WO2016170730A1 - Toner, appareil de formation d'image, et unité de stockage de toner - Google Patents

Toner, appareil de formation d'image, et unité de stockage de toner Download PDF

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Publication number
WO2016170730A1
WO2016170730A1 PCT/JP2016/001703 JP2016001703W WO2016170730A1 WO 2016170730 A1 WO2016170730 A1 WO 2016170730A1 JP 2016001703 W JP2016001703 W JP 2016001703W WO 2016170730 A1 WO2016170730 A1 WO 2016170730A1
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WIPO (PCT)
Prior art keywords
toner
acid
parts
resin
temperature
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PCT/JP2016/001703
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English (en)
Inventor
Yoshitaka Yamauchi
Kazumi Suzuki
Hisashi Nakajima
Saori Yamada
Yu Naito
Akihiro Kaneko
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Ricoh Company, Ltd.
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Priority claimed from JP2015160925A external-priority patent/JP6758591B2/ja
Application filed by Ricoh Company, Ltd. filed Critical Ricoh Company, Ltd.
Priority to EP16782758.3A priority Critical patent/EP3286607A4/fr
Priority to CN201680023296.6A priority patent/CN107533308A/zh
Priority to US15/567,631 priority patent/US10578988B2/en
Publication of WO2016170730A1 publication Critical patent/WO2016170730A1/fr

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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
    • G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
    • G03G9/08795—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775 characterised by their chemical properties, e.g. acidity, molecular weight, sensitivity to reactants
    • 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
    • G03G9/0821—Developers with toner particles characterised by physical parameters
    • 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
    • G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
    • 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

Definitions

  • the present disclosure relates to toners, image forming apparatuses, and toner stored units.
  • Image formation by electrophotography is typically performed through a series of processes, where an electrostatic latent image is formed on a photoconductor, the electrostatic latent image is developed with a developer to form a toner image, the toner image is transferred onto a recording medium, such as paper, and the toner image is then fixed on the recording medium.
  • a developer known are a one-component developer where a magnetic or non-magnetic toner is used independently, and a two-component toner composed of a toner and a carrier.
  • a heat roller system is typically used because of excellent energy efficiency thereof.
  • the heat roller system is a system where a heat roller is directly pressed against a toner image present on a recording medium to fix the toner image onto the recording medium.
  • the heat roller system there is a problem that a large quantity of electricity is required for fixing the toner image. Accordingly, there is a need for improving low-temperature fixing ability of a toner.
  • the toner disclosed in PTL 1 has a structure where domain phases are present in a matrix formed of a vinyl resin, and each domain phase contains crystalline polyester particles dispersed in a hybrid resin composed of amorphous polyester and a vinyl resin.
  • the toner disclosed in PTL 2 is a toner of a core-shell structure, where the core contains crystalline polyester domains in amorphous polyester, and the shell is formed of amorphous polyester.
  • the toner disclosed in PTL 3 has a structure containing two kinds of domain phases; i.e., a domain phase of amorphous polyester and a domain phase of crystalline polyester.
  • the present invention has an object to provide a toner which has excellent low-temperature fixing ability, and excellent heat-resistant storage stability, as well as desirable stress resistance.
  • a toner where a diffraction peak of the toner as measured by X-ray diffraction spectroscopy is present at least in a region where 2 ⁇ is from 20° through 25°, and a difference between Tg1 and Tg2 is 10°C or less, where Tg1 is a glass transition temperature of the toner, as observed in a last heating step, when heating and cooling are performed on the toner by means of a differential scanning calorimeter (DSC) under heating and cooling conditions 1, and Tg2 is a glass transition temperature of the toner, as observed in a last heating step, when heating and cooling are performed on the toner by means of the differential scanning calorimeter (DSC) under heating and cooling conditions 2, the heating and cooling conditions 1 being as follows: a starting temperature is 20°C, and the toner is heated from the starting temperature to 120°C at 10 °C/min, a temperature of the toner is retained at 120°C for
  • the present invention can provide a toner which has excellent low-temperature fixing ability, and excellent heat-resistant storage stability, as well as desirable stress resistance.
  • FIG. 1 is a cross-sectional view illustrating a structure of the image forming apparatus according to the present invention.
  • FIG. 2 is a cross-sectional view illustrating a structure of a process cartridge, which is one example of the toner stored unit according to the present invention.
  • the present invention is described below in detail.
  • the crystalline resin causes crystal transition at a melting point thereof and at the same time rapidly reduces the melt viscosity from a solid state thereof, to thereby develop a fixation function on a recording medium.
  • a melt viscosity of the amorphous resin is gradually reduced from the glass transition temperature thereof. There is a difference of some ten degrees Celsius between the glass transition temperature, and a temperature at which the melt viscosity thereof is reduced sufficiently for developing a fixation function, such as a softening point.
  • the toner of the present invention has the following characteristics. Accordingly, a diffraction peak of the toner as measured by X-ray diffraction spectroscopy is present at least in a region where 2 ⁇ is from 20° through 25°, and a difference in glass transition temperatures of the toner as measured by means of DSC under the following heating and cooling conditions 1 and 2 is 10°C or less. The difference in the glass transition temperatures is particularly preferably in a range of from 0°C through 5°C.
  • Heating and cooling conditions 1 A starting temperature is 20°C, and the toner is heated from the starting temperature to 120°C at 10 °C/min; a temperature of the toner is retained at 120°C for 10 minutes; the toner is cooled to 0°C at 10 °C/min; and a retention time at 0°C is none, and the toner is heated to 150°C at 10 °C/min.
  • a starting temperature is 20°C, and the toner is heated from the starting temperature to 120°C at 10 °C/min; a temperature of the toner is retained at 120°C for 10 minutes; the toner is cooled to 0°C at 10 °C/min; a retention time at 0°C is none, and the toner is heated to 45°C at 10 °C/min, and a temperature of the toner is retained at 45°C for 24 hours; the toner is again cooled to 0°C at 10 °C/min; and a retention time at 0°C is none, and the toner is heated to 150°C at 10 °C/min.
  • the toner of the present invention contains a crystalline resin and an amorphous resin.
  • the crystalline resin and the amorphous resin are incompatible to each other in the toner.
  • the presence of the crystalline resin in the toner can be confirmed by observing a diffraction peak attributed to a crystal segment in X-ray diffraction spectroscopy.
  • the presence of the crystalline polyester in the toner of the present invention can be confirmed, when a diffraction peak is present at least in a region where 2 ⁇ is from 20° through 25°, in X-ray diffraction spectroscopy of the toner.
  • Tg1 and Tg2 are glass transition temperatures observed in DSC when the toner, which has not been subjected to a heating and cooling treatment, is treated under the aforementioned heating and cooling conditions 1 and heating and cooling conditions 2.
  • Tg1 The glass transition temperature of the toner observed in the last heating step, when the toner is subjected to the heating and cooling treatment under the heating and cooling conditions 1.
  • Tg2 The glass transition temperature of the toner observed in the last heating step, when the toner is subjected to the heating and cooling treatment under the heating and cooling conditions 2.
  • a glass transition temperature of the toner is significantly reduced, when the toner is melted at 120°C, followed by quenching.
  • the glass transition temperature is increased again.
  • the deviation width of the glass transition temperatures Tg1 and Tg2 becomes large.
  • the toner preferably satisfies the following relationship.
  • M1 is a mass of a toluene-soluble component of the toner, the toluene-soluble component being prepared by adding the toner in toluene and separating the toluene-soluble component from a toluene-insoluble component
  • M2 is a mass of a chloroform-soluble component of the toner, the chloroform-soluble component being separated from the toluene-insoluble component.
  • the toluene-soluble component contains an amorphous resin, and a composite resin, and the chloroform-soluble component separated from the toluene-insoluble component contains crystalline polyester and a release agent.
  • An amount of the crystalline polyester in the toner is preferably determined depending on an amount of the release agent added into the toner. Specifically, a total amount of the crystalline polyester and the release agent is preferably from 6% by mass through 12% by mass relative to a total amount of the amorphous polyester, the crystalline polyester, the composite resin, and the release agent in the toner.
  • a total amount of the crystalline resin and the release agent is less than 6% by mass, a sufficient effect of improving low-temperature fixing ability cannot be attained.
  • the total amount thereof is greater than 12% by mass, dispersibility of the crystalline polyester is poor, which may increase an amount of loose aggregates, and adversely affect a device, as well as impair low-temperature fixing ability.
  • a component analysis is performed on the toner by means of a pyrolysis-gas chromatography-mass spectrometer (Py-GC/MS)
  • a component analysis is performed on the toner by means of a pyrolysis-gas chromatography-mass spectrometer (Py-GC/MS)
  • an acid monomer, an alcohol monomer, and a vinyl monomer be detected.
  • a monomer composition of the resin contained in the toner can be analyzed by pyrolysis-gas chromatography-mass spectrometry.
  • at least one acid monomer, at least one alcohol monomer, and at least one vinyl monomer are detected, it is judged that a polyester resin and a vinyl resin are contained.
  • a monomer can be analyzed with a fragment pattern (a pattern presenting that an actual monomer is in a state of fragments).
  • an acid monomer and an alcohol monomer be detected, and the acid monomer be higher fatty acid having 6 or more carbon atoms and the alcohol monomer be aliphatic alcohol having 6 or more carbon atoms, when a toluene-insoluble component in the toner is separated, a chloroform-soluble component is separated from the separated toluene-insoluble component, and a component analysis is performed on the separated chloroform-soluble component by a pyrolysis-gas chromatography-mass spectrometer (Py-GC/MS).
  • the chloroform-soluble component separated from the toluene-insoluble component of the toner contains crystalline polyester.
  • the acid component of the crystalline polyester is fatty acid having 6 or more carbon atoms
  • the alcohol component of the crystalline polyester is aliphatic alcohol having 6 or more carbon atoms.
  • the amorphous resin is not particularly limited, as long as the amorphous resin can cause phase separation from a crystalline resin.
