WO2013137366A1 - Toner, developer, and image forming apparatus - Google Patents
Toner, developer, and image forming apparatus Download PDFInfo
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- WO2013137366A1 WO2013137366A1 PCT/JP2013/057112 JP2013057112W WO2013137366A1 WO 2013137366 A1 WO2013137366 A1 WO 2013137366A1 JP 2013057112 W JP2013057112 W JP 2013057112W WO 2013137366 A1 WO2013137366 A1 WO 2013137366A1
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- toner
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- resin
- coalesced
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- G03G9/08755—Polyesters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
- G03G9/0806—Preparation methods whereby the components are brought together in a liquid dispersing medium whereby chemical synthesis of at least one of the toner components takes place
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08797—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their physical properties, e.g. viscosity, solubility, melting temperature, softening temperature, glass transition temperature
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09716—Inorganic compounds treated with organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
Definitions
- the present invention relates to a toner, which is used in image formation performed by an electrophotographic system, such as by a photocopier, electrostatic printing, a printer, a facsimile, and electrostatic recording, and also relates to a developer and image forming apparatus using the toner.
- tandem system is a system of an image forming apparatus, where a plurality of
- electrophotographic photoconductors are aligned in series, an image of each color is formed on each electrophotographic photoconductor, and the images of different colors are
- toner particles can be controlled to have desirable particle diameters, shapes, and surface structures, a piled height (a thickness of an image layer) is kept small, and excellent reproducibility of dots and fine lines can be achieved.
- a piled height a thickness of an image layer
- excellent reproducibility of dots and fine lines can be achieved.
- non-electrostatic adhesion force between the toner particles to the electrophotographic photoconductor, and non-electrostatic adhesion force between the toner particles to the intermediate transfer member increase, and therefore transfer property of the toner is deteriorated.
- deterioration of transfer property considered is to prolong the time that the toner particles receive transfer electric field by widening a width of a secondary transfer nip.
- a contact voltage applying system however, a resulting image quality is degraded, as a contact pressure of a bias roller increases, and moreover use of a bias roller having an enlarged roller diameter is not suitable for a down-sized roller device.
- the non-contact voltage applying system there is a limit to increase the number of chargers. Especially in a high-speed device, it is substantially impossible to widen a nip width to achieve desirable transfer property.
- an external additive As another method for solving the low transfer property, proposed is a method for adjusting a type or amount of an external additive (see, for example, PTL 5).
- use of the external additive having a large particle size can reduce non-electrostatic adhesion force of toner particles, to thereby improve transfer property, developing stability, and cleaning property.
- an effect for improving flowability of a toner becomes small, which may cause filming, and carrier pollution, or impair supplying property of a toner.
- the external additive may be embedded in toner base particles by the stirring stress applied to the toner in a developing device after the usage of a long period. Since the motions of the stirring in a developing device is strong especially in a high-speed device, the embedment of the external additive into the toner base particles tends to be accelerated, and therefore transfer property is deteriorated in a relatively early stage.
- the toner using the crystalline polyester resin has a problem that an external additive tends to be embedded into surfaces of particles of the toner, and transfer property of the toner is deteriorated.
- non-spherical external additive For the purpose of improving the transfer property, proposed is use of a non-spherical external additive (see, for example, PTL 7).
- a non-spherical external additive With the non-spherical external additive, excellent image density can be achieved at initial printing, but the storage stability of the toner is poor, and therefore the image density is lowered as printing is continuously performed for a long period, and the durability of the toner is poor. Moreover, whether the non-spherical particles are cracked and/or collapsed by externally applied loads is not discussed therein, and therefore the aforementioned method is not sufficient.
- An object of the present invention is to provide a toner having high durability such that the toner excels in cleaning ability, storage stability, and image density when used for a long period, as well as having excellent transfer properties in high-speed full-color image formation.
- the means for solving the aforementioned problems are as follows :
- the toner of the present invention contains: toner base particles, each containing at least a binder resin and a releasing agent; and an external additive, wherein the external additive contains non-spherical coalesced particles in each of which primary particles are coalesced together, and wherein the coalesced particles satisfy the following formula (l) : Nx
- Nx is a number of the primary particles present alone relative to 1,000 of the coalesced particles, as observed under a scanning electron microscope after stirring 0.5 g of the coalesced particles and 49.5 g of a carrier placed in a 50 mL bottle for 10 minutes by means of a mixing and stirring device at 67 Hz.
- the present invention can solve the various problems in the art, and can provide a toner having high durability such that the toner excels in cleaning ability, storage stability, and image density when used for a long period, as well as having excellent transfer properties in high-speed full-color image formation.
- FIG. 1 is a photograph depicting an example of the external additive of the toner of the present invention.
- FIG. 2 is a photograph depicting an example of the external additive of the toner of the present invention.
- FIG. 3 is a photograph depicting one example of an evaluation result of the external additive of Example.
- FIG. 4 is a photograph depicting one example of an evaluation result of the external additive of Comparative
- FIG. 5 is a schematic diagram for explaining one example of a process cartridge suitable for use in the image forming apparatus of the present invention.
- FIG. 6 is a schematic diagram for explaining one example of the image forming apparatus of the present invention.
- FIG. 7 is a schematic diagram for explaining another example of the image forming apparatus of the present invention.
- FIG. 8 is a schematic diagram for explaining yet another example of the image forming apparatus of the present invention.
- FIG. 9 is a schematic diagram for explaining one part of the image forming apparatus illustrating in FIG. 8.
- the toner of the present invention contains at least toner base particles, and an external additive, and may further contain other components, if necessary.
- the external additive contains at least coalesced particles, and may further contain other external additives, other than the coalesced particles, if necessary.
- the coalesced particles are each a non-spherical particle in each of which primary particles are coalesced together, and are namely secondary particles formed by coalescencing
- the primary particles are appropriately selected
- examples thereof include inorganic particles (e.g., silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth, chromic oxide, cerium oxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride), and organic particles. These may be used alone or in combination. Among them, silica is preferable.
- silica is preferable.
- the secondary particles are appropriately selected depending on the intended purpose without any limitation, but they are preferably particles (secondary aggregated particles) each formed by chemically bonding the aforementioned primary particles with the below-mentioned treatment agent, such as the particle indicated with the reference number 3 in FIGs. 3 and 4, more preferably particles each formed by chemically bonding the primary particles by a sol-gel method.
- the average particle diameter of the secondary particles i.e., the average particle diameter of the coalesced particles
- the average particle diameter of the secondary particles is appropriately selected depending on the intended purpose without any limitation, but it is preferably 15 nm to 400 nm, more preferably 20 nm to 300 nm, and even more preferably 50 nm to 200 nm.
- the average particle diameter thereof is smaller than 15 nm, the external additive tends to be embedded in the toner base particle, and therefore sufficient durability of the toner cannot be maintained, which may lead to insufficient cleaning ability.
- the average particle diameter thereof is greater than 400 nm, an excessive amount of the external additive is deposited on the toner base particle, and therefore the external additive is easily detached from the toner base particle so that it may not be able to maintain the transfer property of the toner.
- the measurement of the average particle diameter of the secondary particles is performed by dispersing the secondary particles in an appropriate solvent (e.g., THF), removing and drying the solvent on a substrate to prepare a sample, observing the sample and measuring particle diameters of the secondary particles in a visual field under a field emission scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, magnification: x 8,000 to x 10,000).
- an appropriate solvent e.g., THF
- the average particle diameter of the secondary particles is determined by speculating an entire image from a profile of the secondary particle formed by coalescence, and measuring the average value (the number of particles measured: 100 particles or more) of the maximum length (a length of the arrow shown in FIG. 2) of the entire image.
- a production method of the coalesced particles is
- coalesced particles may be prepared in a single stage reaction by allowing the treatment agent present together.
- the production method is described below, but the production method is not limited thereto.
- the treatment agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a silane-based treatment agent, and an
- the silane-based treatment agent is preferably used because a Si-O-Si bond the silane-based treatment agent forms is more stable to heat than a Si-O-C bond the epoxybased
- treatment agent forms.
- a treatment aid e.g., water, and a 1% by mass acetic acid aqueous solution
- acetic acid aqueous solution may be used, as needed.
- the silane-based treatment agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ alkoxy silane (e.g., tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, dimethyldimethoxy silane, dimethyldiethoxy silane, methyldimethoxy silane, methyldiethoxy silane,
- alkoxy silane e.g., tetramethoxy silane, tetraethoxy silane, methyltrimethoxy silane, methyltriethoxy silane, dimethyldimethoxy silane, dimethyldiethoxy silane, methyldimethoxy silane, methyldiethoxy silane,
- silane coupling agent e.g., a silane coupling agent
- N,0-bis(trimethylsilyl)acetoamide, dimethyltrimethylsilylamine, hexamethyl disilazane, and cyclic silazane N,0-bis(trimethylsilyl)acetoamide, dimethyltrimethylsilylamine, hexamethyl disilazane, and cyclic silazane.
- the silane-based treatment agent forms secondary
- aggregations of the primary particles e.g., silica primary particles
- a chemical bond in the following manner.
- silica primary particles are treated with the alkoxy silane or the silane-based coupling agent as the silane-based treatment agent, as represented by the following formula (A), a silanol group bonded to the silica primary particle reacts with an alkoxy group bonded to the silane-based treatment agent to form a new Si-O-Si as a result of the alcohol elimination reaction, to thereby cause secondary aggregation.
- the silica primary particles are treated with the chlorosilane as the silane-based treatment agent, a chloro group of the chlorosilane and a silanol group bonded to the silica primary particle proceed to a dehydrochlorination reaction, and as a result, the silanol group for forming a new Si-O-Si bond forms a new Si-O-Si bond as a result of a dehydration reaction, to thereby cause secondary reaction.
- the silica primary particles are treated with the chlorosilane as the silane-based treatment agent and water is present in the system, first, the chlorosilane and water proceed to hydrolysis to generate a silanol group, and the generated silanol group and a silanol group bonded to the silica primary particle form a new Si-O-Si bond as a result of a dehydration reaction, to thereby cause secondary aggregation.
- silica primary particles are treated with the silazane as the silane-based treatment agent, an amino group and a silanol group bonded to the silica primary particle proceed to an ammonia elimination reaction to form a new Si-O-Si bond, to thereby cause secondary aggregation.
- R denotes an alkyl group.
- the epoxy-based treatment agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a bisphenol A epoxy resin, a bisphenol F epoxy resin, a phenol novolak epoxy resin, a cresol novolak epoxy resin, a bisphenol A novolak epoxy resin, a bisphenol epoxy resin, a glycidylamine epoxy resin, and an alicyclic epoxy resin.
- the epoxy-based treatment agent forms secondary aggregations of the primary particles (e.g., silica primary particles) with a chemical bond, as represented by the following formula (B).
- a silanol group bonded to the silica primary particle carries out an addition reaction to add an oxygen atom of an epoxy group and a carbon atom bonded to the epoxy group of the epoxybased treatment agent to form a new Si-O- C bond, which causes secondary aggregation of the primary particles.
- a blending mass ratio of the primary particle to the treatment agent (primary particle- ' treatment agent) is
- a method for mixing the primary particles with the treatment agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method for mixing by means of a conventional mixer (e.g., a spray dryer).
- a conventional mixer e.g., a spray dryer.
- the treatment agent may be mixed after the primary particles are prepared, or the treatment agent may be added and in present during the primary particles are prepared to thereby perform the preparation with a single stage reaction.
- the firing temperature of the primary particles and the treatment agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 100°C to 2,500°C. Note that, the degree of coalescence increases as the firing temperature increases.
- the firing time of the primary particles and the treatment agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.5 hours to 30 hours.
- coalesced particles are appropriately selected depending on the intended purpose without any limitation, as long as they satisfy the following formula (l), but they also preferably satisfy the following formula (l " l).
- the coalesced particles improve durability of the toner because the coalesced particles maintain the aggregation force (coalescence force) between the primary particles under a certain stirring condition.
- Nx is a number of the primary particles present alone relative to 1,000 of the coalesced particles, as observed under a scanning electron microscope after stirring 0.5 g of the coalesced particles and 49.5 g of a carrier placed in a 50 mL bottle for 10 minutes by means of a mixing and stirring device at 67 Hz.
- the present inventors have attained the following insights based upon the researches the inventors conducted.
- one of the insights is that the toner lowers the durability thereof, when the coalesced particles of the external additive contained in the toner are crashed and/or collapsed, as loads are externally applied, to thereby turn back to the primary particles. Therefore, it was studied not to crack or collapse the coalesced particles of the external additive, which lead to another insight. That is, the durability of the toner can be enhanced by using particles having certain durability as an external additive.
- the number of the coalesced particles turned back to the primary particles due to cracking and or collapse caused by loads applied in a developing device is reduced, and therefore embedding or rolling of the external additive is prevented and a high transferring rate of the toner can be maintained over time.
