WO2013042452A1 - Toner for electrophotography and image formation device using same - Google Patents

Toner for electrophotography and image formation device using same Download PDF

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Publication number
WO2013042452A1
WO2013042452A1 PCT/JP2012/068855 JP2012068855W WO2013042452A1 WO 2013042452 A1 WO2013042452 A1 WO 2013042452A1 JP 2012068855 W JP2012068855 W JP 2012068855W WO 2013042452 A1 WO2013042452 A1 WO 2013042452A1
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Prior art keywords
toner
molecular weight
less
weight
component
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PCT/JP2012/068855
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French (fr)
Japanese (ja)
Inventor
紀川　敬一
澤井　正幸
椿　頼尚
啓吾 三田村
友惟 河野
慎太郎 福岡
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シャープ株式会社
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Publication of WO2013042452A1 publication Critical patent/WO2013042452A1/en

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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
    • G03G9/0821—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
    • G03G9/0802—Preparation methods
    • G03G9/081—Preparation methods by mixing the toner components in a liquefied state; melt kneading; reactive mixing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • G03G9/087—Binders for toner particles
    • G03G9/08742—Binders for toner particles comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • G03G9/08755—Polyesters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G9/00—Developers
    • G03G9/08—Developers with toner particles
    • 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
    • G03G9/087—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 invention relates to an electrophotographic toner that ensures a wide fixing area and does not adversely affect glossiness, and an image forming apparatus using the same.
  • POD Print On Demand
  • a digital printing technology that has been attracting attention as a printing method in the IT era. It is advantageous for small lot printing and short delivery time, and can be used for variable printing. Which has the advantage of being able to perform distributed printing to operate a machine (also referred to as an “image forming apparatus” or “electrophotographic machine”), and its market is expanding.
  • the image forming apparatus that supports POD requires high-speed output (printing), and it is necessary to shorten the contact time between the heat roller and the unfixed image. Therefore, the performance of the toner used melts quickly and is resistant to hot offset. Is required.
  • a belt fixing method has been proposed in order to extend the contact time as much as possible and heat the toner instantaneously with power saving.
  • the releasability from the paper as the recording medium is worse than that in the roller fixing method, so that the toner is required to have higher performance against hot offset.
  • Patent Document 1 the molecular weight distribution of the binder resin measured by gel permeation chromatography has a main peak at a specific molecular weight, and the mechanical shear energy of the kneading process is used.
  • the obtained specific molecular weight has a sub-peak or shoulder, has a specific low molecular weight component below a specific amount, has a tetrahydrofuran (THF) insoluble component below a specific amount, and specifies the glass transition temperature of the binder resin.
  • An electrophotographic toner is described in which the content of the molecular weight component satisfies a specific formula. It is described that the electrophotographic toner is excellent in belt fixing property, hot offset resistance, storage stability and productivity by having such a configuration.
  • the present inventors have used a specific polyester resin as a toner binder resin, while ensuring a wide fixing area and high hot offset resistance performance.
  • the inventors have found that an electrophotographic toner that does not adversely affect glossiness can be obtained, and have completed the present invention.
  • the polyester resin contains at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent, and the polyester resin has the following conditions: In the molecular weight distribution measured by gel permeation chromatograph, (1) The component having a molecular weight of 1 ⁇ 10 6.0 or more is less than 1% and the component having a molecular weight of 1 ⁇ 10 5.3 or more is less than 5%, (2) The component having a molecular weight of 1 ⁇ 10 3.6 or less is less than 20%, (3) the area connecting both ends of the half width of the main peak is 70 to 82%, and (4) the gel component insoluble in tetrahydrofuran is less than 5%, (5) The glass transition temperature is 50 ° C. or higher and 65 ° C. or lower, An electrophotographic toner satisfying the above requirements is provided.
  • an image forming apparatus using the above electrophotographic toner is provided.
  • an electrophotographic toner that secures a wide fixing area and does not adversely affect glossiness, and an image forming apparatus using the same.
  • the electrophotographic toner of the present invention includes When the component having a molecular weight of 1 ⁇ 10 6.0 or more in the condition (1) is less than 0.5% and the component having a molecular weight of 1 ⁇ 10 5.3 or more is less than 2.5%, When the component having a molecular weight of 1 ⁇ 10 3.6 or less in the condition (2) is less than 15%, When the area connecting both ends of the half width of the main peak in the condition (3) is 78 to 82%, When the gel component insoluble in tetrahydrofuran in the condition (4) is less than 2%, When the glass transition temperature in the condition (5) is 55 ° C. or more and 60 ° C.
  • the electrophotographic toner of the present invention is produced by melt-kneading at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent with a mechanical shearing force,
  • the release agent is moderately dispersed and works effectively in hot offset resistance, causing molecular chain scission of high molecular weight resins, converting from molecular weight resins that have an adverse effect on gloss to resins that are effective for fixing and resistant to hot offset.
  • the effect of the present invention is further exhibited.
  • the electrophotographic toner of the present invention includes 0.1 to 20 parts by weight of a colorant and 0.2 to 20 parts by weight of a release agent for the binder resin and 100 parts by weight of the binder resin, respectively. And 0.5 to 3 parts by weight of the charge control agent, the effects of the present invention are further exhibited.
  • FIG. 1 is a schematic cross-sectional view illustrating an example of an image forming apparatus of the present invention.
  • the electrophotographic toner of the present invention includes at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent, and the polyester resin has the following conditions: In the molecular weight distribution measured by gel permeation chromatograph (GPC), (1) The component having a molecular weight of 1 ⁇ 10 6.0 or more is less than 1% and the component having a molecular weight of 1 ⁇ 10 5.3 or more is less than 5%, (2) The component having a molecular weight of 1 ⁇ 10 3.6 or less is less than 20%, (3) the area connecting both ends of the half width of the main peak is 70 to 82%, and (4) the gel component insoluble in tetrahydrofuran is less than 5%, (5) The glass transition temperature is 50 ° C.
  • the toner of the present invention is characterized by using a specific polyester resin as the binder resin.
  • all the regulations relating to the molecular weight of the polyester resin are based on the molecular weight distribution measured by gel permeation chromatography (GPC). The GPC measurement will be described in detail in the examples.
  • Feature (1) is that the component having a molecular weight of 1 ⁇ 10 6.0 or more is less than 1%, preferably less than 0.5%, and the component having a molecular weight of 1 ⁇ 10 5.3 or more is less than 5%, preferably less than 2.5%. That is. That is, by suppressing the content of an excessive high molecular weight component, it is possible to suppress a decrease in glossiness of a fixed image after image formation.
  • the content of each component is preferably 0%.
  • the lower limit of the component having a molecular weight of 1 ⁇ 10 5.3 or more is about 1.5%.
  • Specific components having a molecular weight of 1 ⁇ 10 6.0 or more include, for example, 0.95%, 0.9%, 0.85%, 0.8%, 0.75%, 0.7%, 0.65%, 0.6%, 0.55%, 0.5%, 0.45%, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.15%, 0.1%, 0.05%, 0.04%, 0.03%, 0.02%, and 0.01%.
  • Specific components having a molecular weight of 1 ⁇ 10 5.3 or more include, for example, 4.9%, 4.5%, 4.0%, 3.5%, 3.0%, 2.5%, 2.0%, 1.5%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%.
  • Characteristic (2) is that a component having a molecular weight of 1 ⁇ 10 3.6 or less is less than 20%, preferably less than 15%. That is, by suppressing the content of an excessively low molecular weight component, it is possible to improve the durability of the toner when the toner is fused or loaded due to the low melting point.
  • the content of the above components is preferably as low as possible, but the molecular weight may be close to the main peak, and there is at least about 10%.
  • Specific components having a molecular weight of 1 ⁇ 10 3.6 or less include, for example, 19.5%, 19%, 18.5%, 18%, 17.5%, 17%, 16.5%, 16%, 15.5. %, 15%, 14.5%, 14%, 13.5%, 13%, 12.5%, 12%, 11.5%, 11%, 10.5%, 10%.
  • Characteristic (3) is that the area connecting both ends of the full width at half maximum of the main peak is 70 to 82%, preferably 78 to 82%, more preferably 79 to 80%. That is, a resin having a molecular weight in the vicinity of the main peak plays an important role in the fixing temperature range, and resins having other molecular weight components (low molecular weight and high molecular weight) deteriorate toner durability and lower gloss. cause. Therefore, if the resin having a molecular weight in the vicinity of the main peak is within the above range, the durability of the toner can be improved and an image with high glossiness can be formed. If the area connecting both ends of the half width of the main peak is less than 70%, the glossiness of the fixed image may be lowered. On the other hand, if the area connecting both ends of the half width of the main peak exceeds 82%, the hot offset resistance of the toner may be lowered.
  • the area connecting both ends of the half width of a specific main peak is, for example, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74 %, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, 80.5%, 81%, 81.5% and 82%.
  • Characteristic (4) is that the gel component insoluble in tetrahydrofuran is less than 5%, preferably less than 2%. That is, the more the gel component insoluble in tetrahydrofuran is, the stronger the hot offset is, but the glossiness of the fixed image is significantly reduced. Therefore, the gel component is suppressed to less than 5% and satisfying the feature (1), High glossiness of a fixed image can be obtained.
  • the content of the above components is preferably 0%.
  • gel components insoluble in tetrahydrofuran include 4.9%, 4.8%, 4.7%, 4.6%, 4.5%, 4.4%, 4.3%, and 4.%.
  • 2% 4.1%, 4%, 3.9%, 3.8%, 3.7%, 3.6%, 3.5%, 3.4%, 3.3%, 3.2% 3.1%, 3%, 2.9%, 2.8%, 2.7%, 2.6%, 2.5%, 2.4%, 2.3%, 2.2%, 2 0.1%, 2%, 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1 %, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1% is there.
  • Characteristic (5) is that the glass transition temperature is 50 ° C. or higher and 65 ° C. or lower, preferably 55 ° C. or higher and 60 ° C. or lower.
  • the glass transition temperature of the binder resin is within the above range, a toner that is strong in storage stability and durability and can form a fixed image with high glossiness can be obtained.
  • the glass transition temperature is less than 50 ° C., the hot offset resistance and storage stability of the toner may be deteriorated.
  • the glass transition temperature exceeds 65 ° C., the glossiness of the fixed image may be lowered.
  • Specific glass transition temperatures are, for example, 50 ° C, 50.5 ° C, 51 ° C, 51.5 ° C, 52 ° C, 52.5 ° C, 53 ° C, 53.5 ° C, 54 ° C, 54.5 ° C, 55 ° C, 55.5 ° C, 56 ° C, 56.5 ° C, 57 ° C, 57.5 ° C, 58 ° C, 58.5 ° C, 59 ° C, 59.5 ° C, 60 ° C, 60.5 ° C, 61 ° C 61.5 ° C, 62 ° C, 62.5 ° C, 63 ° C, 63.5 ° C, 64 ° C, 64.5 ° C and 65 ° C.
  • Toner contains at least a binder resin, a colorant, a release agent, and a charge control agent, and may contain a known additive as necessary within a range that does not impair the effects of the present invention. Good.
  • the polyester resin as the binder resin of the toner of the present invention is usually one or more selected from a divalent alcohol component and a trihydric or higher polyhydric alcohol component, a divalent carboxylic acid and a trivalent or higher polyvalent.
  • One or more selected from carboxylic acids can be obtained by polycondensation reaction or esterification or transesterification by a known method.
  • the conditions in the condensation polymerization reaction may be set as appropriate depending on the reactivity of the monomer component, and the reaction may be terminated when the polymer has suitable physical properties.
  • the reaction temperature is about 170 to 250 ° C.
  • the reaction pressure is about 5 mmHg to normal pressure.
  • divalent alcohol component examples include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxy).
  • trihydric or higher polyhydric alcohol component examples include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1 , 2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3, And 5-trihydroxymethylbenzene.
  • one of the above divalent alcohol component and trihydric or higher polyhydric alcohol component can be used alone or in combination of two or more.
  • divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malon
  • examples include acids, n-dodecenyl succinic acid, n-dodecyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and acid anhydrides or lower alkyl esters thereof.
  • Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2,4-naphthalene.
  • Tricarboxylic acid 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, Examples thereof include tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, and acid anhydrides or lower alkyl esters thereof.
  • one of the above divalent carboxylic acids and trivalent or higher polyvalent carboxylic acids can be used alone or in combination of two or more.
  • the polyester resin as the binder resin of the present invention has a molecular weight distribution that satisfies the above conditions.
  • the preferred weight average molecular weight (Mw) is from 44000 to 50000
  • the preferred number average molecular weight (Mn) is from 4500 to 5500
  • the preferred ratio Mw / Mn is from 8 to 10.
  • Specific weight average molecular weights are 44000, 44500, 45000, 45500, 46000, 46500, 47000, 47500, 48000, 48500, 49000, 49500, 50000, for example.
  • the specific number average molecular weight (Mn) is, for example, 4500, 4550, 4600, 4650, 4700, 4750, 4800, 4850, 4900, 4950, 5000, 5050, 5100, 5150, 5200, 5250, 5300, 5350, 5400. , 5450, 5500.
  • Mw / Mn are, for example, 8, 8.05, 8.1, 8.15, 8.2, 8.25, 8.3, 8.35, 8.4, 8.45, 8 .5, 8.55, 8.6, 8.65, 8.7, 8.75, 8.8, 8.85, 8.9, 8.95, 9, 9.05, 9.1, 9 .15, 9.2, 9.25, 9.3, 9.35, 9.4, 9.45, 9.5, 9.55, 9.6, 9.65, 9.7, 9.75 9.8, 9.85, 9.9, 9.95 and 10.
  • Colorant of the toner of the present invention various kinds of organic and inorganic pigments and dyes commonly used in the technical field can be used. For example, black, white, yellow, orange, red, Examples include purple, blue and green colorants.
  • black colorant examples include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, and magnetite.
  • white colorants examples include zinc white, titanium oxide, antimony white, and zinc sulfide.
  • yellow colorants include chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine.
  • Yellow GR Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.
  • orange colorant examples include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, Benzidine Orange G, Indanthren Brilliant Orange GK, C.I. I. Pigment orange 31, C.I. I. And CI Pigment Orange 43.
  • red colorants examples include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, watching red, calcium salt, lake red C, lake red D, and brilliant carmine 6B.
  • purple colorants examples include manganese purple, fast violet B, and methyl violet lake.
  • Blue colorants include, for example, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, induslen blue BC, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. And CI Pigment Blue 60.
  • green colorant examples include chrome green, chromium oxide, pigment green B, micalite green lake, final yellow green G, C.I. I. And CI Pigment Green 7.
  • one of the above colorants may be used alone or in combination of two, and these combinations may be different colors or the same color.
  • Two or more colorants may be used in the form of composite particles.
  • the composite particles can be produced, for example, by adding an appropriate amount of water, lower alcohol or the like to two or more colorants, granulating with a general granulator such as a high speed mill, and drying.
  • a general granulator such as a high speed mill
  • it may be used as a master batch.
  • the composite particles and the master batch are mixed into the toner composition during dry mixing.
  • the blending amount of the colorant is not particularly limited, but is preferably 0.1 to 20 parts by weight, particularly preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin. If the blending amount of the colorant is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
  • the specific blending amount of the colorant is, for example, 0.1, 0.2, 0.5, 1, 2.5, 5, 7.5, 10, 12, with respect to 100 parts by weight of the binder resin. 5, 15, 17.5, 20 parts by weight.
  • release agents commonly used in the art can be used, for example, petroleum waxes such as paraffin wax and microcrystalline wax and derivatives thereof; Fischer-Tropsch wax, polyolefin Hydrocarbon synthetic waxes such as waxes (polyethylene wax, polypropylene wax, etc.), low molecular weight polypropylin waxes and polyolefin polymer waxes (such as low molecular weight polyethylene waxes) and their derivatives; carnauba wax, rice wax and candelilla wax and Derivatives, plant waxes such as wood wax; animal waxes such as beeswax and whale wax; oils and fats synthetic waxes such as fatty acid amides and phenol fatty acid esters; long chain carbo Acid and its derivatives; long-chain alcohols and derivatives thereof; silicone polymer; such as higher fatty acids.
  • the derivatives include oxides, block copolymers of vinyl monomers and waxes,
  • the release agent is preferably a hydrocarbon release agent having a melting point of 70 ° C. or lower.
  • the lower limit is about 60 ° C. If the melting point is 70 ° C. or lower, the effects of the present invention are further exhibited, and this is particularly preferable for low-temperature fixability.
  • Specific melting points of the release agent are, for example, 70 ° C, 69 ° C, 68 ° C, 67 ° C, 66 ° C, 65 ° C, 64 ° C, 63 ° C, 62 ° C, 61 ° C, 60 ° C.
  • the compounding amount of the release agent is not particularly limited, but is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the binder resin. Part is particularly preferred. If the amount of the release agent is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
  • the specific amount of the release agent is, for example, 0.2, 0.5, 1, 2.5, 5, 7.5, 8, 10, 12.5 with respect to 100 parts by weight of the binder resin. 15, 17.5 and 20 parts by weight.
  • Charge control agent As the charge control agent for the toner of the present invention, charge control agents for positive charge control and negative charge control which are commonly used in the technical field can be used.
  • charge control agents for controlling positive charge include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrines, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, triphenylmethane Derivatives, guanidine salts, amidine salts and the like can be mentioned.
  • Examples of the charge control agent for controlling the negative charge include oil-soluble dyes such as oil black and spiron black, metal-containing azo compounds, azo complex dyes, naphthenic acid metal salts, metal complexes and metal salts of salicylic acid and its derivatives ( Examples of the metal include chromium, zinc, zirconium, etc.), boron compounds, fatty acid soaps, long-chain alkyl carboxylates, and resin acid soaps.
