to Ω · m,
The molding resin has a dielectric constant ε (C) of 2.8 pF / m or more and less than 3.8 pF / m at 40 ° C. and 2 kHz, and the dielectric constant ε (A) of the inorganic fine particles at 40 ° C. and 2 kHz. The following formula (1)
30.0 <ε (A) / ε (C) <150.0 (1)
A toner cartridge characterized by satisfying   The shape of the inorganic fine particle is an octahedron that is a convex polyhedron surrounded by eight triangles and / or a hexahedron that is a convex polyhedron surrounded by six quadrangles. Toner cartridge.   The toner cartridge according to claim 1, wherein the inorganic fine particles are hydrophobized. Inorganic fine particles, the toner cartridge according to claim 1 or 2, characterized in that it is hydrophobicized with fatty acids. 40 ° C. of the toner, the dielectric constant at 2 kHz epsilon is (T), the toner cartridge according to any one of claims 1 to 4, characterized in that at most 30.0pF / m or more 80.0pF / m . The toner cartridge according to claim 1, wherein the inorganic fine particles are strontium titanate. The toner cartridge according to claim 1, wherein the colorant is magnetic iron oxide.

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