WO2012101875A1 - Toner pour développement à charge électrostatique - Google Patents

Toner pour développement à charge électrostatique Download PDF

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Publication number
WO2012101875A1
WO2012101875A1 PCT/JP2011/073449 JP2011073449W WO2012101875A1 WO 2012101875 A1 WO2012101875 A1 WO 2012101875A1 JP 2011073449 W JP2011073449 W JP 2011073449W WO 2012101875 A1 WO2012101875 A1 WO 2012101875A1
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Prior art keywords
toner
polyester
resin
low molecular
molecular weight
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PCT/JP2011/073449
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English (en)
Japanese (ja)
Inventor
輝樹 草原
順一 粟村
強 杉本
氷 朱
鈴木　智美
内野倉　理
隆浩 本多
智之 小島
小川　哲
大佑 井上
幸史 佐藤
伊藤　大介
隆太 吉田
祥子 佐藤
Original Assignee
株式会社リコー
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Publication date
Priority claimed from JP2011014780A external-priority patent/JP5748095B2/ja
Application filed by 株式会社リコー filed Critical 株式会社リコー
Priority to US13/637,774 priority Critical patent/US8778588B2/en
Priority to EP11857117.3A priority patent/EP2546698A4/fr
Priority to CN201180016458.0A priority patent/CN102834782B/zh
Publication of WO2012101875A1 publication Critical patent/WO2012101875A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • 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 a toner for developing an electrostatic image, a toner container capable of reducing the volume for containing the toner, and an image forming apparatus equipped with the toner container.
  • Patent Document 1 proposes a developer that regulates the particle size distribution and intends to solve the above-described problems. Specifically, when the volume average particle diameter of the toner is D ( ⁇ m), 90% by mass or more of all toner particles are present in the range of D (3 ⁇ 2) ⁇ 1 to 3 ⁇ 2D, and D ( 3 ⁇ 2) -1 is a toner powder in which particles smaller than 5% by mass are used.
  • the technique is limited to the two-component development method and has an advantage of preventing adverse effects such as fogging and toner scattering during recycling by reducing the ratio of very small particles. On the contrary, since the ratio is too small, it is impossible to obtain a copy faithful to a fine latent image.
  • Patent Document 2 proposes a toner having a specific particle size distribution, but has not yet improved carrier spent and fogging with recycled toner.
  • toner is fixed on an image support by a heat fixing method to obtain a permanent visible copy image.
  • OHP sheet an overhead projector (OHP) transparency sheet
  • OHP sheet an image projected on the OHP is displayed.
  • OHP sheet In order to obtain good light transmissivity, it is required to fix the image surface in a smooth state to prevent scattering of transmitted light and irregular reflection on the image surface during projection.
  • a color toner that can be rapidly transferred to a molten state having a viscoelasticity lower than that of a conventional black toner at a melting point is used as a general method, and the image surface is heated and pressed. It was designed to be easily smoothed.
  • Patent Document 3 a toner having a specific relationship between a volume average particle diameter Dv ( ⁇ m) and a storage elastic modulus G′170 (dyne / cm 2 ) at 170 ° C. is used. Has improved.
  • the storage elastic modulus of the toner becomes large, and when the average particle size becomes small, the low-temperature fixability and the glossiness become disadvantageous, thereby reducing the color reproducibility. End up. That is, it is not easy to achieve both high image quality with a small particle size in recent years, low temperature fixability and color reproducibility.
  • Patent Document 4 proposes a binder resin for toner containing a conventional amorphous polyester and a crystalline polyester having a significant improvement effect compared with the polyester as a measure for improving the low-temperature fixability. Yes.
  • a crystalline polyester and an amorphous polyester are used in combination, the resin composition of the both is close, so that transesterification occurs during melt-kneading and the high crystallinity of the crystalline polyester can be maintained. In other words, the storability of the toner tends to decrease.
  • Patent Document 5 and Patent Document 6 describe a binder resin for toner comprising a crystalline polyester having sebacic acid or adipic acid as a carboxylic acid component and a styrene-acrylic resin, and can be stored at a low temperature. However, further improvement in performance is desired.
  • Patent Document 7 a binder resin for toner containing a specific crystalline polyester and an amorphous hybrid resin is proposed, and a toner having a wide fixable temperature range and excellent durability can be provided. Although described, it has not yet been solved to eliminate fogging and image density unevenness due to poor compatibility of the crystalline polyester with the pigment.
  • JP-A-2-157765 Japanese Patent No. 2896826 Japanese Patent No. 3885241 JP 2001-222138 A JP-A-11-249339 JP 2003-302791 A JP 2004-191516 A JP 2005-338814 A
  • An object of the present invention is to provide a toner for developing an electrostatic charge image having a small particle size that simultaneously satisfies image quality improvement, cleaning property, high colorability, low-temperature fixing property and toner storage property even in a recycling system. It is another object of the present invention to provide a toner for developing an electrostatic image that satisfies both high image quality, low-temperature fixability, toner storage stability, and high colorability in a color toner.
  • An object of the present invention is to provide a toner container capable of reducing the amount of toner powder in the container without causing toner powder packing and an image forming apparatus equipped with the container.
  • a toner comprising a binder resin, a colorant, and a release agent
  • the binder resin contains a low molecular resin component, and the low molecular resin component has a resin softening coefficient (A) represented by the following formula (1): A> 0.165, and an elevated flow tester A storage elastic modulus (dyne / cm 2 ) G ′ (Tfb) where Gf (Tfb) ⁇ 1 ⁇ 10 4 when the outflow start temperature (° C.) measured by the above is Tfb. It is.