  • one of the above charge control agents may be used alone or in combination of two or more.
  • the blending amount of the charge control agent is not particularly limited, but is preferably 0.5 to 3 parts by weight, particularly preferably 1 to 2 parts by weight with respect to 100 parts by weight of the binder resin. If the blending amount of the charge control agent is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
  • the specific blending amount of the charge control agent is, for example, 0.5, 0.75, 1, 1.25, 1.5, 2, 2.25, 2.5 with respect to 100 parts by weight of the binder resin. 3 parts by weight.
  • the toner of the present invention is preferably produced by melting and kneading at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent while applying a mechanical shearing force. That is, by a known method such as a general toner production method, for example, a dry method such as a pulverization method, a suspension polymerization method, an emulsion aggregation method, a dispersion polymerization method, a dissolution suspension method, and a melt emulsion method. Can be produced. Among these, the pulverization method is particularly preferable in that the number of steps is small and the amount of capital investment is small as compared with the wet method.
  • a toner preparation method using a pulverization method will be described.
  • a toner material containing at least a binder resin, a colorant, a release agent and a charge control agent is mixed and melt-kneaded to obtain a kneaded product, and then the kneaded product is cooled, solidified and pulverized, and then If necessary, particle size adjustment such as classification is performed to obtain toner particles.
  • the mixing is preferably a dry type, and a known apparatus commonly used in the technical field can be used as the mixer.
  • a Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), a super mixer (trade name, manufactured by Kawata Co., Ltd.) ), Mechanomill (trade name, manufactured by Okada Seiko Co., Ltd.) and other Henschel type mixing devices, Ong mill (trade name, manufactured by Hosokawa Micron Co., Ltd.), hybridization system (trade name, manufactured by Nara Machinery Co., Ltd.), Cosmo System ( And a mixing device such as a product name, manufactured by Kawasaki Heavy Industries, Ltd.).
  • kneader a known apparatus commonly used in the technical field can be used, and examples thereof include general kneaders such as a twin-screw extruder, a three-roller, and a lab blast mill. Specifically, for example, TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, PCM-30 (all of which are trade names, manufactured by Ikegai Co., Ltd.), etc. Open roll type kneaders such as Extruder and Needex (trade name, manufactured by Mitsui Mining Co., Ltd.) can be mentioned.
  • open roll type kneaders have a strong share (load) during kneading, such as pigments.
  • a colorant, a release agent and the like can be highly dispersed.
  • the high dispersion of the release agent works effectively for hot offset.
  • the polymer component of the binder resin that adversely affects the gloss of the fixed image is converted to a resin having a molecular weight that is effective for fixing and resistant to hot offset.
  • the low molecular weight component of the binder resin hardly changes the molecular weight distribution with respect to a high load during kneading, and the molecular weight component effective for fixing is not cut and durability is not deteriorated.
  • pulverizer As the pulverizer, a known apparatus commonly used in the technical field can be used. For example, a jet pulverizer that pulverizes using a supersonic jet stream, a rotor (rotor) that rotates at high speed, and a stator (liner). And an impact type pulverizer that introduces and crushes the solidified material into the space formed between the two.
  • a well-known apparatus commonly used in the technical field, in particular, a classifier capable of removing excessively pulverized toner base particles by centrifugal force and wind force, such as a swirling wind classifier (rotary wind classifier), can be used.
  • a swirling wind classifier rotary wind classifier
  • the obtained toner particles preferably have a volume average particle size of 3 to 10 ⁇ m, more preferably 5 to 8 ⁇ m. If the volume average particle diameter of the toner particles is within the above range, a high-definition image can be stably formed over a long period of time. When the volume average particle size of the toner particles is less than 3 ⁇ m, the particle size of the toner particles becomes too small, and high charging and low fluidity occur, and the toner cannot be stably supplied to the photoreceptor. There is a risk of image density reduction. On the other hand, if the average particle size of the toner particles exceeds 10 ⁇ m, the particle size of the toner particles becomes too large and a high-definition image may not be obtained. Specific volume average particle diameters of the toner particles are, for example, 3 ⁇ m, 4 ⁇ m, 5 ⁇ m, 6 ⁇ m, 7 ⁇ m, 8 ⁇ m, 9 ⁇ m, and 10 ⁇ m.
  • the toner of the present invention is used as a one-component developer further containing an external additive, or a two-component developer further containing an external additive and a carrier.
  • an external additive is used in order to improve the transportability and chargeability of the toner and the stirrability with the carrier when the toner is used as a two-component developer.
  • external additives commonly used in the technical field can be used, and examples thereof include silica, titanium oxide, and the like, and surface treatment (hydrophobization treatment) is performed with a silicone resin, a silane coupling agent, or the like. Are preferred.
  • the amount of the external additive is preferably 1 to 10 parts by weight and more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the toner.
  • the specific amount of the external additive is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight with respect to 100 parts by weight of the toner.
  • the toner of the present invention can be used in any form of a one-component developer and a two-component developer.
  • a carrier is further added to the toner.
  • a carrier commonly used in the technical field can be used.
  • a single or composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, chromium, etc. and carrier core particles are coated with a coating material. And the like.
  • a coating material a coating material commonly used in the art can be used.
  • These coating materials are selected according to the toner component, and can be used alone or in combination of two or more.
  • the average particle diameter of the carrier is preferably 10 to 100 ⁇ m, more preferably 20 to 50 ⁇ m.
  • Specific volume average particle diameters of the carrier are, for example, 10 ⁇ m, 15 ⁇ m, 20 ⁇ m, 25 ⁇ m, 30 ⁇ m, 35 ⁇ m, 40 ⁇ m, 45 ⁇ m, 50 ⁇ m, 55 ⁇ m, 60 ⁇ m, 65 ⁇ m, 70 ⁇ m, 75 ⁇ m, 80 ⁇ m, 85 ⁇ m, 90 ⁇ m, 95 ⁇ m, 100 ⁇ m.
  • the blending amount of the carrier is preferably 4 to 15 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the toner. Specific amounts of the carrier are, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by weight with respect to 100 parts by weight of the toner.
  • Image forming apparatus The image forming apparatus of the present invention is characterized by using the electrophotographic toner of the present invention.
  • FIG. 1 is a schematic sectional view showing an example thereof. 1 is a direction from the front side of the image forming apparatus 100 toward the back side.
  • the image forming apparatus 100 is an electrophotographic printer, and includes four visible image forming units (yellow visible image forming unit 110Y, magenta visible image forming unit 110M, cyan visible image forming unit 110C, and black visible image).
  • Forming unit 110B a so-called tandem printer in which these are also referred to as “visible image forming unit 110” along the recording paper conveyance path. Specifically, 4 along the conveyance path of the recording paper P formed between the supply tray 120 for supplying the recording paper P (heated material, recording medium) to the visible image forming unit 110 and the fixing device 40. Two visible image forming units 110 are provided.
  • each visible image forming unit 110 superimposes and transfers the respective color toner images onto the recording paper P conveyed by the endless conveying belt 133 which is the recording paper conveying means 130, and then the fixing device 40 causes the recording paper to be transferred.
  • the toner image is fixed to P, thereby forming a full color image.
  • the conveying belt 133 is stretched around the driving roller 131 and the idling roller 132, and rotates around at a predetermined peripheral speed (about 150 to 400 mm / second, for example, 220 mm / second).
  • the recording paper P is transported by electrostatic adsorption to the circulating transport belt 130.
  • Each visible image forming unit 110 is provided with a photosensitive drum 111, and around the photosensitive drum 111, a charging roller 112, an exposure means (laser light irradiation means) 113, a developing device 114, a transfer roller 115, a cleaner. 116 is arranged.
  • the developer Y of the visible image forming unit 110Y contains a developer containing yellow toner
  • the developer M of the visible image forming unit 110M contains a developer containing magenta toner
  • the visible image forming unit 110C contains a developer containing cyan toner
  • the developer B of the visible image forming unit 110B contains a developer containing black toner.
  • the developer may be either a one-component developer or a two-component developer. Further, the toner contained in the one-component developer may be any magnetic, and the carrier contained in the two-component developer may be any magnetic.
  • the toner image is transferred onto the recording paper P.
  • the transfer procedure is as follows. First, the surface of the photosensitive drum 111 is uniformly charged by the charging roller 112, and then the surface of the photosensitive drum 111 is exposed by a laser according to the image information by the laser light irradiation unit 113 to form an electrostatic latent image. Thereafter, the developing device 114 supplies toner to the electrostatic latent image on the surface of the photosensitive drum 111. Thus, the electrostatic latent image is developed (visualized) to generate a toner image.
  • the toner image generated on the surface of the photosensitive drum 111 is recorded on the recording paper conveyed by the conveying belt (conveying means) 130 by the transfer roller 115 to which a bias voltage having a polarity opposite to that of the toner of the toner image is applied.
  • the images are sequentially transferred to P.
  • the recording paper P is peeled off from the conveyance belt 133 at a curved portion of the conveyance belt 133 (portion wound around the driving roller 131) and conveyed to the fixing device 40. Further, in the fixing device 40, an appropriate temperature and pressure are applied to the recording paper P by the fixing belt heated to a predetermined temperature. As a result, the toner on the recording paper P is dissolved, the toner is fixed on the recording paper P, and a robust image is formed on the recording paper P.
  • the glass transition point (° C.) is defined as the temperature at the intersection of the base line extension below the glass transition point and the tangent indicating the maximum slope between the peak rising portion and the peak apex.
  • polyester resin [Molecular weight distribution of polyester resin] A resin sample is dissolved in tetrahydrofuran to a concentration of 0.5 g / 100 mL, and the resulting solution is filtered using a fluororesin filter having a pore size of 2 ⁇ m (manufactured by Sumitomo Electric Industries, Ltd., product number: FP-200). A sample solution is prepared by removing dissolved components.
  • GPC gel permeation chromatography
  • the number average molecular weight (Mn), the weight average molecular weight (Mw) and the ratio (Mw / Mn) of the sample are calculated based on a calibration curve prepared in advance using several types of monodisperse polystyrene as a standard sample. Further, from the obtained molecular weight distribution, a high molecular weight weight ratio (%) of 1 ⁇ 10 6 or higher, a high molecular weight weight ratio (%) of 1 ⁇ 10 5.3 or higher, and a low molecular weight ratio of 1 ⁇ 10 3.6 or lower. (%) And the area ratio (half-width area:%) connecting both ends of the half-width of the main peak are calculated.
  • Example 1 Binder resin: Polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) 91 parts by weight Colorant: Copper phthalocyanine (Pigment Blue 15: 3) 5 parts by weight Release agent: Nonpolar paraffin Wax (manufactured by Nippon Seisaku Co., Ltd., model number: HNP-11) 3 parts by weight Charge control agent: salicylic acid compound (trade name: Bontron E84, manufactured by Orient Chemical Co., Ltd.) 1 part by weight
  • the obtained melt-kneaded product is cooled by a cooling belt, and then coarsely pulverized using a coarse pulverizer (THE ORIENT CO. LTD., Model: VM-16) having a 2 mm screen, and then a jet pulverizer (Nippon Pneumatic Kogyo Co., Ltd., Model: IDS-2) Finely pulverized, and further elbow jet classifier (Nittetsu Mining Co., Ltd., Model: EJ-LABO) 4 kg of 1 toner particle (volume average particle size 6.9 ⁇ m, coefficient of variation 22) was obtained.
  • Example 2 The toner particles (volume) of Example 2 were the same as Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour. An average particle size of 6.9 ⁇ m and a coefficient of variation of 21) 4 kg were obtained.
  • Example 3 The toner particles of Example 3 were the same as Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 120 ° C., a barrel rotation speed of 150 rpm, and a raw material supply speed of 20 kg / hour. Volume average particle size 7.0 ⁇ m, coefficient of variation 24) 4 kg was obtained.
  • Example 4 Toner particles of Example 4 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 120 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour. (Volume average particle diameter 6.8 ⁇ m, coefficient of variation 21) 4 kg was obtained.
  • Example 5 The toner particles (volume) of Example 5 were the same as Example 1 except that polyester resin 2 (Tg: 52 ° C., Tm: 125 ° C., gel component ratio: 2%) was used instead of polyester resin 1. An average particle size of 6.7 ⁇ m and a coefficient of variation of 23) 4 kg were obtained.
  • Example 6 The toner particles (volume) of Example 6 were the same as Example 1 except that polyester resin 3 (Tg: 65 ° C., Tm: 138 ° C., gel component ratio: 5%) was used instead of polyester resin 1. An average particle size of 6.9 ⁇ m and a coefficient of variation of 24) 4 kg were obtained.
  • the toner particles (volume of Comparative Example 1) were the same as in Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder set temperature of 120 ° C., a barrel rotation speed of 100 rpm, and a raw material supply speed of 15 kg / hour. An average particle size of 6.7 ⁇ m and a coefficient of variation of 21) 4 kg were obtained.
  • Comparative Example 2 The melt kneading conditions of the twin-screw extruder were changed to a cylinder set temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour, and instead of 91 parts by weight of the polyester resin 1, polyester resin 1 (Tg: 58 C, Tm: 130 ° C, gel component ratio: 2%) and polyester resin 4 (Tg: 52 ° C, Tm: 120 ° C, gel component ratio: 7%) 27 parts by weight (weight ratio 7: 3) 4 kg of toner particles (volume average particle size 6.9 ⁇ m, coefficient of variation 23) of Comparative Example 2 were obtained in the same manner as Example 1 except that it was used.
  • polyester resin 1 Tg: 58 C, Tm: 130 ° C, gel component ratio: 2
  • polyester resin 4 Tg: 52 ° C, Tm: 120 ° C, gel component ratio: 7%
  • Comparative Example 3 instead of 91 parts by weight of polyester resin 1, 64 parts by weight of polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) and polyester resin 4 (Tg: 52 ° C., Tm: 120 ° C., The toner particles of Comparative Example 3 (volume average particle size of 7) were used in the same manner as Example 1 except that 27 parts by weight (weight ratio 7: 3) was used (same as in Comparative Example 2). 0.1 ⁇ m, coefficient of variation 24) 4 kg was obtained.
  • Comparative Example 4 The melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour (similar to Comparative Example 2), and instead of 91 parts by weight of the polyester resin 1, 45.5 parts by weight of polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) and polyester resin 5 (Tg: 60 ° C., Tm: 140 ° C., gel component ratio: 15%) 4 kg of toner particles (volume average particle size 7.0 ⁇ m, coefficient of variation 23) of Comparative Example 4 were obtained in the same manner as in Example 1 except that 5 parts by weight (weight ratio 5: 5) was used.
  • Comparative Example 5 The toner particles of Comparative Example 5 were prepared in the same manner as in Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 300 rpm, and a raw material supply speed of 20 kg / hour. A volume average particle size of 6.7 ⁇ m and a coefficient of variation of 21) 4 kg were obtained.
  • Comparative Example 6 The toner particles (volume) of Comparative Example 6 were the same as Example 1 except that polyester resin 6 (Tg: 49 ° C., Tm: 120 ° C., gel component ratio: 1%) was used instead of polyester resin 1. 4 kg of an average particle diameter of 6.7 ⁇ m and a coefficient of variation of 21) were obtained.
  • Comparative Example 7 In the same manner as in Example 1 except that polyester resin 7 (Tg: 67 ° C., Tm: 141 ° C., gel component ratio: 2%) was used instead of polyester resin 1, toner particles (volume) of Comparative Example 7 were used. 4 kg of an average particle diameter of 7.2 ⁇ m and a coefficient of variation of 24) were obtained.
  • silica particles manufactured by Nippon Aerosil Co., Ltd., model number: RX-200
  • RX-200 silica particles
  • 1.5 parts by weight with respect to the parts were mixed and mixed using a Henschel mixer (Mitsui Mining Co., Ltd. (currently Nippon Coke Kogyo Co., Ltd., model: FM150)) to obtain 5 kg of externally added toner.
  • a ferrite carrier is mixed with each of the obtained externally added toners using a Nauter mixer (Model: Lab mixer LV-0, manufactured by Hosokawa Micron Co., Ltd.) so that the toner concentration becomes 8% by weight. 2 kg was obtained.
  • ⁇ Glossiness> A commercially available copying machine (Sharp Corporation, model: MX-2300G) is filled with a two-component developer, and the surface temperature of the heating roller is set in increments of 5 ° C. from 130 ° C. to 220 ° C. to form an image. Using a meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: VG2000), an area having a gloss value of 50 or more was examined. The glossiness was evaluated according to the following criteria. ⁇ (Best): Gross value of 50 or higher is 20 ° C or higher. ⁇ (Good): Gloss value of 50 or higher is 15 ° C or higher and lower than 20 ° C. ⁇ (No problem in practical use): Gloss value of 50 or higher is 5 ° C or higher. ⁇ ° C. x (defect): No area with a gloss value of 50 or more
  • Hot offset resistance was evaluated according to the following criteria. ⁇ (Good): Hot offset occurs at 215 ° C. or higher ⁇ (No problem in practical use): Hot offset occurs at 205 ° C. or higher and lower than 215 ° C. ⁇ (Bad): Hot offset occurs at lower than 205 ° C.
  • ⁇ Comprehensive evaluation> The above three types of evaluation results were combined and classified according to the following criteria. ⁇ (Best): All evaluations are ⁇ or more and gloss evaluation is ⁇ . ⁇ (good): The evaluation result has no x and ⁇ is 1 or less. ⁇ (no problem in practical use): There are no x in the evaluation result, and there are two or more ⁇ . ⁇ (defect): The evaluation result has ⁇
  • the toner of the present invention (Examples 1 to 6) is excellent in all of glossiness, hot offset resistance and storage stability.