  • the amorphous resin include amorphous polyester, amorphous polyurethane, amorphous polyurea, amorphous polyamide, amorphous polyether, an amorphous vinyl resin, amorphous, urethane-modified polyester, and amorphous, urea-modified polyester.
  • One of the above-listed amorphous resins may be used alone, or two or more of the above-listed amorphous resins may be used in combination.
  • amorphous polyester is preferable.
  • the amorphous polyester typically includes a constitutional unit derived from an aromatic compound.
  • the aromatic compound is not particularly limited, but examples of the aromatic compound include alkylene oxide adducts of bisphenol A, isophthalic acid, terephthalic acid, and derivatives of the aforementioned compounds.
  • An amount of the constitutional unit derived from the aromatic compound in the amorphous polyester is typically 50% by mass or greater. When the amount of the constitutional unit derived from the aromatic compound in the amorphous polyester is less than 50% by mass, negative-chargeability of a resultant toner may be poor.
  • a glass transition temperature of the amorphous resin is typically from 45°C through 75°C, preferably from 50°C through 70°C. When the glass transition temperature of the amorphous resin is 45°C or higher, a resultant toner has excellent heat-resistant storage stability. When the glass transition temperature of the amorphous resin is 75°C or lower, a resultant toner has excellent low-temperature fixing ability.
  • a softening point of the amorphous resin is typically from 90°C through 150°C, preferably from 90°C through 130°C. When the softening point of the amorphous resin is 90°C or higher, a resultant toner has excellent heat-resistant storage stability. When the softening point of the amorphous resin is 150°C or lower, a resultant toner has excellent low-temperature fixing ability.
  • the weight average molecular weight of the amorphous resin is typically from 1,000 through 100,000, preferably from 2,000 through 50,000, and more preferably from 3,000 through 10,000.
  • the weight average molecular weight of the amorphous resin is 1,000 or greater, a resultant toner has excellent heat-resistant storage stability.
  • the weight average molecular weight of the amorphous resin is 100,000 or less, a resultant toner has excellent low-temperature fixing ability.
  • the weight average molecular weight of the amorphous resin is a molecular weight converted to polystyrene, as measured by gel permeation chromatography.
  • the crystalline resin includes crystalline polyester.
  • the crystalline polyester may be used in combination with at least one selected from the group consisting of crystalline polyurethane, crystalline polyurea, crystalline polyamide, crystalline polyether, a crystalline vinyl resin, crystalline urethane-modified polyester, and crystalline urea-modified polyester.
  • the crystalline polyester can be synthesized through polycondensation between polyol and polycarboxylic acid, through ring-opening polymerization of lactone, through polycondensation of hydroxycarboxylic acid, or through ring-opening polymerization of cyclic esters having from 4 through 12 carbon atoms, corresponding to a dehydration condensate between two or three molecules of hydroxycarboxylic acid.
  • the crystalline polyester is preferably a polycondensate between diol and dicarboxylic acid.
  • diol may be used alone, or diol and trivalent or higher alcohol may be used in combination.
  • the diol is not particularly limited.
  • the diol include: aliphatic diol, such as straight-chain aliphatic diol, and branched-chain aliphatic diol; alkylene ether glycol having from 4 through 36 carbon atoms; adducts of alicyclic diol having from 4 through 36 carbon atoms with alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide) (where the number of moles added is from 1 through 30); adducts of bisphenol with alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide) (where the number of moles added is from 2 through 30); polylactone diol; polybutadiene diol; and a functional group-containing diol, such as a carboxyl group-containing diol, a sulfonic acid group or sulfamic acid group-containing diol, and diol containing salts
  • An amount of the straight-chain aliphatic diol in the diol is typically preferably 80 mol% or greater, more preferably 90 mol% or greater. When the amount of the straight-chain aliphatic diol in the diol is less than 80 mol%, it may be difficult for a resultant toner to attain both low-temperature fixing ability and heat-resistant storage stability.
  • Examples of the straight-chain aliphatic diol having from 2 through 36 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-eicosanediol.
  • ethylene glycol 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,9-nonanediol, and 1,10-decanediol.
  • Examples of the branched-chain aliphatic diol having from 2 through 36 carbon atoms include 1,2-propyleneglycol, butanediol, hexanediol, octanediol, decanediol, dodecanediol, tetradecanediol, neopentyl glycol, and 2,2-diethyl-1,3-propanediol.
  • alkylene ether glycol having from 4 through 36 carbon atoms examples include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
  • alkylene ether glycol having from 4 through 36 carbon atoms examples include diethylene glycol, triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene ether glycol.
  • alicyclic diol having from 4 through 36 carbon atoms examples include 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A.
  • Examples of the bisphenol include bisphenol A, bisphenol F, and bisphenol S.
  • Examples of the polylactone diol include poly( ⁇ -caprolactonediol).
  • Examples of the carboxyl group-containing diol include dialkylolalkanoic acid having from 6 through 24 carbon atoms, such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolheptanoic acid, and 2,2-dimethyloloctanoic acid.
  • Examples of the sulfonic acid group or sulfamic acid group-containing diol include: N,N-bis(2-hydroxyalkyl)sulfamic acid (where the number of carbon atoms in the alkyl group is from 1 through 6) and adducts thereof with alkylene oxides (e.g., ethylene oxide, propylene oxide, and butylene oxide) (where the number of moles added is from 1 through 6), such as N,N-bis(2-hydroxyethyl)sulfamic acid, and a propylene oxide (2 mol) adduct of N,N-bis(2-hydroxyethyl)sulfamic acid; and bis(2-hydroxyethyl)phosphate.
  • N,N-bis(2-hydroxyalkyl)sulfamic acid where the number of carbon atoms in the alkyl group is from 1 through 6
  • alkylene oxides e.g., ethylene oxide, propylene oxide, and butylene oxide
  • Examples of a base used for neutralizing salts of the carboxyl group-containing diol and the sulfonic acid group or sulfamic acid group-containing diol include tertiary amine having from 3 through 30 carbon atoms (e.g., trimethylamine), and alkali metal hydroxide (e.g., sodium hydroxide).
  • tertiary amine having from 3 through 30 carbon atoms (e.g., trimethylamine)
  • alkali metal hydroxide e.g., sodium hydroxide
  • alkylene glycol having from 2 through 12 carbon atoms, carboxyl group-containing diol, and an alkylene oxide adduct of bisphenol.
  • the trivalent or higher polyol is not particularly limited.
  • the trivalent or higher polyol include: alkane polyol, and intramolecular or intermolecular dehydrate thereof, such as glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, sorbitan, and polyglycerin; polyvalent aliphatic alcohol having from 3 through 36 carbon atoms, such as sugars (e.g., sucrose and methyl glucoside), and derivatives thereof; alkylene oxide adducts (where the number of moles added is from 2 through 30) of trisphenol (e.g., trisphenol PA); alkylene oxide adducts (where the number of moles added is from 2 through 30) of a novolak resin (e.g., phenol novolak and cresol novolak); and acryl polyol, such as a copolymer of hydroxyethyl(meth)acrylate and
  • trivalent or higher polyvalent aliphatic alcohol, and an alkylene oxide adduct of a novolak resin are preferable, and the alkylene oxide adduct of a novolak resin is more preferable.
  • dicarboxylic acid may be used alone, or dicarboxylic acid and trivalent or higher carboxylic acid may be used in combination.
  • the dicarboxylic acid is not particularly limited, but examples thereof include: aliphatic dicarboxylic acid, such as straight-chain aliphatic dicarboxylic acid, and branched-chain aliphatic dicarboxylic acid; and aromatic dicarboxylic acid.
  • straight-chain aliphatic dicarboxylic acid is preferable.
  • aliphatic dicarboxylic acid examples include: alkane dicarboxylic acid having from 4 through 36 carbon atoms, such as succinic acid, adipic acid, sebacic acid, azelaic acid, dodecane dicarboxylic acid, octadecane dicarboxylic acid, and decylsuccinic acid; alkene dicarboxylic acid having from 4 through 36 carbon atoms, such as alkenyl succinic acid (e.g., dodecenylsuccinic acid, pentadecenylsuccinic acid, and octadecenylsuccinic acid), maleic acid, fumaric acid, and citraconic acid; and alicyclic dicarboxylic acid having from 6 through 40 carbon atoms, such as dimer acid (e.g., dimerized linoleic acid).
  • alkane dicarboxylic acid having from 4 through 36 carbon atoms such as succin
  • aromatic dicarboxylic acid examples include aromatic dicarboxylic acid having from 8 through 36 carbon atoms, such as phthalic acid, isophthalic acid, terephthalic acid, t-butyl isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-biphenyldicarboxylic acid.
  • the trivalent or higher carboxylic acid is not particularly limited, but examples thereof include aromatic polycarboxylic acid having from 9 through 20 carbon atoms, such as trimellitic acid, and pyromellitic acid.
  • anhydrides or alkyl esters having from 1 through 4 carbon atoms e.g., methyl ester, ethyl ester, and isopropyl ester
  • anhydrides or alkyl esters having from 1 through 4 carbon atoms e.g., methyl ester, ethyl ester, and isopropyl ester
  • single use of aliphatic dicarboxylic acid is preferable, and single use of adipic acid, sebacic acid, dodecanedicarboxylic acid, terephthalic acid, or isophthalic acid is more preferable. It is also preferable that aliphatic dicarboxylic acid and aromatic dicarboxylic acid be used in combination. Use of aliphatic dicarboxylic acid, and terephthalic acid, isophthalic acid, or t-butyl isophthalic acid in combination is more preferable. An amount of the aromatic dicarboxylic acid in the polycarboxylic acid is preferably 20 mol% or less.
  • the lactone is not particularly limited, but examples thereof include monolactone having from 3 through 12 carbon atoms, such as ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone. Among the above-listed lactone, ⁇ -caprolactone is preferable.
  • a catalyst e.g., a metal oxide, and an organic metal compound
  • diol e.g., ethylene glycol and diethylene glycol
  • examples of a commercial product of a ring-opening polymerized product of the lactone include H1P, H4, H5, H7 of PLACCEL series (available from Daicel Corporation).