  • ⁇ 3> The toner according to ⁇ 2>, wherein the low molecular weight polyester has a weight average molecular weight of 2,000 to 10,000.
  • ⁇ 4> The toner according to any one of ⁇ 2> to ⁇ 3>, wherein the low molecular polyester has an acid value of 1.0 mgKOH to 50.0 mgKOH / g. ⁇ 5>
  • ⁇ 6> The toner according to any one of ⁇ 1> to ⁇ 5>, wherein the binder resin further includes a crystalline polyester resin including a polyhydric alcohol component and a carboxylic acid component.
  • ⁇ 7> The toner according to ⁇ 6>, wherein the crystalline polyester resin contains more aromatic components than the low-molecular polyester.
  • ⁇ 8> The toner according to any one of ⁇ 6> to ⁇ 7>, wherein a mass ratio of the low molecular weight polyester to the crystalline polyester (low molecular weight polyester / crystalline polyester) is 1.5 or more and 2 or less.
  • ⁇ 9> The above ⁇ 6>, wherein the binder resin satisfies the following formula (2) between the solubility parameter (SP) value SP (a) of the crystalline polyester and the solubility parameter value SP (b) of the low molecular weight polyester.
  • ⁇ 12> The toner according to any one of ⁇ 10> to ⁇ 11>, wherein the binder resin precursor includes a modified polyester resin.
  • ⁇ 13> The toner according to any one of ⁇ 1> to ⁇ 12>, wherein the toner has an average circularity of 0.94 to 0.99.
  • ⁇ 14> The toner according to any one of ⁇ 1> to ⁇ 13>, wherein the toner has a volume average particle diameter of 3 ⁇ m to 7 ⁇ m.
  • ⁇ 15> The toner according to any one of ⁇ 1> to ⁇ 14>, wherein the toner has a volume average particle diameter Dv / number average particle diameter Dn of 1.30 or less.
  • ⁇ 16> The toner according to any one of ⁇ 1> to ⁇ 15>, wherein particles having a particle size of 2 ⁇ m or less are 1% by number to 20% by number.
  • a two-component developer comprising the toner according to any one of ⁇ 1> to ⁇ 16> and a carrier.
  • a toner container comprising a flexible member capable of reducing volume by 60% or more and filled with the toner according to any one of ⁇ 1> to ⁇ 16>.
  • the developing means has a toner container filled with toner, an air inflow means for injecting air into the toner container, a pump means for supplying the toner as fluid into the toner container, and the toner from the cartridge.
  • a toner supply device having a toner feed tube for feeding to the developing means;
  • the toner container is the toner container described in ⁇ 18>.
  • the present invention it is possible to provide a toner for developing an electrostatic charge image having a small particle diameter that simultaneously satisfies high image quality, cleanability, low-temperature fixability, toner storage stability, and high colorability in a recycling system.
  • a color toner it is possible to provide a toner for developing an electrostatic image having high image quality, low-temperature fixability, OHP permeability, and high colorability.
  • FIG. 1 is an explanatory diagram illustrating a method of supplying toner from a toner container to a developing unit.
  • FIG. 2 is a schematic diagram illustrating an example of a toner container.
  • FIG. 3 is a schematic view when the toner container is reduced in volume.
  • FIG. 4 is a schematic diagram of a toner supply device including a toner container, an air supply device, and a powder pump.
  • FIG. 5 is a flow curve by an elevated flow tester.
  • the toner of the present invention a toner container capable of containing the toner and capable of volume reduction, and an image forming apparatus equipped with the toner container will be described in detail.
  • a fixing process is required.
  • the toner does not soften, and it is necessary for the toner to be melted and fixed instantaneously by the heat energy at the time of fixing.
  • the binder resin has a resin softening coefficient (A) of A> 0.165 and G ′ (Tfb) ⁇ 1 ⁇ 10. It was found that the low-molecular resin component of No. 4 contains both low-temperature fixability and toner storage stability and can simultaneously satisfy high colorability.
  • the present invention is a toner containing a binder resin, a colorant, and a release agent, the binder resin contains a low molecular resin component,
  • the low molecular resin component has a resin softening coefficient (A) represented by the following formula (1) of A> 0.165, and an outflow start temperature (° C.) measured by an elevated flow tester is Tfb. Since the storage elastic modulus (dyne / cm 2 ) G ′ (Tfb) is G ′ (Tfb) ⁇ 1 ⁇ 10 4 , the difference between the softening temperature and the outflow start temperature is small.
  • the rubber flat area is narrow, the transition from the solid state to the fluidized area is performed quickly, sharp meltability at the time of fixing is improved, high low-temperature fixability is obtained, and at the same time heat resistant storage stability is achieved.
  • It can be A
  • the low molecular resin component refers to a component having a molecular weight of 1,000 or more and less than 10,000.
  • the outflow start temperature Tfb measured by the elevated flow tester is the temperature at which flow starts through the rubber flat region in the rheological behavior of the resin, and G ′ (Tfb) is the storage elasticity at that temperature.
  • the storage elastic modulus G ′ (Tfb) at the outflow start temperature can be adjusted by the composition blending ratio of the resin components blended in the resin.
  • the resin softening coefficient (A) is an index indicating the degree of change in the storage elastic modulus with respect to the temperature change before and after the outflow start temperature, and that the resin softening coefficient (A) is large before and after the outflow start temperature.