  • the toner (Comparative Example 1) containing a binder resin containing a high molecular weight component exceeding the specified amount of the present invention is inferior in gloss.
  • the toner containing the binder resin containing the low molecular weight component exceeding the specified amount of the present invention (Comparative Example 2) is inferior in hot offset resistance and storage stability.
  • the toner (Comparative Example 4) containing a gel component insoluble in tetrahydrofuran of the binder resin exceeding the specified amount of the present invention is inferior in gloss.
  • a toner (Comparative Example 5) in which the area connecting both ends of the half width of the main peak in the molecular weight distribution of the binder resin exceeds the specified amount of the present invention (Comparative Example 5) is inferior in hot offset resistance.
  • the toner (Comparative Example 6) in which the glass transition temperature of the binder resin is less than the specified value of the present invention is inferior in hot offset resistance and storage stability.
  • a toner (Comparative Example 7) in which the glass transition temperature of the binder resin exceeds the specified value of the present invention is inferior in gloss.

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Abstract

A toner for electrophotography which comprises a polyester resin as a binder resin, a coloring material, a release agent and a charge control agent as the essential components, wherein the polyester resin satisfies the following requirements: in the molecular weight distribution as determined by gel permeation chromatography, (1) the fraction of molecules having molecular weights of 1 × 106.0 or more is less than 1% and the fraction of molecules having molecular weights of 1 × 105.3 or more is less than 5%, (2) the fraction of molecules having molecular weights of 1 × 103.6 or less is less than 20%, and (3) the area formed by linking both ends of the half-width of the main peak is 70 to 82%; and further (4) the tetrahydrofuran-insoluble gel content is less than 5%, and (5) the glass transition temperature is 50 to 65°C.

Description

電子写真用トナーおよびそれを用いた画像形成装置Toner for electrophotography and image forming apparatus using the same
　本発明は、広い定着領域を確保しつつかつ光沢度に悪影響を及ぼさない電子写真用トナーおよびそれを用いた画像形成装置に関する。 BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrophotographic toner that ensures a wide fixing area and does not adversely affect glossiness, and an image forming apparatus using the same.
　ＰＯＤ（プリントオンデマンド）は、ＩＴ時代の印刷方式として注目されるデジタル印刷技術であり、小ロット印刷や短納期に有利、バリアブル印刷が可能、１つのデータから通信機能を利用して複数の出力機（「画像形成装置」、「電子写真機」ともいう）を作動させる分散印刷が可能などの利点があり、その市場が拡大しつつある。 POD (Print On Demand) is a digital printing technology that has been attracting attention as a printing method in the IT era. It is advantageous for small lot printing and short delivery time, and can be used for variable printing. Which has the advantage of being able to perform distributed printing to operate a machine (also referred to as an “image forming apparatus” or “electrophotographic machine”), and its market is expanding.
　ＰＯＤに対応する画像形成装置では高速出力（印刷）が要求され、ヒートローラと未定着画像の接触時間を短くする必要があることから、使用するトナーの性能は、素早く溶けかつホットオフセットに強いことが要求される。
　また、上記の接触時間を可能な限り延ばしかつ省電力で瞬間的にトナーを加熱するために、ベルト定着方式が提案されている。但し、ベルト定着方式では、ローラ定着方式に比べて記録媒体である紙との剥離性が悪くなるために、トナーはよりホットオフセットに強い性能が要求される。 The image forming apparatus that supports POD requires high-speed output (printing), and it is necessary to shorten the contact time between the heat roller and the unfixed image. Therefore, the performance of the toner used melts quickly and is resistant to hot offset. Is required.
A belt fixing method has been proposed in order to extend the contact time as much as possible and heat the toner instantaneously with power saving. However, in the belt fixing method, the releasability from the paper as the recording medium is worse than that in the roller fixing method, so that the toner is required to have higher performance against hot offset.
　一般的にトナーのホットオフセット性能を強化するためには、トナーの結着樹脂中に高分子量のゲル成分が添加されるが、定着画像の光沢度が著しく低下するという問題がある。
　また、省電力化のため低温定着化が提案されているが、過度なトナーの低融点化は、トナーカートリッジ状態での輸送時における保存安定性および現像槽内でのシェアが掛かった状態でのトナーの耐久性の悪化を招くという問題がある。
　以上のことから、高速出力の画像形成装置に使用されるトナーでは、ホットオフセットに強いこと、十分な光沢度を有すること、および保存安定性・耐久性が高いことが要求される。 In general, in order to enhance the hot offset performance of the toner, a high molecular weight gel component is added to the binder resin of the toner, but there is a problem that the glossiness of the fixed image is remarkably lowered.
In addition, low-temperature fixing has been proposed to save power, but excessively low toner melting point is a condition that requires storage stability during transportation in the toner cartridge state and share in the developing tank. There is a problem that the durability of the toner is deteriorated.
From the above, the toner used in the high-speed output image forming apparatus is required to be resistant to hot offset, have sufficient glossiness, and have high storage stability and durability.
　日本特開２００２－２３４１９号公報（特許文献１）には、結着樹脂がゲルパーミエーションクロマトグラフにより測定される分子量分布において、特定分子量にメインピークを有し、混練工程の機械的剪断エネルギーにより得られた特定分子量のサブピークもしくはショルダーを有し、特定量以下の特定の低分子量成分を有し、特定量以下のテトラヒドロフラン（ＴＨＦ）不溶解成分を有し、結着樹脂のガラス転移温度と特定分子量成分の含有量とが特定式を満足する電子写真用トナーが記載されている。そして、このような構成を有することにより、電子写真用トナーが、ベルト定着性、耐ホットオフセット性、保存性および生産性に優れることが記載されている。 In Japanese Patent Application Laid-Open No. 2002-23419 (Patent Document 1), the molecular weight distribution of the binder resin measured by gel permeation chromatography has a main peak at a specific molecular weight, and the mechanical shear energy of the kneading process is used. The obtained specific molecular weight has a sub-peak or shoulder, has a specific low molecular weight component below a specific amount, has a tetrahydrofuran (THF) insoluble component below a specific amount, and specifies the glass transition temperature of the binder resin. An electrophotographic toner is described in which the content of the molecular weight component satisfies a specific formula. It is described that the electrophotographic toner is excellent in belt fixing property, hot offset resistance, storage stability and productivity by having such a configuration.
日本特開２００２－２３４１９号公報Japanese Patent Laid-Open No. 2002-23419
　しかしながら、特許文献１の先行技術では、定着画像の光沢度の低下について、また上記のように光沢度を低下させる要因である結着樹脂の高分子量成分を削減することについては検討されておらず、特許文献１による電子写真用トナーでは定着画像の高い光沢度は期待できない。また、特許文献１の先行技術では、トナーのホットオフセット性能を強化するために、テトラヒドロフラン（ＴＨＦ）不溶解成分を特定量以下にすることが記載されているが、これは定着画像の光沢度の向上とは逆行する真逆の考えである。 However, in the prior art of Patent Document 1, no consideration has been given to the reduction of the glossiness of the fixed image and the reduction of the high molecular weight component of the binder resin, which is a factor for reducing the glossiness as described above. The high glossiness of a fixed image cannot be expected with the toner for electrophotography according to Patent Document 1. Further, in the prior art of Patent Document 1, in order to enhance the hot offset performance of the toner, it is described that the tetrahydrofuran (THF) insoluble component is set to a specific amount or less. Improvement is the opposite idea.
　本発明は、広い定着領域および高い耐ホットオフセット性能を確保しつつかつ光沢度に悪影響を及ぼさない電子写真用トナーおよびそれを用いた画像形成装置を提供することを課題とする。 It is an object of the present invention to provide an electrophotographic toner that secures a wide fixing area and high anti-hot offset performance and does not adversely affect glossiness, and an image forming apparatus using the same.
　本発明者らは、上記の課題を解決するために鋭意研究を行った結果、トナーの結着樹脂に特定のポリエステル樹脂を用いることにより、広い定着領域および高い耐ホットオフセット性能を確保しつつかつ光沢度に悪影響を及ぼさない電子写真用トナーが得られることを見出し、本発明を完成するに到った。 As a result of intensive studies to solve the above problems, the present inventors have used a specific polyester resin as a toner binder resin, while ensuring a wide fixing area and high hot offset resistance performance. The inventors have found that an electrophotographic toner that does not adversely affect glossiness can be obtained, and have completed the present invention.
　かくして、本発明によれば、少なくとも結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を含み、前記ポリエステル樹脂が、次の条件：
　ゲルパーミエーションクロマトグラフにより測定される分子量分布において、
（１）分子量１×１０6.0以上の成分が１％未満でかつ分子量１×１０5.3以上の成分が５％未満であり、
（２）分子量１×１０3.6以下の成分が２０％未満であり、
（３）メインピークの半値幅の両端を結ぶ面積が７０～８２％であり、かつ
（４）テトラヒドロフランに不溶なゲル成分が５％未満であり、
（５）ガラス転移温度が５０℃以上６５℃以下である、
を満たす電子写真用トナーが提供される。 Thus, according to the present invention, the polyester resin contains at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent, and the polyester resin has the following conditions:
In the molecular weight distribution measured by gel permeation chromatograph,
(1) The component having a molecular weight of 1 × 10 6.0 or more is less than 1% and the component having a molecular weight of 1 × 10 5.3 or more is less than 5%,
(2) The component having a molecular weight of 1 × 10 3.6 or less is less than 20%,
(3) the area connecting both ends of the half width of the main peak is 70 to 82%, and (4) the gel component insoluble in tetrahydrofuran is less than 5%,
(5) The glass transition temperature is 50 ° C. or higher and 65 ° C. or lower,
An electrophotographic toner satisfying the above requirements is provided.
　また、本発明によれば、上記の電子写真用トナーを用いた画像形成装置が提供される。 Further, according to the present invention, an image forming apparatus using the above electrophotographic toner is provided.
　本発明によれば、広い定着領域を確保しつつかつ光沢度に悪影響を及ぼさない電子写真用トナーおよびそれを用いた画像形成装置を提供することができる。 According to the present invention, it is possible to provide an electrophotographic toner that secures a wide fixing area and does not adversely affect glossiness, and an image forming apparatus using the same.
　また、本発明の電子写真用トナーは、
　条件（１）における分子量１×１０6.0以上の成分が０．５％未満でかつ分子量１×１０5.3以上の成分が２．５％未満である場合に、
　条件（２）における分子量１×１０3.6以下の成分が、１５％未満である場合に、
　条件（３）におけるメインピークの半値幅の両端を結ぶ面積が７８～８２％である場合に、
　条件（４）におけるテトラヒドロフランに不溶なゲル成分が、２％未満である場合に、
　条件（５）におけるガラス転移温度が、５５℃以上６０℃以下である場合に、
　結着樹脂における重量平均分子量（Ｍｗ）が４４０００～５００００であり、数平均分子量（Ｍｎ）が４５００～５５００であり、それらの比Ｍｗ／Ｍｎが８～１０である場合に、
耐ホットオフセット性能を維持しながらより高い光沢度を実現することができる。 In addition, the electrophotographic toner of the present invention includes
When the component having a molecular weight of 1 × 10 6.0 or more in the condition (1) is less than 0.5% and the component having a molecular weight of 1 × 10 5.3 or more is less than 2.5%,
When the component having a molecular weight of 1 × 10 3.6 or less in the condition (2) is less than 15%,
When the area connecting both ends of the half width of the main peak in the condition (3) is 78 to 82%,
When the gel component insoluble in tetrahydrofuran in the condition (4) is less than 2%,
When the glass transition temperature in the condition (5) is 55 ° C. or more and 60 ° C. or less,
When the weight average molecular weight (Mw) in the binder resin is 44000 to 50000, the number average molecular weight (Mn) is 4500 to 5500, and the ratio Mw / Mn thereof is 8 to 10,
Higher gloss can be achieved while maintaining hot offset resistance.
　また、本発明の電子写真用トナーは、少なくとも結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を機械的剪断力を付加して溶融混練することにより製造されることにより、離型剤が適度に分散され耐ホットオフセットに有効に働き、高分子量の樹脂の分子鎖切断が起き、光沢に悪影響を及ぼす分子量の樹脂から定着に有効でかつホットオフセットに強い分子量の樹脂に変換され、本発明の効果がさらに発揮される。
　さらに、本発明の電子写真用トナーは、前記結着樹脂と、前記結着樹脂１００重量部に対してそれぞれ０．１～２０重量部の着色剤、０．２～２０重量部の離型剤および０．５～３重量部の帯電制御剤とを含む場合に、本発明の効果がさらに発揮される。 In addition, the electrophotographic toner of the present invention is produced by melt-kneading at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent with a mechanical shearing force, The release agent is moderately dispersed and works effectively in hot offset resistance, causing molecular chain scission of high molecular weight resins, converting from molecular weight resins that have an adverse effect on gloss to resins that are effective for fixing and resistant to hot offset. The effect of the present invention is further exhibited.
Further, the electrophotographic toner of the present invention includes 0.1 to 20 parts by weight of a colorant and 0.2 to 20 parts by weight of a release agent for the binder resin and 100 parts by weight of the binder resin, respectively. And 0.5 to 3 parts by weight of the charge control agent, the effects of the present invention are further exhibited.
本発明の画像形成装置の一例を示す概略断面図である。1 is a schematic cross-sectional view illustrating an example of an image forming apparatus of the present invention.
　本発明の電子写真用トナー（以下「トナー」ともいう）は、少なくとも結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を含み、前記ポリエステル樹脂が、次の条件：
　ゲルパーミエーションクロマトグラフ（ＧＰＣ）により測定される分子量分布において、
（１）分子量１×１０6.0以上の成分が１％未満でかつ分子量１×１０5.3以上の成分が５％未満であり、
（２）分子量１×１０3.6以下の成分が２０％未満であり、
（３）メインピークの半値幅の両端を結ぶ面積が７０～８２％であり、かつ
（４）テトラヒドロフランに不溶なゲル成分が５％未満であり、
（５）ガラス転移温度が５０℃以上６５℃以下である、
を満たすことを特徴とする。
　すなわち、本発明のトナーは、結着樹脂に特定のポリエステル樹脂を用いることを特徴とする。
　本発明において、ポリエステル樹脂の分子量に関する規定は、全てゲルパーミエーションクロマトグラフ（ＧＰＣ）により測定される分子量分布に基づく。なお、ＧＰＣ測定については実施例において詳述する。 The electrophotographic toner of the present invention (hereinafter also referred to as “toner”) includes at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent, and the polyester resin has the following conditions:
In the molecular weight distribution measured by gel permeation chromatograph (GPC),
(1) The component having a molecular weight of 1 × 10 6.0 or more is less than 1% and the component having a molecular weight of 1 × 10 5.3 or more is less than 5%,
(2) The component having a molecular weight of 1 × 10 3.6 or less is less than 20%,
(3) the area connecting both ends of the half width of the main peak is 70 to 82%, and (4) the gel component insoluble in tetrahydrofuran is less than 5%,
(5) The glass transition temperature is 50 ° C. or higher and 65 ° C. or lower,
It is characterized by satisfying.
That is, the toner of the present invention is characterized by using a specific polyester resin as the binder resin.
In the present invention, all the regulations relating to the molecular weight of the polyester resin are based on the molecular weight distribution measured by gel permeation chromatography (GPC). The GPC measurement will be described in detail in the examples.
　特徴（１）は、分子量１×１０6.0以上の成分が１％未満、好ましくは０．５％未満でかつ分子量１×１０5.3以上の成分が５％未満、好ましくは２．５％未満であることである。
　すなわち、過度な高分子量成分の含有量を抑えることで、画像形成後における定着画像の光沢度の低下を抑えることができる。
　各成分の含有量は０％であることが好ましい。分子量１×１０5.3以上の成分の下限は１．５％程度である。 Feature (1) is that the component having a molecular weight of 1 × 10 6.0 or more is less than 1%, preferably less than 0.5%, and the component having a molecular weight of 1 × 10 5.3 or more is less than 5%, preferably less than 2.5%. That is.
That is, by suppressing the content of an excessive high molecular weight component, it is possible to suppress a decrease in glossiness of a fixed image after image formation.
The content of each component is preferably 0%. The lower limit of the component having a molecular weight of 1 × 10 5.3 or more is about 1.5%.
　具体的な分子量１×１０6.0以上の成分は、例えば、０．９５％、０．９％、０．８５％、０．８％、０．７５％、０．７％、０．６５％、０．６％、０．５５％、０．５％、０．４５％、０．４％、０．３５％、０．３％、０．２５％、０．２％、０．１５％、０．１％、０．０５％、０．０４％、０．０３％、０．０２％、０．０１％である。
　具体的な分子量１×１０5.3以上の成分は、例えば、４．９％、４．５％、４．０％、３．５％、３．０％、２．５％、２．０％、１．５％、１．０％、０．９％、０．８％、０．７％、０．６％、０．５％、０．４％、０．３％、０．２％、０．１％である。 Specific components having a molecular weight of 1 × 10 6.0 or more include, for example, 0.95%, 0.9%, 0.85%, 0.8%, 0.75%, 0.7%, 0.65%, 0.6%, 0.55%, 0.5%, 0.45%, 0.4%, 0.35%, 0.3%, 0.25%, 0.2%, 0.15%, 0.1%, 0.05%, 0.04%, 0.03%, 0.02%, and 0.01%.