  • the hydroxycarboxylic acid used for the polycondensation is not particularly limited, but examples thereof include glycolic acid and lactic acid (e.g., L-form, D-form, and a racemic body).
  • the hydroxycarboxylic acid used for the cyclic ester is not particularly limited, but examples thereof include glycolide and lactide (e.g., L-form, D-form, and a racemic body). Among the above-listed hydroxycarboxylic acid, L-lactide and D-lactide are preferable.
  • a catalyst e.g., metal oxide, and an organic metal compound
  • Polyester diol or polyester dicarboxylic acid can be synthesized by modifying a terminal of a polycondensation product of hydroxycarboxylic acid, or a terminal of a ring-opening polymerization product of cyclic ester to be a hydroxyl group or a carboxyl group.
  • a melting point of the crystalline resin is typically from 60°C through 110°C, preferably from 70°C through 100°C.
  • the melting point of the crystalline resin is 60°C or higher, a resultant toner has sufficient heat-resistant storage stability.
  • the melting point of the crystalline resin is 110°C or lower, a resultant toner has sufficient low-temperature fixing ability.
  • the melting point can be measured by means of a differential scanning calorimeter TA-60WS and DSC-60 (available from Shimadzu Corporation).
  • the softening point can be measured by means of a flow tester capillary rheometer CFT-500D (available from Shimadzu Corporation).
  • a softening point of the crystalline resin is typically from 80°C through 130°C, preferably from 90°C through 130°C.
  • the softening point of the crystalline resin is 80°C or higher, a resultant toner has sufficient heat-resistant storage stability.
  • the softening point of the crystalline resin is 130°C or lower, a resultant toner has sufficient low-temperature fixing ability.
  • the softening point is 90°C or higher, moreover, a difference between the viscosity of the crystalline resin and the viscosity of the amorphous resin can be made small, hence it is easy to apply shear. As a result, the crystalline resin can be finely dispersed.
  • a crystalline resin having a melting point of from 60°C through 80°C, and a softening point of from 80°C through 130°C is synthesized, typically, an aromatic compound is not used, and only an aliphatic compound is used.
  • a diameter of the dispersed crystalline polyester in the toner is preferably 50 nm or greater but 200 nm or smaller, particularly preferably 50 nm or greater but 100 nm or smaller.
  • the diameter of the dispersed crystalline polyester is 50 nm or greater but 200 nm or smaller, an interface area between the crystalline polyester and the amorphous polyester is sufficiently ensured, to thereby exhibit an excellent plasticity effect owing to the crystalline polyester.
  • a resultant toner is sufficiently deformed at the time of fixing, and therefore offset hardly occurs at a low temperature range.
  • the dispersed diameter is preferably made smaller.
  • the dispersed diameter of the crystalline polyester in the toner can be confirmed by dying with ruthenium tetroxide, followed by observing backscattered electron image with a scanning electron microscope. Because the amorphous polyester is dyed, the amorphous polyester is observed as a bright area in the backscattered electron image. Because the crystalline polyester is not easily dyed, on the other hand, the crystalline polyester is observed as an undyed area (dark area) in the backscattered electron image. The diameter of the crystalline polyester dispersed can be evaluated by observing the difference in contrast between the crystalline polyester and the amorphous polyester. In the case where the toner contains a composite resin, the composite resin can be distinguished, because the composite resin is dyed with ruthenium tetroxide in the intermediate degree between the amorphous polyester and the crystalline polyester.
  • a vinyl resin is preferably contained in the toner. It is particularly preferable that the vinyl resin constitute a composite resin with a polyester resin.
  • the composite resin can function as a dispersing agent for the crystalline polyester, because the solubility parameter of the composite resin of the vinyl resin and the polyester resin falls between the solubility parameter of the crystalline polyester resin and the solubility parameter of the amorphous polyester resin.
  • the polyester resin and the vinyl resin constituting the composite resin may be referred to as a polyester resin segment and a vinyl resin segment, respectively.
  • the vinyl resin segment contains a constitutional component derived from a bireactive monomer in an amount of 3% by mass or greater but 15% by mass or less, relative to the vinyl resin segment.
  • a proportion of the vinyl resin in the toner is preferably 20% by mass or less.
  • the proportion of the vinyl resin is 20% by mass or less, there is no concern regarding insufficient heat-resistant storage stability of a resultant toner due to low Tg of the toner.
  • Examples of a carboxylic acid component which is a raw material monomer of the polyester segment of the composite resin, include aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and trivalent or higher polyvalent carboxylic acid.
  • the carboxylic acid component preferably contains either or both of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid.
  • acid anhydrides or alkyl (where the number of carbon atoms is 1 or more but 3 or less) esters of the above-listed carboxylic acids may be used.
  • the carboxylic acid component one of the above-listed carboxylic acids may be used alone, or two or more of the above-listed carboxylic acids may be used in combination.
  • aromatic dicarboxylic acid examples include terephthalic acid, phthalic acid, and isophthalic acid.
  • terephthalic acid is preferable for the purpose of attaining a toner which has both low-temperature fixing ability and heat-resistant storage stability, and produces a print having excellent bending resistance.
  • an amount of the aromatic dicarboxylic acid in the carboxylic acid component is preferably 55 mol% or greater, more preferably 60 mol% or greater, and even more preferably 65 mol% or greater.
  • the amount thereof is preferably 80 mol% or less, more preferably 75 mol% or less, and even more preferably 70 mol% or less.
  • the aliphatic dicarboxylic acid preferably contains aliphatic dicarboxylic acid having from 2 through 6 carbon atoms.
  • Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • the examples of the aliphatic dicarboxylic acid also include succinic acid substituted by an alkyl group having from 1 through 20 carbon atoms or an alkenyl group having from 2 through 20 carbon atoms, such as dodecyl succinic acid, dodecenylsuccinic acid, and octenylsuccinic acid.
  • succinic acid substituted by an alkyl group having from 1 through 20 carbon atoms or an alkenyl group having from 2 through 20 carbon atoms such as dodecyl succinic acid, dodecenylsuccinic acid, and octenylsuccinic acid.
  • fumaric acid, dodecenylsuccinic acid, and octenylsuccinic acid are preferable, and fumaric acid is more preferable, for the purpose of attaining a toner, which has both low-temperature fixing ability and heat-resistant storage stability, and produces a print having excellent bending resistance.
  • an amount of the aliphatic dicarboxylic acid in the carboxylic acid component is preferably 10 mol% or greater, more preferably 15 mol% or greater, even more preferably 20 mol% or greater, and yet even more preferably 25 mol% or greater. Moreover, the amount thereof is preferably 50 mol% or less, more preferably 45 mol% or less, even more preferably 40 mol% or less, and yet even more preferably 35 mol% or less.
  • a molar ratio (aliphatic dicarboxylic acid/aromatic dicarboxylic acid) of the aliphatic dicarboxylic acid to the aromatic dicarboxylic acid is preferably from 20/80 through 50/50, more preferably from 25/75 through 45/55, and even more preferably from 30/70 through 40/60.
  • a total amount of the aliphatic dicarboxylic acid and the aromatic dicarboxylic acid in the carboxylic acid component is preferably 90 mol% or greater, more preferably from 95 mol% through 100 mol%, even more preferably from 99 mol% through 100 mol%, and yet even more preferably 100 mol%.
  • an alcohol component which is a raw material monomer of the polyester segment of the composite resin
  • examples of an alcohol component include aliphatic diol, aromatic diol, and trivalent or higher polyvalent alcohol.
  • aromatic diol is preferable.
  • the alcohol component one of the above-listed alcohols may be used alone or in combination.
  • the alcohol component of the polyester segment of the composite resin preferably contains an alkylene oxide adduct of bisphenol A, which is represented by the following formula (I), in view of heat-resistant storage stability, durability, and low-temperature fixing ability of a toner.
  • R is an alkylene group having 2 or 3 carbon atoms; and x and y are each an average number of moles of the alkyleneoxy group added, and each depict a positive number.
  • the sum of x and y is preferably 1 or greater, more preferably 1.5 or greater, and more preferably 2 or greater, but is preferably 16 or less, more preferably 5 or less, and even more preferably 3 or less.
  • alkylene oxide adduct of bisphenol A which is represented by the formula (I)
  • examples of the alkylene oxide adduct of bisphenol A include polyoxypropylene adducts of 2,2-bis(4-hydroxyphenyl)propane, and polyoxyethylene adducts of 2,2-bis(4-hydroxyphenyl)propane.
  • the alkylene oxide adduct of bisphenol A which is represented by the formula (I) is contained in the alcohol component in an amount of preferably from 70 mol% through 100 mol%, more preferably from 80 mol% through 100 mol%, and even more preferably from 90 mol% through 100 mol%.
  • a ratio of the carboxylic acid component to 100 parts by mol of the alcohol component, which is a raw material monomer of the polyester segment of the composite resin is preferably 70 parts by mol or greater, more preferably 80 parts by mol or greater, even more preferably 85 parts by mol or greater, and even more preferably 90 parts by mol, but is preferably 110 parts by mol or less, more preferably 100 parts by mol or less, and even more preferably 95 parts by mol or less.
  • vinyl resin segment examples of raw material monomers of the vinyl resin segment include: styrene; styrene derivatives, such as ⁇ -methylstyrene, and vinyl toluene; alkyl (meth)acrylate; vinyl esters, such as vinyl propionate; ethylenically monocarboxylic acid esters, such as dimethylaminoethyl (meth)acrylate; vinyl ethers, such as vinyl methyl ether; vinylidene halogen compounds, such as vinylidene chloride; and N-vinyl compounds, such as N-vinylpyrrolidone.
  • the term “(meth)acrylic acid” means at least one of acrylic acid and methacrylic acid.
  • the vinyl resin segment is preferably a styrene resin for improving compatibility to the crystalline polyester to improve dispersibility of the crystalline polyester in a toner.
  • a toner has excellent low-temperature fixing ability, and heat-resistant storage stability, and produces a print having excellent bending resistance.