- the cohesive power of the coalesced particles is weak (e.g., the case where the ratio of the primary particles present alone [the reference number 4, in FIG. 4] relative to 1,000 coalesced particles is greater than 30%, as illustrated in FIG. 4), the number of the coalesced particles turned back to the primary particles due to cracking and or collapse caused by loads applied in a developing device is increased, which increases a proportion of the spherical primary particles. Therefore, rolling or embedding of the external additive tends to occur, and a high transferring rate of the toner is difficult to maintain over time.
- the primary particles means particles that are not coalesced to other primary particles after stirring the coalesced particles by the mixing and stirring device under the aforementioned stirring conditions, and include particles which are became primary particles by crack or collapse of the coalesced particles after the stirring, and particles which are present as primary particles before the stirring.
- the primary particles include particles that are not coalesced to other primary particles, such as the particles indicated with the reference number 4 in FIGs. 3 and 4.
- shapes of the primary particle are appropriately selected depending on the intended purpose without any limitation, provided that they are shapes which primary particles are not coalesced to each other.
- the primary particles are commonly present in the substantially spherical state.
- a method for confirming how the primary particles are present is appropriately selected depending on the intended purpose without any limitation, but preferred is a method in which the primary particles are observed under a scanning electron microscope (SEM) to confirm that the primary particles are present alone.
- SEM scanning electron microscope
- a method for measuring the average particle diameter of the primary particles is appropriately selected depending on the intended purpose without any limitation.
- the average particle diameter thereof is measured by measuring the average value of the particle diameters of the primary particles (the number of particles measured- " 100 particles or more) in the visual field as observed under a scanning electron microscope (FE-SEM, accelerating voltage ' - 5 kV to 8 kV, magnification'- x 8,000 to x 10,000).
- coalescencing a plurality of particles is confirmed by the observation under the scanning electron microscope, such coalesced particle is counted as one coalesced particle.
- coalesced particles is, for example, as follows.
- the coalesced particles and primary particles are observed under the scanning electron microscope with the particle concentration and
- observation magnification enable to distinguish a profile of each of the coalesced and primary particles.
- the number can be determined as a number of the primary particles relative to 1,000 coalesced particles in the observing field.
- the observing field for example, the predetermined few visual fields or regions under the scanning electron microscope, preferably adjacent few visual fields or regions, can be appropriately set so that the number of the coalesced particles observed is to be 1,000 or more .
- ROKING MILL manufactured by SEIWA GIKEN Co., Ltd.
- the carrier is appropriately selected depending on the intended purpose without any limitation, but preferred is a coated ferrite powder obtained by applying an acrylic resin-silicone resin coating layer forming solution containing alumina particles to surfaces of a baked ferrite powder, and drying the coated solution.
- the 50 mL bottle is appropriately selected depending on the intended purpose without any
- An average of degrees of coalescence (the particle diameter of secondary particles/ the average particle diameter of primary particles) of the coalesced particles is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1.5 to 4.0.
- coalescence is less than 1.5, the external additive tends to roll into recesses formed in surfaces of the toner base particles, and therefore excellent transfer property of a toner may not be achieved.
- the external additive tends to be detached from the toner, the carrier may be contaminated with the external additive, or the external additive may damage the photoconductor, which may cause image defects over time.
- a method for confirming whether primary particles are coalesced to each other in the coalesced particles is appropriately selected depending on the intended purpose without any
- SEM scanning electron microscope
- coalesced particles contributes high flowability of the toner, and prevents the external additive from being embedded or rolled even when load is applied to the toner, such as by being stirred in a developing device, and therefore high transferring rate of the toner can be maintained.
- An amount of the external additive is appropriately selected depending on the intended purpose without any
- the toner base particles contain at least a binder resin and a releasing agent.
- the toner base particles are preferably formed by the method containing: dissolving or dispersing at least the binder resin and the releasing agent in an organic solvent to prepare a solution or dispersion; adding the solution or dispersion to an aqueous phase to prepare a dispersion solution; and removing the organic solvent from the dispersion liquid, and more preferably formed by the method containing: adding the solution or dispersion to an aqueous phase to proceed to a crosslink or elongation reaction; and removing the organic solvent from the obtained dispersion liquid.
- the binder resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a polyester resin, a silicone resin, a styrene-acryl resin, a styrene resin, an acrylic resin, an epoxy resin, a diene-based resin, a phenol resin, a terpene resin, a coumarin resin, an amide-imide resin, a butyral resin, a urethane resin, and a vinylethylene acetate resin. These may be used alone or in combination. Among them, preferred are a polyester resin, and a combination of a polyester resin with any of the
- binder resin exclusive of the polyester resin, because these have sufficient flexibility with the small molecular weight thereof. Moreover, a crystalline resin is preferable as a resulting toner has excellent low temperature fixing ability and form a smooth image surface.
- the polyester resin is appropriately selected depending on the intended purpose without any limitation, but it is preferably an unmodified polyester resin, or a modified polyester resin. These may be used alone or in combination.
- the unmodified polyester resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a polyester resin formed from polyol represented by the following general formula, and polycarboxylic acid represented by the following general formula (2).
- A denotes a C 1-C20 alkyl group, an alkylene group, an aromatic group that may have a substituent, or a heterocyclic aromatic group! and m denotes an integer of 2 to 4.
- B denotes a C 1-C20 alkyl group, an alkylene group, an aromatic group that may have a
- n is an integer of 2 to 4.
- the polyol represented by the general formula (l) is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol,
- polypropylene glycol polytetramethylene glycol, sorbitol
- dipentaerythritol tripentaerythritol
- 1,2,4-butanetriol 1,2,4-butanetriol
- 2-methyM,2,4-butanetriol trimethylol ethane, trimethylol propane, 1,3,5-trihydroxymethyl benzene, bisphenol A, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide adduct, hydrogenated bisphenol A, hydrogenated bisphenol A ethylene oxide adduct, and hydrogenated bisphenol A propylene oxide adduct. These may be used alone or in combination.
- the polycarboxylic acid represented by the general formula (2) is appropriately selected depending on the intended purpose without any limitation, and examples thereof include maleic acid, fumaric acid, citraconic acid, itaconic acid,
- glutaconic acid phthalic acid, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malonic acid, n-dodecenyl succinic acid, iso-octyl succinic acid, iso-dodecenyl succinic acid, n-dodecyl succinic acid, iso-dodecyl succinic acid, n-octenyl succinic acid, n-octyl succinic acid, iso-octenyl succinic acid, iso-octyl succinic acid, 1,2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
- tetracarboxylic acid diphenylsulfone tetracarboxylic acid, and ethylene glycol bis(trimellitic acid) . These may be used alone or in combination.
- the modified polyester resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a resin obtained through an elongation reaction and/or crosslink reaction of an active hydrogen
- polyester prepolymer may be referred to as "polyester prepolymer hereinafter.
- the elongation reaction and/or crosslink reaction may be terminated with a reaction terminator (e.g., diethyl amine, dibutyl amine, butyl amine, lauryl amine, and a compound obtained by blocking monoamine, such as a ketimine compound), as needed.
- a reaction terminator e.g., diethyl amine, dibutyl amine, butyl amine, lauryl amine, and a compound obtained by blocking monoamine, such as a ketimine compound
- the active hydrogen group-containing compound functions as an elongation agent or crosslink agent during an elongation reaction or crosslink reaction of the polyester prepolymer in an aqueous medium.
- the active hydrogen group-containing compound is appropriately selected depending on the intended purpose without any limitation, provided that it is a compound containing an active hydrogen group.
- the polyester prepolymer is an isocyanate group-containing polyester
- group-containing compound is preferably amine because it can yield a modified polyester resin of high molecular weight.
- the active hydrogen group is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a hydroxyl group (alcoholic hydroxyl group or phenolic hydroxyl group), an amino group, a carboxyl group, and a mercapto group. These may be included as per se or a mixture.
- group-containing compound is appropriately selected depending on the intended purpose without any limitation, and examples thereof include diamine, trivalent or higher polyamine, amino alcohol, amino mercaptan, amino acid, and a compound in which an amino group of any of the aforementioned amines is blocked.
- diamine include aromatic diamine (e.g., phenylene diamine, diethyltoluene diamine, and
- Examples of the amino alcohol include ethanol amine, and hydroxyethyl aniline.
- Examples of the amino mercaptan include aminoethyl mercaptan, and aminopropyl mercaptan.
- Examples of the amino acid include aminopropionic acid, and aminocaproic acid.
- Examples of the compound in which an amino group of these amines is blocked include a ketimine compound and oxazoline compound, which are obtained from any of these amines (e.g., the diamine, the trivalent or higher polyamine, the amino alcohol, the amino mercaptan, and the amino acid) and ketones (e.g., acetone, methyl ethyl ketone, and methyl isobutyl ketone). These may be used alone or in combination. Among them, particularly preferred as the amines are diamine, and a mixture of diamine and a small amount of trivalent or higher polyamine.
- group-containing compound is appropriately selected depending on the intended purpose without any limitation, provided that it is a polymer containing at least a group reactive with the active hydrogen group-containing compound.
- the polymer reactive with the active hydrogen group-containing compound is
- a urea bond generating group -containing polyester resin preferably a urea bond generating group -containing polyester resin (RMPE), more preferably an isocyanate group-containing polyester prepolymer, because of high flouidity during melting, excellent transparency, easy adjustment of a molecular weight of a high molecular weight component, excellent oil-less low temperature fixing ability and releasing property of a resulting dry toner.
- RMPE urea bond generating group -containing polyester resin
- the isocyanate group-containing polyester prepolymer is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a
- polycondensate prepared from polyol and polycarboxylic acid, and a prepolymer prepared through a reaction between an active hydrogen group-containing polyester resin and polyisocyanate.
- the polyol is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ diol, such as alkylene glycol (e.g., ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, and 1,6-hexanediol), alkylene ether glycol (e.g., diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol), alicyclic diol (e.g., 1,4-cyclohexane dimethanol, and hydrogenated bisphenol A), bisphenol (e.g., bisphenol A, bisphenol F, and bisphenol S), an alkylene oxide(e.g., ethylene oxide, propylene oxide, and butylene oxide) adduct of the alicyclic diol, an alkylene oxide (e.g., ethylene oxide, propylene oxide, and buty
- the diol is preferably C2-C12 alkylene glycol, and an alkylene oxide adduct of bisphenol (e.g., a bisphenol A ethylene oxide (2 mol) adduct, a bisphenol A
- An amount of the polyol in the isocyanate group-containing polyester prepolymer is appropriately selected depending on the intended purpose without any limitation. For example, it is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass. When the amount thereof is smaller than 0.5% by mass, a resulting toner may have insufficient hot offset
- the polycarboxylic acid is appropriately selected depending on the intended purpose without any limitation, and examples thereof include " alkylene dicarboxylic acid (e.g., succinic acid, adipic acid, and sebacic acid) ; alkenylene
- dicarboxylic acid e.g., maleic acid, and fumaric acid
- aromatic dicarboxylic acid e.g., terephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid
- trivalent or higher polycarboxylic acid e .g., C9-C20 aromatic polycarboxylic acid, such as
- the polycarboxylic acid is preferably C4-C20 alkenylene dicarboxylic acid, and C8-C20 aromatic dicarboxylic acid. Note that, instead of the
- polycarboxylic acid anhydride or lower alkyl ester (e.g., methyl ester, ethyl ester, and isopropyl ester) of the polycarboxylic acid may be used.
- anhydride or lower alkyl ester e.g., methyl ester, ethyl ester, and isopropyl ester
- a blending ratio of the polyol and the polycarboxylic acid is appropriately selected depending on the intended purpose without any limitation, but it is determined as an equivalent ratio [OH]/[COOH] of hydroxyl groups [OH] of the polyol to carboxyl groups [COOH] of the polycarboxylic acid, which is preferably 2/1 to 1/1, more preferably 1.5/1 to 1/1, and even more preferably 1.3/1 to 1.02/1.
- the polyisocyanate is appropriately selected depending on the intended purpose without any limitation, and examples thereof include: aliphatic polyisocyanate (e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanato methyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and
- aliphatic polyisocyanate e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanato methyl caproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, and
- alicyclic polyisocyanate e.g., isophorone diisocyanate, and cyclohexylmethane diisocyanate
- aromatic diisocyanate e.g., tolylene diisocyanate, diphenyl methane diisocyanate, 1,5-naphthylene diisocyanate
- diphenylether-4,4'-diisocyanate aromatic aliphatic diisocyanate (e.g., ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylene diisocyanate); isocyanurate (e.g., tris(isocyanatoalkyl)isocyanurate, and
- a resulting toner may have insufficient offset resistance.
- the equivalent ratio [NCO]/[OH] is more than 5/1, a resulting toner may have insufficient low temperature fixing ability.
- An amount of the polyisocyanate in the isocyanate- group polyester prepolymer is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.5% by mass to 40% by mass, more preferably 1% by mass to 30% by mass, and even more preferably 2% by mass to 20% by mass.
- an amount thereof is smaller than 0.5% by mass, a resulting toner may have insufficient offset resistance, and therefore it may be difficult to achieve both storage stability and low temperature fixing ability of the toner.