  • the storage elastic modulus changes greatly, indicating that it is a sharp melt. Since the low-molecular resin component is a collection of molecules having various molecular weights and molecular structures, all the molecules do not flow at the same time but partially start to flow. Therefore, for example, the resin softening coefficient (A) can be made larger than 0.165 by aligning the molecular weight and molecular structure.
  • the low molecular weight resin component is allowed to react slowly over a long period of time, and the reaction system is depressurized and promoted in the latter half of the polycondensation reaction of the divalent monomer, and then the trivalent or higher monomer is added. It is preferable that the molecular weight and the molecular structure are made uniform by reacting with each other.
  • the number average molecular weight of the low molecular resin component is preferably 1,200 to 4,000, the weight average molecular weight is preferably 2,000 to 10,000, and more preferably 2,200 to 7,000.
  • the molecular weight distribution (Mw / Mn) represented by the ratio between the weight average molecular weight (Mw) and the number average molecular weight (Mn) is preferably 1.1 to 3.
  • the low molecular resin component is preferably a low molecular polyester, and is a monomer containing an alcohol component composed of a divalent or higher polyhydric alcohol and a carboxylic acid component composed of a divalent or higher polyvalent carboxylic acid compound. Is obtained.
  • the alcohol component and carboxylic acid component of the low molecular weight polyester can be the same as the crystalline polyester resin described later, apart from the blending amount of each of these components, but the alcohol component has the following general formula: It is preferable to include the etherified diphenol represented by (1), and it is more preferable to include 50% by mass or more of those in which R is C 2 H 4 and x and y are all 1.
  • R represents an alkylene group having 2 to 3 carbon atoms, and x and y are both 1 to 10 numbers.
  • the glass transition temperature Tg of the low molecular polyester is preferably 35 ° C. to 65 ° C., more preferably 40 ° C. to 50 ° C.
  • the acid value of the low molecular weight polyester is preferably 1.0 mgKOH / g to 50.0 mgKOH / g, more preferably 5 mgKOH / g to 25 mgKOH / g, and still more preferably 10 mgKOH / g to 25 mgKOH / g.
  • the hydroxyl value of the low molecular weight polyester is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g to 120 mgKOH / g, still more preferably 20 mgKOH / g to 80 mgKOH / g. If the hydroxyl value is less than 5 mgKOH / g, it may be disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
  • the storage elastic modulus G ′ in the present invention is measured using, for example, a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics).
  • Measuring jig A parallel plate having a diameter of 7.9 mm is used.
  • Measurement sample Toner is heated and melted and molded into a cylindrical sample having a diameter of about 8 mm and a height of 3 mm.
  • Measurement frequency 1Hz
  • Measurement temperature 50 ° C to 230 ° C
  • Measurement strain setting The initial value is set to 0.1%, and measurement is performed in the automatic measurement mode.
  • Sample extension correction Adjust in automatic measurement mode.
  • Ts and Tfb were measured using an elevated flow tester (manufactured by Shimadzu Corporation) according to the method described in JIS K72101. While heating a sample of 1 cm 3 at a heating rate of 6 ° C./min, a load of 10 kg / cm 2 is applied by a plunger, and a nozzle having a diameter of 0.5 mm and a length of 1 mm is pushed out. Draw a volume-temperature curve. The flow curve of this flow tester becomes data as shown in FIG. 5, and each temperature can be read therefrom.
  • A is a measurement start temperature
  • B Ts (softening temperature)
  • C Tfb (outflow start temperature)
  • D is a 1/2 outflow temperature
  • E is a measurement end temperature.
  • binder resin of the toner of the present invention one or two or more resins can be used in combination in addition to the low molecular weight polyester.
  • binder resin for toners For example, a polyester resin, a polyol resin, a polystyrene resin, a polystyrene acrylic resin etc. are mentioned.
  • the main component of the adhesive base material in the toner is a polyester resin, compatibility is improved at the time of fixing, and glossiness is improved when used in a low-temperature fixing property or a full-color image forming apparatus.
  • a polyester resin is preferable, and it is more preferable that the resin is crystalline.
  • the content of the polyester resin in the binder resin is preferably 50% by mass to 100% by mass, the acid value of the binder resin is 1.0 mgKOH / g to 50.0 mgKOH / g, and the glass transition point is The temperature is preferably 35 ° C. to 65 ° C.
  • the crystalline polyester resin exhibits good heat-resistant storage until just before the outflow start temperature. Above the outflow start temperature, the viscosity of the toner binder rapidly decreases in combination with the low molecular weight polyester, giving the toner a sharp melt property. It is considered possible. In addition, the toner release width (difference between the minimum fixing temperature and the hot offset occurrence temperature) can be improved, and a toner exhibiting good fixability can be obtained.
  • the mass ratio of the low molecular polyester to the crystalline polyester is preferably 1.5 or more and 2 or less, and more preferably 1.7 or more and 1.8 or less. When the mass ratio is less than 1.5, the low-temperature fixability may be deteriorated, and when it exceeds 2, the heat resistant storage stability may be deteriorated.
  • solubility parameter (SP) value SP (a) of the crystalline polyester and the solubility parameter value SP (b) of the low molecular polyester preferably satisfy the following formula (2).
  • solubility parameter (SP) value SP (a) of the crystalline polyester and the solubility parameter value SP (b) of the low molecular weight polyester are calculated based on the respective blending amounts of the monomer components used in the polymerization.
  • Each polymerization unit is calculated from each monomer component unit as shown in the following formula, assuming that the polymerization rate is calculated and all the polymerization components are incorporated in the polymer chain in the mass fraction charged.