  • a suitable main raw material monomer of the vinyl resin is preferably styrene, or a styrene derivative, such as ⁇ -methylstyrene, and vinyl toluene, and is more preferably styrene.
  • the vinyl resin segment contains a constitutional component derived from a bireactive monomer described below.
  • raw material monomers of the vinyl resin also contain a bireactive monomer.
  • the lower limit of an amount of the styrene derivative in the raw material monomers of the vinyl resin is preferably 50% by mass or greater, more preferably 60% by mass or greater, even more preferably 70% by mass or greater, and yet even more preferably 75% by mass or greater.
  • the upper limit thereof is preferably 97% by mass or less, more preferably 96.8% by mass or less, even more preferably 96.5% by mass or less, yet even more preferably 96% by mass or less, and particularly preferably 85% by mass or less.
  • the copolymer component is preferably alkyl (meth)acrylate.
  • the number of carbon atoms in the alkyl group of the alkyl (meth)acrylate is preferably from 1 through 22, more preferably from 8 through 18.
  • the number of carbon atoms of the alkyl ester is the number of carbon atoms derived from an alcohol component constituting the ester.
  • Specific examples of the alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, (iso)propyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, (iso or tertiary)butyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, and (iso)stearyl (meth)acrylate.
  • 2-ethylhexyl(meth)acrylate is preferable, and 2-ethylhexylacrylate is more preferable.
  • the terms “(iso or tertiary)” and “(iso)” mean to include both a case where the corresponding iso or tertiary group is present, and a case where the corresponding iso or tertiary group is absent. In the case where these groups are absent, the term represents normal (n-).
  • the term “(meth)acrylate” includes both acrylate and methacrylate.
  • the lower limit of an amount of the alkyl (meth)acrylate in the raw material monomers of the vinyl resin is preferably 5% by mass or greater, more preferably 10% by mass or greater, even more preferably 15% by mass or greater, and yet even more preferably 18% by mass or greater.
  • the upper limit thereof is preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and yet even more preferably 25% by mass or less.
  • the lower limit of an amount of the raw material monomers of the vinyl resin segment in the raw material monomers of the composite resin is preferably 10 parts by mass or greater, more preferably 20 parts by mass or greater, even more preferably 30 parts by mass or greater, yet even more preferably 40 parts by mass or greater, and particularly preferably 45 parts by mass or greater, relative to 100 parts by mass of the raw material monomers of the polyester segment.
  • the upper limit thereof is preferably 75 parts by mass or less, more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less, yet even more preferably 60 parts by mass or less, and particularly preferably 55 parts by mass or less.
  • a bireactive monomer used in the constitutional component derived from the bireactive monomer include a compound containing, in a molecule thereof, at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an epoxy group, a primary amino group, and a secondary amino group.
  • a compound containing at least one of a hydroxyl group and a carboxyl group, and a compound having an ethylenically unsaturated bond with a carboxyl group is more preferable, in view of reactivity.
  • Use of the aforementioned bireactive monomer can further improve dispersibility of the crystalline polyester.
  • bireactive monomer examples include acrylic acid, methacrylic acid, maleic acid, and maleic anhydride.
  • acrylic acid or methacrylic acid is more preferable as the bireactive monomer.
  • the lower limit of an amount of the constitutional component derived from the bireactive monomer in the vinyl resin segment of the composite resin is preferably 3% by mass or greater, more preferably 3.2% by mass or greater, even more preferably 3.5% by mass or greater, and yet even more preferably 4% by mass or greater.
  • the upper limit thereof is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and yet even more preferably 4.5% by mass or less.
  • the lower limit of a softening point of the composite resin for use in the present invention is preferably 90°C or higher, more preferably 95°C or higher, even more preferably 100°C or higher, yet even more preferably 105°C or higher, and particularly preferably 110°C or higher.
  • the upper limit of the softening point thereof is preferably 140°C or lower, more preferably 130°C or lower, even more preferably 125°C or lower, yet even more preferably 120°C or lower, and particularly preferably 115°C or lower.
  • the lower limit of a glass transition temperature of the composite resin for use in the present invention is preferably 50°C or higher, more preferably 52°C or higher, and even more preferably 55°C or higher.
  • the upper limit of the glass transition temperature thereof is preferably 75°C or lower, more preferably 65°C or lower, and even more preferably 62°C or lower.
  • the lower limit of an acid value of the composite resin is preferably 1 mgKOH/g or greater, more preferably 5 mgKOH/g or greater, even more preferably 10 mgKOH/g or greater, and yet even more preferably 15 mgKOH/g or greater.
  • the upper limit of the acid value thereof is preferably 40 mgKOH/g or less, more preferably 35 mgKOH/g or less, even more preferably 20 mgKOH/g or less, and yet even more preferably 18 mgKOH/g or less.
  • the softening point, glass transition temperature, and acid value can be easily adjusted by adjusting a composition of raw material monomers, a molecular weight thereof, or an amount of a catalyst, or choice of reaction conditions.
  • a total amount of the polyester segment, the vinyl resin segment, and the constitutional component derived from the bireactive monomer in the composite resin is preferably 90 mol% or greater, more preferably 95 mol% or greater, even more preferably 99 mol% or greater, and yet even more preferably 100 mol%.
  • the composite resin can be produced by the following method.
  • the production method of the composite resin is a method containing: (A) performing a condensation polymerization reaction between an alcohol component and a carboxylic acid component, followed by (B) performing an addition polymerization reaction of raw material monomers of a vinyl resin segment, and optionally a bireactive monomer.
  • the bireactive monomer is preferably supplied to a reaction system together with other raw material monomers of the vinyl resin segment.
  • a catalyst such as an esterification catalyst and an esterification accelerator, may be used.
  • a polymerization initiator and a polymerization inhibitor may be used. The aforementioned method is preferably performed in one container.
  • a temperature of the condensation polymerization reaction is preferably 220°C or higher, more preferably 225°C or higher, and even more preferably 230°C or higher, but is preferably 245°C or lower, more preferably 240°C or lower, and even more preferably 238°C or lower.
  • a temperature of the addition polymerization reaction is preferably 120°C or higher, more preferably 140°C or higher, even more preferably 160°C or higher, and yet even more preferably 200°C or higher, but is preferably 235°C or lower, more preferably 230°C or lower, even more preferably 225°C or lower, and yet even more preferably 220°C or lower.
  • the reaction is preferably accelerated by reducing the pressure of the reaction system in the latter-half of the polymerization.
  • esterification catalyst As for the esterification catalyst suitably used for the condensation polymerization, the same esterification catalyst used for the production of the crystalline polyester can be suitably used.
  • One of the above-listed esterification catalysts may be used alone, or two or more of the above-listed esterification catalysts may be used in combination.
  • the titanium compound is preferably a titanium compound including a Ti-O bond, preferably a compound containing an alkoxy group having from 1 through 28 carbon atoms, an alkenyloxy group having from 1 through 28 carbon atoms, or an acyloxy group having from 1 through 28 carbon atoms.
  • tin(II) compound free from Sn-C bonds include a tin(II) compound containing a Sn-O bond, and a tin(II) compound containing a Sn-X bond (X is a halogen atom).
  • the tin(II) compound free from Sn-C bonds is more preferably a tin(II) compound containing a Sn-O bond.
  • tin(II) di(2-ethylhexanoate) is even more preferable, in view of reactivity, adjustment of a molecular weight, and adjustment of physical properties of the resin.
  • the abundance of the esterification catalyst relative to 100 parts by mass of a total amount of the alcohol component and the carboxylic acid component is preferably 0.1 parts by mass or greater, more preferably 0.2 parts by mass or greater, even more preferably 0.3 parts by mass or greater, and yet even more preferably 0.5 parts by mass or greater, but is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, and even more preferably 1 part by mass or less.
  • esterification accelerator As for the esterification accelerator, the same esterification accelerator used for the production of the crystalline polyester can be suitably used.
  • the esterification accelerator is preferably gallic acid in view of reactivity.
  • the abundance of the esterification accelerator in the condensation polymerization reaction relative to 100 parts by mass of a total amount of the alcohol component and carboxylic acid component supplied to the condensation polymerization reaction is, in view of reactivity, preferably 0.001 parts by mass or greater, more preferably 0.01 parts by mass or greater, and even more preferably 0.02 parts by mass or greater, but is preferably 0.1 parts by mass or less, more preferably 0.05 parts by mass or less, and even more preferably 0.03 parts by mass or less.
  • the abundance of the esterification accelerator means a total amount of the esterification promotor supplied for the condensation polymerization reaction.
  • a mass ratio (esterification accelerator/esterification catalyst) of the esterification accelerator to the esterification catalyst is preferably 0.01 or greater, more preferably 0.02 or greater, and even more preferably 0.03 or greater, but is preferably 0.1 or less, more preferably 0.08 or less, and even more preferably 0.05 or less.
  • the toner may further contain a release agent (wax), a colorant, a charge-controlling agent, and a flow improving agent.
  • the release agent is not particularly limited, but examples of the release agent include solid silicone wax, higher fatty acid, higher alcohol, montan-based ester wax, polyethylene wax, and polypropylene wax.
  • the above-listed release agents may be used in combination.
  • free-fatty acid carnauba wax, montan wax, and oxidized rice wax are exemplified.
  • the above-listed waxes may be used in combination.
  • the carnauba wax is fine crystals, and preferably has an acid value of 5 mgKOH/g or less.
  • the montan wax typically means montan-based wax purified from minerals, and preferably has an acid value of from 5 mgKOH/g through 14 mgKOH/g.
  • the oxidized rice wax is air-oxidized rice bran wax, and preferably has an acid value of from 10 mgKOH/g through 30 mgKOH/g.
  • the glass transition temperature of the release agent is typically preferably from 70°C through 90°C. When the glass transition temperature of the release agent is lower than 70°C, heat-resistant storage stability of a resultant toner may be poor. When the glass transition temperature of the release agent is higher than 90°C, cold offset resistance of a resultant toner may be poor, or paper may be wrapped around a fixing device.