- the amount thereof is greater than 40% by mass, a resulting toner may have insufficient low temperature fixing ability.
- the average number of isocyanate groups contained in one molecule of the isocyanate group-containing polyester prepolymer is preferably 1 or more, more preferably 1.2 to 5, and even more preferably 1.5 to 4.
- a molecular weight of the polyester resin modified with a urea bond generating group (RMPE) becomes small, which may adversely affect hot offset resistance of a resulting toner.
- a blending ratio of the isocyanate group-containing polyester prepolymer and the amine is appropriately selected depending on the intended purpose without any limitation, but it is determined as a mixing equivalent ratio [NCO]/[NHx] of the isocyanate groups [NCO] in the isocyanate group-containing polyester prepolymer to the amino groups [NHx] in the amine, which is preferably 1/3 to 3/1, more preferably 1/2 to 2/1, and even more preferably 1/1.5 to 1.5/1.
- the mixing equivalent ([NCO]/[NHx]) is less than 1/3, low temperature fixing ability of a resulting toner may be impaired.
- the mixing equivalent ([NCO]/[NHx]) is more than 3/1, a molecular weight of the urea-modified polyester resin becomes small, which may
- a synthesis method of the polymer reactive with the active hydrogen group -containing compound is appropriately selected depending on the intended purpose without any limitation.
- examples of the synthesis method include a method, which contains heating the polyol and the polycarboxylic acid to 150°C to 280°C under the presence of a conventional esterification catalyst (e.g., titanium butoxide, and dibutyl tin oxide) to generate a reaction product optionally with appropriately reducing the pressure, removing water from the reaction system to obtain hydroxyl group-containing polyester, followed by reacting the hydroxyl group-containing polyester with the polyisocyanate at 40°C to 140°C to thereby synthesize the isocyanate group-containing polyester prepolymer.
- a conventional esterification catalyst e.g., titanium butoxide, and dibutyl tin oxide
- the weight average molecular weight (Mw) of the active hydrogen group-containing compound is appropriately selected depending on the intended purpose without any limitation, but it is preferably 3,000 to 40,000, more preferably 4,000 to 30,000, as in a molecular weight distribution measured by gel permeation chromatography (GPC) of a tetrahydrofuran (THF) soluble component thereof.
- GPC gel permeation chromatography
- THF tetrahydrofuran
- the weight average molecular weight (Mw) can be measured, for example, in the following manner.
- a column is stabilized in a heat chamber of 40°C.
- tetrahydrofuran (THF) as a column solvent is flown into the column at the flow rate of 1 mL/min, 50 ⁇ to 200 ⁇ - ⁇ of a tetrahydrofuran resin sample solution whose sample concentration is adjusted to 0.05% by mass to 0.6% by mass is injected to carry out a measurement.
- THF tetrahydrofuran
- the molecular weight distribution of the sample is calculated from the relationship with a logarithmic value and count number of a calibration curve formed by a plurality of monodisperse polystyrene standard samples.
- standard polystyrene samples for forming a calibration curve standard polystyrene samples (of Pressure Chemical Co. , or Tosoh Corporation) having molecular weights of 6x l0 2 , 2.1X 10 2 , 4x l0 2 , 1.75X 10 4 , l. lx lO 5 , 3.9x l0 5 , 8.6x l0 5 , 2x l0 6 , and 4.48x l0 6 are used, it is preferred that at least 10 standard polystyrene samples be used.
- an RI (refractive index) detector can be used.
- the releasing agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include natural wax, such as vegetable wax (e.g. carnauba wax, cotton wax, Japan wax, and rice wax), animal wax (e.g., bees wax and lanolin), mineral wax (e.g., ozokelite and ceresin), and petroleum wax (e.g., paraffin wax, microcrystalline wax and petrolatum).
- natural wax such as vegetable wax (e.g. carnauba wax, cotton wax, Japan wax, and rice wax), animal wax (e.g., bees wax and lanolin), mineral wax (e.g., ozokelite and ceresin), and petroleum wax (e.g., paraffin wax, microcrystalline wax and petrolatum).
- vegetable wax e.g. carnauba wax, cotton wax, Japan wax, and rice wax
- animal wax e.g., bees wax and lanolin
- mineral wax e.g., ozokelite and ceresin
- petroleum wax e.
- Further examples include ⁇ a fatty acid amide compound, such as 1,2-hydroxystearic acid amide, stearic amide, phthalic anhydride imide and chlorinated hydrocarbons! lowmolecular-weight crystalline polymer resins such as acrylic homopolymers (e.g., polyn-stearyl methacrylate and poly-n-lauryl methacrylate) and acrylic copolymers (e.g., n-stearyl acrylate-ethyl methacrylate copolymers); and crystalline polymers having a long alkyl group as a side chain.
- wax having a melting point of 50°C to 120°C is preferred.
- wax having a melting point of 50°C to 120°C, because such wax can effectively function as a releasing agent at an interface between a fixing roller and a toner, and therefore hot offset resistance can be improved without applying a releasing agent, such as an oil, to the fixing roller.
- the melting point of the releasing agent is appropriately selected depending on the intended purpose without any
- the melting point of the releasing agent can be determined by measuring the maximum endothermic peak using a
- melt viscosity of the releasing agent is appropriately selected depending on the intended purpose without any
- the melt viscosity thereof is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps.
- the melt viscosity is lower than 5 cps, releasing property may be low.
- the melt viscosity is greater than 1,000 cps, the releasing agent cannot be exhibit an effect of improving hot offset resistance and low temperature fixing ability.
- An amount of the releasing agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 40% by mass or less, more preferably 3% by mass to 30% by mass. When the amount thereof is greater than 40% by mass, flowability of the toner may be impaired.
- the releasing agent is preferably present in the dispersed state in the toner base particle.
- the releasing agent and the binder resin are preferably not compatible to each other.
- a method for finely dispersing the releasing agent in the toner base particle is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method containing applying shear force during kneading in the course of the toner production to thereby disperse the releasing agent.
- the dispersed state of the releasing agent can be
- the smaller dispersed diameter of the releasing agent is more preferable. When the dispersed diameter of the releasing agent is too small, however, bleeding of the releasing agent may be insufficient. If the releasing agent can be confirmed with the magnification of 10,000, it can be said that the releasing agent is present in the dispersed state. When the releasing agent cannot be confirmed with the magnification of x 10,000, bleeding of the releasing agent becomes insufficient during fixing even through the releasing agent is very finely dispersed.
- components are appropriately selected depending on the intended purpose without any limitation, and examples thereof include a colorant, a layered inorganic mineral, a magnetic material, a cleaning improving agent, a flow improving agent, and a charge controlling agent.
- the colorant is appropriately selected from dyes and pigments known in the art depending on the intended purpose without any limitation, and examples thereof include carbon black, a nigrosin dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G and G), cadmium yellow, yellow iron oxide, yellow ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN and R), pigment yellow L, benzidine yellow (G and GR), permanent yellow (NCG), vulcan fast yellow (5G, R), tartrazinelake, quinoline yellow lake, anthrasan yellow BGL, isoindolinon yellow, colcothar, red lead, lead vermilion, cadmium red, cadmium mercury red, antimony vermilion, permanent red 4R, parared, fiser red, parachloroorthonitro anilin red, lithol fast scarlet G, brilliant fast scarlet, brilliant carmine BS, permanent red (F2R, F4R, FRL
- An amount of the colorant in the toner is appropriately selected depending on the intended purpose without any
- the colorant may be used as a master batch in which the colorant forms a composite with a resin.
- the resin is
- polyester resin polymer of styrene or substitution thereof (e.g.,
- polystyrene, polyp'chlorostyrene, and polyvinyl examples include polystyrene, polyp'chlorostyrene, and polyvinyl); styrene copolymer (e.g., styrene-p-chlorostyrene copolymer,
- styrene-propylene copolymer styrene-vinyl toluene copolymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer,
- styrene-acrylonitrile copolymer styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer,
- styrene-maleic acid copolymer and styrene-maleic acid ester copolymer); and others, such as polymethyl methacrylate, polybutyl methacrylate, a polycinyl chloride resin, a polyvinyl acetate resin, a polyethylene resin, a polypropylene resin, an epoxy resin, an epoxy polyol resin, a polyurethane resin, a polyamide resin, a polyvinyl butyral resin, a polyacryl resin, rosin, modified rosin, a terpene resin, an aliphatic hydrocarbon resin, an alicyclic hydrocarbon resin, an aromatic petroleum resin, chlorinated paraffin, and paraffin wax. These may be used alone or in combination.
- a production method of the master batch is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method containing mixing and/or kneading the resin for the master batch, the colorant, and an organic solvent at high shear force to produce a master batch. Note that, the organic solvent is added to enhance the interaction between the colorant and the binder resin.
- another production method of the master batch is appropriately selected depending on the intended purpose without any limitation, but it is preferably a hlashing method in which an aqueous paste containing a colorant is mixed and kneaded with a resin and an organic solvent, and then the colorant is transferred to the resin to remove the water and the organic solvent.
- This method is preferably used because a wet cake of the colorant is used as it is, and it is not necessary to dry the wet cake of the colorant to prepare a colorant.
- a high-shearing disperser e.g., a three-roll mill
- a three-roll mill is preferably used.
- the layered inorganic mineral is appropriately selected depending on the intended purpose without any limitation, provided that it is a mineral in which layers each having a thickness of several nanometers are laminated, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and a mixture thereof. These may be used alone or in combination.
- a modified layered mineral is preferable as it can be deformed during granulation of a toner, exhibit a function of controlling charge, and is excellent in low temperature fixing ability
- a modified layered inorganic mineral in which a layered inorganic mineral having a montmorillonite basic crystal structure is modified with organic cations, and an organic modified montmorillonite and bentonite are preferable as they can easily adjust the viscosity without adversely affecting the properties of a toner.
- the modified layered inorganic compound is preferably obtained by modifying at least part of the layered inorganic mineral with organic ions.
- a resulting modified layered inorganic compound has appropriate hydrophobic property, and give an oil phase, which contains a toner
- composition and/or a toner composition precursor non-Newtonian viscosity to deform toner particles.
- An amount of the modified layered inorganic mineral contained in the toner base particles is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.05% by mass to 5% by mass.
- the magnetic material is appropriately selected depending on the intended purpose without any limitation, and examples thereof include iron powder, magnetite, and ferrite. Among them, a white magnetic material is preferable in terms of a color tone.
- the cleaning improving agent is appropriately selected depending on the intended purpose without any limitation, provided that it is an agent to be added to the toner in order to remove the residual developer on a photoconductor or a primary transfer member.
- examples thereof include : metal salts of fatty acid such as stearic acid (e.g. zinc stearate, and calcium
- the volume average particle diameter of the polymer particles is appropriately selected depending on the intended purpose without any limitation, but the polymer particles preferably have a relatively narrow particle size distribution, more preferably having the volume average particle diameter of 0.01 ⁇ to 1 ⁇ .
- the flow improving agent is an agent used to perform a surface treatment to improve hydrophobicity so as to prevent the toner from reducing its fluidity and charging properties in high humidity environments.
- examples thereof include a silane coupling agent, a sililating agent, a silane coupling agent having a fluoroalkyl group, an organic titanate-based coupling agent, an aluminum-based coupling agent, silicone oil, and modified silicone oil.
- Silica or titanium oxide is particularly preferably used as hydrophobic silica or hydrophobic titanium oxide, by surface treating the silica or titanium oxide with the
- the charge controlling agent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include nigrosine dyes, triphenylmethane dyes, chrome-containing metal complex dyes, molybdic acid chelate pigments, rhodamine dyes, alkoxy amines, quaternary
- ammonium salts including fluorine-modified quaternary ammonium salts
- alkylamides including fluorine-modified quaternary ammonium salts
- phosphorus including phosphorus, phosphorus
- tungsten tungsten compounds, fluorine-based active agents, metal salts of salicylic acid, metal salts of salicylic acid derivatives, copper phthalocyanine, perylene, quinacridon, azo-based pigments, and polymer compound having a functional group (e.g., sulfonic acid group, carboxyl group, and quaternary ammonium salt).
- a functional group e.g., sulfonic acid group, carboxyl group, and quaternary ammonium salt.
- Examples of the trade names of the commercial products usable as the charge controlling agent include ⁇ nigrosine dye BONTRON 03, quaternary ammonium salt BONTRON P-51, metal-containing azo dye BONTRON S-34, oxynaphthoic
- An amount of the charge controlling agent is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 parts by mass to 10 parts by mass, more preferably 0.2 parts by mass to 5 parts by mass, relative to 100 parts by mass of the binder resin.
- the amount thereof is greater than 10 parts by mass, the electrostatic propensity of the resulting toner is excessively large, and therefore an effect of the charge controlling agent is reduced and electrostatic force to a developing roller increases, which may reduce flowability of the toner, or reduce image density of images formed with the resulting toner.
- the charge controlling agent may be added by dissolving and dispersing after melting and kneading together with the master batch or the resin, or added by dissolving or dispersing directly in the organic solvent, or added by fixing on a surface of each toner particle after the preparation of the toner particles.