  • the solubility parameter of the polymer was obtained and the sum of those values multiplied by the respective weight fractions was used as the solubility parameter of the polymer.
  • the solubility parameter in the present invention is a solubility parameter at 25 ° C., and is described in, for example, the above-mentioned (RF Fedors, Polym. Eng. Sci., 14, 147 (1974)).
  • (delta) overall is a solubility parameter [(cal / ml) ⁇ 1/2 > / 25 (degreeC)] of a polymer.
  • w i is the mass fraction calculated from each monomer ⁇ e i is the sum of the cohesive energies per unit functional group of each monomer component (cal / mol)
  • ⁇ v i is the sum of molecular volumes per unit functional group (cc / mol / 25 ° C.)
  • the crystalline polyester resin will be described. There is no restriction
  • the aromatic component-containing polyester preferably contains more aromatic components than the low-molecular polyester.
  • R 1 and R 2 may be the same as or different from each other, and represent a hydrogen atom or a hydrocarbon group.
  • a hydrocarbon group There is no restriction
  • the alkyl group is preferably one having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, n-hexyl group, Examples include isohexyl group, n-heptyl group, n-octyl group, isooctyl group, n-decyl group, isodecyl group and the like.
  • the alkenyl group preferably has 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, and an octenyl group.
  • the aryl group preferably has 6 to 24 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a styryl group, a mesityl group, a cinnamyl group, a phenethyl group, and a benzhydryl group.
  • R 3 represents a divalent hydrocarbon group having 1 to 20 carbon atoms, and more preferably one having 1 to 10 carbon atoms.
  • an alkylene group represented by — (CH 2 ) p— (wherein p represents 1 to 20), and the like can be mentioned.
  • —CH 2 —, —CH 2 CH 2 —, —CH 2 CH 2 CH 2 — and —CH 2 C (CH 3 ) H— are particularly preferred.
  • M represents an integer of 1 to 10, more preferably 1 to 3.
  • n represents the degree of polymerization and represents an integer of 1 or more.
  • the molecular weight distribution of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably sharp, and the lower the molecular weight, the better the low-temperature fixability.
  • the peak position is 3.5 to 4 by gel permeation chromatography (GPC) of the soluble component of orthodichlorobenzene. It is preferably in the range of 0.0 and the half width of the peak is 1.5 or less.
  • the weight average molecular weight (Mw) of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 1,000 to 30,000, and preferably 1,200 to 20,000. Is more preferable. When the weight average molecular weight is less than 1,000, the storage stability may be deteriorated, and when it exceeds 30,000, the sharp melt property may be deteriorated.
  • the number average molecular weight (Mn) of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 500 to 6,000 is preferable, and 700 to 5,500 is more preferable.
  • the molecular weight distribution (Mw / Mn) represented by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) is not particularly limited and can be appropriately selected according to the purpose. 2 to 8 are preferred.
  • Mw / Mn molecular weight distribution
  • production may be difficult and costly.
  • it exceeds 8 the sharp melt property may be deteriorated.
  • the melting temperature (Tm) of the pre-crystalline polyester resin (sometimes referred to as “F1 / 2 temperature”) is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a differential scanning calorimeter DSC endothermic peak temperature in the DSC curve obtained by DSC measurement is preferably 50 ° C. to 150 ° C., more preferably 60 ° C. to 130 ° C.
  • the melting temperature (Tm) is less than 50 ° C., the heat-resistant storage stability is deteriorated, and blocking may easily occur at the temperature inside the developing device.
  • the melting temperature (Tm) exceeds 150 ° C., the lower limit fixing temperature is increased. For this reason, low temperature fixability may not be obtained.
  • an acid value of the said crystalline polyester resin there is no restriction
  • the acid value of the crystalline polyester resin can be measured, for example, by dissolving in 1,1,1,3,3,3-hexafluoro-2-propanol and titrating.
  • the hydroxyl value of the crystalline polyester resin is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 0 mgKOH / g to 50 mgKOH / g is preferable, and 5 mgKOH / g to 50 mgKOH / g is more preferable. When the hydroxyl value exceeds 50 mgKOH / g, it may be impossible to achieve a predetermined low-temperature fixability and good charging characteristics.
  • the hydroxyl value of the crystalline polyester resin can be measured, for example, by dissolving in 1,1,1,3,3,3-hexafluoro-2-propanol and titrating.
  • the crystalline polyester resin can be synthesized, for example, by subjecting an alcohol component and an acid component to a polycondensation reaction.
  • the diol compound preferably has, for example, 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms such as 1,4-butanediol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, , 6-hexanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, bisphenol A alkylene oxide adduct, derivatives thereof, and the like. These can be used individually by 1 type and can use 2 or more types together.
  • 1,4-butanediol and 1,6-hexanediol are preferable.
  • the amount of the diol compound used is preferably 80 mol% or more, more preferably 85 mol% to 100 mol% in the alcohol component. If the content of the diol compound in the alcohol component is less than 80 mol%, the production efficiency may deteriorate.
  • the acid component is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include carboxylic acids having a carbon double bond, dicarboxylic acid compounds, and polyvalent carboxylic acid compounds. Of these, dicarboxylic acid compounds are preferred. As the dicarboxylic acid compound, for example, those having 2 to 8 carbon atoms are preferable, and those having 2 to 6 carbon atoms are more preferable.
  • the amount of the dicarboxylic acid compound used is preferably 80 mol% or more, more preferably 85 mol% to 100 mol% in the acid component.
  • the production efficiency may deteriorate.