  • a mass ratio of the release agent to the binder resin is typically from 0.01 through 0.20, preferably from 0.03 through 0.10. When the mass ratio of the release agent to the binder resin is less than 0.01, a resultant toner may have poor hot offset resistance. When the mass ratio of the release agent to the binder resin is greater than 0.20, a resultant toner may have poor transferring properties and durability.
  • the colorant is not particularly limited, as long as the colorant is a pigment or a dye.
  • the colorant include: yellow pigments, such as cadmium yellow, mineral fast yellow, nickel titanium yellow, Naples yellow, Naphthol Yellow S, Hansa Yellow G, Hansa Yellow 10G, Benzidine Yellow GR, quinoline yellow lake, Permanent Yellow NCG, and tartrazine lake; orange pigments, such as molybdate orange, Permanent Orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, benzidine orange G, and Indanthrene Brilliant Orange GK; red pigments, such as red iron oxide, cadmium red, Permanent Red 4R, lithol red, pyrazolone red, watching red calcium salt, Lake Red D, Brilliant Carmine 6B, eosin lake, Rhodamine Lake B, alizarin lake, and Brilliant Carmine 3B; purple pigments, such as Fast Violet B, and methyl violet lake; blue pigments, such as cobalt blue, alkal
  • the charge-controlling agent is not particularly limited.
  • Examples of the charge-controlling agent include: nigrosine, and azine dyes containing an alkyl group having from 2 through 16 carbon atoms (Japanese Examined Patent Publication No. 42-1627); basic dyes and lake pigments thereof, such as C.I. Basic Yellow 2 (C.I. 41000), C.I. Basic Yellow 3, C.I. Basic Red 1 (C.I. 45160), C.I. Basic Red 9 (C.I. 42500), C.I. Basic Violet 1 (C.I. 42535), C.I. Basic Violet 3 (C.I. 42555), C.I. Basic Violet 10 (C.I. 45170), C.I. Basic Violet 14 (C.I.
  • C.I. Basic Blue 1 C.I. 42025
  • C.I. Basic Blue 3 C.I. 51005
  • C.I. Basic Blue 5 C.I. 42140
  • C.I. Basic Blue 7 C.I. 42595
  • C.I. Basic Blue 9 C.I. 52015
  • C.I. Basic Blue 24 C.I. 52030
  • C.I. Basic Blue 25 C.I. 52025
  • C.I. Basic Blue 26 C.I. 44045
  • C.I. Basic Green 1 C.I. 42040
  • C.I. Basic Green 4 C.I. 42000
  • quaternary ammonium salts such as C.I. Solvent Black 8 (C.I.
  • dialklyl tin such as dibutyl tin, and dioctyl tin
  • dialkyl tin borate compounds polyamine resins, such as guanidine derivatives, amino-group containing vinyl polymers, and amino group-containing condensation polymers
  • dialkyl salicylate e.g., Zn, Al, Co, Cr, and Fe
  • metal e.g., Zn, Al, Co, Cr, and Fe
  • a material constituting the flow improving agent is not particularly limited, but examples of the material include silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, silica sand, montmorillonite, 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.
  • the above-listed materials may be used in combination.
  • silica, alumina, titanium oxide are preferable.
  • the flow improving agent preferably contains a silicon element constituting a silicon compound, such as silica, and optionally a metal element (a dope compound).
  • the metal element is not particularly limited, but examples of the metal element include Mg, Ca, Ba, Al, Ti, Ti, V, Sr, Zr, Zn, Ga, Ge, Cr, Mn, Fe, Co, Ni, and Cu.
  • the flow improving agent may be surface-treated with a hydrophobizing agent.
  • the hydrophobizing agent is not particularly limited, but examples thereof include a silane coupling agent, a sililation agent, a fluoroalkyl group-containing silane coupling agent, an organic titanate-based coupling agent, an aluminium-based coupling agent, and silicone oil.
  • An amount of the flow improving agent in the toner is typically from 0.1% by mass through 5% by mass.
  • the average primary particle diameter of the flow improving agent is typically from 5 nm through 1,000 nm, preferably from 5 nm through 500 nm. Note that, the average primary particle diameter of the flow improving agent is an average value of long diameters of 100 particles or more, as measured by means of a transmission electron microscope.
  • the toner of the present invention preferably has a melting point in a range of from 70°C through 100°C.
  • the melting point of the toner is 70°C or higher, sufficient heat-resistant storage stability of a resultant toner is attained.
  • the melting point of the toner is 100°C or lower, sufficient low-temperature fixing ability of a resultant toner is attained.
  • the melting point of the toner is attributed to the crystalline resin contained in the toner.
  • the glass transition temperature of the toner is preferably 55°C or higher for ensuring heat-resistant storage stability of the toner.
  • a softening point measured on a chloroform-soluble component is preferably 90°C or higher, where the chloroform-soluble component is prepared by separating the toluene-insoluble component in the toner and separating the chloroform-soluble component from the toluene-insoluble component.
  • the chloroform-soluble component separated from the toluene-insoluble component contains a crystalline resin.
  • a weight average particle diameter (D4) of the toner is typically from 3 ⁇ m through 8 ⁇ m, preferably from 4 ⁇ m through 7 ⁇ m.
  • a ratio of the weight average particle diameter (D4) of the toner to a number average particle diameter (D1) of the toner is typically from 1.00 through 1.40, preferably from 1.05 through 1.30. Note that, the number average particle diameter (D1) and the weight average particle diameter (D4) of the toner can be measured by the Coulter Counter method.
  • An image forming apparatus of the present invention includes at least a photoconductor, a charging unit configured to charge the photoconductor, an exposing unit configured to expose the photoconductor charged to light to form an electrostatic latent image, a developing unit configured to develop the electrostatic latent image formed on the photoconductor with the developer of the present invention to form a toner image, a transfer unit configured to transfer the toner image to a recording medium, and a fixing unit configured to fix the toner image transferred on the recording medium.
  • the image forming apparatus may further include other units, if necessary.
  • An image forming method according to the present invention includes at least a charging step, an exposure step, a developing step, a transfer step, and a fixing step. The image forming method may further include other steps, if necessary.
  • a material, structure, and size of the photoconductor are not particularly limited, and are appropriately selected from those known in the art.
  • Examples of the material of the photoconductor include: inorganic photoconductors, such as amorphous silicon and selenium; and organic photoconductors, such as polysilane and phthalopolymethine.
  • inorganic photoconductors such as amorphous silicon and selenium
  • organic photoconductors such as polysilane and phthalopolymethine.
  • amorphous silicon is preferable in view of a long service life thereof.
  • the charging unit is appropriately selected depending on the intended purpose without any limitation.
  • the charging unit include conventional contact chargers, equipped with a conductive or semiconductive roller, brush, film, or rubber blade, and non-contact chargers utilizing corona discharge, such as corotron, and scorotron.
  • the charging step can be performed by applying voltage to a surface of the photoconductor using the charging unit.
  • a shape of the charging unit in addition to a roller, any form, such as a magnetic brush, and a fur brush, can be used.
  • the shape of the charging unit can be selected depending on specifications and forms of the image forming apparatus.
  • the charging unit is not limited to the contact charging unit. Use of the contact charging unit is however preferable, because it is possible to attain an image forming apparatus in which an amount of ozone generated from the charging unit is reduced.
  • the exposing unit is appropriately selected depending on the intended purpose without any limitation, except that the exposing unit is capable of imagewise exposing the charged surface of the photoconductor by the charging unit to light.
  • Examples of the exposing unit include various exposing units, such as a copy optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system.
  • a light source used in the exposing unit is appropriately selected depending on the intended purpose without any limitation.
  • the light source examples include common light-emitting devices such as a fluorescent lamp, a tungsten lamp, a halogen lamp, a mercury lamp, a sodium lamp, a light-emitting diode (LED), a laser diode (LD) and an electroluminescence (EL).
  • various filters such as a sharp-cut filter, a band-pass filter, an infrared cut filter, a dichroic filter, an interference filter and a color conversion filter may be used for emitting only light having a desired wavelength range.
  • the exposing step can be performed by imagewise exposing the surface of the photoconductor to light using the exposing unit.
  • a back-exposure system may be employed.
  • the back-exposure system is a system where the photoconductor is imagewise exposed to light from the back side of the photoconductor.
  • the developing unit is appropriately selected depending on the intended purpose without any limitation, except that the developing unit includes a toner, with which the electrostatic latent image formed on the photoconductor is developed to form a toner image that is a visible image.
  • the developing step is appropriately selected depending on the intended purpose without any limitation, except that the developing step includes developing the electrostatic latent image formed on the photoconductor with the toner to form a toner image that is a visible image.
  • the developing step can be performed by the developing unit.
  • the developing unit is preferably a developing device, which contains a stirring device configured to stir the toner to cause friction and charge the toner, and a developer bearing member containing a magnetic-field generating unit fixed inside the developer bearing member, and being configured to bear a developer containing the toner on a surface of the developer bearing member.
  • the transfer unit is appropriately selected depending on the intended purpose without any limitation, except that the transfer unit is a member configured to transfer the visible image onto a recording medium.
  • a preferable embodiment of the transfer unit is a transfer unit that contains a primary transfer unit configured to transfer visible images on an intermediate transfer member to form a composite transfer image, and a secondary transfer unit configured to transfer the composite transfer image onto a recording medium.
  • the transfer step is appropriately selected depending on the intended purpose without any limitation, except that the transfer step contains transferring the visible image onto a recording medium.
  • a preferable embodiment of the transfer step is a step containing primarily transferring the visible image onto an intermediate transfer member and secondarily transferring the visible image onto the recording medium.
  • the transfer step can be performed by charging the photoconductor using a transfer charger to transfer the visible image, and can be performed by the transfer unit.
  • an image secondary transferred onto the recording medium is a color image composed of toners of a plurality of colors
  • a toner of each color is sequentially overlapped on the intermediate transfer member to form an image on the intermediate transfer member, and the superimposed image on the intermediate transfer member is secondary transferred on the recording medium at once by the intermediate transfer unit.