- the production method of the toner is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method for producing a toner using a pulverization method, and a method for producing a toner using a polymerization method. Among them, the method for producing a toner using the polymerization method is preferable as a toner of small diameter can be obtained.
- the polymerization method is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a suspension polymerization method, a dissolution suspension method, and an emulsification
- a dissolution suspension method is preferable.
- the dissolution suspension method is appropriately selected depending on the intended purpose without any limitation, but it preferably contains an oil phase preparation step , an aqueous phase preparation step, an emulsifying or dispersing step, a solvent removing step, a washing and drying step, and an external additive treating step.
- a specific example of the dissolution suspension method is appropriately selected depending on the intended purpose without any limitation, but it is preferably a method containing " - dissolving or dispersing in an organic solvent at least the binder resin and the colorant to prepare a solution or a dispersion; adding the solution or dispersion to an aqueous phase and emulsifying or dispersing the solurion or dispersion in the aqueous phase to prepare an emulsion or a dispersion liquid;
- an ester elongation method is preferable.
- This method can yield a toner having the excellently dispersed releasing agent, and excellent flowability. Such toner can be transported to a developing device without forming a dead space in a developer transporting device.
- the oil phase preparation step is dissolving or dispersing in an organic solvent a toner material containing at least the binder resin and the colorant to prepare an oil phase (a solution or dispersion of the toner material).
- the organic solvent is appropriately selected depending on the intended purpose without any limitation, but it is preferably an organic solvent having a boiling point of lower than 150°C in view of easiness of removal thereof.
- the organic solvent having a boiling point of lower than 150°C is appropriately selected depending on the intended purpose without any limitation, and examples thereof include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1, 1,2-trichloroethane,
- dichloroethylidene methyl acetate, ethyl acetate, methyl ethyl ketone, and methyl isobutyl ketone. These may be used alone or in combination. Among them, preferred are ethyl acetate, toluene, xylene, benzene, methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride, and particularly preferred is ethyl acetate.
- the aqueous phase preparation step is preparing an aqueous phase (aqueous medium).
- the aqueous phase is appropriately selected depending on the intended purpose without any limitation, and examples thereof include water, a solvent miscible with water, and a mixture thereof. These may be used alone or in combination. Among them, water is preferable.
- the solvent miscible with water include alcohol (e.g., methanol, isopropanol, and ethylene glycol), dimethyl formamide, tetrahydrofuran, cellosolve (e.g., Methyl Cellosolve ® ), and lower ketone (e.g., acetone, and methyl ethyl ketone).
- the emulsifying or dispersing step is dispersing the oil phase in the aqueous phase to prepare an emulsion or a
- the materials for the toner material are not necessarily mixed at the time when particles are formed in an aqueous phase, and the materials may be added after forming particles.
- the colorant can be added by a conventional dyeing method.
- An amount of the aqueous phase used relative to 100 parts by mass of the toner material is appropriately selected depending on the intended purpose without any limitation, but it is preferably 100 parts by mass to 1,000 parts by mass. When the amount thereof is less than 100 parts by mass, a dispersed state of the toner material may not be desirable and therefore toner particles of the predetermined particle size may not be obtained. When the amount thereof is greater than 1,000 parts by mass, it may be economically undesirable.
- a dispersant may be used, as needed. Use of the dispersant is preferable as it can achieve a sharp particle size distribution, and stabilize a dispersion state.
- the dispersant used in the emulsifying or dispersing step is appropriately selected depending on the intended purpose without any limitation, and examples thereof include an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, an anionic surfactant having a fluoroalkyl group, a cationic surfactant having a fluoroalkyl group, an inorganic compound (e.g., tricalcium phosphate, calcium
- MMA polymer particles e.g., MMA polymer particles (l ⁇ ), MMA polymer particles (3 ⁇ ), styrene particles (0.5 ⁇ ), styrene particles (2 ⁇ ), and syrene-acrylonitrile polymer particles (l ⁇ )
- a surfactant having a fluoroalkyl group is preferable because it can exhibit an effect with a small amount thereof.
- Examples of a commercial name of the dispersant include ⁇ SURFLON S- 111, S- 112, S- 113, S- 121 (all manufactured by Asahi Glass Co., Ltd.); FLUORAD FC-93, FC-95, FC-98, FC- 129, FC- 135 (all manufactured by Sumitomo 3M Limited); UNIDYNE DS- 101, DS- 102, DS-202 (all manufactured by DAIKIN INDUSTRIES, LTD.); MEGAFAC F- 110, F- 120, F- 113, F- 150, F- 191, F-812, F-824, F-833 (all manufactured by DIC Corporation); EFTOP EF- 102, 103, 104, 105, 112, 123A, 123B, 132, 306A, 501, 201, 204, (all manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.); FUTARGENT F- 100, F-300, F150 (all manufactured by NEOS COMPANY LIMITED); S
- the dispersant When the dispersant is used, the dispersant may be left on surfaces of the toner particles, but the dispersant is preferably washed and removed from the toner particles after the reaction in view of charging properties of the toner.
- a solvent capable of dissolving the modified polyester after the reaction of the polyester prepolymer is preferably used to give a sharp particle size distribution and lower the viscosity of the toner material.
- the solvent is preferably a volatile solvent having a boiling point of lower than 100°C in view of easiness of removal thereof, and examples of such solvent include- a solvent miscible with water, such as toluene, xylene, benzene, carbon
- tetrahydrofuran and methanol. These may be used alone or in combination.
- an aromatic solvent such as toluene, and xylene
- a halogenated hydrocarbon such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride.
- An amount of the solvent is appropriately selected depending on the intended purpose without any
- the solvent is preferably 0 parts by mass to 300 parts by mass, more preferably 0 parts by mass to 100 parts by mass, and even more preferably 25 parts by mass to 70 parts by mass, relative to 100 parts by mass of the polyester prepolymer.
- the solvent is removed by heating under atmospheric pressure or reduced pressure.
- a dispersion stabilizer is preferably used in combination.
- the dispersion stabilizer is appropriately selected depending on the intended purpose without any limitation, provided that it is a material stabilizing dispersed droplets with a polymer protective colloid, or water-insoluble organic particles. Examples thereof include: acid such as acrylic acid, methacrylic acid, crcyanoacrylic acid, a-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, and maleic anhydride; a (meth)acrylic monomer having a hydroxyl group, such as ⁇ -hydroxyethyl acrylate, ⁇ -hydroxyethyl methacrylate, ⁇ -hydroxypropyl acrylate,
- vinyl alcohol and ethers thereof e.g., vinyl methyl ether, vinyl ethyl ether, and vinyl propyl ether
- ester of vinyl alcohol e.g., vinyl acetate, vinyl propionate, and vinyl butyrate
- a compound having a carboxyl group ' a stabilizer, such as acryl amide, methacryl amide, diacetone acryl amide, and a methylol compound thereof
- acid chloride such as acrylic acid chloride, and methacrylic acid chloride
- polyoxyethylene-based stabilizer such as polyoxyethylene, polyoxypropylene, polyoxyethylene alkyl amine
- polyoxypropylene alkyl amine polyoxyethylene alkyl amide, polyoxypropylene alkyl amide, polyoxyethylene nonylphenyl ether, polyoxyethylene laurylphenyl ether, polyoxyethylene stearylphenyl ester, and polyoxyethylene nonylphenyl ester; and cellulose, such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.
- calcium phosphate is preferably removed from the particles by dissolving calcium phosphate with acid, such as hydrochloric acid, followed by washing with water. Note that, the removal of calcium phosphate may also be performed by decomposing with enzyme.
- a disperser used in the emulsifying or dispersing step is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a low speed shearing disperser, a high speed shearing disperser, a friction disperser, a high pressure jet disperser, and an ultrasonic wave disperser.
- the high speed shearing disperser is preferable because it is capable of controlling particle diameters of dispersed elements (oil droplets) to 2 ⁇ to 20 ⁇ .
- the conditions such as the rotation number, dispersing time, and dispersing temperature, are appropriately selected depending on the intended purpose.
- the rotation number is appropriately selected depending on the intended purpose without any
- the dispersion time is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.1 minutes to 5 minutes in the case of the batch system.
- the dispersing temperature is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0°C to 150°C, more preferably 40°C to 98°C, under the pressure. Note that, generally, higher the dispersing temperature is, easier the dispersing is.
- the solvent removing step is removing the organic solvent from the emulsion or dispersion liquid (e.g., a dispersion liquid, such an emulsified slurry).
- a method for removing the organic solvent is appropriately selected depending on the intended purpose without any limitation, and examples thereof include ⁇ a method where a temperature of an entire system is gradually increased to evaporate the organic solvent contained in the oil droplets, ' and a method where the dispersion liquid is sprayed (by a spray dryer, belt dryer, rotary kiln, or the like) in a dry atmosphere(e.g., heated gas, such as air, nitrogen, carbon dioxide, and combustion gas) to remove the organic solvent in the oil droplets.
- heated gas such as air, nitrogen, carbon dioxide, and combustion gas
- the washing and drying step is washing and drying the toner base particles.
- the toner base particles may be further subjected to classification.
- the classifying can be performed by removing the fine particles component by means of a cyclone, a decanter, a centrifugal separator, or the like. Alternatively, the classification can be performed after drying the toner base particles. Note that, the undesirable fine particles or coarse particles obtained from the classification may be used again for formation of particles. In this case, the fine particles or coarse particles may be in the wet state .
- the external additive treating step is mixing and treating the dried toner base particles with the external additive that satisfies the parameter specified in the present invention. Once the toner base particles are mixed with the external additive, the toner of the present invention is obtained.
- a device used for the mixing is appropriately selected depending on the intended purpose without any limitation, but it is preferably HENSCHEL MIXER (manufactured by Nippon Cole & Engineering Co., Ltd.).
- a mechanical impact may be applied.
- a method for applying the mechanical impact is appropriately selected depending on the intended purpose without any limitation, and examples thereof include : a method containing applying an impact to a mixture with a high-speed rotating blade!
- a device used in such method is appropriately selected depending on the intended purpose without any limitation. Examples thereof include ANGMILL (product of Hosokawa Micron Corporation), an apparatus produced by modifying I type mill (product of Nippon Pneumatic Mfg. Co., Ltd.) so that the pulverizing air pressure thereof is decreased, a hybridization system (product of Nara Machinery Co., Ltd.), a krypton system (product of Kawasaki Heavy Industries, Ltd.) and an automatic mortar.
- ANGMILL product of Hosokawa Micron Corporation
- I type mill product of Nippon Pneumatic Mfg. Co., Ltd.
- a hybridization system product of Nara Machinery Co., Ltd.
- a krypton system product of Kawasaki Heavy Industries, Ltd.
- a ratio (Dv/Dn) of the volume average particle diameter (Dv) to number average particle diameter (Dn) of the toner is appropriately selected depending on the intended purpose without any limitation, but it is preferably 1.30 or less, more preferably 1.00 to 1.30.
- the ratio (Dv/Dn) is less than 1.00, in case of a two-component developer, the toner is fused on the surfaces of carrier particles after being stirred for a long period in a developing device, which may lead to low charging ability of the carrier, or poor cleaning ability.
- toner filming to a developing roller, or a toner fusion to a member, such as a blade for reducing a thickness of a toner layer tends to occur.
- the ratio (Dv/Dn) is more than 1.30, it is difficult to form an image having high resolution and high image quality, and particle diameters of the toner particles may significantly change after the toner is supplied to the developer to compensate the spent toner.
- the ratio (Dv/Dn) is within the aforementioned more preferable range, it is advantageous because excellent storage stability, low
- the volume average particle diameter (Dv) of the toner is appropriately selected depending on the intended purpose without any limitation, but it is preferably 2 ⁇ to 8 ⁇ , more preferably 3 ⁇ to 7 ⁇ .
- Dv volume average particle diameter
- the Dv thereof is smaller than 2 ⁇ , cleaning property of the toner may be impaired.
- the Dv thereof is greater than 8 ⁇ , a fine line reproducibility may be significantly impaired.
- the Dv is within the aforementioned preferable range, it is advantageous because both fine line reproducibility and cleaning property can be achieved.
- the volume average particle diameter (Dv) and number average particle diameter (Dn) of the toner can be measured by means of a particle size analyzer (Multisizer III, manufactured by Bechman Coulter, Inc.) with an aperture size of 100 ⁇ , and using an analysis software (Beckman Coulter Multisizer 3
- This dispersion liquid is subjected to a measurement using the particle size analyzer and a solution for measurement (ISOTON III, Bechman Coulter, Inc.).
- the measurement is performed by adding the toner sample dropwise in a manner that the
- concentration indicated by the device is in the range of 8% ⁇ 2%. It is important for this measuring method that the concentration is kept in the range of 8% ⁇ 2% in view of the measuring
- the average circularity of the toner is appropriately selected depending on the intended purpose without any
- the average circularity preferably satisfy- ' 1.00 ⁇ (1-B)/(1-A) ⁇ 4.00, more preferably 1.25 ⁇ (l-B)/(l-A) ⁇ 3.00, and even more preferably 1.40 ⁇ (l-B)/(l-A) ⁇ 2.50, where A is the average circularity of the particles in the range of 0.7 ⁇ to (Dn/2) ⁇ , and B is the average circularity of the particles in the range of 0.7 ⁇ to (Dn x 2) ⁇ .