  • the polyvalent carboxylic acid compound include trimellitic acid, pyromellitic acid, acid anhydrides thereof, alkyl esters having 1 to 3 carbon atoms of these acids, and the like.
  • the polycondensation reaction is not particularly limited and may be appropriately selected depending on the intended purpose.
  • the reaction is carried out at 120 ° C. to 230 ° C. using an esterification catalyst, a polymerization inhibitor, etc. in an inert gas atmosphere. This can be done.
  • the reaction system is depressurized in the latter half of the polycondensation reaction, or the crystallinity and softening point of the crystalline polyester resin are controlled.
  • a trihydric or higher polyhydric alcohol such as glycerin is added as the alcohol component, and a trihydric or higher polyvalent carboxylic acid such as trimellitic anhydride is added as the acid component.
  • a shaped polyester may be obtained or the like.
  • a modified polyester resin (MPE) capable of reacting with a compound having an active hydrogen group can be used for improving heat resistant storage stability.
  • the modified polyester resin is preferably at least partially compatible with other binder resin components in terms of low-temperature fixability and hot offset resistance. Therefore, the modified polyester component and the other binder resin component are preferably composed of similar compositions (monomers).
  • the reactive modified polyester resin (RMPE) capable of reacting with a compound having an active hydrogen group (hereinafter, the polyester resin is also simply referred to as polyester) has, for example, a functional group that reacts with active hydrogen such as an isocyanate group. Polyester prepolymers and the like are included.
  • the polyester prepolymer preferably used in the present invention is a polyester prepolymer (A) having an isocyanate group.
  • the polyester prepolymer (A) having an isocyanate group is produced by reacting a polyisocyanate (PIC) with a polycondensate of a polyol (PO) and a polycarboxylic acid (PC) and having an active hydrogen group.
  • PIC polyisocyanate
  • PO polycondensate of a polyol
  • PC polycarboxylic acid
  • active hydrogen group possessed by the polyester include a hydroxyl group (alcoholic hydroxyl group and phenolic hydroxyl group), an amino group, a carboxyl group, a mercapto group, and the like. Among these, an alcoholic hydroxyl group is preferable.
  • Examples of the polyol include diol (DIO) and trivalent or higher polyol (TO), and DIO alone or a mixture of DIO and a small amount of TO is preferable.
  • Examples of the diol include alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol, triethylene glycol, Dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol F, bisphenol S, etc.) ); Adducts of alkylene oxides (ethylene oxide, propylene oxide, butylene oxide, etc.) of the above alicyclic diols; Alkylene
  • alkylene glycols having 2 to 12 carbon atoms preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use.
  • trihydric or higher polyols examples include trihydric or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (trisphenol PA, Phenol novolac, cresol novolak, etc.); alkylene oxide adducts of the above trivalent or higher polyphenols.
  • PC polycarboxylic acid
  • Dicarboxylic acids include alkylene dicarboxylic acids (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acids (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, etc.) ).
  • alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms.
  • the trivalent or higher polycarboxylic acid include aromatic polycarboxylic acids having 9 to 20 carbon atoms (such as trimellitic acid and pyromellitic acid).
  • polycarboxylic acid you may make it react with a polyol using the above-mentioned acid anhydride or lower alkyl ester (Methyl ester, ethyl ester, isopropyl ester, etc.).
  • the ratio of the polyol and the polycarboxylic acid is usually 2/1 to 1/1, preferably 1.5 / 1 to 1/1 / as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 1, more preferably 1.3 / 1 to 1.02 / 1.
  • polyisocyanate As polyisocyanate (PIC), aliphatic polyisocyanate (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanate (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); aromatic Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); araliphatic diisocyanates ( ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylxylylene diisocyanate, etc.); isocyanurates; polyisocyanates such as phenol derivatives, oximes, caprolactam, etc. And a combination of two or more of these.
  • PIC polyisocyanate
  • aliphatic polyisocyanate tetramethylene diisocyanate, hexam
  • the ratio of the polyisocyanate is usually 5/1 to 1/1, preferably 4/1 to 1, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. .2 / 1, more preferably 2.5 / 1 to 1.5 / 1.
  • [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate.
  • the content of the polyisocyanate (PIC) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5% by mass to 40% by mass, preferably 1% by mass to 30% by mass, and more preferably 2%. % By mass to 20% by mass.
  • the content is less than 0.5% by mass, the hot offset resistance is deteriorated, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
  • the content exceeds 40% by mass, the low-temperature fixability may be deteriorated.
  • the number of isocyanate groups contained per molecule in the polyester prepolymer (A) having isocyanate groups is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is a piece. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
  • a urea-modified polyester resin (UMPE) can be obtained by reacting this with an amine (B). This exhibits an excellent effect as a toner binder.
  • Examples of amines (B) as compounds having an active hydrogen group include diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and B1 ⁇ Examples thereof include those in which the amino group of B5 is blocked (B6).
  • Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′-dimethyldicyclohexylmethane, diamine) Cyclohexane, isophorone diamine, etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine, etc.) and the like.
  • Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine.
  • Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline.
  • Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan.
  • Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid.
  • Examples of B1 to B5 blocked amino groups (B6) include ketimine compounds and oxazolidine compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.
  • the molecular weight of a modified polyester such as urea-modified polyester can be adjusted by using an elongation terminator.
  • the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).
  • the ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B).
  • the ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2.
  • [NCO] / [NHx] is more than 2 or less than 1/2, the molecular weight of the urea-modified polyester is lowered, and the hot offset resistance is deteriorated.