Specific components having a molecular weight of 1 × 10 5.3 or more include, for example, 4.9%, 4.5%, 4.0%, 3.5%, 3.0%, 2.5%, 2.0%, 1.5%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1%.
　特徴（２）は、分子量１×１０3.6以下の成分が２０％未満、好ましくは１５％未満であることである。
　すなわち、過度な低分子量成分の含有量を抑えることで、低融点に起因するトナー同士の融着や負荷が掛かったときのトナーの耐久性を向上させることができる。
　上記成分の含有量は、少ない方がよいが、メインピークと分子量が近いこともあり、少なくとも１０％程度は存在する。 Characteristic (2) is that a component having a molecular weight of 1 × 10 3.6 or less is less than 20%, preferably less than 15%.
That is, by suppressing the content of an excessively low molecular weight component, it is possible to improve the durability of the toner when the toner is fused or loaded due to the low melting point.
The content of the above components is preferably as low as possible, but the molecular weight may be close to the main peak, and there is at least about 10%.
　具体的な分子量１×１０3.6以下の成分は、例えば、１９．５％、１９％、１８．５％、１８％、１７．５％、１７％、１６．５％、１６％、１５．５％、１５％、１４．５％、１４％、１３．５％、１３％、１２．５％、１２％、１１．５％、１１％、１０．５％、１０％である。 Specific components having a molecular weight of 1 × 10 3.6 or less include, for example, 19.5%, 19%, 18.5%, 18%, 17.5%, 17%, 16.5%, 16%, 15.5. %, 15%, 14.5%, 14%, 13.5%, 13%, 12.5%, 12%, 11.5%, 11%, 10.5%, 10%.
　特徴（３）は、メインピークの半値幅の両端を結ぶ面積が７０～８２％、好ましくは７８～８２％、より好ましくは７９～８０％であることである。
　すなわち、メインピーク付近の分子量の樹脂が定着可能温度域に対して重要な役割を担い、それ以外の分子量成分（低分子量および高分子量）の樹脂は、トナー耐久性を悪化させ、光沢度の低下を引き起こす。
　したがって、メインピーク付近の分子量の樹脂が上記の範囲内であれば、トナーの耐久性を高め、光沢度の高い画像を形成できる。
　メインピークの半値幅の両端を結ぶ面積が７０％未満では、定着画像の光沢度が低下することがある。一方、メインピークの半値幅の両端を結ぶ面積が８２％を超えると、トナーの耐ホットオフセット性が低下することがある。 Characteristic (3) is that the area connecting both ends of the full width at half maximum of the main peak is 70 to 82%, preferably 78 to 82%, more preferably 79 to 80%.
That is, a resin having a molecular weight in the vicinity of the main peak plays an important role in the fixing temperature range, and resins having other molecular weight components (low molecular weight and high molecular weight) deteriorate toner durability and lower gloss. cause.
Therefore, if the resin having a molecular weight in the vicinity of the main peak is within the above range, the durability of the toner can be improved and an image with high glossiness can be formed.
If the area connecting both ends of the half width of the main peak is less than 70%, the glossiness of the fixed image may be lowered. On the other hand, if the area connecting both ends of the half width of the main peak exceeds 82%, the hot offset resistance of the toner may be lowered.
　具体的なメインピークの半値幅の両端を結ぶ面積は、例えば、７０％、７０．５％、７１％、７１．５％、７２％、７２．５％、７３％、７３．５％、７４％、７４．５％、７５％、７５．５％、７６％、７６．５％、７７％、７７．５％、７８％、７８．５％、７９％、７９．５％、８０％、８０．５％、８１％、８１．５％、８２％である。 The area connecting both ends of the half width of a specific main peak is, for example, 70%, 70.5%, 71%, 71.5%, 72%, 72.5%, 73%, 73.5%, 74 %, 74.5%, 75%, 75.5%, 76%, 76.5%, 77%, 77.5%, 78%, 78.5%, 79%, 79.5%, 80%, 80.5%, 81%, 81.5% and 82%.
　特徴（４）は、テトラヒドロフランに不溶なゲル成分が５％未満、好ましくは２％未満であることである。
　すなわち、テトラヒドロフランに不溶なゲル成分が多い程、ホットオフセットには強くなるが、定着画像の光沢度の著しい低下を引き起こすので、ゲル成分を５％未満に抑え、特徴（１）を満たすことにより、定着画像の高い光沢度を得ることができる。
　上記成分の含有量は０％であることが好ましい。 Characteristic (4) is that the gel component insoluble in tetrahydrofuran is less than 5%, preferably less than 2%.
That is, the more the gel component insoluble in tetrahydrofuran is, the stronger the hot offset is, but the glossiness of the fixed image is significantly reduced. Therefore, the gel component is suppressed to less than 5% and satisfying the feature (1), High glossiness of a fixed image can be obtained.
The content of the above components is preferably 0%.
　具体的なテトラヒドロフランに不溶なゲル成分は、例えば、４．９％、４．８％、４．７％、４．６％、４．５％、４．４％、４．３％、４．２％、４．１％、４％、３．９％、３．８％、３．７％、３．６％、３．５％、３．４％、３．３％、３．２％、３．１％、３％、２．９％、２．８％、２．７％、２．６％、２．５％、２．４％、２．３％、２．２％、２．１％、２％、１．９％、１．８％、１．７％、１．６％、１．５％、１．４％、１．３％、１．２％、１．１％、１％、０．９％、０．８％、０．７％、０．６％、０．５％、０．４％、０．３％、０．２％、０．１％である。 Specific examples of gel components insoluble in tetrahydrofuran include 4.9%, 4.8%, 4.7%, 4.6%, 4.5%, 4.4%, 4.3%, and 4.%. 2%, 4.1%, 4%, 3.9%, 3.8%, 3.7%, 3.6%, 3.5%, 3.4%, 3.3%, 3.2% 3.1%, 3%, 2.9%, 2.8%, 2.7%, 2.6%, 2.5%, 2.4%, 2.3%, 2.2%, 2 0.1%, 2%, 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.1 %, 1%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%, 0.4%, 0.3%, 0.2%, 0.1% is there.
　特徴（５）は、ガラス転移温度が５０℃以上６５℃以下、好ましくは５５℃以上６０℃以下であることである。
　結着樹脂のガラス転移温度が上記の範囲内にあることで、保存安定性や耐久性に強く、光沢度の高い定着画像を形成し得るトナーが得られる。
　ガラス転移温度が５０℃未満では、トナーの耐ホットオフセット性および保存性が低下することがある。一方、ガラス転移温度が６５℃を超えると、定着画像の光沢度が低下することがある。 Characteristic (5) is that the glass transition temperature is 50 ° C. or higher and 65 ° C. or lower, preferably 55 ° C. or higher and 60 ° C. or lower.
When the glass transition temperature of the binder resin is within the above range, a toner that is strong in storage stability and durability and can form a fixed image with high glossiness can be obtained.
When the glass transition temperature is less than 50 ° C., the hot offset resistance and storage stability of the toner may be deteriorated. On the other hand, when the glass transition temperature exceeds 65 ° C., the glossiness of the fixed image may be lowered.
　具体的なガラス転移温度は、例えば、５０℃、５０．５℃、５１℃、５１．５℃、５２℃、５２．５℃、５３℃、５３．５℃、５４℃、５４．５℃、５５℃、５５．５℃、５６℃、５６．５℃、５７℃、５７．５℃、５８℃、５８．５℃、５９℃、５９．５℃、６０℃、６０．５℃、６１℃、６１．５℃、６２℃、６２．５℃、６３℃、６３．５℃、６４℃、６４．５℃、６５℃である。 Specific glass transition temperatures are, for example, 50 ° C, 50.5 ° C, 51 ° C, 51.5 ° C, 52 ° C, 52.5 ° C, 53 ° C, 53.5 ° C, 54 ° C, 54.5 ° C, 55 ° C, 55.5 ° C, 56 ° C, 56.5 ° C, 57 ° C, 57.5 ° C, 58 ° C, 58.5 ° C, 59 ° C, 59.5 ° C, 60 ° C, 60.5 ° C, 61 ° C 61.5 ° C, 62 ° C, 62.5 ° C, 63 ° C, 63.5 ° C, 64 ° C, 64.5 ° C and 65 ° C.
（１）トナー
　本発明のトナーは、少なくとも結着樹脂、着色剤、離型剤および帯電制御剤を含み、本発明の効果を阻害しない範囲で必要に応じて公知の添加剤を含んでいてもよい。 (1) Toner The toner of the present invention contains at least a binder resin, a colorant, a release agent, and a charge control agent, and may contain a known additive as necessary within a range that does not impair the effects of the present invention. Good.
（結着樹脂）
　本発明のトナーの結着樹脂としてのポリエステル樹脂は、通常、２価のアルコール成分および３価以上の多価アルコール成分から選ばれる１種以上と、２価のカルボン酸および３価以上の多価カルボン酸から選ばれる１種以上とを、公知の方法により縮重合反応もしくはエステル化、エステル交換反応により得られる。
　縮重合反応における条件は、モノマー成分の反応性により適宜設定すればよく、また重合体が好適な物性になった時点で反応を終了させればよい。例えば、反応温度は１７０～２５０℃程度、反応圧力は５ｍｍＨｇ～常圧程度である。 (Binder resin)
The polyester resin as the binder resin of the toner of the present invention is usually one or more selected from a divalent alcohol component and a trihydric or higher polyhydric alcohol component, a divalent carboxylic acid and a trivalent or higher polyvalent. One or more selected from carboxylic acids can be obtained by polycondensation reaction or esterification or transesterification by a known method.
The conditions in the condensation polymerization reaction may be set as appropriate depending on the reactivity of the monomer component, and the reaction may be terminated when the polymer has suitable physical properties. For example, the reaction temperature is about 170 to 250 ° C., and the reaction pressure is about 5 mmHg to normal pressure.
　２価のアルコール成分としては、例えば、ポリオキシプロピレン（２．２）－２，２－ビス（４－ヒドロキシフェニル）プロパン、ポリオキシプロピレン（３．３）－２，２－ビス（４－ヒドロキシフェニル）プロパン、ポリオキシプロピレン（２．０）－２，２－ビス（４－ヒドロキシフェニル）プロパン、ポリオキシプロピレン（２．０）－ポリオキシエチレン（２．０）－２，２－ビス（４－ヒドロキシフェニル）プロパン、ポリオキシプロピレン（６）－２，２－ビス（４－ヒドロキシフェニル）プロパンなどのビスフェノールＡのアルキレンオキシド付加物；エチレングリコール、ジエチレングリコール、トリエチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，４－ブタンジオール、ネオペンチルグリコール、１，４－ブテンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，４－シクロヘキサンジメタノール、ジプロピレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレングリコールなどのジオール類；ビスフェノールＡ；ビスフェノールＡのプロピレン付加物；ビスフェノールＡのエチレン付加物；水素添加ビスフェノールＡなどが挙げられる。 Examples of the divalent alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,2-bis (4-hydroxy). Phenyl) propane, polyoxypropylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis ( Alkylene oxide adducts of bisphenol A such as 4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene Glycol, 1,3-propylene glycol, 1,4-butanediol, ne Diols such as pentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Bisphenol A; propylene adduct of bisphenol A; ethylene adduct of bisphenol A; hydrogenated bisphenol A and the like.
　３価以上の多価アルコール成分としては、例えば、ソルビトール、１，２，３，６－ヘキサンテトロール、１，４－ソルビタン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、スクロース（蔗糖）、１，２，４－ブタントリオール、１，２，５－ペンタントリオール、グリセロール、２－メチルプロパントリオール、２－メチル－１，２，４－ブタントリオール、トリメチロールエタン、トリメチロールプロパン、１，３，５－トリヒドロキシメチルベンゼンなどが挙げられる。
　本発明においては、上記の２価のアルコール成分および３価以上の多価アルコール成分の１種を単独でまたは２種以上を組み合わせて用いることができる。 Examples of the trihydric or higher polyhydric alcohol component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose, 1 , 2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3, And 5-trihydroxymethylbenzene.
In the present invention, one of the above divalent alcohol component and trihydric or higher polyhydric alcohol component can be used alone or in combination of two or more.
　２価のカルボン酸として、例えば、マレイン酸、フマル酸、シトラコン酸、イタコン酸、グルタコン酸、フタル酸、イソフタル酸、テレフタル酸、シクロヘキサンジカルボン酸、コハク酸、アジピン酸、セバチン酸、アゼライン酸、マロン酸、ｎ－ドデセニルコハク酸、ｎ－ドデシルコハク酸、ｎ－オクチルコハク酸、イソオクテニルコハク酸、イソオクチルコハク酸およびこれらの酸無水物もしくは低級アルキルエステルなどが挙げられる。 Examples of divalent carboxylic acids include maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, malon Examples include acids, n-dodecenyl succinic acid, n-dodecyl succinic acid, n-octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and acid anhydrides or lower alkyl esters thereof.
　３価以上の多価カルボン酸としては、例えば、１，２，４－ベンゼントリカルボン酸、１，２，５－ベンゼントリカルボン酸、２，５，７－ナフタレントリカルボン酸、１，２，４－ナフタレントリカルボン酸、１，２，４－ブタントリカルボン酸、１，２，５－ヘキサントリカルボン酸、１，３－ジカルボキシル－２－メチル－２－メチレンカルボキシプロパン、１，２，４－シクロヘキサントリカルボン酸、テトラ（メチレンカルボキシル）メタン、１，２，７，８－オクタンテトラカルボン酸、ピロメリット酸、エンポール三量体酸およびこれらの酸無水物もしくは低級アルキルエステルなどが挙げられる。
　本発明においては、上記の２価のカルボン酸および３価以上の多価カルボン酸の１種を単独でまたは２種以上を組み合わせて用いることができる。 Examples of the trivalent or higher polyvalent carboxylic acid include 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, and 1,2,4-naphthalene. Tricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,2,4-cyclohexanetricarboxylic acid, Examples thereof include tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, and acid anhydrides or lower alkyl esters thereof.
In the present invention, one of the above divalent carboxylic acids and trivalent or higher polyvalent carboxylic acids can be used alone or in combination of two or more.
　本発明の結着樹脂としてのポリエステル樹脂は、上記のような条件を満たす分子量分布を有する。
　好ましい重量平均分子量（Ｍｗ）は４４０００～５００００であり、好ましい数平均分子量（Ｍｎ）は４５００～５５００であり、好ましいそれらの比Ｍｗ／Ｍｎは８～１０である。 The polyester resin as the binder resin of the present invention has a molecular weight distribution that satisfies the above conditions.
The preferred weight average molecular weight (Mw) is from 44000 to 50000, the preferred number average molecular weight (Mn) is from 4500 to 5500, and the preferred ratio Mw / Mn is from 8 to 10.
　具体的な重量平均分子量（Ｍｗ）は、例えば、４４０００、４４５００、４５０００、４５５００、４６０００、４６５００、４７０００、４７５００、４８０００、４８５００、４９０００、４９５００、５００００である。
　具体的な数平均分子量（Ｍｎ）は、例えば、４５００、４５５０、４６００、４６５０、４７００、４７５０、４８００、４８５０、４９００、４９５０、５０００、５０５０、５１００、５１５０、５２００、５２５０、５３００、５３５０、５４００、５４５０、５５００である。
　具体的な比Ｍｗ／Ｍｎは、例えば、８、８．０５、８．１、８．１５、８．２、８．２５、８．３、８．３５、８．４、８．４５、８．５、８．５５、８．６、８．６５、８．７、８．７５、８．８、８．８５、８．９、８．９５、９、９．０５、９．１、９．１５、９．２、９．２５、９．３、９．３５、９．４、９．４５、９．５、９．５５、９．６、９．６５、９．７、９．７５、９．８、９．８５、９．９、９．９５、１０である。 Specific weight average molecular weights (Mw) are 44000, 44500, 45000, 45500, 46000, 46500, 47000, 47500, 48000, 48500, 49000, 49500, 50000, for example.
The specific number average molecular weight (Mn) is, for example, 4500, 4550, 4600, 4650, 4700, 4750, 4800, 4850, 4900, 4950, 5000, 5050, 5100, 5150, 5200, 5250, 5300, 5350, 5400. , 5450, 5500.
Specific ratios Mw / Mn are, for example, 8, 8.05, 8.1, 8.15, 8.2, 8.25, 8.3, 8.35, 8.4, 8.45, 8 .5, 8.55, 8.6, 8.65, 8.7, 8.75, 8.8, 8.85, 8.9, 8.95, 9, 9.05, 9.1, 9 .15, 9.2, 9.25, 9.3, 9.35, 9.4, 9.45, 9.5, 9.55, 9.6, 9.65, 9.7, 9.75 9.8, 9.85, 9.9, 9.95 and 10.
（着色剤）
　本発明のトナーの着色剤としては、当該技術分野で常用される有機系および無機系の様々な種類および色の顔料および染料を用いることができ、例えば、黒色、白色、黄色、橙色、赤色、紫色、青色および緑色の着色剤が挙げられる。 (Coloring agent)
As the colorant of the toner of the present invention, various kinds of organic and inorganic pigments and dyes commonly used in the technical field can be used. For example, black, white, yellow, orange, red, Examples include purple, blue and green colorants.
　黒色の着色剤としては、例えば、カーボンブラック、酸化銅、二酸化マンガン、アニリンブラック、活性炭、非磁性フェライト、磁性フェライトおよびマグネタイトなどが挙げられる。
　白色の着色剤としては、例えば、亜鉛華、酸化チタン、アンチモン白、硫化亜鉛などが挙げられる。 Examples of the black colorant include carbon black, copper oxide, manganese dioxide, aniline black, activated carbon, nonmagnetic ferrite, magnetic ferrite, and magnetite.