- the circularity is defined as follows ⁇
- the circularity SR (boundary length of a circle having the same area to that of a projected area of a particle /boundary length of a projected image of a particle)
- the value is closer to 1.00.
- the average circularity of the toner is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.95 to 0.98. When the average circularity is less than 0.95, uniformity in an image is impaired during developing, transfer property of the toner from an electrophotographic photoconductor to an intermediate transfer member, or from the intermediate transfer member to a recording medium is impaired so that uniform transfer may not be performed. When the average circularity is within the
- predetermined container is charged with 100 mL to 150 mL of water, from which impurity solids have been removed in advance, followed by adding as a dispersant, 0.1 mL to 0.5 mL of a surfactant, and adding 0.1 g to 935 g of a measuring sample.
- a resulting suspension liquid, in which the sample is dispersed, is dispersed for about 1 minute to about 3 minutes by means of a ultrasonic wave disperser, and the resulting dispersion liquid having a concentration of 3,000 particles ⁇ L to 10,000
- the developer of the present invention contains at least the toner of the present invention, and may further contain other components, if necessary.
- the developer may be a
- the toner of the present invention is used as a one-component magnetic or non-magnetic toner.
- the developer is preferably a two-component developer containing at least the toner of the present invention and the carrier.
- the carrier contains magnetic core particles, and a coating resin that coats each core particle, and may further contain electroconductive powder, and a silane coupling agent.
- a mass ratio of the carrier and the toner contained in the developer is appropriately selected depending on the intended purpose without any limitation, but the developer preferably contains 1 part by mass to 10 parts by mass of the toner relative to 100 parts by mass of the carrier.
- the core particles are appropriately selected depending on the intended purpose without any limitation, provided that they are core particles having the magnetic charge of 40 emu/g or more when the magnetic field of 1,000 oersted (Oe) is applied to the carrier.
- core particles include a ferromagnetic material (e.g., iron, and cobalt), magnetite, hematite, Li-based ferrite,
- the core particles can be obtained by classifying primary granulated product before firing, firing the classified particle to prepare baked particles,
- classifying the baked particles to prepare groups of particles having different particle size distributions, and mixing a plurality of the groups of the particles.
- a method for classifying the core particles is appropriately selected depending on the intended purpose without any
- a conventional classifying method using a screen classifier, a gravitational classifier, a centrifugal classifier, or an inertial classifier can be used.
- a method using an air classifier e.g., a gravitational classifier, a centrifugal classifier, and an inertial classifier
- excellent productivity can be achieved and a classification point can be easily changed.
- the coating resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include an amino-based resin, a urea-formaldehyde resin, a melamine resin, a guanamine resin, a urea resin, a polyamine resin, a polyvinyl-based resin, a polyvinylidene-based resin, an acrylic resin, a polymethyl methacrylate resin, polyacrylonitrile resin, a polyvinyl acetate resin, a polyvinyl alcohol resin, a polyvinyl butyral, a polystyrene-based resin (e.g., a polystyrene resin, and a styrene-acryl copolymer resin), a halogenated olefin resin (e.g., polyvinyl chloride), a polyester-based resin (e.g., a polyethylene terephthalate resin, and a polybutylene terephthalate resin), a
- the silicone resin is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a straight silicone resin,' and a modified silicone resin, such as epoxymodified silicone, acryl-modified silicone, phenol-modified silicone, urethane-modified silicone,
- polyester-modified silicone and alkyd-modified silicone.
- Examples of a commercial product of the straight silicone resin include - KR271, KR272, KR282, KR252, KR255, and KR152 (all manufactured by Shin-Etsu Chemical Co., Ltd.), ' and SR2400, and SR2406 (both manufactured by Dow Corning Toray Co., Ltd.).
- Examples of a commercial product of the modified silicone resin include: ES- 1001N, KR-5208, KR-5203, KR-206, and KR-305 (all manufactured by Shin-Etsu Chemical Co., Ltd.), ' and SR2115, and SR2110 (both manufactured by Dow Corning Toray Co., Ltd.).
- a resin used in combination with the silicone is
- styrene-based resin such as polystyrene, chloropolystyrene, polya-methyl styrene, a styrene-chlorostyrene copolymer, a styrene-propylene copolymer, a styrene-butadiene copolymer, a styrene-vinyl chloride copolymer, a styrene-vinyl acetate copolymer, a styrene-maleic acid copolymer, a styrene-acrylic acid ester copolymer (e.g., a styrene-methyl acrylate copolymer, a styrene-ethyl acrylate copolymer, a styrene-butyl acrylate copolymer, a styrene-octyl acrylate copolymer
- styrene-phenyl acrylate copolymer e.g., a styrene-phenyl acrylate copolymer
- a styrene-methacrylic ester copolymer e.g., a styrene-methyl methacrylate copolymer, a styrene-ethyl methacrylate copolymer, a styrene-butyl
- a compound suitably used in combination with the silicone resin is appropriately selected depending on the intended purpose without any limitation, but it is preferably an amino silane coupling agent, as a carrier having excellent durability can be obtained.
- An amount of the amino silane coupling agent contained in the coating layer is appropriately selected
- examples thereof include a method containing forming a coating layer on each surface of the core particles to thereby prepare the carrier.
- a method for forming a coating layer on each surface of the core particles is appropriately selected depending on the intended purpose without any
- a thickness of the coating layer on the surface of the core particle is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.02 ⁇ to 1 ⁇ , more preferably 0.03 ⁇ to 0.8 ⁇ . Note that, as the thickness of the coating layer is extremely thin, the particle diameter of the carrier in which the coating layer has been formed on each surface of the core particles and the particle diameter of the carrier core particles are substantially the same. ⁇ Properties of Carrier-
- the carrier is appropriately selected depending on the intended purpose without any limitation, but it is preferably a carrier having a sharp particle size distribution, and uniform particle size. It is preferred that the carrier and the carrier core particles whose number average particle diameter (Dp) as well as weight average particle diameter (Dw) are regulated be used.
- the weight average particle diameter Dw of the carrier is appropriately selected depending on the intended purpose without any limitation, but it is preferably 15 ⁇ to 40 ⁇ .
- the weight average particle diameter (Dw) of the carrier is calculated from the particle size distribution (a relationship between a proportion of numbers of particles and particle diameters) measured on number basis.
- the weight average particle diameter (Dw) of the carrier can be represented by the following formula (i) '
- D is a representing particle diameter ( ⁇ ) of particles present in each channel
- n is a total number of the particles present in each channel.
- the channel means a length for equally dividing the particle diameter range in a particle size distribution diagram, and in the present invention, 2 ⁇ is used as the channel.
- the representing particle diameter of the particles present in each channel the minimum value of the particle diameters of the particles present in each channel is used.
- the bulk density of the carrier is appropriately selected depending on the intended purpose without any limitation, but it is preferably 2.15 g/cm 3 to 2.70 g/cm 3 , more preferably 2.25 g/cm 3 to 2.60 g/cm 3 , in view of the influence to a carrier deposition.
- the carrier particles become porous or irregularities in a profile of a surface of a carrier particle increase, and therefore a substantial magnetic value per particle is small even the magnetic charge (emu/g) of the core particle at 1 KOe is large, which is
- the bulk density is made greater than 2.70 g/cm 3 by increasing the firing temperature, core particles tend to be fused to each other, and it may be difficult to break down the fused particles.
- the bulk density is measured in the following manner in accordance with a metal powder-apparent density testing method (JIS-Z-2504).
- JIS-Z-2504 The carrier is naturally flown out from an orifice having a diameter of 2.5 mm to a cylindrical stainless steel container having the volume of 25 cm 3 , which is placed directly under the orifice until the container is overflowed with the carrier.
- the carrier at the top of the container is scraped out in once
- the electrical resistivity (logR) of the carrier is
- the electrical resistivity (logR) is lower than 11.0 ⁇ -cm, in the case that a developing gap (the minimum distance between the photoconductor and the developing sleeve) is narrow, carrier deposition tends to occur as charge is lead to the carrier.
- the electrical resistivity is greater than 17.0 ⁇ -cm, the edge effect is enhanced to reduce the image density in a solid image area, and charge having an opposite polarity to that of the toner tends to accumulated to charge the carrier, so that the carrier
- a method for adjusting the electrical resistivity (logR) of the carrier is appropriately selected depending on the intended purpose without any limitation, and examples thereof include a method for adjusting the electrical resistivity of the carrier by adjusting the resistivity of the coating resin on the core particle; a method for adjusting the electrical resistivity of the carrier by adjusting a thickness of the coating layer; and a method for adjusting the resistivity of the coating resin by adding the electroconductive powder to the coating resin layer.
- the electroconductive powder is appropriately selected depending on the intended purpose without any limitation, and examples thereof include'- metal, such as electroconductive ZnO, and Al; metal oxide, such as selenium oxide, alumina,
- Sn02 prepared by various method, and Sn02 doped with various elements
- boride such as T1B2, nB2, and M0B2
- silicon carbide an electroconductive polymer, such as polyacetylene, polyparaphenylene,
- the electroconductive powder can be provided to the carrier in the following manner. Specifically, after adding the electroconductive powder to a solvent used for coating or a coating resin solution, the mixture is uniformly dispersed by means of a disperser using a media (e.g., a ball mill, and a bead mill), or a stirrer equipped with a high-speed rotating blade, to thereby prepare a coating layer forming dispersion liquid, and coating core particles with the coating layer forming dispersion liquid, to thereby prepare a carrier.
- a media e.g., a ball mill, and a bead mill
- a stirrer equipped with a high-speed rotating blade to thereby prepare a coating layer forming dispersion liquid
- the average particle diameter of the electroconductive powder is appropriately selected depending on the intended purpose without any
- the magnetic charge of the carrier is appropriately selected depending on the intended purpose without any
- the magnetic charge of the carrier when a magnetic field of 1,000 oersted (Oe) is applied is the magnetic charge required for forming a magnetic brush.
- the magnetic charge can be measured in the following manner.
- a B'H tracer (BHU-60, manufactured by Riken Denshi Co., Ltd.) is used as a measuring device.
- a cylindrical cell is filled with 1 g of carrier core particles and set in the device.
- the magnetic field is gradually increased up to 3,000 oersted (Oe), followed by gradually decreased to 0.
- the magnetic field of the opposite direction is gradually increased to 3,000 oersted (Oe), followed by gradually decreased to 0.
- the magnetic field of the same direction to that of the initial magnetic field is applied.
- a B-H curve is drawn, and a magnetic moment of 1,000 oersted is calculated from the curve.
- the magnetic charge of the carrier is fundamentally determined by a magnetic material used as core particles.
- the process cartridge can be used for the image forming apparatus of the present invention, and contains a latent electrostatic image bearing member (an electrophotographic photoconductor), and a developing unit configured to develop using the toner of the present invention to form a visible image.
- the process cartridge can be detachably mounted in the image forming apparatus of the present invention.
- the process cartridge 800 illustrated in FIG. 5 contains a photoconductor 801, a charging unit 802, a
- the photoconductor 801 is rotationally driven at a certain rim speed, and during the rotation of the photoconductor 801, the peripheral surface of the photoconductor 801 is uniformly charged with the predetermined positive or negative potential by the charging unit 802.
- imagewise exposure light is applied from an image exposing unit (e.g., slit exposure, and laser beam scanning exposure) to thereby sequentially form a latent electrostatic image on the peripheral surface of the photoconductor 801.
- an image exposing unit e.g., slit exposure, and laser beam scanning exposure
- electrostatic image is turned into a toner image by means of the developing unit 803, and the developed toner image is
- the recording medium on which the image has been transferred is separated from the surface of the photoconductor and guided to an image forming unit, which is not illustrated in FIG. 5, and then is discharged from the device as a photocopy.
- the surface of the photoconductor 801 after the image transfer is cleaned by means the cleaning unit 806 by removing the residual toner from the transfer. Further, the surface of the photoconductor 801 is diselectrified, followed by being repeatedly used for image formation.
- the image forming apparatus of the present invention houses the toner or developer of the present invention, and contains at least a latent electrostatic image bearing member (an electrophotographic photoconductor), a latent electrostatic image forming unit, a developing unit, a transfer unit, and a fixing unit, preferably further contains a toner transporting unit, and may further contain other units, if necessary.
- the image forming apparatus is suitably used as a full-color image forming
- the latent electrostatic image forming unit is a unit combining a charging unit and an exposing unit.
- the image forming apparatus is appropriately selected depending on the intended purpose without any limitation, but it is preferably a high-speed image forming apparatus capable of forming an image at speed of 55 sheets/min or faster with the recording medium of A4 size, where the recording medium is fed in the direction along the shorter side of the recording medium.
- the image forming apparatus is preferably equipped with a controlling unit capable of carrying out such image formation.