  • the amines (B) act as a crosslinking agent or an extender for the modified polyester that can react with a compound having an active hydrogen group.
  • the polyester modified with a urea bond may contain a urethane bond together with a urea bond.
  • the molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.
  • the urea-modified polyester used in the present invention is produced by a one-shot method or a prepolymer method.
  • the urea-modified polyester used in the present invention is produced by a one-shot method or a prepolymer method which will be described later.
  • a polyol and a polycarboxylic acid are mixed with 150 to 150 in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide.
  • polyisocyanate at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group.
  • this A is reacted with amines (B) at 0 to 140 ° C.
  • a solvent can be used if necessary.
  • Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to polyisocyanates (PIC) such as tetrahydrofuran (such as tetrahydrofuran).
  • PIC inert to polyisocyanates
  • this PE When using a polyester (PE) not modified with a urea bond, this PE is produced in the same manner as in the case of a polyester having a hydroxyl group, and this is dissolved in a solution after completion of the reaction of the urea-modified polyester. Mix.
  • the weight average molecular weight of the modified polyester such as urea-modified polyester is usually 10,000 or more, preferably 20,000 to 10,000,000, and more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates.
  • the number average molecular weight of the modified polyester such as urea-modified polyester is not particularly limited, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight.
  • the mass ratio of MPE to the other binder resin component is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, and particularly preferably 7 / 93-20 / 80. If the mass ratio of MPE is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.
  • the temperature (TG ′) at which the measurement frequency is 20 Hz is 10000 dyne / cm is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates.
  • the temperature (T ⁇ ) at which the poise is 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 ° C. to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates.
  • TG ′ is preferably higher than T ⁇ from the viewpoint of achieving both low-temperature fixability and hot offset resistance.
  • the difference between TG ′ and T ⁇ (TG′ ⁇ T ⁇ ) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more, and the upper limit of a difference is not specifically limited.
  • the difference between T ⁇ and Tg is preferably 0 ° C to 100 ° C. More preferably, it is 10 ° C to 90 ° C, and particularly preferably 20 ° C to 80 ° C.
  • the glass transition temperature (Tg) of the entire toner binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, it is preferably 30 ° C. to 80 ° C., more preferably 40 ° C. to 65 ° C., 55 More preferably, the temperature is from 65 ° C to 65 ° C. When the glass transition temperature (Tg) is less than 30 ° C, the heat-resistant storage stability may be deteriorated, and when it exceeds 80 ° C, the low-temperature fixability may be deteriorated.
  • the weight average molecular weight (Mw) of the entire toner binder is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2,000 to 90,000 is preferable, and 2,500 to 30,000 is preferable. More preferred. When the weight average molecular weight is less than 2,000, the heat resistant storage stability may be deteriorated, and when it exceeds 90,000, the low temperature fixability may be deteriorated.
  • the colorant is not particularly limited, and all known dyes and pigments can be used.
  • the colorant can also be used as a master batch combined with a resin.
  • a master batch By using the master batch, it is possible to prevent the compatibility of the crystalline polyester and the pigment from being lowered and to obtain a highly colored toner.
  • styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, or a polymer of a substituted product thereof; Styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copoly
  • This master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force to obtain a master batch.
  • an organic solvent can be used in order to enhance the interaction between the colorant and the resin.
  • a so-called flushing method called watering paste containing water of a colorant is mixed and kneaded together with a resin and an organic solvent, and the colorant is transferred to the resin side to remove moisture and organic solvent components. Since it can be used as it is, it does not need to be dried and is preferably used.
  • a high shear dispersion device such as a three-roll mill is preferably used.
  • the toner of the present invention may contain a wax as a release agent together with a toner binder and a colorant.
  • the wax is not particularly limited and known ones can be used. Examples thereof include polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbon (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. Can be mentioned. Of these, carbonyl group-containing waxes are preferred.
  • carbonyl group-containing wax examples include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18-octadecanediol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylenediamine dibehenyl amide, etc.); polyalkylamides (tristearyl trimellitic acid) Amide etc.); dialkyl ketone (distearyl ketone etc.) etc.
  • the melting point of the wax is usually 40 ° C. to 160 ° C., preferably 50 ° C. to 120 ° C., more preferably 60 ° C. to 90 ° C. When the melting point is less than 40 ° C., the heat resistant storage stability is adversely affected. When the melting point exceeds 160 ° C., a cold offset tends to occur during fixing at a low temperature.
  • the melt viscosity of the wax is preferably 5 cps to 1,000 cps, more preferably 10 cps to 100 cps, as a measured value at a temperature 20 ° C. higher than the melting point.
  • the content of the wax in the toner is usually 0% by mass to 40% by mass, and preferably 3% by mass to 30% by mass.
  • the toner of the present invention may contain a charge control agent as necessary.
  • the charge control agent is not particularly limited and all known ones can be used.
  • nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines examples include quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds, tungsten simple substances or compounds, fluorine activators, salicylic acid metal salts, and metal salts of salicylic acid derivatives. .
  • the content of the charge control agent is determined by the toner production method including the type of toner binder resin, the presence / absence of additives used as necessary, and the dispersion method, and is not limited uniquely. However, it is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight with respect to 100 parts by weight of the toner binder resin. When the content exceeds 10 parts by mass, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, and the fluidity of the developer is lowered. In addition, the image density may be reduced.
  • charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch or resin, and of course, they can be added directly when dissolved and dispersed in an organic solvent, or they can be fixed on the toner surface after preparation of toner particles. May be.