  • the intermediate transfer member is appropriately selected from conventional transfer members depending on the intended purpose without any limitation. Examples of the intermediate transfer member suitably include a transfer belt.
  • the transfer unit (the primary transfer unit and the secondary transfer unit) preferably includes at least a transfer device configured to charge the visible image to release the visible image formed on the photoconductor to the side of the recording medium.
  • the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a press transfer roller, and an adhesion transfer device.
  • the recording medium is typically plain paper, but the recording medium is appropriately selected depending on the intended purpose without any limitation, except that an unfixed image after developing can be transferred onto the recording medium.
  • a PET base for OHP can also be used.
  • the fixing unit is appropriately selected depending on the intended purpose without any limitation, except that the fixing unit is a member configured to fix the transferred image on the recording medium.
  • the fixing unit is preferably a conventional heat pressure member. Examples of the heat pressure member include a combination of a heat roller, and a press roller, and a combination of a heat roller, a press roller, and an endless belt.
  • the fixing step is appropriately selected depending on the intended purpose without any limitation, except that the fixing step contains fixing the visible image transferred on the recording medium.
  • the fixing step may be performed every time the toner image composed of the toner of each color is transferred onto the recording medium.
  • the fixing step may be performed once on a state where toner images of the toners of all colors are laminated.
  • the fixing step can be performed by the fixing unit.
  • the heating by the heat pressure member is typically preferably performed at a temperature range of from 80°C through 200°C.
  • a conventional optical fixing device may be used in combination with or instead of the fixing unit, depending on the intended purpose.
  • the contact pressure in the fixing step is appropriately selected depending on the intended purpose without any limitation, but the contact pressure is preferably from 10 N/cm 2 through 80 N/cm 2 .
  • a developer of the present invention includes at least the toner, and may further include appropriately selected other components, such as a carrier, if necessary.
  • a carrier such as a carrier for the developer.
  • a two-component developer containing a toner and a carrier is preferably used, because a service life is improved.
  • the carrier is appropriately selected depending on the intended purpose without any limitation, but the carrier is preferably a carrier which contains carrier particles each containing a core, and a resin layer covering the core.
  • a material of the core is appropriately selected depending on the intended purpose without any limitation. Examples of the material include a manganese-strontium-based material of from 50 emu/g through 90 emu/g, and a manganese-magnesium-based material of from 50 emu/g through 90 emu/g.
  • a high magnetic material such as iron powder (100 emu/g or greater) and magnetite (from 75 emu/g through 120 emu/g)
  • a low magnetic material such as a copper/zinc-based material of from 30 emu/g through 80 emu/g, is preferably used, because an impact of the developer in the form of a brush to the photoconductor can be weakened, and a high quality image can be formed.
  • the volume average particle diameter of the cores is appropriately selected depending on the intended purpose without any limitation, but the volume average particle diameter thereof is preferably from 10 ⁇ m through 150 ⁇ m, more preferably from 40 ⁇ m through 100 ⁇ m.
  • the volume average particle diameter is smaller than 10 ⁇ m, an amount of fine powder in the carrier increases to reduce magnetization per particle, and thus scattering of the carrier may be caused.
  • the volume average particle diameter is greater than 150 ⁇ m, a specific surface area of the carrier as a whole decreases, to thereby cause toner scattering.
  • a full-color image having a large solid image area is formed, moreover, reproducibility of, particularly, the solid image area may be poor.
  • the toner is mixed in use with the carrier.
  • An amount of the carrier in the two-component developer is appropriately selected depending on the intended purpose without any limitation.
  • the amount of the carrier relative to 100 parts by mass of the two-component developer is preferably from 90 parts by mass through 98 parts by mass, more preferably from 93 parts by mass through 97 parts by mass.
  • the developer of the present invention can be suitably used for image formation performed by various conventional electrophotographic methods, such as a magnetic one-component developing method, a non-magnetic one-component developing method, and a two-component developing method.
  • a magnetic one-component developing method inside the developing unit, the toner and the carrier are mixed and stirred, and the toner is charged by the frictions caused during the mixing and stirring.
  • the toner is held on a surface of a rotating magnetic roller in the form of a brush, to thereby form a magnetic brush.
  • the magnet roller is disposed adjacent to the photoconductor. Part of the toner constituting the magnetic brush formed on the surface of the magnetic roller is moved onto the surface of the photoconductor by an electrical suction force.
  • the electrostatic latent image is developed with the toner, and a visible image formed of the toner is formed on the surface of the photoconductor.
  • Examples of the other units include a cleaning unit, a charge eliminating unit, a recycling unit, and a controlling unit.
  • Examples of the other steps include a cleaning step, a charge eliminating step, a recycling step, and a controlling step.
  • the cleaning unit is appropriately selected depending on the intended purpose without any limitation, except that the cleaning unit is a unit capable of removing the toner remaining on the photoconductor.
  • the cleaning unit include a magnetic brush cleaner, an electrostatic brush cleaner, a magnetic roller cleaner, a blade cleaner, a brush cleaner, and a wave cleaner.
  • the cleaning step is appropriately selected depending on the intended purpose without any limitation, except that the cleaning step is a step capable of removing the toner remaining on the photoconductor.
  • the cleaning step can be performed by the cleaning unit.
  • the charge eliminating unit is appropriately selected depending on the intended purpose without any limitation, except that the charge eliminating unit is a unit configured to apply a charge eliminating bias to the photoconductor for charge elimination.
  • Examples of the charge eliminating unit include a charge eliminating lamp.
  • the charge eliminating step is appropriately selected depending on the intended purpose without any limitation, except that the charge eliminating step is a step including applying a charge eliminating bias to the photoconductor for charge elimination.
  • the charge eliminating step can be performed by the charge eliminating unit.
  • the recycling unit is appropriately selected depending on the intended purpose without any limitation, except that the recycling unit is a unit configured to recycle the toner removed by the cleaning unit into the developing device.
  • Examples of the recycling unit include conventional conveying units.
  • the recycling step is appropriately selected depending on the intended purpose without any limitation, except that the recycling step is a step containing recycling the toner removed by the cleaning unit into the developing device.
  • the recycling step can be performed by the recycling unit.
  • An image forming apparatus 1 is a printer, but the image forming apparatus is not particularly limited as long as an image can be formed with a toner, and may be a photocopier, a facsimile, or a multifunction peripheral.
  • the image forming apparatus 1 contains a paper feeding unit 210, a conveying unit 220, an image forming unit 230, a transfer unit 240, and a fixing device 250.
  • the paper feeding unit 210 contains a paper feeding cassette 211 loaded with a pile of paper P to be fed, and a paper feeding roller 212 configured to feed the paper P in the paper feeding cassette 211 one sheet at a time.
  • the conveying unit 220 contains a roller 221 configured to transport the paper P fed by the paper feeding roller 212 to the direction of the transfer unit 240, a pair of timing rollers 222 configured to nip the edge of the paper P transported by the roller 221 to stand by, and to send the paper to the transfer unit 240 at a predetermined timing, and a paper ejecting roller 223 configured to eject the paper P, on which a color toner image has been fixed, onto a paper ejecting tray 224.
  • the image forming unit 230 contains, from the left to right in the drawing, an image forming unit Y configured to form an image using a developer containing a yellow toner, an image forming unit C using a developer containing a cyan toner, an image forming unit M using a developer containing a magenta toner, and an image forming unit K using a developer containing a black toner, with predetermined spaces between the aforementioned image forming units and an exposure device 233.
  • any image forming unit is referred to among the image forming units (Y, C, M, and K), it is merely indicated as an image forming unit.
  • the developer contains a toner and a carrier.
  • the four image forming units (Y, C, M, and K) use mutually different developers, but mechanical structures thereof are substantially the same.
  • the transfer unit 240 contains a driving roller 241 and a driven roller 242, an intermediate transfer belt 243 capable of rotating counterclockwise in the drawing, along the movement of the driving roller 241, primary transfer rollers (244Y, 244C, 244M, and 244K) disposed to face the photoconductor drum 231 via the intermediate transfer belt 243, and a secondary counter roller 245 and a secondary transfer roller 246 disposed to face each other via the intermediate transfer belt 243 in a transferring position where a toner image is transferred to paper.
  • a heater is disposed inside the fixing device 250.
  • the fixing device 250 contains a fixing belt 251 configured to heat the paper P, and a press roller 252 configured to rotatably press the fixing belt 251 to form a nip.
  • a toner stored unit of the present invention is a unit which has a function of storing a toner and stores a toner.
  • Examples of the toner stored unit include a toner container, a developing device, and a process cartridge.
  • the toner container refers to a container storing a toner therein.
  • the developing device refers to a unit storing a toner therein and configured to perform development.
  • the process cartridge refers to an integrated unit of at least an image bearer (also referred to as a photoconductor) and a developing unit, and is detachably mounted in an image forming apparatus.
  • the process cartridge may further contain at least one selected from the group consisting of a charging unit, an exposing unit, and a cleaning unit.
  • a process cartridge of the present invention is designed to be detachably mounted in various image forming apparatuses, and includes at least a photoconductor configured to bear an electrostatic latent image, and a developing unit configured to develop the electrostatic latent image born on the photoconductor with the developer of the present invention to form a toner image.
  • the process cartridge of the present invention may further include other members, if necessary.
  • the developing unit contains at least a developer container housing therein the developer of the present invention, and a developer bearing member configured to bear the developer housed in the developer container and convey the developer.
  • the developing unit may contain a regulating member configured to regulate a thickness of the developer born on the developer bearing member.
  • FIG. 2 One example of the process cartridge of the present invention is illustrated in FIG. 2.
  • the process cartridge 110 includes a photoconductor drum 10, a corona charger 58, a developing device 40, a transfer roller 80, and a cleaning device 90.
  • Glass transition temperature and melting point A glass transition temperature and a melting point were measured by means of a thermal analysis workstation, TA-60WS and a differential scanning calorimeter, DSC-60 (available from Shimadzu Corporation) under the following conditions.
  • heating and cooling conditions are varied depending on the intended purpose.
  • the measurement was performed under the following conditions, unless otherwise stated.