Examples of white colorants include zinc white, titanium oxide, antimony white, and zinc sulfide.
　黄色の着色剤としては、例えば、黄鉛、亜鉛黄、カドミウムイエロー、黄色酸化鉄、ミネラルファストイエロー、ニッケルチタンイエロー、ネーブルイエロー、ナフトールイエローＳ、ハンザイエローＧ、ハンザイエロー１０Ｇ、ベンジジンイエローＧ、ベンジジンイエローＧＲ、キノリンイエローレーキ、パーマネントイエローＮＣＧ、タートラジンレーキ、Ｃ．Ｉ．ピグメントイエロー１２、Ｃ．Ｉ．ピグメントイエロー１３、Ｃ．Ｉ．ピグメントイエロー１４、Ｃ．Ｉ．ピグメントイエロー１５、Ｃ．Ｉ．ピグメントイエロー１７、Ｃ．Ｉ．ピグメントイエロー９３、Ｃ．Ｉ．ピグメントイエロー９４、Ｃ．Ｉ．ピグメントイエロー１３８などが挙げられる。 Examples of yellow colorants include chrome yellow, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navel yellow, naphthol yellow S, Hansa yellow G, Hansa yellow 10G, benzidine yellow G, and benzidine. Yellow GR, Quinoline Yellow Lake, Permanent Yellow NCG, Tartrazine Lake, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 138, and the like.
　橙色の着色剤としては、例えば、赤色黄鉛、モリブデンオレンジ、パーマネントオレンジＧＴＲ、ピラゾロンオレンジ、バルカンオレンジ、インダスレンブリリアントオレンジＲＫ、ベンジジンオレンジＧ、インダスレンブリリアントオレンジＧＫ、Ｃ．Ｉ．ピグメントオレンジ３１、Ｃ．Ｉ．ピグメントオレンジ４３などが挙げられる。 Examples of the orange colorant include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, Vulcan orange, Indanthrene Brilliant Orange RK, Benzidine Orange G, Indanthren Brilliant Orange GK, C.I. I. Pigment orange 31, C.I. I. And CI Pigment Orange 43.
　赤色の着色剤としては、例えば、ベンガラ、カドミウムレッド、鉛丹、硫化水銀、カドミウム、パーマネントレッド４Ｒ、リソールレッド、ピラゾロンレッド、ウオッチングレッド、カルシウム塩、レーキレッドＣ、レーキレッドＤ、ブリリアントカーミン６Ｂ、エオシンレーキ、ローダミンレーキＢ、アリザリンレーキ、ブリリアントカーミン３Ｂ、Ｃ．Ｉ．ピグメントレッド２、Ｃ．Ｉ．ピグメントレッド３、Ｃ．Ｉ．ピグメントレッド５、Ｃ．Ｉ．ピグメントレッド６、Ｃ．Ｉ．ピグメントレッド７、Ｃ．Ｉ．ピグメントレッド１５、Ｃ．Ｉ．ピグメントレッド１６、Ｃ．Ｉ．ピグメントレッド４８：１、Ｃ．Ｉ．ピグメントレッド５３：１、Ｃ．Ｉ．ピグメントレッド５７：１、Ｃ．Ｉ．ピグメントレッド１２２、Ｃ．Ｉ．ピグメントレッド１２３、Ｃ．Ｉ．ピグメントレッド１３９、Ｃ．Ｉ．ピグメントレッド１４４、Ｃ．Ｉ．ピグメントレッド１４９、Ｃ．Ｉ．ピグメントレッド１６６、Ｃ．Ｉ．ピグメントレッド１７７、Ｃ．Ｉ．ピグメントレッド１７８、Ｃ．Ｉ．ピグメントレッド２２２などが挙げられる。 Examples of red colorants include bengara, cadmium red, red lead, mercury sulfide, cadmium, permanent red 4R, risor red, pyrazolone red, watching red, calcium salt, lake red C, lake red D, and brilliant carmine 6B. Eosin Lake, Rhodamine Lake B, Alizarin Lake, Brilliant Carmine 3B, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. And CI Pigment Red 222.
　紫色の着色剤としては、例えば、マンガン紫、ファストバイオレットＢ、メチルバイオレットレーキなどが挙げられる。 Examples of purple colorants include manganese purple, fast violet B, and methyl violet lake.
　青色の着色剤としては、例えば、紺青、コバルトブルー、アルカリブルーレーキ、ビクトリアブルーレーキ、フタロシアニンブルー、無金属フタロシアニンブルー、フタロシアニンブルー部分塩素化物、ファーストスカイブルー、インダスレンブルーＢＣ、Ｃ．Ｉ．ピグメントブルー１５、Ｃ．Ｉ．ピグメントブルー１５：２、Ｃ．Ｉ．ピグメントブルー１５：３、Ｃ．Ｉ．ピグメントブルー１６、Ｃ．Ｉ．ピグメントブルー６０などが挙げられる。 Blue colorants include, for example, bitumen, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, phthalocyanine blue partially chlorinated, first sky blue, induslen blue BC, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 16, C.I. I. And CI Pigment Blue 60.
　緑色の着色剤としては、例えば、クロムグリーン、酸化クロム、ピクメントグリーンＢ、マイカライトグリーンレーキ、ファイナルイエローグリーンＧ、Ｃ．Ｉ．ピグメントグリーン７などが挙げられる。 Examples of the green colorant include chrome green, chromium oxide, pigment green B, micalite green lake, final yellow green G, C.I. I. And CI Pigment Green 7.
　本発明においては、上記の着色剤の１種を単独でまたは２種を組み合わせて用いることができ、それらの組み合わせは異色であっても同色であってもよい。
　また２種以上の着色剤を複合粒子化して用いてもよい。
　複合粒子は、例えば、２種以上の着色剤に適量の水、低級アルコールなどを添加し、ハイスピードミルなどの一般的な造粒機で造粒し、乾燥させることによって製造できる。
　さらに、結着樹脂中に着色剤を均一に分散させるために、マスターバッチ化して用いてもよい。
　複合粒子およびマスターバッチは、乾式混合の際にトナー組成物に混入される。 In the present invention, one of the above colorants may be used alone or in combination of two, and these combinations may be different colors or the same color.
Two or more colorants may be used in the form of composite particles.
The composite particles can be produced, for example, by adding an appropriate amount of water, lower alcohol or the like to two or more colorants, granulating with a general granulator such as a high speed mill, and drying.
Furthermore, in order to disperse the colorant uniformly in the binder resin, it may be used as a master batch.
The composite particles and the master batch are mixed into the toner composition during dry mixing.
　着色剤の配合量は特に限定されないが、結着樹脂１００重量部に対して０．１～２０重量部が好ましく、０．２～１０重量部が特に好ましい。
　着色剤の配合量が上記の範囲内であれば、トナーの各種物性を損なうことなしに、高い画像濃度を有し、画質品位の非常に良好な画像を形成することができる。
　具体的な着色剤の配合量は、結着樹脂１００重量部に対して、例えば、０．１、０．２、０．５、１、２．５、５、７．５、１０、１２．５、１５、１７．５、２０重量部である。 The blending amount of the colorant is not particularly limited, but is preferably 0.1 to 20 parts by weight, particularly preferably 0.2 to 10 parts by weight, based on 100 parts by weight of the binder resin.
If the blending amount of the colorant is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
The specific blending amount of the colorant is, for example, 0.1, 0.2, 0.5, 1, 2.5, 5, 7.5, 10, 12, with respect to 100 parts by weight of the binder resin. 5, 15, 17.5, 20 parts by weight.
（離型剤）
　本発明のトナーの離型剤としては、当該技術分野で常用される離型剤を用いることができ、例えば、パラフィンワックスおよびマイクロクリスタリンワックスならびにそれらの誘導体などの石油系ワックス；フィッシャートロプシュワックス、ポリオレフィンワックス（ポリエチレンワックス、ポリプロピレンワックスなど）、低分子量ポリプロピリンワックスおよびポリオレフィン系重合体ワックス（低分子量ポリエチレンワックスなど）ならびにそれらの誘導体などの炭化水素系合成ワックス；カルナバワックス、ライスワックスおよびキャンデリラワックスならびにそれらの誘導体、木蝋などの植物系ワックス；蜜蝋、鯨蝋などの動物系ワックス；脂肪酸アミドおよびフェノール脂肪酸エステルなどの油脂系合成ワックス；長鎖カルボン酸およびその誘導体；長鎖アルコールおよびその誘導体；シリコーン系重合体；高級脂肪酸などが挙げられる。
　上記の誘導体には、酸化物、ビニル系モノマーとワックスとのブロック共重合物、ビニル系モノマーとワックスとのグラフト変性物などが含まれる。
　本発明においては、上記の離型剤の１種を単独でまたは２種以上を組み合わせて用いることができる。 (Release agent)
As the release agent for the toner of the present invention, release agents commonly used in the art can be used, for example, petroleum waxes such as paraffin wax and microcrystalline wax and derivatives thereof; Fischer-Tropsch wax, polyolefin Hydrocarbon synthetic waxes such as waxes (polyethylene wax, polypropylene wax, etc.), low molecular weight polypropylin waxes and polyolefin polymer waxes (such as low molecular weight polyethylene waxes) and their derivatives; carnauba wax, rice wax and candelilla wax and Derivatives, plant waxes such as wood wax; animal waxes such as beeswax and whale wax; oils and fats synthetic waxes such as fatty acid amides and phenol fatty acid esters; long chain carbo Acid and its derivatives; long-chain alcohols and derivatives thereof; silicone polymer; such as higher fatty acids.
The derivatives include oxides, block copolymers of vinyl monomers and waxes, graft modified products of vinyl monomers and waxes, and the like.
In this invention, 1 type of said mold release agent can be used individually or in combination of 2 or more types.
　離型剤は、融点７０℃以下の炭化水素系離型剤であるのが好ましい。その下限は６０℃程度である。
　融点が７０℃以下であれば、本発明の効果がさらに発揮され、特に低温定着性において好ましい。
　具体的な離型剤の融点は、例えば、７０℃、６９℃、６８℃、６７℃、６６℃、６５℃、６４℃、６３℃、６２℃、６１℃、６０℃である。 The release agent is preferably a hydrocarbon release agent having a melting point of 70 ° C. or lower. The lower limit is about 60 ° C.
If the melting point is 70 ° C. or lower, the effects of the present invention are further exhibited, and this is particularly preferable for low-temperature fixability.
Specific melting points of the release agent are, for example, 70 ° C, 69 ° C, 68 ° C, 67 ° C, 66 ° C, 65 ° C, 64 ° C, 63 ° C, 62 ° C, 61 ° C, 60 ° C.
　離型剤の配合量は特に限定されないが、結着樹脂１００重量部に対して０．２～２０重量部が好ましく、０．５～１０重量部がより好ましく、１．０～８．０重量部が特に好ましい。
　離型剤の配合量が上記の範囲内であれば、トナーの各種物性を損なうことなしに、高い画像濃度を有し、画質品位の非常に良好な画像を形成することができる。
　具体的な離型剤の配合量は、結着樹脂１００重量部に対して、例えば、０．２、０．５、１、２．５、５、７．５、８、１０、１２．５、１５、１７．５、２０重量部である。 The compounding amount of the release agent is not particularly limited, but is preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the binder resin. Part is particularly preferred.
If the amount of the release agent is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
The specific amount of the release agent is, for example, 0.2, 0.5, 1, 2.5, 5, 7.5, 8, 10, 12.5 with respect to 100 parts by weight of the binder resin. 15, 17.5 and 20 parts by weight.
（帯電制御剤）
　本発明のトナーの帯電制御剤としては、当該技術分野で常用される正電荷制御用および負電荷制御用の電荷制御剤を用いることができる。 (Charge control agent)
As the charge control agent for the toner of the present invention, charge control agents for positive charge control and negative charge control which are commonly used in the technical field can be used.
　正電荷制御用の電荷制御剤としては、例えば、ニグロシン染料、塩基性染料、四級アンモニウム塩、四級ホスホニウム塩、アミノピリン、ピリミジン化合物、多核ポリアミノ化合物、アミノシラン、ニグロシン染料およびその誘導体、トリフェニルメタン誘導体、グアニジン塩、アミジン塩などが挙げられる。
　負電荷制御用の電荷制御剤としては、例えば、オイルブラック、スピロンブラックなどの油溶性染料、含金属アゾ化合物、アゾ錯体染料、ナフテン酸金属塩、サリチル酸およびその誘導体の金属錯体および金属塩（金属はクロム、亜鉛、ジルコニウムなど）、ホウ素化合物、脂肪酸石鹸、長鎖アルキルカルボン酸塩、樹脂酸石鹸などが挙げられる。 Examples of charge control agents for controlling positive charge include nigrosine dyes, basic dyes, quaternary ammonium salts, quaternary phosphonium salts, aminopyrines, pyrimidine compounds, polynuclear polyamino compounds, aminosilanes, nigrosine dyes and derivatives thereof, triphenylmethane Derivatives, guanidine salts, amidine salts and the like can be mentioned.
Examples of the charge control agent for controlling the negative charge include oil-soluble dyes such as oil black and spiron black, metal-containing azo compounds, azo complex dyes, naphthenic acid metal salts, metal complexes and metal salts of salicylic acid and its derivatives ( Examples of the metal include chromium, zinc, zirconium, etc.), boron compounds, fatty acid soaps, long-chain alkyl carboxylates, and resin acid soaps.
　本発明においては、上記の帯電制御剤の１種を単独でまたは２種以上を組み合わせて用いることができる。
　帯電制御剤の配合量は特に限定されないが、結着樹脂１００重量部に対して０．５～３重量部が好ましく、１～２重量部が特に好ましい。
　帯電制御剤の配合量が上記の範囲内であれば、トナーの各種物性を損なうことなしに、高い画像濃度を有し、画質品位の非常に良好な画像を形成することができる。
　具体的な帯電制御剤の配合量は、結着樹脂１００重量部に対して、例えば、０．５、０．７５、１、１．２５、１．５、２、２．２５、２．５、３重量部である。 In the present invention, one of the above charge control agents may be used alone or in combination of two or more.
The blending amount of the charge control agent is not particularly limited, but is preferably 0.5 to 3 parts by weight, particularly preferably 1 to 2 parts by weight with respect to 100 parts by weight of the binder resin.
If the blending amount of the charge control agent is within the above range, an image having a high image density and a very good image quality can be formed without impairing various physical properties of the toner.
The specific blending amount of the charge control agent is, for example, 0.5, 0.75, 1, 1.25, 1.5, 2, 2.25, 2.5 with respect to 100 parts by weight of the binder resin. 3 parts by weight.
（トナーの製造方法）
　本発明のトナーは、少なくとも、結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を機械的剪断力を付加して溶融混練することにより製造されるのが好ましい。すなわち、一般的なトナーの製造方法、例えば粉砕法などの乾式法、懸濁重合法、乳化凝集法、分散重合法、溶解懸濁法および溶融乳化法などの湿式法のような公知の方法により作製することができる。これらの中でも、粉砕法は、湿式などに比較して工程が少なく設備投資額も少なく済むなどの点で特に好ましい。
　以下粉砕法によるトナー作製方法を説明する。 (Toner production method)
The toner of the present invention is preferably produced by melting and kneading at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent while applying a mechanical shearing force. That is, by a known method such as a general toner production method, for example, a dry method such as a pulverization method, a suspension polymerization method, an emulsion aggregation method, a dispersion polymerization method, a dissolution suspension method, and a melt emulsion method. Can be produced. Among these, the pulverization method is particularly preferable in that the number of steps is small and the amount of capital investment is small as compared with the wet method.
Hereinafter, a toner preparation method using a pulverization method will be described.
　粉砕法によるトナーの作製では、少なくとも結着樹脂、着色剤、離型剤および帯電制御剤を含むトナー材料を混合・溶融混練して混練物を得、次いで混練物を冷却固化・粉砕し、その後必要に応じて分級などの粒度調整を行い、トナー粒子を得る。 In the preparation of toner by a pulverization method, a toner material containing at least a binder resin, a colorant, a release agent and a charge control agent is mixed and melt-kneaded to obtain a kneaded product, and then the kneaded product is cooled, solidified and pulverized, and then If necessary, particle size adjustment such as classification is performed to obtain toner particles.
　混合は乾式が好ましく、混合機としては、当該技術分野で常用される公知の装置を使用でき、例えば、ヘンシェルミキサ（商品名、三井鉱山株式会社製）、スーパーミキサ（商品名、株式会社カワタ製）、メカノミル（商品名、岡田精工株式会社製）などのヘンシェルタイプの混合装置、オングミル（商品名、ホソカワミクロン株式会社製）、ハイブリダイゼーションシステム（商品名、株式会社奈良機械製作所製）、コスモシステム（商品名、川崎重工業株式会社製）などの混合装置が挙げられる。 The mixing is preferably a dry type, and a known apparatus commonly used in the technical field can be used as the mixer. For example, a Henschel mixer (trade name, manufactured by Mitsui Mining Co., Ltd.), a super mixer (trade name, manufactured by Kawata Co., Ltd.) ), Mechanomill (trade name, manufactured by Okada Seiko Co., Ltd.) and other Henschel type mixing devices, Ong mill (trade name, manufactured by Hosokawa Micron Co., Ltd.), hybridization system (trade name, manufactured by Nara Machinery Co., Ltd.), Cosmo System ( And a mixing device such as a product name, manufactured by Kawasaki Heavy Industries, Ltd.).