  • the toner of the present invention preferably contains a layered inorganic mineral in which at least a part of ions between layers of the resin fine particles or the layered inorganic mineral is modified with organic ions in order to improve heat resistant storage stability.
  • the resin fine particles move to the oil phase side by dispersing in the water phase, and the layered inorganic mineral is pushed out to the surface of the oil droplets by dispersing in the oil phase, so that it can be present on the surface of the toner base particles.
  • the resin fine particles are required to have a glass transition point (Tg) of 50 ° C. to 70 ° C.
  • Tg glass transition point
  • the glass transition point (Tg) is less than 50 ° C., the toner storage stability is deteriorated and stored. In addition, blocking occurs in the developing machine.
  • the glass transition point (Tg) is higher than 70 ° C., the resin fine particles inhibit the adhesiveness to the fixing paper, and the fixing minimum temperature is increased.
  • the weight average molecular weight is 100,000 or less. Preferably it is 50,000 or less. The lower limit is usually 4,000. When the weight average molecular weight exceeds 100,000, the resin fine particles hinder the adhesion to the fixing paper, and the fixing minimum temperature increases.
  • the resin fine particles may be any resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin.
  • a thermoplastic resin or a thermosetting resin for example, vinyl resin, polyurethane resin, epoxy resin, polyester resin, polyamide Examples thereof include resins, polyimide resins, silicon resins, phenol resins, melamine resins, urea resins, aniline resins, ionomer resins, and polycarbonate resins.
  • the resin fine particles two or more of the above resins may be used in combination. Of these, preferred is a vinyl resin, a polyurethane resin, an epoxy resin, a polyester resin, or a combination resin thereof because an aqueous dispersion of fine spherical resin particles is easily obtained.
  • vinyl resin examples include polymers obtained by homopolymerization or copolymerization of vinyl monomers, such as styrene- (meth) acrylic acid ester resins, styrene-butadiene copolymers, and (meth) acrylic acid-acrylic acid ester polymers. Styrene-acrylonitrile copolymer, styrene-maleic anhydride copolymer, styrene- (meth) acrylic acid copolymer, and the like.
  • the average particle size of the resin fine particles is preferably 5 nm to 200 nm, and more preferably 20 nm to 150 nm.
  • the modified layered inorganic mineral is preferably one having a smectite basic crystal structure modified with an organic cation.
  • a metal cation can be introduce
  • a hydrophilic property is high when a metal anion is introduced, a layered inorganic compound in which at least a part of the metal cation is modified with an organic anion is preferable.
  • Examples of the organic ion modifier of the layered inorganic mineral obtained by modifying at least part of the ions of the layered inorganic mineral with organic ions include quaternary alkyl ammonium salts, phosphonium salts and imidazolium salts. Quaternary alkyl ammonium salts are preferred. Examples of the quaternary alkylammonium include trimethylstearylammonium, dimethylstearylbenzylammonium, dimethyloctadecylammonium, oleylbis (2-hydroxyethyl) methylammonium and the like.
  • organic ion modifier examples include branched, unbranched or cyclic alkyl (C1 to C44), alkenyl (C1 to C22), alkoxy (C8 to C32), hydroxyalkyl (C2 to C22), ethylene oxide, propylene oxide, and the like.
  • examples include sulfates, sulfonates, carboxylates, or phosphates.
  • a carboxylic acid having an ethylene oxide skeleton is preferred.
  • the content of the layered inorganic mineral obtained by modifying a part of the toner material with organic ions is preferably 0.05% by mass to 2% by mass.
  • the layered inorganic mineral partially modified with organic ions can be selected as appropriate, and examples thereof include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof.
  • organically modified montmorillonite or bentonite is preferable because the viscosity can be easily adjusted without affecting the toner characteristics and the addition amount can be reduced.
  • layered inorganic minerals partially modified with organic cations include, for example, Bentone 3, Bentone 38, Bentone 38V (above, manufactured by Leox), Thixogel VP (manufactured by United catalyst), Kraton 34, Kraton 40, Quartium 18 bentonite such as Clayton XL (above, Southern Clay), etc .; Steallarco such as Bentone 27 (made by Leox), Thixogel LG (made by United catalyst), Clayton AF, Clayton APA (above, made by Southern Clay) Quanium 18 / benzalkonium bentonite such as Clayton HT, Clayton PS (manufactured by Southern Clay, Inc.). Among these, Clayton AF and Clayton APA are particularly preferable.
  • the layered inorganic mineral partially modified with an organic anion one obtained by modifying DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd.) with an organic anion represented by the following general formula (1) is particularly preferable.
  • Examples of the following general formula (1) include Hytenol 330T (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).
  • General formula (1) [Wherein R 1 represents an alkyl group having 13 carbon atoms, and R 2 represents an alkylene group having 2 to 6 carbon atoms. n represents an integer of 2 to 10, and M represents a monovalent metal element. ]
  • the modified layered inorganic mineral it has moderate hydrophobicity, and therefore tends to be present at the interface of the droplets, so that the surface is unevenly distributed and the heat resistant storage stability and chargeability of the toner can be exhibited.
  • inorganic fine particles can be preferably used as the external additive for assisting the fluidity, developability and chargeability of the colored resin particles (toner base particles) obtained in the present invention.
  • the primary particle diameter of the inorganic fine particles is preferably 5 nm to 100 nm, more preferably 10 nm to 50 nm.
  • the specific surface area by the BET method is preferably 20 m 2 / g to 500 m 2 / g.