- the image forming method contains at least a latent electrostatic image forming step, a developing step, a
- the transferring step , and a fixing step preferably further contains a toner transporting step, and may further contain other steps, as needed.
- the image forming method is suitably used as a full-color image forming method, and the toner of the present invention is used in the developing step.
- the latent electrostatic image forming step is a combination of a charging step and an exposing step.
- the full-color image forming apparatus is preferably a tandem image forming apparatus, which contains a plurality of a set consisting of an electrophotographic photoconductor, a charging unit, an exposing unit, a developing unit, a primary transfer unit, and a cleaning unit.
- the tandem image forming apparatus which is equipped with a plurality of
- the tandem image forming apparatus has an advantage that it can correspond to high-speed printing.
- toner images of different colors are formed respectively with different electrophotographic photoconductors, and the toner images are laminated to form a full-color image, a variation in the amount of the toner used for developing among toner particles of different colors, if there are variations in properties, such that charging properties are different between toner particles of different colors, a change in a color tone of a secondary color becomes significant as a result of mixing colors, which lowers color reproducibility.
- the toner used in the tandem image forming apparatus It is therefore important for the toner used in the tandem image forming apparatus that an amount of the toner used for developing is stabilized (there is no variation between toner particles of different colors) to control balance of colors, and a deposition properties to an electrophotographic photoconductor and to a recording medium is uniformed between the toner particles of the different colors.
- the toner of the present invention is suitable for use in the tandem image forming apparatus.
- the latent electrostatic image forming step is forming a latent electrostatic image on the latent electrostatic image bearing member, and can be carried out by the latent electrostatic image forming unit.
- a material, shape, structure or size of the latent electrostatic image bearing member is appropriately selected depending on the intended purpose without any
- Examples of the material thereof include - an inorganic material, such as amorphous silicone, and selenium; and an organic material such as polysilane, and
- the shape thereof is preferably a drum shape.
- the latent electrostatic image forming unit is a unit combining a charging unit, and an exposing unit.
- the charging unit is appropriately selected depending on the intended purpose without any limitation, and examples thereof include conventional contact chargers known in the art equipped with conductive or semiconductive roller, brush, film, rubber blade, or the like, and conventional non-contact charger using corona discharge such as corotron and scorotron..
- the exposing unit is appropriately selected depending on the intended purpose without any limitation, and examples thereof include various exposing devices, such as a reproduction optical exposing device, a rod-lens array exposing device, a laser optical exposure device, a liquid crystal shutter optical device, and an LED optical device.
- a light source in the exposing device include a light source capable of securing high luminance, such as light emitting diode (LED), laser diode (LD) (i.e. a semiconductor laser), and electroluminescence (EL).
- LED light emitting diode
- LD laser diode
- EL electroluminescence
- the developing step can be carried out by the developing unit, and is developing the latent electrostatic image with a toner to form a visible image.
- the developing unit is appropriately selected depending on the intended purpose without any
- the developing device may employ a dry developing system, or a wet developing system.
- the developing device may be a developing device for a single color, or a
- the developing device for multiple colors.
- Suitable examples of the developing device include a developing device which contains a stirring device configured to stir the developer to cause frictions, to thereby charge the developer, and a magnet roller capable of rotating.
- the toner of the present invention and the carrier are mixed and stirred, and the toner is charged with the friction caused by the mixing and stirring.
- the charged toner is held on a surface of a rotating magnetic roller in the state of brush, to thereby form a magnetic brush.
- the magnet roller is provided adjacent to the
- the electrophotographic photoconductor and therefore part of the toner of the present invention constituting the magnetic brush on the surface of the magnetic roller is moved to the surface of the electrophotographic photoconductor by electric suction force.
- the latent electrostatic image is developed with the toner so that a visible image formed of the toner is formed on the surface of the electrophotographic photoconductor.
- the transferring step can be performed by the transfer unit, and is transferring the visible image onto a recording medium.
- the transfer unit is a unit configured to transfer the visible image onto a recording medium, but the transfer unit employs a method for directly transferring the visible image from the surface of the electrophotographic photoconductor to the recording medium, and a method using an intermediate transfer member, in which the visible image is primary transferred to the intermediate transfer member, followed by secondary
- the transferring step uses the intermediate transfer member, and contain primary transferring the visible image onto the intermediate transfer member, followed by secondary transferring the visible image onto the recording medium.
- the toner used is typically those of two or more colors, preferably a full-color toner. Therefore, the transferring step preferably contains a primary transferring step, which contains transferring visible images to the intermediate transfer member to form a composite transfer image, and a secondary transferring step, which contains transferring the composite transfer image to a recording medium.
- the linear velocity of the toner image transferred to a recording medium is appropriately selected depending on the intended purpose without any limitation, but it is preferably 300 mm/sec to 1,000 mm/sec.
- the transfer time at the nip in the secondary transfer unit is appropriately selected depending on the intended purpose without any limitation, but it is preferably 0.5 msec to 20 msec.
- the fixing step can be performed by the fixing unit, and is fixing the transfer image transferred to the recording medium.
- the fixing unit is appropriately selected depending on the intended purpose without any limitation, but it is preferably a heating and pressing member.
- the heating and pressing member include a combination of a heating roller and a pressing roller, and a combination of a heating roller, a pressing roller, and an endless belt.
- the heating is typically preferably performed at temperature of 80°C to 200°C.
- the fixing may be performed every time the toner image of each color is transferred to the recording medium, or performed once toner images of all colors have been laminated.
- the toner transporting step can be performed by the toner transporting unit, and is supplying a supplemental toner stored in a storing container to the developing unit depending on an amount of the toner consumed by image formation.
- the toner transporting unit is a unit configured to supply supplemental toner stored in a storing container to the developing unit depending on an amount of the toner consumed by image formation.
- diselectrification unit ' a cleaning step and a cleaning unit; a recycling step and a recycling unit! and controlling step and a controlling unit.
- the diselectrification step can be performed by the diselectrification unit, and is applying diselectrification bias to the electrophotographic photoconductor to diselectrify.
- the diselectrification unit is appropriately selected from conventional diselectrification units without any limitation, provided that it is capable of applying diselectrification bias to the
- electrophotographic photoconductor and suitable examples thereof include a diselectrification lamp.
- the cleaning step can be performed by the cleaning unit, and is removing the toner remained on the electrophotographic photoconductor.
- the cleaning unit is appropriately selected from conventional cleaners without any limitation, provided that it is capable of removing the electrophotographic toner remained on the electrophotographic photoconductor.
- Preferable examples thereof include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a web cleaner.
- the recycling step can be performed by the recycling unit, and is recycling the toner removed by the cleaning step to the developing unit.
- the recycling unit is not particularly limited, and examples thereof include conventional transporting units.
- the controlling step can be performed by the controlling unit, and is controlling each step.
- the controlling unit is appropriately selected depending on the intended purpose without any limitation, provided that it is capable of controlling the operation of each unit, and examples thereof include devices, such as a sequencer, and a computer.
- FIG. 6 illustrates one example of the image forming apparatus for use in the present invention.
- the image forming apparatus 100A is equipped with a photoconductor 10, which is a drum photoconductor image bearing member, a charging device 20, which is a charging unit, an exposing device 30, which is an exposing unit, a developing device 40, which is a developing unit, an intermediate transfer member 50, a cleaning device 60, which is a cleaning unit, and a diselectrification lamp 70, which is a diselectrification Unit .
- the intermediate transfer member 50 illustrated in FIG. 6 is an endless belt, and is designed to rotate in the direction indicated with an arrow by three rollers 51 disposed inside the intermediate transfer member 50 to support the intermediate transfer member 50. Part of the three rollers 51 also functions as a transfer bias roller capable of applying a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 50.
- the cleaning device 90 having a cleaning blade is provided, and the transfer roller 80 serving as the transfer unit capable of applying a transfer bias for transferring (secondary transferring) a developed image (i.e. the toner image) to the recording medium 95 serving as a final recording medium is provided to face the intermediate transfer member 50.
- the corona charger 58 which is configured to apply a charge to the toner image on the intermediate transfer member 50, is provided in the area situated between the contact area of the
- the developing device 40 illustrated in FIG. 6 consists of a developing belt 41 serving as the developer bearing member, and a black developing device 45K, a yellow developing device 45Y, a magenta developing device 45M, and a cyan developing device 45C, which are provided next to the developing device 41.
- the black developing device 45K is equipped with a
- the yellow developing device 45Y is equipped with a developer-retention section 42Y, a developer supply roller 43Y, and a developing roller 44Y
- the magenta developing unit 45M is equipped with a developer-retention section 42M, a developer supply roller 43M, and a developing roller 44M
- the cyan developing device 45C is equipped with a developer-retention section 42C, a developer supply roller 43C, and a developing roller 44C.
- the developing belt 41 is an endless belt, which is rotatably supported by a plurality of belt rollers, and at part of which is in contact with the photoconductor 10.
- the latent electrostatic image formed on the photoconductor 10 is developed with a developer supplied from the developing device 40, to thereby form a toner image.
- the toner image is transferred (primary transferred) to the intermediate transfer member 50 by the voltage applied from the roller 51, and is then transferred (secondary transferred) to a recording medium 95.
- a transferred image is formed on the recording medium 95. Note that, the toner remained on the
- photoconductor 10 is removed by a cleaning device 60 having a cleaning blade, the charge of the photoconductor 10 is removed by the diselectrification lamp 70.
- FIG. 7 Another example of the image forming apparatus for use in the present invention is illustrated in FIG. 7.
- the image forming apparatus 100B has the same structure and exhibits the same effect to those of the image forming apparatus 100A, provided that the image forming apparatus 100B is not equipped with a developing belt, and a black developing unit 45K, a yellow developing unit 45Y, a magenta developing unit 45M, and a cyan developing unit 45C are provided to face the photoconductor 10 in a surrounding area of the photoconductor 10.
- the reference numbers of FIG. 7, which are also used in FIG. 6, denote the same to those in FIG. 6.
- the image forming apparatus lOOC is a tandem color image forming apparatus.
- the image forming apparatus lOOC is equipped with an apparatus main body 150, a feeding table 200, a scanner 300, and an automatic document feeder (ADF) 400.
- ADF automatic document feeder
- An intermediate transfer member 50 in the form of an endless belt is provided in the central part of the apparatus main body 150.
- the intermediate transfer member 50 is rotatably supported by support rollers 14, 15, and 16 in the clockwise direction in FIG. 8.
- an intermediate transfer member cleaning device 17 configured to remove the residual toner on the intermediate transfer member 50 is provided.
- developing device 120 in which four image forming units 18, i.e. yellow, cyan, magenta, and black image forming units, are aligned along the traveling direction of the intermediate transfer member 50, is provided.
- an exposing device 21 is provided in the surrounding area of the tandem developing device 120.
- a secondary transfer device 22 is provided at the opposite side of the intermediate transfer member 50 to the side where the tandem developing device 120 is provided.
- a secondary transfer belt 24, which is an endless belt, is supported by a pair of rollers 23, and is designed so that recording paper transported on the secondary transfer belt 24 and the intermediate transfer member 50 can be in contact with each other.
- a fixing device 25 is provided in the surrounding area of the secondary transfer device 22.
- the fixing device 25 is equipped with a fixing belt 26, which is an endless belt, and a pressure roller 27 disposed so as to press against the fixing belt 26.
- a sheet reverser 28 which is configured to reverse the transfer paper to perform image formation on both sides of the transfer paper, is provided in the surrounding area of the secondary transfer device 22 and the fixing device 25.
- the image forming unit 18 of each color in the tandem developing device 120 contains a photoconductor 10, a charger 59 configured to uniformly charge the photoconductor 10, an exposing device 21 configured to apply light (L in FIG.
- a developing device 61 configured to develop the latent electrostatic image using a toner of each color to form a toner image of each color on the photoconductor 10
- a transfer charger 62 configured to transfer the toner image of each color to an intermediate transfer member 50, a photoconductor cleaning device 63, and a diselectrification device 64.
- a document is set on a document table 130 of the automatic document feeder (ADF) 400.
- the automatic document feeder (ADF) 400 is opened, a document is set on a contact glass 32 of the scanner 300, and then the ADF 400 is closed.
- the scanner 300 is driven to scan the document with a first carriage 33 equipped with a light source and a second carriage 34 equipped with a mirror.
- the scanner 300 is immediately driven in the same manner as mentioned. During this scanning operation, light applied from a light source of the first carriage 33 is reflected on the surface of the document, the reflected light from the
- the document is further reflected by a mirror of the second carriage 34, and passed through an image formation lens 35, which is then received by a read sensor 36.
- the color document (color image) is read, and image information of black, yellow, magenta, and cyan is obtained.
- the image information of each color, black, yellow, magenta or cyan is transmitted to respective image forming unit 18 (a black image forming unit, a yellow image forming unit, a magenta image forming unit, and a cyan image forming unit) of the tandem developing device 120, to thereby form a toner image of each color.
- a toner image formed on the photoconductor for black 10K, a toner image formed on the photoconductor for yellow 10Y, a toner image formed on the photoconductor for magenta 10M, and a toner image formed on the photoconductor for cyan IOC are sequentially transferred (primary transferred) to the intermediate transfer member 50.