　混練機としては、当該技術分野で常用される公知の装置を使用でき、例えば、二軸押出機、三本ロール、ラボブラストミルなどの一般的な混練機が挙げられる。具体的には、例えば、ＴＥＭ－１００Ｂ（商品名、東芝機械株式会社製）、ＰＣＭ－６５／８７、ＰＣＭ－３０（以上いずれも商品名、株式会社池貝製）などの１軸または２軸のエクストルーダ、ニーデックス（商品名、三井鉱山株式会社製）などのオープンロール方式の混練機が挙げられ、これらの中でも、オープンロール方式の混練機は、混練時のシェア（負荷）が強く顔料などの色材および離型剤などを高分散できる点で好ましい。特に、離型剤の高分散は、ホットオフセットに有効に働く。
　また、混練時の高負荷により、定着画像の光沢に悪影響を及ぼす結着樹脂の高分子成分は、分子鎖が切断され、定着に有効でかつホットオフセットに強い分子量の樹脂に変換される。一方、結着樹脂の低分子量成分は、混練時の高負荷に対して分子量分布を殆ど変えず、定着に有効な分子量成分が切断されて耐久性が悪化することはない。 As the kneader, a known apparatus commonly used in the technical field can be used, and examples thereof include general kneaders such as a twin-screw extruder, a three-roller, and a lab blast mill. Specifically, for example, TEM-100B (trade name, manufactured by Toshiba Machine Co., Ltd.), PCM-65 / 87, PCM-30 (all of which are trade names, manufactured by Ikegai Co., Ltd.), etc. Open roll type kneaders such as Extruder and Needex (trade name, manufactured by Mitsui Mining Co., Ltd.) can be mentioned. Among these, open roll type kneaders have a strong share (load) during kneading, such as pigments. This is preferable in that a colorant, a release agent and the like can be highly dispersed. In particular, the high dispersion of the release agent works effectively for hot offset.
In addition, due to the high load during kneading, the polymer component of the binder resin that adversely affects the gloss of the fixed image is converted to a resin having a molecular weight that is effective for fixing and resistant to hot offset. On the other hand, the low molecular weight component of the binder resin hardly changes the molecular weight distribution with respect to a high load during kneading, and the molecular weight component effective for fixing is not cut and durability is not deteriorated.
　粉砕機としては、当該技術分野で常用される公知の装置を使用でき、例えば、超音速ジェット気流を利用して粉砕するジェット式粉砕機、高速で回転する回転子（ロータ）と固定子（ライナ）との間に形成される空間に固化物を導入して粉砕する衝撃式粉砕機が挙げられる。 As the pulverizer, a known apparatus commonly used in the technical field can be used. For example, a jet pulverizer that pulverizes using a supersonic jet stream, a rotor (rotor) that rotates at high speed, and a stator (liner). And an impact type pulverizer that introduces and crushes the solidified material into the space formed between the two.
　分級には、当該技術分野で常用される公知の装置、特に旋回式風力分級機（ロータリー式風力分級機）のような遠心力および風力により過粉砕トナー母粒子を除去できる分級機を使用できる。 For the classification, a well-known apparatus commonly used in the technical field, in particular, a classifier capable of removing excessively pulverized toner base particles by centrifugal force and wind force, such as a swirling wind classifier (rotary wind classifier), can be used.
　得られるトナー粒子の体積平均粒径は、好ましくは３～１０μｍであり、より好ましくは５～８μｍである。
　トナー粒子の体積平均粒径が上記の範囲内であれば、高精細な画像を長期にわたって安定して形成することができる。トナー粒子の体積平均粒径が３μｍ未満では、トナー粒子の粒径が小さくなり過ぎ、高帯電化および低流動化が起こり、感光体にトナーを安定して供給することができなくなり、地肌かぶりおよび画像濃度の低下などが発生するおそれがある。一方、トナー粒子の平均粒径が１０μｍを超えると、トナー粒子の粒径が大きくなり過ぎ、高精細な画像が得られないことがある。
　具体的なトナー粒子の体積平均粒径は、例えば、３μｍ、４μｍ、５μｍ、６μｍ、７μｍ、８μｍ、９μｍ、１０μｍである。 The obtained toner particles preferably have a volume average particle size of 3 to 10 μm, more preferably 5 to 8 μm.
If the volume average particle diameter of the toner particles is within the above range, a high-definition image can be stably formed over a long period of time. When the volume average particle size of the toner particles is less than 3 μm, the particle size of the toner particles becomes too small, and high charging and low fluidity occur, and the toner cannot be stably supplied to the photoreceptor. There is a risk of image density reduction. On the other hand, if the average particle size of the toner particles exceeds 10 μm, the particle size of the toner particles becomes too large and a high-definition image may not be obtained.
Specific volume average particle diameters of the toner particles are, for example, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, and 10 μm.
　本発明のトナーは、外添剤をさらに含む１成分現像剤、または外添剤およびキャリアをさらに含む２成分現像剤として用いられる。
（外添剤）
　本発明のトナーは、その搬送性および帯電性ならびにトナーを二成分現像剤にする場合のキャリアとの撹拌性などを向上させるために外添剤が用いられる。
　外添剤としては、当該技術分野で常用される外添剤を用いることができ、例えば、シリカ、酸化チタンなどが挙げられ、シリコーン樹脂、シランカップリング剤などにより表面処理（疎水化処理）されているものが好ましい。
　外添剤の配合量は、トナー１００重量部に対して１～１０重量部が好ましく、２～５重量部がより好ましい。
　具体的な外添剤の配合量は、トナー１００重量部に対して、例えば、１、２、３、４、５、６、７、８、９、１０重量部である。 The toner of the present invention is used as a one-component developer further containing an external additive, or a two-component developer further containing an external additive and a carrier.
(External additive)
In the toner of the present invention, an external additive is used in order to improve the transportability and chargeability of the toner and the stirrability with the carrier when the toner is used as a two-component developer.
As the external additive, external additives commonly used in the technical field can be used, and examples thereof include silica, titanium oxide, and the like, and surface treatment (hydrophobization treatment) is performed with a silicone resin, a silane coupling agent, or the like. Are preferred.
The amount of the external additive is preferably 1 to 10 parts by weight and more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the toner.
The specific amount of the external additive is, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 parts by weight with respect to 100 parts by weight of the toner.
（キャリア）
　本発明のトナーは、１成分現像剤、２成分現像剤のいずれの形態でも使用することができる。
　２成分現像剤として使用する場合、トナーにさらにキャリアを配合する。
　キャリアとしては、当該技術分野で常用されるキャリアを用いることができ、例えば、鉄、銅、亜鉛、ニッケル、コバルト、マンガン、クロムなどからなる単独または複合フェライトおよびキャリア芯粒子を被覆物質で表面被覆したものなどが挙げられる。
　被覆物質としては、当該技術分野で常用される被覆物質を用いることができ、例えば、ポリテトラフルオロエチレン、モノクロロトリフルオロエチレン重合体、ポリフッ化ビニリデン、シリコーン樹脂、ポリエステル、ジターシャーリーブチルサリチル酸の金属化合物、スチレン系樹脂、アクリル系樹脂、ポリアミド、ポリビニルブチラール、ニグロシン、アミノアクリレート樹脂、塩基性染料、塩基性染料のレーキ物、シリカ微粉末、アルミナ微粉末などが挙げられる。これらの被覆物質は、トナー成分に応じて選択し、１種を単独でまたは２種以上を組み合わせて用いることができる。 (Career)
The toner of the present invention can be used in any form of a one-component developer and a two-component developer.
When used as a two-component developer, a carrier is further added to the toner.
As the carrier, a carrier commonly used in the technical field can be used. For example, a single or composite ferrite composed of iron, copper, zinc, nickel, cobalt, manganese, chromium, etc. and carrier core particles are coated with a coating material. And the like.
As the coating material, a coating material commonly used in the art can be used. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester, and a metal compound of ditertiary butylsalicylic acid Styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, aminoacrylate resin, basic dye, basic dye lake, silica fine powder, alumina fine powder, and the like. These coating materials are selected according to the toner component, and can be used alone or in combination of two or more.
　キャリアの平均粒径は、好ましくは１０～１００μｍ、さらに好ましくは２０～５０μｍである。
　具体的なキャリアの体積平均粒径は、例えば、１０μｍ、１５μｍ、２０μｍ、２５μｍ、３０μｍ、３５μｍ、４０μｍ、４５μｍ、５０μｍ、５５μｍ、６０μｍ、６５μｍ、７０μｍ、７５μｍ、８０μｍ、８５μｍ、９０μｍ、９５μｍ、１００μｍである。
　キャリアの配合量は、トナー１００重量部に対して４～１５重量部が好ましく、５～１０重量部がより好ましい。
　具体的なキャリアの配合量は、トナー１００重量部に対して、例えば、４、５、６、７、８、９、１０、１１、１２、１３、１４、１５重量部である。 The average particle diameter of the carrier is preferably 10 to 100 μm, more preferably 20 to 50 μm.
Specific volume average particle diameters of the carrier are, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm. It is.
The blending amount of the carrier is preferably 4 to 15 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the toner.
Specific amounts of the carrier are, for example, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 parts by weight with respect to 100 parts by weight of the toner.
（２）画像形成装置
　本発明の画像形成装置は、本発明の電子写真用トナーを用いたことを特徴とする。 (2) Image forming apparatus The image forming apparatus of the present invention is characterized by using the electrophotographic toner of the present invention.
　本発明の画像形成装置について、その一例を示す概略断面図である図１を用いて詳細に説明する。なお、図１におけるＡ方向は、画像形成装置１００の正面から裏面に向けた方向である。 The image forming apparatus of the present invention will be described in detail with reference to FIG. 1, which is a schematic sectional view showing an example thereof. 1 is a direction from the front side of the image forming apparatus 100 toward the back side.
　画像形成装置１００は、電子写真方式のプリンタであり、４つの可視像形成ユニット（イエロー可視像形成ユニット１１０Ｙ、マゼンタ可視像形成ユニット１１０Ｍ、シアン可視像形成ユニット１１０Ｃおよびブラック可視像形成ユニット１１０Ｂ：これらを合わせて「可視像形成ユニット１１０」ともいう）を記録紙搬送路に沿って配列した所謂タンデム式のプリンタである。
　具体的には、可視像形成ユニット１１０に記録紙Ｐ（被加熱材、記録媒体）を供給する供給トレイ１２０と定着装置４０との間に形成される記録紙Ｐの搬送路に沿って４つの可視像形成ユニット１１０が配設されている。そして、記録紙搬送手段１３０である無端状の搬送ベルト１３３によって搬送される記録紙Ｐに対して各可視像形成ユニット１１０が各色トナー像を重ねて転写し、その後、定着装置４０が記録紙Ｐに対してトナー像を定着し、これによりフルカラー画像が形成される。 The image forming apparatus 100 is an electrophotographic printer, and includes four visible image forming units (yellow visible image forming unit 110Y, magenta visible image forming unit 110M, cyan visible image forming unit 110C, and black visible image). Forming unit 110B: a so-called tandem printer in which these are also referred to as “visible image forming unit 110” along the recording paper conveyance path.
Specifically, 4 along the conveyance path of the recording paper P formed between the supply tray 120 for supplying the recording paper P (heated material, recording medium) to the visible image forming unit 110 and the fixing device 40. Two visible image forming units 110 are provided. Then, each visible image forming unit 110 superimposes and transfers the respective color toner images onto the recording paper P conveyed by the endless conveying belt 133 which is the recording paper conveying means 130, and then the fixing device 40 causes the recording paper to be transferred. The toner image is fixed to P, thereby forming a full color image.
　搬送ベルト１３３は、駆動ローラ１３１とアイドリングローラ１３２とに架けられており、所定の周速度（１５０～４００ｍｍ／秒程度、例えば２２０ｍｍ／秒）に制御されて周回する。記録紙Ｐは、周回している搬送ベルト１３０に静電吸着することによって搬送される。 The conveying belt 133 is stretched around the driving roller 131 and the idling roller 132, and rotates around at a predetermined peripheral speed (about 150 to 400 mm / second, for example, 220 mm / second). The recording paper P is transported by electrostatic adsorption to the circulating transport belt 130.
　各可視像形成ユニット１１０においては、感光体ドラム１１１が備えられ、この感光体ドラム１１１の周囲に、帯電ローラ１１２、露光手段（レーザ光照射手段）１１３、現像器１１４、転写ローラ１１５、クリーナー１１６が配置されている。 Each visible image forming unit 110 is provided with a photosensitive drum 111, and around the photosensitive drum 111, a charging roller 112, an exposure means (laser light irradiation means) 113, a developing device 114, a transfer roller 115, a cleaner. 116 is arranged.
　可視像形成ユニット１１０Ｙの現像器Ｙにはイエロートナーを含む現像剤が収容され、可視像形成ユニット１１０Ｍの現像器Ｍにはマゼンタトナーを含む現像剤が収容され、可視像形成ユニット１１０Ｃの現像器Ｃにはシアントナーを含む現像剤が収容され、可視像形成ユニット１１０Ｂの現像器Ｂにはブラックトナーを含む現像剤が収容されている。
　なお、現像剤は、一成分現像剤、二成分現像剤のいずれであってもよい。
　また、一成分現像剤に含まれるトナーは、磁性のいずれであってもよく、二成分現像剤に含まれるキャリアは、磁性のいずれであってもよい。 The developer Y of the visible image forming unit 110Y contains a developer containing yellow toner, the developer M of the visible image forming unit 110M contains a developer containing magenta toner, and the visible image forming unit 110C. The developer C contains a developer containing cyan toner, and the developer B of the visible image forming unit 110B contains a developer containing black toner.
The developer may be either a one-component developer or a two-component developer.
Further, the toner contained in the one-component developer may be any magnetic, and the carrier contained in the two-component developer may be any magnetic.
　そして、各可視像形成ユニット１１０において、記録紙Ｐ上にトナー像が転写されるが、この転写の手順は以下の通りである。まず、帯電ローラ１１２によって感光体ドラム１１１表面を一様に帯電し、その後、レーザ光照射手段１１３によって画像情報に応じて感光体ドラム１１１表面をレーザで露光して静電潜像を形成する。さらにその後、感光体ドラム１１１表面の静電潜像に対して現像器１１４によってトナーが供給される。これにより、前記静電潜像が現像（顕像化）されてトナー画像が生成される。そして、感光体ドラム１１１表面に生成されたトナー画像は、このトナー画像のトナーとは逆極性のバイアス電圧が印加された転写ローラ１１５によって、搬送ベルト（搬送手段）１３０にて搬送される記録紙Ｐに順次転写されるようになっている。 In each visible image forming unit 110, the toner image is transferred onto the recording paper P. The transfer procedure is as follows. First, the surface of the photosensitive drum 111 is uniformly charged by the charging roller 112, and then the surface of the photosensitive drum 111 is exposed by a laser according to the image information by the laser light irradiation unit 113 to form an electrostatic latent image. Thereafter, the developing device 114 supplies toner to the electrostatic latent image on the surface of the photosensitive drum 111. Thus, the electrostatic latent image is developed (visualized) to generate a toner image. The toner image generated on the surface of the photosensitive drum 111 is recorded on the recording paper conveyed by the conveying belt (conveying means) 130 by the transfer roller 115 to which a bias voltage having a polarity opposite to that of the toner of the toner image is applied. The images are sequentially transferred to P.
　その後、記録紙Ｐは、搬送ベルト１３３の湾曲箇所（駆動ローラ１３１に巻き付いている部分）において搬送ベルト１３３から剥離し、定着装置４０に搬送される。さらに、定着装置４０において、所定の温度に加熱された定着ベルトによって記録紙Ｐに適度な温度と圧力とが与えられる。これにより、記録紙Ｐのトナーは溶解し、トナーが記録紙Ｐに定着し、記録紙Ｐ上に堅牢な画像が形成される。 Thereafter, the recording paper P is peeled off from the conveyance belt 133 at a curved portion of the conveyance belt 133 (portion wound around the driving roller 131) and conveyed to the fixing device 40. Further, in the fixing device 40, an appropriate temperature and pressure are applied to the recording paper P by the fixing belt heated to a predetermined temperature. As a result, the toner on the recording paper P is dissolved, the toner is fixed on the recording paper P, and a robust image is formed on the recording paper P.
　以下に実施例および比較例により本発明を具体的に説明するが、これらの実施例により本発明が限定されるものではない。
　実施例および比較例において、各物性値を以下に示す方法により測定した。
　なお、複数のポリエステル樹脂を併用する場合には、予め調製しておいた混合樹脂について測定した。 EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples.
In Examples and Comparative Examples, each physical property value was measured by the following method.
In addition, when using together some polyester resin, it measured about the mixed resin prepared previously.
［ポリエステル樹脂のガラス転移温度（Ｔｇ）：℃］
　示差走査熱量計（セイコー電子工業株式会社（現　セイコーインスツル株式会社）製、型式：ＤＳＣ２１０）を用いて、昇温速度１０℃／分で温度２００℃まで昇温し、降温速度１００℃／分で温度－１０℃まで冷却した樹脂試料を３分間放置し、その後、昇温速度６０℃／分で温度２５℃まで昇温し２分間保持して、昇温速度１０℃／分で加熱しながら測定を開始する。ガラス転移点以下のベースラインの延長線とピークの立ち上がり部分からピークの頂点までの間の最大傾斜を示す接線との交点の温度をガラス転移点（℃）とする。 [Glass transition temperature (Tg) of polyester resin: ° C.]