  • Starting temperature 20°C Heating speed: 10 °C/min Ending temperature: 150°C Retention time: none Cooling speed: 10 °C/min Ending temperature: 20°C Retention time: none Heating speed: 10 °C/min (The glass transition temperature observed in this heating step was employed.) Ending temperature: 150°C
  • the heating and cooling conditions 1 and the heating and cooling conditions 2 specified in the present invention are as follows. (Heating and cooling conditions 1) Starting temperature: 20°C Heating speed: 10 °C/min Ending temperature: 120°C Retention time: 10 min Cooling speed: 10 °C/min Ending temperature: 0°C Retention time: none Heating speed: 10 °C/min (The glass transition temperature observed in this heating step was employed.) Ending temperature: 150°C
  • Heating and cooling conditions 2 Starting temperature: 20°C Heating temperature: 10 °C/min Ending temperature: 120°C Retention time: 10 min Cooling speed: 10 °C/min Ending temperature: 0°C Retention time: none Heating speed: 10 °C/min Ending temperature: 45°C Retention time: 24 h Cooling speed: 10 °C/min Ending temperature: 0°C Retention time: none Heating speed: 10 °C/min (The glass transition temperature observed in this heating step was employed.) Ending temperature: 150°C
  • the measurement results were analyzed by means of data analysis software, TA-60, version 1.52 (available from Shimadzu Corporation).
  • the glass transition temperature or the melting point in the DSC curve can be judged based on whether there is a change in a base line before and after heat absorption at the time of heating.
  • the base line changes for the glass transition temperature, but not for the melting point.
  • the glass transition temperature was defined with an onset temperature, but the glass transition temperature was calculated by the following method. Specifically, the minimum peak temperature, and the minimum peak minus 10°C on the DrDSC curve, which was the DSC differential curve for heating, were designated, and the glass transition temperature was calculated using a tangent intersection calculation function of an analysis software. Moreover, the melting point was calculated by determining the endothermic peak temperature without causing a change in the base line.
  • Softening point A softening point was measured by means of a flow tester capillary rheometer, CFT-500D (available from Shimadzu Corporation). Specifically, a load of 1.96 MPa was applied to a sample (1 g) by a plunger with heating the sample at the heating speed of 6 °C/min, to push out the sample from a nozzle having a diameter of 1 mm and a length of 1 mm. The dropped amount of the plunger of the flow tester relative to the temperature was plotted. The temperature at which a half of the sample was flown out was determined as a softening point.
  • X-ray diffraction peak An X-ray diffraction peak was observed by means of the following device under the following measuring conditions.
  • X-ray diffraction device D8 ADVANCE, available from Bruker AXS X-ray source: Cu-K ⁇ line (wavelength: 0.15418 nm)
  • Measurement range: 2 ⁇ from 5° through 60° Step gap: 0.02° Scanning speed: 1 °/min
  • the toner particles were embedded in an epoxy resin, followed by slicing the epoxy resin into an ultrathin cut piece of about 100 nm. The cut piece was then dyed with ruthenium tetroxide. A backscattered electron image thereof was observed by means of a thermal FE-SEM (ULTRA55, available from Zeiss) with the accelerating voltage of 0.8 kV. Because the undyed area was observed as a dark area, the undyed area could be distinguished from the dyed area (bright area).
  • the toner for use may be the toner with external additive, or the toner without external additive, or the toner from which external additive has been removed.
  • a cross-section of the toner particle was dyed with a 0.5% by weight ruthenium tetroxide aqueous solution, followed by observing the cross-section under a scanning electron microscope (SEM) under reflected electron conditions.
  • the average diameter was measured from the contrast in color in the cross-section of the toner particle.
  • an image analysis was performed using an image analysis software (product name: A-zoukun, available from Asahi Kasei Engineering Corporation) to determine a circle equivalent diameter, and a value of the circle equivalent diameter was determined as the average diameter.
  • the main conditions were as follows. Analysis method: particle analyzing mode Brightness of particles: dark Analysis item: circle equivalent diameter Binarization threshold: 100 or less
  • Heating temperature 320°C
  • Column: Ultra ALLOY-5L 30 m
  • Crystalline Resin A1 was found to have a melting point of 75°C and a softening point of 92°C.
  • Crystalline Resin A2 was found to have a melting point of 75°C and a softening point of 85°C.
  • Crystalline Resin A3 was found to have a melting point of 65°C and a softening point of 92°C.
  • Crystalline Resin A4 was found to have a melting point of 105°C and a softening point of 92°C.
  • Crystalline Resin A5 was found to have a melting point of 110°C and a softening point of 92°C.
  • Crystalline Resin A6 was found to have a melting point of 115°C and a softening point of 92°C.
  • Amorphous Resin B1 having a glass transition temperature of 61°C and a softening point of 110°C.
  • Amorphous Resin B2 having a glass transition temperature of 55°C and a softening point of 106°C.
  • Amorphous Resin B3 was found to have a glass transition temperature of 62°C and a softening point of 112°C.
  • a mixed solution containing 270 parts of acrylic acid, 4,800 parts of styrene, 1,200 parts of 2-ethylhexylacrylate, and 250 parts of dibutyl peroxide serving as a radical polymerization initiator was added dropwise over 1 hour. Thereafter, the temperature of the resultant mixture was maintained at 160°C for 30 minutes, followed by heating up to 200°C. The mixture was then further allowed to react for 1 hour under a reduced pressure of 8 kPa, followed by cooling to 180°C. Thereafter, 4 parts of a radical polymerization inhibitor (4-t-butylcatechol) and 240 parts of fumaric acid were added to the reaction mixture, and the resultant was heated to 210°C over 2 hours.
  • a radical polymerization inhibitor (4-t-butylcatechol) and 240 parts of fumaric acid
  • Composite Resin C1 was found to have a glass transition temperature of 59°C and a softening point of 112°C.
  • Example 1 -Production of Toner 1- Crystalline Resin A1: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts
  • the above-listed toner raw materials were mixed in advance by means of HENSCHEL MIXER (FM20B, available from NIPPON COKE & ENGINEERING CO., LTD.), followed by kneading by a continuous twin-open-roll kneader KNEADEX (available from NIPPON COKE & ENGINEERING CO., LTD.) to thereby obtain a kneaded product.
  • HENSCHEL MIXER FM20B, available from NIPPON COKE & ENGINEERING CO., LTD.
  • KNEADEX available from NIPPON COKE & ENGINEERING CO., LTD.
  • the continuous twin-open-roll kneader for use had a roll outer diameter of 0.14 m, and an effective roll length of 0.8 m.
  • the rotational speed of the heating roll was 34 r/min (circumferential velocity: 4.8 m/min)
  • the rotational speed of the cooling roll was 29 r/min (circumferential velocity: 4.1 m/min)
  • the roll gap was 0.2 mm.
  • the temperatures of the heating and cooling media in the rolls the temperatures were set as follows. The temperature of the heating roll at the side where the raw materials were introduced was 125°C, and the temperature thereof at the side where the kneaded product was discharged was 75°C.
  • the temperature of the cooling roll at the side where the raw materials were introduced was 35°C, and the temperature thereof at the side where the kneaded product was discharged was 30°C. Moreover, the supply speed of the raw material mixture was set to 5 kg/h.
  • the kneaded product was coarsely ground by an atomizer, to thereby obtain a coarsely ground product having the maximum diameter of 2 mm or smaller.
  • the obtained coarsely ground product was finely ground by an impact jet mill, IDS5 (available from Nippon Pneumatic Mfg., Co., Ltd.), the wind pressure of which at the time of grinding was adjusted to 0.5 MPa.
  • the finely ground product was then classified by an air classifier, DS5 (available from Nippon Pneumatic Mfg., Co., Ltd.) with the volume median diameter (D50) of 6.5 ⁇ m ⁇ 0.3 ⁇ m as a target, to thereby obtain toner base particles.
  • DS5 air classifier
  • D50 volume median diameter
  • 1.0 part of an additive, HDK-2000 (available from Clariant K.K.), and 1.0 part of an additive, H05TD (available from Clariant K.K.) were mixed with 100 parts by mass of the toner base particles, and the mixture was stirred by HENSCHEL MIXER, to thereby produce Toner 1.
  • Example 2 -Production of Toner 2- Crystalline Resin A2: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 2 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 3 Provided of Toner 3- Crystalline Resin A1: 10 parts Amorphous Resin B1: 52 parts Composite Resin C1: 36 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 3 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 4 (Example 4) -Production of Toner 4- Crystalline Resin A3: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 4 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 5 (Example 5) -Production of Toner 5 Crystalline Resin A4: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 5 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 6 -Production of Toner 6- Crystalline Resin A1: 10 parts Amorphous Resin B2: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 6 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 7 -Production of Toner 7- Crystalline Resin A5: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 7 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 8 -Production of Toner 8- Crystalline Resin A1: 10 parts Amorphous Resin B1: 88 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 8 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 9 Provide of Toner 9- Crystalline Resin A1: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts
  • the above-listed toner raw materials were mixed in advance by means of HENSCHEL MIXER (FM20B, available from NIPPON COKE & ENGINEERING CO., LTD.), followed by kneading by a continuous twin-open-roll kneader KNEADEX (available from NIPPON COKE & ENGINEERING CO., LTD.) to thereby obtain a kneaded product.
  • the kneaded product was coarsely ground by an atomizer, to thereby obtain a coarsely ground product having the maximum diameter of 2 mm
  • the same continuous twin-open-roll kneader as the one used in Example 1 was used, but the kneading conditions were changed as follows. Specifically, the temperature of the heating roll at the side where the raw materials were introduced was set to 135°C, the temperature thereof at the side where the kneaded product was discharged was set to 85°C, the temperature of the cooling roll at the side where the raw materials were introduced was set to 35°C, and the temperature thereof at the side where the kneaded product was discharged was set to 40°C. Moreover, the supply speed of the raw material mixture was set to 8 kg/h.
  • the obtained coarsely ground product was finely ground by an impact jet mill, IDS5 (available from Nippon Pneumatic Mfg., Co., Ltd.), the wind pressure of which at the time of grinding was adjusted to 0.5 MPa.