- the black toner image, the yellow toner image, the magenta toner image, and the cyan toner image are superimposed to form a composite color image (a color transfer image).
- one of the feeding rollers 142a is selectively rotated to eject a sheet (recording paper) from one of multiple feeder cassettes 144 of a paper bank 143, the ejected sheets are separated one by one by a separation roller 145 to send to a feeder path 146, and then transported by a transport roller 147 into a feeder path 148 within the apparatus main body 150. The sheet transported in the feeder path 148 is then bumped against a registration roller 49 to stop.
- sheets (recording paper) on a manual-feeding tray 52 are ejected by rotating a feeding roller 142, separated one by one by a
- the registration roller 49 is generally earthed at the time of the use, but it may be biased for removing paper dust of the recording paper.
- the registration roller 49 is rotated synchronously with the movement of the composite color image (color transfer image) superimposed on the intermediate transfer member 50, to thereby send the recording paper between the intermediate transfer member 50 and the secondary transfer device 22.
- the recording paper on which the color image has been transferred is transported by a secondary transfer device 22 to send to a fixing device 25.
- the composite color image (color transfer image) is fixed to the recording paper by heat and pressure.
- the recording paper is changed its traveling direction by a switch craw 55, ejected by an ejecting roller 56, and then stacked on an output tray 57.
- the recording paper is changed its traveling direction by the switch craw 55, reversed by the sheet reverser 28 to send to a transfer position, to thereby record an image on the back side thereof.
- the recording paper is ejected by the ejecting roller 56, and stacked on the output tray 57. Note that, after transferring the image, the residual toner on the intermediate transfer member 50 is cleaned by the intermediate transfer member cleaning device 17.
- External Additives A to T were each produced by mixing primary particles having the average particle diameter as depicted in Table 1 with a treatment agent by spray drying, and firing under the conditions as depicted in Table 1, to thereby make the primary particles coalesced to each other.
- External Additives U to Y were each produced by merely subjecting primary particles having the average particle diameter as depicted in Table 1 to a hydrophobic treatment, without performing a treatment with the treatment agent.
- the treatment agent was prepared by adding 0.1 parts of a treatment aid (water, or 1% acetic acid aqueous solution) to 1 part of methyltrimethoxy silane.
- a treatment aid water, or 1% acetic acid aqueous solution
- the average particle diameter and shape of the secondary particles produced by coalescencing the primary particles are depicted in Table 1.
- the measurement of the average particle diameter of the secondary particles was performed by dispersing the secondary particles in tetrahydrofuran, removing the solvent on a substrate to dry and prepare a sample, and measuring the particle diameters of the secondary particles of the sample in the visual field as observed under a field emission scanning electron microscope (FE-SEM, accelerating voltage: 5 kV to 8 kV, magnification: x 8,000 to x 10,000).
- FE-SEM field emission scanning electron microscope
- the average particle diameter of the secondary particles was determined by speculating an entire image from a profile of the secondary particle formed by coalescence, and measuring the average value (the number of particles measured ' - 100 particles or more) of the maximum length (a length of the arrow shown in FIG. 2) of the entire image.
- the following starting materials of a carrier were dispersed by a Homomixer for 10 minutes, to thereby an acrylic resin-silicone resin coating layer forming solution containing alumina particles.
- the coating layer forming solution was applied to surfaces of core particles, i.e., baked ferrite powder [(MgO) l.8(MnO)49.5(Fe2O 3 )48.0; the weight average particle diameter ' - 25 ⁇ ] by a spira coater (manufactured by OKADA SEIKO CO., LTD.) to give a thickness of 0.15 ⁇ , and the coating solution was dried to thereby obtain a coated ferrite powder.
- the obtained coated ferrite powder was left and baked in an electric furnace for 1 hour at 150°C.
- the ferrite powder bulk was crushed using a sieve having an opening size of 106 ⁇ , to thereby obtain a carrier.
- the film thickness was measured by observing a cross-section of the carrier under a transmission electron microscope to observe a coating layer covering the carrier surface.
- the coating layer thickness was determined as the average value of the coating layer covering the carrier surface as measured by the observation. In the manner as mentioned, Carrier A having the weight average particle diameter of 35 ⁇ was obtained.
- Silicone resin solution (solid content: 23%) 65.0 parts [SR2410, manufactured by Dow Corning Toray
- a 50 mL bottle (manufactured by NICHIDEN-RIKA GLASS CO., LTD.) was charged with 50 g of a developer containing 0.5 g of each of External Additives A to T and 49.5 g of Carrier A.
- the developer was stirred for 10 minutes by means of ROKING MILL (manufactured by SEIWA GIKEN Co., Ltd.) at 67 Hz.
- the stirred developer was diluted and dispersed in tetrahydrofuran (THF) to separate the external additive to the side of a
- K to Y denote External Additives K to Y, respectively.
- Unmodified Polyester Resin 1 had the number average molecular weight (Mn) of 2, 100, the weight average molecular weight (Mw) of 5,600, and glass transition temperature (Tg) of 55°C.
- a 5 L four necked flask equipped with a nitrogen inlet tube, a condenser, a stirrer, and a thermocouple was charged with 229 parts of a bisphenol A ethylene oxide (2 mol) adduct, 529 parts of a bisphenol A propylene oxide (3 mol) adduct, 208 parts of terephthalic acid, 46 parts of adipic acid, and 2 parts of dibutyl tin oxide, and the mixture was allowed to react for 7 hours at 230°C under atmospheric pressure, and further reacted for 4 hours under the reduced pressure of 10 mmHg to 15 mmHg.
- a 5 L four necked flask equipped with a nitrogen inlet tube, a condenser, a stirrer, and a thermocouple was charged with 2,300 parts of 1,6-hexanediol, 2,530 parts of fumaric acid, 291 parts of trimellitic anhydride, and 4.9 parts of hydroquinone, and the mixture was allowed to react for 5 hours at 160°C. Then, the resulting reaction liquid was heated to 200°C, and reacted for 1 hour, followed by further reacting for 1 hour under the pressure of 8.3 kPa to thereby synthesize Crystalline Polyester Resin 1.
- Crystalline Polyester Resin 1 and 400 parts ethyl acetate were heated to 75°C to dissolve Crystalline Polyester Resin 1. Thereafter, the obtained solution was quenched in a ice-water bath at the rate of 27°C/min.
- 500 mL of glass beads (diameter: 3 mm) was added, and the mixture was subjected to grinding for 10 hours by means of a batch type sand mill
- HENSCHEL MIXER manufactured by Nippon Cole & Engineering Co., Ltd.
- 1,000 parts of water, 540 parts of carbon black (Printex35, manufactured by Evonik Degussa Japan Co., Ltd.,, DBP oil absorption value-- 42 ml/lOOg, pH: 9.5)
- 1,200 parts of Unmodified Polyester Resin 1 were mixed.
- the resulting mixture was kneaded for 30 minutes at 150°C with a two-roll kneader, and then was rolled and cooled, followed by pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation), to thereby obtain Master Batch 1.
- HENSCHEL MIXER manufactured by Nippon Cole & Engineering Co., Ltd.
- 1,200 parts of water, 540 parts of carbon black (Printex35, manufactured by Evonik Degussa Japan Co., Ltd.,, DBP oil absorption value: 42 ml/lOOg, pH: 9.5)
- 1,200 parts of Unmodified Polyester Resin 2 were mixed.
- the resulting mixture was kneaded for 30 minutes at 150°C with a two-roll kneader, and then was rolled and cooled, followed by pulverized with a pulverizer (manufactured by Hosokawa Micron Corporation), to thereby obtain Master Batch 2.
- a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen-inlet tube was charged with 682 parts of a bisphenol A ethylene oxide (2 mol) adduct, 81 parts of a bisphenol A propylene oxide (2 mol) adduct, 283 parts of terephthalic acid, 22 parts of trimellitic anhydride, and 2 parts of dibutyl tin oxide, and the resulting mixture was allowed to react for 8 hours at 230°C under atmospheric pressure, followed by further reacted for 5 hours under the reduced pressure of 10 mmHg to 15 mmHg, to thereby obtain Intermediate Polyester 1.
- Intermediate Polyester 1 had the number average molecular weight of 2, 100, the weight average molecular weight of 9,500, Tg of 55°C, acid value of 0.5, and hydroxyl value of 51.
- a reaction vessel equipped with a cooling tube, a stirrer, and a nitrogen-inlet tube was charged with 410 parts of Intermediate Polyester 1, 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate, and the mixture was allowed to react for 5 hours at 100°C, to thereby obtain Polyester Prepolymer 1.
- Polyester 1 had the number average molecular weight of 2, 100, the weight average molecular weight of 9,500, Tg of 55°C, acid value of 0.5, and hydroxyl value of 51.
- Prepolymer 1 had the free isocyanate rate of 1.53%.
- a reaction vessel equipped with a stirring bar and a
- thermometer was charged with 170 parts of isophorone diamine and 75 parts of methyl ethyl ketone, and the mixture was allowed to react for 5 hours at 50°C, to thereby obtain Ketimine Compound 1.
- Ketimine Compound 1 had the amine value of 418.
- a reaction vessel equipped with a stirring bar and a
- thermometer was charged with 683 parts of water, 16 parts of a sodium salt of sulfuric acid ester of methacrylic acid-ethylene oxide adduct (ELEMINOL RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 83 parts of styrene, 83 parts of methacrylic acid, 110 parts of butyl acrylate, and 1 part of ammonium persulfate, and the resulting mixture was stirred for 15 minutes at 400 rpm to thereby obtain a white emulsion. The obtained emulsion was heated until the internal system temperature reached 75°C, and then was allowed to react for 5 hours.
- ELEMINOL RS-30 sodium salt of sulfuric acid ester of methacrylic acid-ethylene oxide adduct
- Resin Particle Dispersion Liquid 1 was an aqueous dispersion liquid of a vinyl resin (a copolymer of styrene/methacrylic acid/butyl acrylate/sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct).
- Resin Particle Dispersion Liquid 1 had the volume average particle diameter (as measured by LA-920, manufactured by Horiba, Ltd.) of 9 nm.
- a reaction vessel equipped with a stirring bar and a
- thermometer was charged with 683 parts of water, 11 parts of a sodium salt of sulfuric acid ester of methacrylic acid-ethylene oxide adduct (ELEMINOL RS-30, manufactured by Sanyo Chemical Industries, Ltd.), 138 parts of styrene, 138 parts of methacrylic acid, and 1 part of ammonium persulfate, and the resulting mixture was stirred for 15 minutes at 400 rpm to thereby obtain a white emulsion. The obtained emulsion was heated until the internal system
- Resin Particle Dispersion Liquid 2 which was an aqueous dispersion liquid of a vinyl resin (a copolymer of styrene/methacrylic acid/butyl acrylate/sodium salt of sulfuric acid ester of methacrylic acid ethylene oxide adduct).
- Particle Dispersion Liquid 2 had the volume average particle diameter (as measured by LA-920) of 0.14 ⁇ . Part of Resin
- a beaker was charged with 100 parts of Unmodified Polyester Resin 1 and 130 parts of ethyl acetate, and the mixture was stirred to dissolve Unmodified Polyester Resin 1.
- 10 parts of carnauba wax molecular weight: 1,800, acid value- ' 2.5, penetration degree ⁇ 1.5 mm (40°O)
- 10 parts of Master Batch 1 were added, and the resulting mixture was dispersed by means of a bead mill (ULTRA VISCOMILL, manufactured by AIMEX CO., Ltd.) under the conditions ⁇ a liquid feed rate of 1 kg/hr, disc circumferential velocity of 6 m/s, 0.5 mm-zirconia beads packed to 80% by volume, and 3 passes to prepare a raw material solution, to thereby obtain Oil Phase 1 (a solution or dispersion of toner material).
- a vessel was charged with 150 parts of Aqueous Phase 1, and Aqueous Phase 1 was stirred by TK Homomixer (manufactured by PRIMIX Corporation) at 12,000 rpm. To this, 100 parts of Oil Phase 1 was added, and the mixture was mixed for 10 minutes to thereby prepare Emulsified Slurry 1 (an emulsion or dispersion liquid).
- TK Homomixer manufactured by PRIMIX Corporation
- ion-exchanged water was added to the resulting filtration cake.
- the obtained mixture was mixed and re-dispersed (at 12,000 rpm for 10 minutes) by TK Homomixer, followed by subjecting the resultant to filtration.
- TK Homomixer To the obtained filtration cake, 300 parts of
- To 100 parts of Toner Base Particles 1 2.0 parts of External Additive A, 2.0 parts of silica having the volume average particle diameter of 20 nm (manufactured by Nippon Aerosil Co., Ltd.), 0.6 parts of titanium oxide having the volume average particle diameter of 20 nm (manufactured by TAYCA CORPORATION) were added, and the mixture was mixed by HENSCHEL MIXER. The resultant was passed through a sieve with a mesh opening size of 500, to thereby obtain Toner 1.