Using a differential scanning calorimeter (Seiko Electronics Co., Ltd. (current Seiko Instruments Inc.), model: DSC210), the temperature was raised to 200 ° C. at a temperature rising rate of 10 ° C./min, and the temperature decreasing rate was 100 ° C./min. The resin sample cooled to −10 ° C. was allowed to stand for 3 minutes, and then heated to a temperature of 25 ° C. at a temperature rising rate of 60 ° C./minute, held for 2 minutes, and heated at a temperature rising rate of 10 ° C./minute. Start measurement. The glass transition point (° C.) is defined as the temperature at the intersection of the base line extension below the glass transition point and the tangent indicating the maximum slope between the peak rising portion and the peak apex.
［ポリエステル樹脂の軟化温度（Ｔｍ）：℃］
　流動特性評価装置高化式フローテスター（株式会社島津製作所製、型式：ＣＦＴ－５００Ｄ）を用いて、樹脂試料１ｇを昇温速度６℃／分で加熱しながら、プランジャーにより１．９６ＭＰａの荷重を与え、直径１ｍｍ、長さ１ｍｍのノズルを押し出すようにして、フローテスターのプランジャー降下量（流れ値）－温度曲線を描き、そのＳ字曲線の高さをｈとするときｈ／２に対応する温度（樹脂の半分が流出した温度）を軟化点（℃）とする。 [Softening temperature of polyester resin (Tm): ° C]
A 1.96 MPa load was applied by a plunger while heating 1 g of a resin sample at a heating rate of 6 ° C./min using a flow characteristic evaluation device Koka-type flow tester (manufactured by Shimadzu Corporation, model: CFT-500D). Draw a nozzle with a diameter of 1 mm and a length of 1 mm to draw a plunger drop amount (flow value) -temperature curve of the flow tester, and when the height of the S-curve is h, h / 2 The corresponding temperature (temperature at which half of the resin flows out) is defined as the softening point (° C.).
［ポリエステル樹脂のゲル成分率：％］
　ポリエステル樹脂０．５ｇを秤量し、１級テトロヒドロフラン１８ｍｌとスターラーピースと共に容量２０ｍｌスクリュー管瓶に入れて３０分間攪拌する。予め重量を測定したＰＴＦＥろ紙（アドバンテック社製、製品名：ＰＦ０２０）をセットした桐山ロートに得られた樹脂溶液を透過させ、ＰＴＦＥろ紙を充分に乾燥させる。不溶解成分ごとＰＴＦＥろ紙の重量を測定し、次式によりゲル成分率（％）を計算する。
　ゲル成分率（％）＝
　［（不溶解成分重量＋ろ紙重量）－（透過処理前のろ紙重量）］／０．５ｇ×１００ [Gel component ratio of polyester resin:%]
0.5 g of polyester resin is weighed and placed in a 20 ml screw tube bottle together with 18 ml of primary tetrohydrofuran and a stirrer piece and stirred for 30 minutes. The resin solution obtained is passed through a Kiriyama funnel set with PTFE filter paper (product name: PF020, manufactured by Advantech Co., Ltd.) whose weight has been measured in advance, and the PTFE filter paper is sufficiently dried. The weight of PTFE filter paper is measured together with the insoluble components, and the gel component ratio (%) is calculated by the following formula.
Gel component ratio (%) =
[(Insoluble component weight + filter paper weight) − (filter paper weight before permeation treatment)] / 0.5 g × 100
［ポリエステル樹脂の分子量分布］
　濃度０．５ｇ／１００ｍＬになるように樹脂試料をテトラヒドロフランに溶解させ、得られた溶液をポアサイズ２μｍのフッ素樹脂フィルター（住友電気工業株式会社製、品番：ＦＰ－２００）を用いて濾過して不溶解成分を除いて試料溶液とする。
　ゲルパーミエーションクロマトグラフィー（ＧＰＣ）装置（東ソー株式会社製、型式：HLC-8320GPC EcoSEC）に、溶解液としてテトラヒドロフランを毎分１ｍＬの流速で流通させ、温度４０℃のカラム恒温槽（東ソー株式会社製、型式：ＣＯ－８０１０）中で分析カラム（東ソー株式会社製、型式：ＧＭＨＸＬ＋Ｇ３０００ＨＸＬ）を安定化させ、その分析カラムに試料溶液１００μＬを注入し測定する。数種類の単分散ポリスチレンを標準試料として予め作成した検量線に基づいて、試料の数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）およびそれらの比率（Ｍｗ／Ｍｎ）を算出する。
　また、得られた分子量分布から、１×１０6以上の高分子量の重量割合（％）、１×１０5.3以上の高分子量の重量割合（％）、１×１０3.6以下の低分子量の重量割合（％）およびメインピークの半値幅の両端を結ぶ面積割合（半値幅面積：％）を算出する。 [Molecular weight distribution of polyester resin]
A resin sample is dissolved in tetrahydrofuran to a concentration of 0.5 g / 100 mL, and the resulting solution is filtered using a fluororesin filter having a pore size of 2 μm (manufactured by Sumitomo Electric Industries, Ltd., product number: FP-200). A sample solution is prepared by removing dissolved components.
Through a gel permeation chromatography (GPC) apparatus (manufactured by Tosoh Corporation, model: HLC-8320GPC EcoSEC), tetrahydrofuran as a solution was circulated at a flow rate of 1 mL / min, and a column thermostat (manufactured by Tosoh Corporation) at a temperature of 40 ° C. , Model: CO-8010), an analytical column (manufactured by Tosoh Corporation, model: GMHXL + G3000HXL) is stabilized, and 100 μL of a sample solution is injected into the analytical column and measured. The number average molecular weight (Mn), the weight average molecular weight (Mw) and the ratio (Mw / Mn) of the sample are calculated based on a calibration curve prepared in advance using several types of monodisperse polystyrene as a standard sample.
Further, from the obtained molecular weight distribution, a high molecular weight weight ratio (%) of 1 × 10 6 or higher, a high molecular weight weight ratio (%) of 1 × 10 5.3 or higher, and a low molecular weight weight ratio of 1 × 10 3.6 or lower. (%) And the area ratio (half-width area:%) connecting both ends of the half-width of the main peak are calculated.
［トナー粒子の体積平均粒径（μｍ）および変動係数］
　粒度分布測定装置（ベックマンコールター社製、型式：コールターマルチサイザーII）を用いて、アパチャー径：１００μｍ、測定粒径範囲：２～６０μｍ、解析ソフト（ベックマンコールター社製、型式：コールターマルチサイザーアキュコンプ　バージョン１．１９）、電解液（ベックマンコールター社製、型式：アイソトンII）、分散液ポリオキシエチレンラウリルエーテルＨＬＢ１３．６（花王株式会社製、品番：エマルゲン１０９Ｐ）５％電解液の条件で、分散液５ｍｌに測定試料１０ｍｇを添加し、超音波分散機にて１分間分散させ、その後電解液２５ｍｌを添加し、さらに超音波分散機にて１分間分散させ、ビーカーに電解液１００ｍｌと分散液を加え、３万個の粒子の粒径を２０秒で測定できる濃度で、３万個の粒子を測定し、その粒度分布を求める。得られた粒度分布から体積平均粒径（μｍ）および変動係数を算出する。 [Volume average particle diameter (μm) and coefficient of variation of toner particles]
Using a particle size distribution analyzer (Beckman Coulter, model: Coulter Multisizer II), aperture diameter: 100 μm, measured particle size range: 2-60 μm, analysis software (Beckman Coulter, model: Coulter Multisizer AccuComp Version 1.19), electrolyte (Beckman Coulter, model: Isoton II), dispersion polyoxyethylene lauryl ether HLB 13.6 (Kao Corporation, product number: Emulgen 109P) 5% electrolyte Add 10 mg of the measurement sample to 5 ml of the liquid, disperse with an ultrasonic disperser for 1 minute, then add 25 ml of the electrolytic solution, further disperse with an ultrasonic disperser for 1 minute, and add 100 ml of the electrolytic solution and the dispersion to the beaker. In addition, measure 30,000 particles at a concentration that can measure the particle size of 30,000 particles in 20 seconds, Determination of the particle size distribution. The volume average particle size (μm) and coefficient of variation are calculated from the obtained particle size distribution.
（トナー粒子の製造）
（実施例１）
　結着樹脂：ポリエステル樹脂１（Ｔｇ：５８℃、Ｔｍ：１３０℃、ゲル成分率：２％）　９１重量部
　着色剤：銅フタロシアニン（ピグメントブルー１５：３）　５重量部
　離型剤：無極性パラフィンワックス（日本精▲蝋▼株式会社製、型番：ＨＮＰ－１１）　３重量部
　帯電制御剤：サリチル酸系化合物（オリエント化学工業株式会社製、商品名：ボントロンＥ８４）　１重量部 (Manufacture of toner particles)
Example 1
Binder resin: Polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) 91 parts by weight Colorant: Copper phthalocyanine (Pigment Blue 15: 3) 5 parts by weight Release agent: Nonpolar paraffin Wax (manufactured by Nippon Seisaku Co., Ltd., model number: HNP-11) 3 parts by weight Charge control agent: salicylic acid compound (trade name: Bontron E84, manufactured by Orient Chemical Co., Ltd.) 1 part by weight
　ヘンシェルミキサ（三井鉱山株式会社（現　日本コークス工業株式会社）製、型式：ＦＭ２０Ｃ）を用いて、上記のトナー原料を３分間、前混合した後、二軸押出機（株式会社池貝製、型式：ＰＣＭ－３０）を用いて、シリンダ設定温度１２０℃、バレル回転数１５０ｒｐｍ、原料供給速度１５ｋｇ／時間で溶融混練して溶融混練物６ｋｇを得た。
　得られた溶融混練物を、冷却ベルトで冷却させた後、φ２ｍｍのスクリーンを有する粗砕機（ＴＨＥ ＯＲＩＥＮＴ ＣＯ. ＬＴＤ.製、型式：ＶＭ－１６）を用いて粗粉砕し、次いでジェット式粉砕機（日本ニューマチック工業株式会社製、型式：ＩＤＳ－２）を用いて微粉砕し、さらにエルボージェット分級機（日鉄鉱業株式会社製、型式：ＥＪ－ＬＡＢＯ）を用いて分級して、実施例１のトナー粒子（体積平均粒径６．９μｍ、変動係数２２）４ｋｇを得た。 Using a Henschel mixer (manufactured by Mitsui Mining Co., Ltd. (currently Nihon Coke Kogyo Co., Ltd., model: FM20C), the above toner raw material was premixed for 3 minutes, and then a twin-screw extruder (manufactured by Ikekai Co., Ltd., model: PCM-30) was melt-kneaded at a cylinder setting temperature of 120 ° C., a barrel rotation speed of 150 rpm, and a raw material supply speed of 15 kg / hour to obtain 6 kg of a melt-kneaded product.
The obtained melt-kneaded product is cooled by a cooling belt, and then coarsely pulverized using a coarse pulverizer (THE ORIENT CO. LTD., Model: VM-16) having a 2 mm screen, and then a jet pulverizer (Nippon Pneumatic Kogyo Co., Ltd., Model: IDS-2) Finely pulverized, and further elbow jet classifier (Nittetsu Mining Co., Ltd., Model: EJ-LABO) 4 kg of 1 toner particle (volume average particle size 6.9 μm, coefficient of variation 22) was obtained.
（実施例２）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１００℃、バレル回転数２００ｒｐｍ、原料供給速度２０ｋｇ／時間に変更したこと以外は実施例１と同様にして、実施例２のトナー粒子（体積平均粒径６．９μｍ、変動係数２１）４ｋｇを得た。 (Example 2)
The toner particles (volume) of Example 2 were the same as Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour. An average particle size of 6.9 μm and a coefficient of variation of 21) 4 kg were obtained.
（実施例３）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１２０℃、バレル回転数１５０ｒｐｍ、原料供給速度を２０ｋｇ／時間に変更したこと以外は実施例１と同様にして、実施例３のトナー粒子（体積平均粒径７．０μｍ、変動係数２４）４ｋｇを得た。 (Example 3)
The toner particles of Example 3 were the same as Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 120 ° C., a barrel rotation speed of 150 rpm, and a raw material supply speed of 20 kg / hour. Volume average particle size 7.0 μm, coefficient of variation 24) 4 kg was obtained.
（実施例４）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１２０℃、バレル回転数を２００ｒｐｍ、原料供給速度を２０ｋｇ／時間に変更したこと以外は実施例１と同様にして、実施例４のトナー粒子（体積平均粒径６．８μｍ、変動係数２１）４ｋｇを得た。 (Example 4)
Toner particles of Example 4 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 120 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour. (Volume average particle diameter 6.8 μm, coefficient of variation 21) 4 kg was obtained.
（実施例５）
　ポリエステル樹脂１の代わりに、ポリエステル樹脂２（Ｔｇ：５２℃、Ｔｍ：１２５℃、ゲル成分率：２％）を用いたこと以外は実施例１と同様にして、実施例５のトナー粒子（体積平均粒径６．７μｍ、変動係数２３）４ｋｇを得た。 (Example 5)
The toner particles (volume) of Example 5 were the same as Example 1 except that polyester resin 2 (Tg: 52 ° C., Tm: 125 ° C., gel component ratio: 2%) was used instead of polyester resin 1. An average particle size of 6.7 μm and a coefficient of variation of 23) 4 kg were obtained.
（実施例６）
　ポリエステル樹脂１の代わりに、ポリエステル樹脂３（Ｔｇ：６５℃、Ｔｍ：１３８℃、ゲル成分率：５％）を用いたこと以外は実施例１と同様にして、実施例６のトナー粒子（体積平均粒径６．９μｍ、変動係数２４）４ｋｇを得た。 (Example 6)
The toner particles (volume) of Example 6 were the same as Example 1 except that polyester resin 3 (Tg: 65 ° C., Tm: 138 ° C., gel component ratio: 5%) was used instead of polyester resin 1. An average particle size of 6.9 μm and a coefficient of variation of 24) 4 kg were obtained.
（比較例１）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１２０℃、バレル回転数１００ｒｐｍ、原料供給速度１５ｋｇ／時間に変更したこと以外は実施例１と同様にして、比較例１のトナー粒子（体積平均粒径６．７μｍ、変動係数２１）４ｋｇを得た。 (Comparative Example 1)
The toner particles (volume of Comparative Example 1) were the same as in Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder set temperature of 120 ° C., a barrel rotation speed of 100 rpm, and a raw material supply speed of 15 kg / hour. An average particle size of 6.7 μm and a coefficient of variation of 21) 4 kg were obtained.
（比較例２）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１００℃、バレル回転数２００ｒｐｍ、原料供給速度２０ｋｇ／時間に変更し、ポリエステル樹脂１の９１重量部の代わりに、ポリエステル樹脂１（Ｔｇ：５８℃、Ｔｍ：１３０℃、ゲル成分率：２％）６４重量部およびポリエステル樹脂４（Ｔｇ：５２℃、Ｔｍ：１２０℃、ゲル成分率：７％）２７重量部（重量比７：３）を用いたこと以外は実施例１と同様にして、比較例２のトナー粒子（体積平均粒径６．９μｍ、変動係数２３）４ｋｇを得た。 (Comparative Example 2)
The melt kneading conditions of the twin-screw extruder were changed to a cylinder set temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour, and instead of 91 parts by weight of the polyester resin 1, polyester resin 1 (Tg: 58 C, Tm: 130 ° C, gel component ratio: 2%) and polyester resin 4 (Tg: 52 ° C, Tm: 120 ° C, gel component ratio: 7%) 27 parts by weight (weight ratio 7: 3) 4 kg of toner particles (volume average particle size 6.9 μm, coefficient of variation 23) of Comparative Example 2 were obtained in the same manner as Example 1 except that it was used.
（比較例３）
　ポリエステル樹脂１の９１重量部の代わりに、ポリエステル樹脂１（Ｔｇ：５８℃、Ｔｍ：１３０℃、ゲル成分率：２％）６４重量部およびポリエステル樹脂４（Ｔｇ：５２℃、Ｔｍ：１２０℃、ゲル成分率：７％）２７重量部（重量比７：３）を用いたこと（比較例２と同様）以外は実施例１と同様にして、比較例３のトナー粒子（体積平均粒径７．１μｍ、変動係数２４）４ｋｇを得た。 (Comparative Example 3)
Instead of 91 parts by weight of polyester resin 1, 64 parts by weight of polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) and polyester resin 4 (Tg: 52 ° C., Tm: 120 ° C., The toner particles of Comparative Example 3 (volume average particle size of 7) were used in the same manner as Example 1 except that 27 parts by weight (weight ratio 7: 3) was used (same as in Comparative Example 2). 0.1 μm, coefficient of variation 24) 4 kg was obtained.
（比較例４）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１００℃、バレル回転数２００ｒｐｍ、原料供給速度２０ｋｇ／時間に変更し（比較例２と同様）、ポリエステル樹脂１の９１重量部の代わりに、ポリエステル樹脂１（Ｔｇ：５８℃、Ｔｍ：１３０℃、ゲル成分率：２％）４５．５重量部およびポリエステル樹脂５（Ｔｇ：６０℃、Ｔｍ：１４０℃、ゲル成分率：１５％）４５．５重量部（重量比５：５）を用いたこと以外は実施例１と同様にして、比較例４のトナー粒子（体積平均粒径７．０μｍ、変動係数２３）４ｋｇを得た。 (Comparative Example 4)
The melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 200 rpm, and a raw material supply speed of 20 kg / hour (similar to Comparative Example 2), and instead of 91 parts by weight of the polyester resin 1, 45.5 parts by weight of polyester resin 1 (Tg: 58 ° C., Tm: 130 ° C., gel component ratio: 2%) and polyester resin 5 (Tg: 60 ° C., Tm: 140 ° C., gel component ratio: 15%) 4 kg of toner particles (volume average particle size 7.0 μm, coefficient of variation 23) of Comparative Example 4 were obtained in the same manner as in Example 1 except that 5 parts by weight (weight ratio 5: 5) was used.