  • the finely ground product was then classified by an air classifier, DS5 (available from Nippon Pneumatic Mfg., Co., Ltd.) with the volume median diameter (D50) of 6.5 ⁇ m ⁇ 0.3 ⁇ m as a target, to thereby obtain toner base particles.
  • Example 10 -Production of Toner 10- Crystalline Resin A1: 10 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts
  • the above-listed toner raw materials were mixed in advance by means of HENSCHEL MIXER (FM20B, available from NIPPON COKE & ENGINEERING CO., LTD.), followed by melted and kneaded at the temperature of from 100°C through 130°C by means of a monoaxial kneader (Cokneader, available from Buss Compounding Systems AG), to thereby obtain a kneaded product.
  • HENSCHEL MIXER FM20B, available from NIPPON COKE & ENGINEERING CO., LTD.
  • the kneaded product was coarsely ground down to the range of from 200 ⁇ m through 300 ⁇ m by Rotoplex. Subsequently, the coarsely ground product was finely ground by a counter jet mill (100AFG, available from HOSOKAWA MICRON CORPORATION) with appropriately adjusting the grinding air pressure to give the weight average particle diameter of 6.2 ⁇ m ⁇ 0.3 ⁇ m.
  • the resultant ground product was classified by an air classifier (EJ-LABO, available from MATSUBO Corporation) with appropriately adjusting an opening degree of a louver to give a weight average particle diameter of 7.0 ⁇ m ⁇ 0.2 ⁇ m, and a ratio (weight average particle diameter/number average particle diameter) of 1.20 or less, to thereby obtain toner base particles.
  • EJ-LABO air classifier
  • H05TD available from Clariant K.K.
  • Example 11 -Production of Toner 11- Crystalline Resin A1: 10 parts Amorphous Resin B3: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 11 was produced in the same manner as in the production of Toner 1, except that the above-listed materials were used.
  • Example 12 -Production of Toner 12- Crystalline Resin A1: 7 parts Amorphous Resin B1: 58 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 5 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 12 was produced in the same manner as in the production of Toner 10, except that the above-listed materials were used.
  • Example 13 -Production of Toner 13- Crystalline Resin A1: 7 parts Amorphous Resin B1: 57 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 6 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 13 was produced in the same manner as in the production of Toner 10, except that the above-listed materials were used.
  • Example 14 -Production of Toner 14- Crystalline Resin A1: 4 parts Amorphous Resin B1: 64 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 14 was produced in the same manner as in the production of Toner 10, except that the above-listed materials were used.
  • Example 15 -Production of Toner 15- Crystalline Resin A1: 3 parts Amorphous Resin B1: 65 parts Composite Resin C1: 30 parts Carnauba Wax (WA-05, available from CERARICA NODA Co., Ltd.): 2 parts Colorant (C-44, available from Mitsubishi Chemical Corporation): 8 parts Toner 15 was produced in the same manner as in the production of Toner 10, except that the above-listed materials were used.
  • the measurements included a difference (Tg variation width) between the glass transition temperature observed in the last heating step in the heating and cooling conditions 1, and the glass transition temperature observed in the last heating step in the heating and cooling conditions 2, a diffraction peak of the toner as measured by X-ray diffraction analysis, the average diameter of the undyed areas after dying a cross-section of the toner with ruthenium, a melting point, and a glass transition temperature.
  • pyrolysis-gas chromatography-mass spectrometry was performed on the toner to detect monomers. An amount of the vinyl monomer detected was determined by means of a nuclear magnetic resonance spectrometer (NMR).
  • M2/(M1+M2), and softening points of a toluene-insoluble component, and a chloroform-soluble component were measured.
  • M1 is a mass of a toluene-soluble component
  • M2 is a mass of the chloroform-soluble component, when the toner was added to toluene to separate the toluene-soluble component from the toluene-insoluble component, and the chloroform-soluble component is separated from the separated toluene-soluble component.
  • a solid image in the size of 3 cm ⁇ 8 cm was formed on a photocopy printing sheet ⁇ 70> (available from RICOH JAPAN Corp.) with a toner deposition amount of 0.85 mg/cm 2 ⁇ 0.1 mg/cm 2 by means of a modified device of an electrophotographic photocopier (MF-200, available from Ricoh Company Limited), a fixing unit of which had been modified with a Teflon (registered trade mark) roller serving as a fixing roller. Thereafter, the solid image was fixed with varying a temperature of the fixing belt of the device.
  • a surface of the fixed image was scratched with a ruby needle (radius of a tip: from 260 mm through 320 mm, point angle: 60°) at a load of 50 g by means of a scratch drawing testing device AD-401 (available from Ueshima Seisakusho Co., Ltd.).
  • the drawn surface was then strongly rubbed 5 times with fibers (HANICOT #440, available from Haniron K.K.).
  • the temperature of the fixing belt at which scraping of the image was almost nonexistent was regarded as the minimum fixing temperature.
  • the solid image was formed at the position that was 3.0 cm apart from the edge of the sheet along the feeding direction, and the speed for passing the sheet through the nip of the fixing device was 280 mm/s.
  • the minimum fixing temperature was evaluated based on the following criteria. The result of D was regarded as unacceptable. (Evaluation criteria) A: Lower than 140°C B: 140°C or higher but lower than 145°C C: 145°C or higher but lower than 150°C D: 150°C or higher
  • Heat-resistant storage stability-Penetration degree A 10 mL glass container was charged with each toner, and was then left to stand in a thermostat of 50°C for 24 hours. The toner was then cooled to 25°C, and was subjected to a measurement of a penetration degree (mm) by a penetration test (JIS K2235-1991). The results were evaluated based on the following criteria. The larger the value of the penetration degree is, the more preferable heat-resistant storage stability of the toner is. The heat-resistant storage stability was evaluated based on the value of the penetration degree (mm) according to the following criteria. The result of D was regarded as unacceptable. A: 15 mm or greater B: 10 mm or greater but less than 15 mm C: 5 mm or greater but less than 10 mm D: Less than 5 mm
  • Stress resistance Amount of loose aggregates as pressed at normal temperature
  • a toner was weighed in an amount of 0.5 g in a tube for centrifuge, followed by rotating by means of a centrifugal separator CP100MX (available from Hitachi Koki Co., Ltd.) for 5 minutes at 25°C, and the rotational speed of 8,500 rpm (applied pressure: 0.25 MPa). Thereafter, the resultant was sieved through a mesh having an opening size of 106 ⁇ m. The amount of the loose aggregates remaining on the mesh was measured. The stress resistance was evaluated based on the value of the amount of the loose aggregates according to the following criteria. The result of D was regarded as unacceptable. (Evaluation criteria) A: 150 mg/g or less B: Greater than 150 mg/g but 200 mg/g or less C: Greater than 200 mg/g but 250 mg/g or less D: Greater than 250 mg/g
  • Stress resistance Number of white missing spots
  • IMAGIO MP C5002 available from Ricoh Company Limited. Thereafter, the presence of areas where the toner was missing in the image area was observed, when a solid image formed on the entire sheet was output. Then, stress resistance was evaluated. Note that, the number of the areas where the toner was missing in the image area in the form of white spots was counted, and was determined as the number of white missing spots. A level with which there was no problem on practical use was 2 or less white missing spots in the image of A4.
  • image forming apparatus 10 photoconductor drum 40 developing device 58 corona charger 80 transfer roller 90 cleaning device 110 process cartridge 210 paper feeding unit 211 paper feeding cassette 212 paper feeding roller 220 conveying unit 221 roller 222 timing roller 223 paper ejecting roller 224 paper ejecting tray 230 image forming unit 231 photoconductor drum 232 charger 233 exposing device 240 transfer unit 241 driving roller 242 driven roller 243 intermediate transfer belt 244Y, 244C, 244M, 244K primary transfer roller 245 secondary counter roller 246 secondary transfer roller 250 fixing device 251 fixing belt 252 press roller P paper

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Abstract

L'invention a trait à un toner, un pic de diffraction du toner tel que mesuré grâce à une spectroscopie par diffraction des rayons X étant présent au moins dans une région où 2θ est de 20 à 25°, et la différence entre Tg1 et Tg2 étant de 10 °C ou moins, Tg1 étant la température de transition vitreuse du toner, telle qu'observée lors d'une dernière étape de chauffage, quand le chauffage et le refroidissement sont réalisés sur le toner au moyen d'un calorimètre à compensation de puissance (DSC) dans les conditions de chauffage et de refroidissement (1) définies dans la description, et Tg2 étant la température de transition vitreuse du toner, telle qu'observée au cours d'une dernière étape de chauffage, lorsque le chauffage et le refroidissement sont réalisés sur le toner au moyen du calorimètre à compensation de puissance (DSC) dans les conditions de chauffage et de refroidissement (2) définies dans la description.
PCT/JP2016/001703 2015-04-21 2016-03-24 Toner, appareil de formation d'image, et unité de stockage de toner WO2016170730A1 (fr)

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EP16782758.3A EP3286607A4 (fr) 2015-04-21 2016-03-24 Toner, appareil de formation d'image, et unité de stockage de toner
CN201680023296.6A CN107533308A (zh) 2015-04-21 2016-03-24 调色剂、图像形成设备和调色剂存储单元
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130244162A1 (en) * 2012-03-15 2013-09-19 Saori Yamada Toner, image forming apparatus, image forming method, and process cartridge
US20130252160A1 (en) * 2011-09-15 2013-09-26 Masashi Nagayama Toner for forming electrophotographic image, method for manufacturing toner for forming electrophotographic image, image forming method, and process cartridge
JP2014232169A (ja) * 2013-05-28 2014-12-11 花王株式会社 トナー用結着樹脂組成物
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US20130244162A1 (en) * 2012-03-15 2013-09-19 Saori Yamada Toner, image forming apparatus, image forming method, and process cartridge
JP2014232169A (ja) * 2013-05-28 2014-12-11 花王株式会社 トナー用結着樹脂組成物
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