- Toner 2 to Toner 10 were produced in the same manner as in Example 1, provided that External Additive A was replaced to
- a vessel equipped with a stirring bar and a thermometer was charged with 378 parts of Unmodified Polyester Resin 2, 110 parts of carnauba wax, 22 parts of a charge controlling agent (CCA, salicylic acid metal complex E-84, manufactured by Orient Chemical
- Raw Material Solution 2 (1,324 parts) was transferred to a vessel, and the carbon black and wax were dispersed y means of a bead mill (ULTRA).
- a vessel was charged with 664 parts of Oil Phase 2, 109.4 parts of Polyester Prepolymer 1, 73.9 parts of Crystalline Polyester Dispersion Liquid 1, and 4.6 parts of Ketimine Compound 1.
- the resulting mixture was mixed by means of TK Homomixer
- a vessel equipped with a stirrer and a thermometer was charged with Emulsified Slurry 2.
- the solvent therein was removed for 8 hours at 30°C, followed by aging for 4 hours at 45°C, to thereby obtain Dispersion Slurry 2.
- Additive A 2.0 parts of silica having the volume average particle diameter of 20 nm (manufactured by Nippon Aerosil Co., Ltd.), 0.6 parts of titanium oxide having the volume average particle diameter of 20 nm (manufactured by TAYCA CORPORATION) were added, and the mixture was mixed by HENSCHEL MIXER. The resultant was passed through a sieve with a mesh opening size of 500, to thereby obtain Toner 11.
- Toner 12 to Toner 20 were each obtained in the same manner as in Example 11, provided that External Additive A was replaced with External Additives B to J as depicted in Table 2, respectively.
- Unmodified Polyester Resin 1 After sufficiently stirring and mixing 80 parts of Unmodified Polyester Resin 1, 5 parts of paraffin wax (HNP-9, manufactured by NIPPON SEIRO CO., LTD., melting point: 75°C), and 10 parts of Master Batch 1 in HENSCHEL MIXER, the resulting mixture was heated and melted for 30 minutes at 130°C by a roll mill, followed by cooling to room temperature. The obtained kneaded product was roughly pulverized into 200 ⁇ to 400 ⁇ by a hammer mill. Next, the pulverized product was further pulverized and classified by means of a pulverizing classification device (manufactured by
- Toner Base Particles 3 (100 parts) was mixed with 2.0 parts of External Additive A, 2.0 parts of silica having the volume average particle diameter of 20 nm (manufactured by Nippon Aerosil Co., Ltd.), and 0.6 parts of titanium oxide having the volume average particle diameter of 20 nm (manufactured by TAYCA CORPORATION) by means of HENSCHEL MIXER, and the
- Toner 22 to Toner 30 were produced in the same manner as in Example 21, provided that External Additive A was replaced with External Additives B to J depicted in Table 2, respectively.
- Particles 4 (100 parts) was mixed with 2.0 parts of External Additive A, 2.0 parts of silica having the volume average particle diameter of 20 nm (manufactured by Nippon Aerosil Co., Ltd.), and 0.6 parts of titanium oxide having the volume average particle diameter of 20 nm (manufactured by TAYCA CORPORATION) by means of HENSCHEL MIXER, and the resultant was passed through a sieve with a mesh opening size of 500, to thereby obtain Toner 31.
- Toner 32 to Toner 40 were produced in the same manner as in Example 31, provided that External Additive A was replaced with External Additives B to J depicted in Table 2, respectively.
- Toner 41 to Toner 55 were produced in the same manner as in Example 1, provided that External Additive A was replaced with External Additives K to Y as depicted in Table 2, respectively.
- Each toner produced in Examples and Comparative Examples and Carrier A were used.
- Each toner (7 parts) was uniformly mixed with 100 parts of Carrier A by means of a tubular mixer which was configured to drive a container in a rolling motion to stir, and the toner and the carrier were charged to thereby produce a
- a difference with blank was less than 0.005.
- a difference with blank was less than 0.005.
- the toner After storing the toner in the environment having the temperature of 40°C and the relative humidity of 70%RH for 2 weeks, the toner was sieved with a sieve having a mesh size of 200 for 1 minute, and a remaining rate of the toner on the mesh was measured. The results were evaluated based on the following criteria. The smaller the residual rate of the toner is, more excellent storage stability is. Note that, “A”, “B” and “C” were judged as acceptable, and "D" was judged as unacceptable.
- the residual rate was 0.1% or more but less than 0.5%.
- the toner of the present invention gives excellent cleaning ability, storage stability, and image density, has high durability, and gives excellent image quality upon usage of a long term, as well as exhibiting excellent transfer property upon high-speed full-color image formation, and therefore the toner of the present invention can be suitably used in image formation of an electrophotographic system using a photocopier, electrostatic printing, a printer, a facsimile, and electrostatic recording.
- Aspects of the present invention are as follows, for example.
- a toner including: toner base particles; and an external additive, the toner base particles each including a binder resin and a releasing agent, wherein the external additive includes non-spherical coalesced particles in each of which primary particles are coalesced together, and wherein the coalesced particles satisfy the following formula
- Nx is a number of the primary particles present alone relative to 1,000 of the coalesced particles, as observed under a scanning electron microscope after stirring 0.5 g of the coalesced particles and 49.5 g of a carrier placed in a 50 mL bottle for 10 minutes by means of a mixing and stirring device at 67 Hz.
- Nx is a number of the primary particles present alone relative to 1,000 of the coalesced particles, as observed under a scanning electron microscope after stirring 0.5 g of the coalesced particles and 49.5 g of a carrier placed in a 50 mL bottle for 10 minutes by means of a mixing and stirring device at 67 Hz.
- ⁇ 6> The toner according to any one of ⁇ 1> to ⁇ 5>, wherein the toner base particles are obtained through a process including: dissolving or dispersing at least the binder resin and the releasing agent in an organic solvent to prepare a solution or a dispersion> ' adding the solution or the dispersion to an aqueous phase to prepare a dispersion liquid) ' and removing the organic solvent from the dispersion liquid.
- the binder resin includes a polyester resin.
- a developer including:
- An image forming apparatus including:
- a latent electrostatic image forming unit configured to form a latent electrostatic image on the latent electrostatic image bearing member
- a developing unit which houses the toner according to any one of ⁇ 1> to ⁇ 7>, or the developer according to ⁇ 8>, and is configured to develop the latent electrostatic image to form a visible image * '
- a transfer unit configured to transfer the visible image onto a recording medium
- a fixing unit configured to fix the visible image transferred onto the recording medium.
- the image forming apparatus is capable of forming images at the speed of 55 sheets/min or faster with the recording medium of A4 size, where the recording medium is fed in a direction along the shorter side of the recording medium.
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
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KR1020147027576A KR101908171B1 (en) | 2012-03-14 | 2013-03-07 | Toner, developer, and image forming apparatus |
CA2867294A CA2867294C (en) | 2012-03-14 | 2013-03-07 | Toner, developer, and image forming apparatus |
ES13761035.8T ES2633734T3 (en) | 2012-03-14 | 2013-03-07 | Toner, developer and imaging device |
RU2014141159/04A RU2569677C1 (en) | 2012-03-14 | 2013-03-07 | Toner, developer and image formation device |
US14/384,490 US20150104739A1 (en) | 2012-03-14 | 2013-03-07 | Toner, developer, and image forming apparatus |
AU2013233118A AU2013233118B2 (en) | 2012-03-14 | 2013-03-07 | Toner, developer, and image forming apparatus |
EP13761035.8A EP2825915B1 (en) | 2012-03-14 | 2013-03-07 | Toner, developer, and image forming apparatus |
CN201380022520.6A CN104272195B (en) | 2012-03-14 | 2013-03-07 | Toner, developer and image forming apparatus |
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JP2012057365A JP5817601B2 (en) | 2012-03-14 | 2012-03-14 | Toner, developer, and image forming apparatus |
JP2012-057365 | 2012-03-14 |
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WO2013137366A1 true WO2013137366A1 (en) | 2013-09-19 |
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US (1) | US20150104739A1 (en) |
EP (1) | EP2825915B1 (en) |
JP (1) | JP5817601B2 (en) |
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CN (1) | CN104272195B (en) |
AU (1) | AU2013233118B2 (en) |
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Cited By (3)
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US20150309435A1 (en) * | 2014-04-25 | 2015-10-29 | Kabushiki Kaisha Toshiba | Toner |
US9291931B2 (en) | 2013-02-21 | 2016-03-22 | Ricoh Company, Ltd. | Electrostatic charge image developing toner |
US9523931B2 (en) | 2013-02-05 | 2016-12-20 | Ricoh Company, Ltd. | Toner, developer and image forming apparatus |
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JPH0623885B2 (en) * | 1986-08-29 | 1994-03-30 | キヤノン株式会社 | Development device |
JP6127537B2 (en) * | 2013-01-25 | 2017-05-17 | 株式会社リコー | Toner, developer, and image forming apparatus |
RU2654858C1 (en) | 2014-04-23 | 2018-05-23 | Рикох Компани, Лтд. | Toner and method of manufacture of toner |
WO2016021393A1 (en) | 2014-08-06 | 2016-02-11 | 株式会社リコー | Toner |
JP6471460B2 (en) | 2014-11-04 | 2019-02-20 | 株式会社リコー | Toner and toner production method |
JP2017107138A (en) | 2015-01-05 | 2017-06-15 | 株式会社リコー | Toner, toner storage unit, and image forming apparatus |
JP6865525B2 (en) | 2015-01-05 | 2021-04-28 | 株式会社リコー | Toner, toner accommodating unit and image forming apparatus |
CN107209466B (en) * | 2015-02-17 | 2020-09-22 | 株式会社理光 | Toner, toner-containing unit, and image-forming apparatus |
JP6492813B2 (en) | 2015-03-13 | 2019-04-03 | 株式会社リコー | Toner, toner storage unit and image forming apparatus |
JP6520471B2 (en) | 2015-06-29 | 2019-05-29 | 株式会社リコー | Toner, developer, developer containing unit and image forming apparatus |
JP2017097216A (en) | 2015-11-26 | 2017-06-01 | 株式会社リコー | Toner, toner storage unit, and image forming apparatus |
JP6727803B2 (en) | 2015-12-21 | 2020-07-22 | キヤノン株式会社 | Toner and toner manufacturing method |
EP3425453B1 (en) | 2016-03-03 | 2019-11-13 | Ricoh Company, Ltd. | Toner, toner containing unit, and image forming apparatus |
JP2018045093A (en) * | 2016-09-14 | 2018-03-22 | シャープ株式会社 | Toner, two-component developer using the same, developing device, and image forming apparatus |
JP2018045112A (en) * | 2016-09-15 | 2018-03-22 | コニカミノルタ株式会社 | Toner for electrostatic charge image development |
JP6900245B2 (en) | 2017-06-09 | 2021-07-07 | キヤノン株式会社 | toner |
JP7229701B2 (en) | 2018-08-28 | 2023-02-28 | キヤノン株式会社 | toner |
US11054757B2 (en) | 2018-09-27 | 2021-07-06 | Ricoh Company, Ltd. | Toner, image forming apparatus, image forming method, and process cartridge |
JP7151413B2 (en) * | 2018-11-22 | 2022-10-12 | 株式会社リコー | Electrophotographic image forming carrier, electrophotographic image forming developer, electrophotographic image forming method, electrophotographic image forming apparatus and process cartridge |
JP7338396B2 (en) | 2019-10-18 | 2023-09-05 | 株式会社リコー | Toner, Toner Manufacturing Method, Developer, Toner Storage Unit, Image Forming Apparatus and Image Forming Method |
JP2023000504A (en) | 2021-06-18 | 2023-01-04 | 株式会社リコー | Image forming apparatus and image forming method |
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US9523931B2 (en) | 2013-02-05 | 2016-12-20 | Ricoh Company, Ltd. | Toner, developer and image forming apparatus |
US9291931B2 (en) | 2013-02-21 | 2016-03-22 | Ricoh Company, Ltd. | Electrostatic charge image developing toner |
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US10078284B2 (en) | 2014-04-25 | 2018-09-18 | Kabushiki Kaisha Toshiba | Toner |
Also Published As
Publication number | Publication date |
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EP2825915A1 (en) | 2015-01-21 |
JP2013190646A (en) | 2013-09-26 |
AU2013233118B2 (en) | 2015-03-19 |
CN104272195B (en) | 2019-06-14 |
US20150104739A1 (en) | 2015-04-16 |
KR101908171B1 (en) | 2018-10-15 |
EP2825915B1 (en) | 2017-06-14 |
CA2867294A1 (en) | 2013-09-19 |
KR20140131567A (en) | 2014-11-13 |
CN104272195A (en) | 2015-01-07 |
RU2569677C1 (en) | 2015-11-27 |
ES2633734T3 (en) | 2017-09-25 |
JP5817601B2 (en) | 2015-11-18 |
AU2013233118A1 (en) | 2014-09-18 |
CA2867294C (en) | 2017-04-04 |
EP2825915A4 (en) | 2015-03-25 |
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