（比較例５）
　二軸押出機の溶融混練の条件を、シリンダ設定温度１００℃、バレル回転数３００ｒｐｍ、原料供給速度を２０ｋｇ／時間に変更したこと以外は実施例１と同様にして、比較例５のトナー粒子（体積平均粒径６．７μｍ、変動係数２１）４ｋｇを得た。 (Comparative Example 5)
The toner particles of Comparative Example 5 were prepared in the same manner as in Example 1 except that the melt kneading conditions of the twin screw extruder were changed to a cylinder setting temperature of 100 ° C., a barrel rotation speed of 300 rpm, and a raw material supply speed of 20 kg / hour. A volume average particle size of 6.7 μm and a coefficient of variation of 21) 4 kg were obtained.
（比較例６）
　ポリエステル樹脂１の代わりに、ポリエステル樹脂６（Ｔｇ：４９℃、Ｔｍ：１２０℃、ゲル成分率：１％）を用いたこと以外は実施例１と同様にして、比較例６のトナー粒子（体積平均粒径６．７μｍ、変動係数２１）を４ｋｇ得た。 (Comparative Example 6)
The toner particles (volume) of Comparative Example 6 were the same as Example 1 except that polyester resin 6 (Tg: 49 ° C., Tm: 120 ° C., gel component ratio: 1%) was used instead of polyester resin 1. 4 kg of an average particle diameter of 6.7 μm and a coefficient of variation of 21) were obtained.
（比較例７）
　ポリエステル樹脂１の代わりに、ポリエステル樹脂７（Ｔｇ：６７℃、Ｔｍ：１４１℃、ゲル成分率：２％）を用いたこと以外は実施例１と同様にして、比較例７のトナー粒子（体積平均粒径７．２μｍ、変動係数２４）を４ｋｇ得た。 (Comparative Example 7)
In the same manner as in Example 1 except that polyester resin 7 (Tg: 67 ° C., Tm: 141 ° C., gel component ratio: 2%) was used instead of polyester resin 1, toner particles (volume) of Comparative Example 7 were used. 4 kg of an average particle diameter of 7.2 μm and a coefficient of variation of 24) were obtained.
（外添トナーおよび二成分現像剤の製造）
　得られた実施例１～６および比較例１～７のトナー粒子のそれぞれに、外添剤（流動化剤）としてシリカ粒子（日本アエロジル株式会社製、型番：ＲＸ－２００）をトナー粒子１００重量部に対して１．５重量部添加し、ヘンシェルミキサ（三井鉱山株式会社（現　日本コークス工業株式会社）製、型式：ＦＭ１５０）を用いて混合し、外添トナー　５ｋｇを得た。
　得られた外添トナーのそれぞれに、フェライトキャリアをトナー濃度が８重量％になるよう、ナウターミキサー（ホソカワミクロン株式会社製、型式：ラボミキサーＬＶ－０）を用いて混合し、二成分現像剤２ｋｇを得た。 (Manufacture of external additive toner and two-component developer)
In each of the obtained toner particles of Examples 1 to 6 and Comparative Examples 1 to 7, silica particles (manufactured by Nippon Aerosil Co., Ltd., model number: RX-200) were used as an external additive (fluidizing agent) 100 weights of toner particles. 1.5 parts by weight with respect to the parts were mixed and mixed using a Henschel mixer (Mitsui Mining Co., Ltd. (currently Nippon Coke Kogyo Co., Ltd., model: FM150)) to obtain 5 kg of externally added toner.
A ferrite carrier is mixed with each of the obtained externally added toners using a Nauter mixer (Model: Lab mixer LV-0, manufactured by Hosokawa Micron Co., Ltd.) so that the toner concentration becomes 8% by weight. 2 kg was obtained.
（トナーの評価）
　実施例１～６および比較例１～７のトナー粒子を用いて製造した外添トナーおよび二成分現像剤を用いて、トナーの各物性を以下に示す方法により測定・評価した。 (Evaluation of toner)
Using the externally added toner and the two-component developer produced using the toner particles of Examples 1 to 6 and Comparative Examples 1 to 7, the physical properties of the toner were measured and evaluated by the following methods.
＜光沢性＞
　市販の複写機（シャープ株式会社製、型式：ＭＸ-２３００Ｇ）に二成分現像剤を充填し、加熱ローラの表面温度を１３０℃から２２０℃まで５℃刻みに設定して画像を形成し、グロスメーター（日本電色工業株式会社製、型式：ＶＧ２０００）を用いてグロス値が５０以上の領域を調べた。
　以下の基準で光沢性を評価した。
　　◎（最良）：グロス値５０以上領域が２０℃以上
　　○（良好）：グロス値５０以上領域が１５℃以上２０℃未満
　　△（実用上問題なし）：グロス値５０以上領域が、５℃以上１５℃未満
　　×（不良）：グロス値５０以上領域が存在しない <Glossiness>
A commercially available copying machine (Sharp Corporation, model: MX-2300G) is filled with a two-component developer, and the surface temperature of the heating roller is set in increments of 5 ° C. from 130 ° C. to 220 ° C. to form an image. Using a meter (manufactured by Nippon Denshoku Industries Co., Ltd., model: VG2000), an area having a gloss value of 50 or more was examined.
The glossiness was evaluated according to the following criteria.
◎ (Best): Gross value of 50 or higher is 20 ° C or higher. ○ (Good): Gloss value of 50 or higher is 15 ° C or higher and lower than 20 ° C. △ (No problem in practical use): Gloss value of 50 or higher is 5 ° C or higher. <° C. x (defect): No area with a gloss value of 50 or more
＜耐ホットオフセット性＞
　光沢性の評価と同様にして、ホットオフセットが発生する温度を調べた。
　以下の基準で耐ホットオフセット性を評価した。
　　○（良好）：ホットオフセットが２１５℃以上で発生する
　　△（実用上問題なし）：ホットオフセットが２０５℃以上２１５℃未満で発生する
　　×（不良）：ホットオフセットが２０５℃未満で発生する <Hot offset resistance>
Similarly to the evaluation of glossiness, the temperature at which hot offset occurs was examined.
Hot offset resistance was evaluated according to the following criteria.
○ (Good): Hot offset occurs at 215 ° C. or higher Δ (No problem in practical use): Hot offset occurs at 205 ° C. or higher and lower than 215 ° C. × (Bad): Hot offset occurs at lower than 205 ° C.
＜保存性＞
　容量５０ｍＬのポリ容器に外添トナー１００ｇを密閉し、５５℃で４８時間放置した。その後、取出したトナーを＃１００メッシュ（目開き１５０μｍ）のふるいに掛け、ふるい上に残存するトナーの重量を測定し、トナー全重量に対する割合として残存量を求め、以下の基準で保存性を評価した。
　数値が低いほど、トナーがブロッキングを起こさず、保存性が良好であることを示す。
　　○（良好）：残存量０％（トナーの残存なし）
　　△（実用上問題なし）：残存量５％未満
　　×（不良）：残存量５％以上 <Preservability>
100 g of externally added toner was sealed in a 50 mL capacity plastic container and allowed to stand at 55 ° C. for 48 hours. Then, the removed toner is passed through a # 100 mesh (mesh 150 μm) sieve, the weight of the toner remaining on the sieve is measured, the remaining amount is obtained as a percentage of the total toner weight, and the storage stability is evaluated according to the following criteria. did.
A lower numerical value indicates that the toner does not block and the storage stability is better.
○ (good): 0% remaining (no toner remaining)
Δ (No problem in practical use): Remaining amount less than 5% × (Bad): Remaining amount 5% or more
＜総合評価＞
　上記３種の評価結果を総合して以下の基準で分類した。
　　◎（最良）：全ての評価で○以上であり、かつ光沢評価が◎である。
　　○（良好）：評価結果に×がなく、△が１個以下である。
　　△（実用上問題なし）：評価結果に×がなく、△が２個以上ある。
　　×（不良）：評価結果に×がある <Comprehensive evaluation>
The above three types of evaluation results were combined and classified according to the following criteria.
◎ (Best): All evaluations are ◯ or more and gloss evaluation is ◎.
○ (good): The evaluation result has no x and Δ is 1 or less.
Δ (no problem in practical use): There are no x in the evaluation result, and there are two or more Δ.
× (defect): The evaluation result has ×
　表１の結果から次のことがわかる。
（１）本発明のトナー（実施例１～６）は、光沢性、耐ホットオフセット性および保存性の全てにおいて優れている。
（２）本発明の規定量を超える高分子量成分を含む結着樹脂を含むトナー（比較例１）は、光沢性に劣る。
（３）本発明の規定量を超える低分子量成分を含む結着樹脂を含むトナー（比較例２）は、耐ホットオフセット性および保存性に劣る。
（４）結着樹脂の分子量分布におけるメインピークの半値幅の両端を結ぶ面積が本発明の規定量未満であるトナー（比較例３）は、光沢性に劣る。
（５）本発明の規定量を超える結着樹脂のテトラヒドロフランに不溶なゲル成分を含むトナー（比較例４）は、光沢性に劣る。
（６）結着樹脂の分子量分布におけるメインピークの半値幅の両端を結ぶ面積が本発明の規定量を超えるトナー（比較例５）は、耐ホットオフセット性に劣る。
（７）結着樹脂のガラス転移温度が本発明の規定値未満であるトナー（比較例６）は、耐ホットオフセット性および保存性に劣る。
（８）結着樹脂のガラス転移温度が本発明の規定値を超えるトナー（比較例７）は、光沢性に劣る。 The following can be seen from the results in Table 1.
(1) The toner of the present invention (Examples 1 to 6) is excellent in all of glossiness, hot offset resistance and storage stability.
(2) The toner (Comparative Example 1) containing a binder resin containing a high molecular weight component exceeding the specified amount of the present invention is inferior in gloss.
(3) The toner containing the binder resin containing the low molecular weight component exceeding the specified amount of the present invention (Comparative Example 2) is inferior in hot offset resistance and storage stability.
(4) The toner (Comparative Example 3) in which the area connecting both ends of the half width of the main peak in the molecular weight distribution of the binder resin is less than the specified amount of the present invention (Comparative Example 3) is inferior in gloss.
(5) The toner (Comparative Example 4) containing a gel component insoluble in tetrahydrofuran of the binder resin exceeding the specified amount of the present invention is inferior in gloss.
(6) A toner (Comparative Example 5) in which the area connecting both ends of the half width of the main peak in the molecular weight distribution of the binder resin exceeds the specified amount of the present invention (Comparative Example 5) is inferior in hot offset resistance.
(7) The toner (Comparative Example 6) in which the glass transition temperature of the binder resin is less than the specified value of the present invention is inferior in hot offset resistance and storage stability.
(8) A toner (Comparative Example 7) in which the glass transition temperature of the binder resin exceeds the specified value of the present invention is inferior in gloss.
　４０　定着装置
　Ｐ　記録紙（記録材）
　１００　画像形成装置
　１１０Ｙ　イエロー可視像形成ユニット
　１１０Ｍ　マゼンタ可視像形成ユニット
　１１０Ｃ　シアン可視像形成ユニット
　１１０Ｂ　ブラック可視像形成ユニット
　１１１　感光体ドラム
　１１２　帯電ローラ
　１１３　露光手段（レーザ光照射手段）
　１１４　現像器
　１１５　転写ローラ
　１１６　クリーナー
　１２０　供給トレイ
　１３０　記録紙搬送手段
　１３１　駆動ローラ
　１３２　アイドリングローラ
　１３３　無端状の搬送ベルト
　Ａ　図面方向
　Ｙ　イエロートナーを含む現像剤が収容された現像器
　Ｃ　シアントナーを含む現像剤が収容された現像器
　Ｍ　マゼンタトナーを含む現像剤が収容された現像器
　Ｂ　ブラックトナーを含む現像剤が収容された現像器 40 Fixing device P Recording paper (recording material)
DESCRIPTION OF SYMBOLS 100 Image forming apparatus 110Y Yellow visible image forming unit 110M Magenta visible image forming unit 110C Cyan visible image forming unit 110B Black visible image forming unit 111 Photosensitive drum 112 Charging roller 113 Exposure means (laser light irradiation means)
114 Developing Unit 115 Transfer Roller 116 Cleaner 120 Supply Tray 130 Recording Paper Conveying Means 131 Drive Roller 132 Idling Roller 133 Endless Conveying Belt A Drawing Direction Y Developing Unit Containing Developer Containing Yellow Toner C Developing Containing Cyan Toner Developer in which developer is contained M Developer in which developer containing magenta toner is contained B Developer in which developer containing black toner is contained

Claims (10)

  1. 　少なくとも結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を含み、前記ポリエステル樹脂が、次の条件：
    　ゲルパーミエーションクロマトグラフにより測定される分子量分布において、
    （１）分子量１×１０6.0以上の成分が１％未満でかつ分子量１×１０5.3以上の成分が５％未満であり、
    （２）分子量１×１０3.6以下の成分が２０％未満であり、
    （３）メインピークの半値幅の両端を結ぶ面積が７０～８２％であり、かつ
    （４）テトラヒドロフランに不溶なゲル成分が５％未満であり、
    （５）ガラス転移温度が５０℃以上６５℃以下である、
    を満たす電子写真用トナー。     At least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent, and the polyester resin has the following conditions:
    In the molecular weight distribution measured by gel permeation chromatograph,
    (1) The component having a molecular weight of 1 × 10 6.0 or more is less than 1% and the component having a molecular weight of 1 × 10 5.3 or more is less than 5%,
    (2) The component having a molecular weight of 1 × 10 3.6 or less is less than 20%,
    (3) the area connecting both ends of the half width of the main peak is 70 to 82%, and (4) the gel component insoluble in tetrahydrofuran is less than 5%,
    (5) The glass transition temperature is 50 ° C. or higher and 65 ° C. or lower,
    An electrophotographic toner that meets the requirements.
  2. 　前記条件（３）におけるメインピークの半値幅の両端を結ぶ面積が、７８～８２％である請求項１に記載の電子写真用トナー。 The toner for electrophotography according to claim 1, wherein an area connecting both ends of the half width of the main peak in the condition (3) is 78 to 82%.
  3. 　前記条件（１）における分子量１×１０6.0以上の成分が０．５％未満でかつ分子量１×１０5.3以上の成分が２．５％未満である請求項１に記載の電子写真用トナー。 2. The electrophotographic toner according to claim 1, wherein a component having a molecular weight of 1 × 10 6.0 or more in the condition (1) is less than 0.5% and a component having a molecular weight of 1 × 10 5.3 or more is less than 2.5%.
  4. 　前記条件（２）における分子量１×１０3.6以下の成分が、１５％未満である請求項１に記載の電子写真用トナー。 2. The electrophotographic toner according to claim 1, wherein a component having a molecular weight of 1 × 10 3.6 or less in the condition (2) is less than 15%.
  5. 　前記条件（４）におけるテトラヒドロフランに不溶なゲル成分が、２％未満である請求項１に記載の電子写真用トナー。 The electrophotographic toner according to claim 1, wherein the gel component insoluble in tetrahydrofuran under the condition (4) is less than 2%.
  6. 　前記条件（５）におけるガラス転移温度が、５５℃以上６０℃以下である請求項１に記載の電子写真用トナー。 2. The electrophotographic toner according to claim 1, wherein the glass transition temperature in the condition (5) is 55 ° C. or higher and 60 ° C. or lower.
  7. 　前記結着樹脂における重量平均分子量（Ｍｗ）が４４０００～５００００であり、数平均分子量（Ｍｎ）が４５００～５５００であり、それらの比Ｍｗ／Ｍｎが８～１０である請求項１に記載の電子写真用トナー。 2. The electron according to claim 1, wherein the binder resin has a weight average molecular weight (Mw) of 44000 to 50000, a number average molecular weight (Mn) of 4500 to 5500, and a ratio Mw / Mn of 8 to 10. Toner for photography.
  8. 　前記電子写真用トナーが、少なくとも、前記結着樹脂としてのポリエステル樹脂、着色剤、離型剤および帯電制御剤を機械的剪断力を付加して溶融混練することにより製造される請求項１に記載の電子写真用トナー。 The electrophotographic toner is produced by melting and kneading at least a polyester resin as a binder resin, a colorant, a release agent, and a charge control agent while applying a mechanical shearing force. Toner for electrophotography.
  9. 　前記電子写真用トナーが、前記結着樹脂と、前記結着樹脂１００重量部に対してそれぞれ０．１～２０重量部の着色剤、０．２～２０重量部の離型剤および０．５～３重量部の帯電制御剤とを含む請求項１に記載の電子写真用トナー。 The electrophotographic toner comprises 0.1 to 20 parts by weight of a colorant, 0.2 to 20 parts by weight of a release agent and 0.5 parts by weight with respect to the binder resin and 100 parts by weight of the binder resin, respectively. The toner for electrophotography according to claim 1, comprising -3 parts by weight of a charge control agent.
  10. 　請求項１に記載の電子写真用トナーを用いた画像形成装置。 An image forming apparatus using the electrophotographic toner according to claim 1.
PCT/JP2012/068855 2011-09-21 2012-07-25 Toner for electrophotography and image formation device using same WO2013042452A1 (en)

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JP2008116960A (en) * 2001-07-06 2008-05-22 Ricoh Co Ltd Method of fixing toner in image forming apparatus

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