  • the use ratio of the inorganic fine particles is preferably 0.01% by mass to 5% by mass of the toner, and more preferably 0.01% by mass to 2.0% by mass.
  • the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, silica sand, clay, mica, wollastonite.
  • Diatomaceous earth chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride and the like.
  • polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, polycondensation system such as methacrylate ester, acrylate copolymer, silicone, benzoguanamine, nylon, thermosetting
  • polycondensation system such as methacrylate ester, acrylate copolymer, silicone, benzoguanamine, nylon, thermosetting
  • examples thereof include polymer particles made of a resin.
  • Such external additives can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity.
  • silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferred surface treatment agents. It is done.
  • a cleaning improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium may be added.
  • the cleaning improver include fatty acids such as zinc stearate, calcium stearate, and stearic acid.
  • fatty acids such as zinc stearate, calcium stearate, and stearic acid.
  • metal salts such as polymer fine particles produced by soap-free emulsion polymerization such as polymethyl methacrylate fine particles and polystyrene fine particles.
  • the polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 ⁇ m to 1 ⁇ m.
  • the toner of the present invention can be produced by the following method, but is not limited thereto.
  • ⁇ Toner production method in aqueous medium an oil phase in which a toner material containing a binder resin or a binder resin precursor, a colorant, and a release agent is dissolved or dispersed in an organic solvent is dispersed in an aqueous medium, and modified as necessary.
  • the toner base particles obtained by treatment, solvent removal, washing, and drying are used, and suspension polymerization, emulsion polymerization, polymer suspension, and the like can also be used.
  • the aqueous medium water alone may be used, but a solvent miscible with water may be used in combination.
  • miscible solvent examples include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methyl cellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.), and the like.
  • the toner particles can be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group with an amine (B) in an aqueous medium.
  • a method for stably forming a dispersion composed of urea-modified polyester or prepolymer (A) in an aqueous medium the composition of a toner raw material composed of urea-modified polyester or prepolymer (A) is added to the aqueous medium. And a method of dispersing by shearing force.
  • the prepolymer (A) and other toner components are water-based. Mixing may be performed when the dispersion is formed in the medium, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium.
  • other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.
  • the dispersion method is not particularly limited, and known equipment such as a low-speed shearing type, a high-speed shearing type, a friction type, a high-pressure jet type, and an ultrasonic wave can be applied.
  • a high-speed shearing method is preferable in order to make the particle size of the dispersion 2 ⁇ m to 20 ⁇ m.
  • the number of rotations is not particularly limited, but is usually 1000 rpm to 30,000 rpm, preferably 5,000 rpm to 20,000 rpm.
  • the dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 minutes to 5 minutes.
  • the temperature at the time of dispersion is usually 0 ° C.
  • the dispersion of the urea-modified polyester or prepolymer (A) has a low viscosity and is easy to disperse.
  • the amount of the aqueous medium used is usually 50 parts by mass to 2,000 parts by mass, preferably 100 parts by mass to 1,000 parts by mass with respect to 100 parts by mass of the toner composition (composition) containing urea-modified polyester and prepolymer (A). Part.
  • the amount used is less than 50 parts by mass, the dispersed state of the toner composition is poor and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 2,000 parts by mass, it is not economical.
  • a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.
  • the amines (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or the amines may be reacted after being dispersed in the aqueous medium. (B) may be added to cause a reaction from the particle interface.
  • urea-modified polyester is preferentially generated on the surface of the toner to be produced, and a concentration gradient can be provided inside the particles.
  • Anionic surfactants such as alkylbenzene sulfonates, ⁇ -olefin sulfonates, phosphates, etc. as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water
  • Amine salt types such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride
  • Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives such as alanine, dodecyldi (aminoethyl) glycine, di (octy
  • a surfactant having a fluoroalkyl group by using a surfactant having a fluoroalkyl group, the effect can be increased in a very small amount.
  • Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6 to C11).
  • DS-102 (Daikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF-102 , 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fagento F-100, F150 (manufactured by Neos).
  • cationic surfactants include aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, benzaza Luconium salt, benzethonium chloride, pyridinium salt, imidazolinium salt, trade names include Surflon S-121 (Asahi Glass), Florard FC-135 (Sumitomo 3M), Unidyne DS-202 (Daikin Industries) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products), and Footgent F-300 (manufactured by Neos).
  • aliphatic primary, secondary or secondary amine acids having a fluoroalkyl group aliphatic quaternary ammonium salts
  • calcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can also be used as inorganic compound dispersants that are hardly soluble in water.
  • the dispersed droplets may be stabilized with a polymer protective colloid.
  • a polymer protective colloid for example, acrylic acid, methacrylic acid, ⁇ -cyanoacrylic acid, ⁇ -cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, and other (meth) acrylic single monomers containing hydroxyl groups
  • the calcium phosphate salt is removed from the fine particles by a method such as dissolving the calcium phosphate salt with an acid such as hydrochloric acid and washing with water. To do. It can also be removed by operations such as enzymatic degradation.
  • the dispersant can remain on the surface of the toner particles. However, it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.
  • a solvent in which the urea-modified polyester or the prepolymer (A) is soluble can be used. It is preferable to use a solvent in that the particle size distribution becomes sharp.
  • the solvent is preferably volatile with a boiling point of less than 100 ° C. from the viewpoint of easy removal.
  • solvent examples include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more.
  • aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform, and carbon tetrachloride are particularly preferable.
  • the amount of the solvent to be used with respect to 100 parts by mass of the prepolymer (A) is usually 0 part by mass to 300 parts by mass, preferably 0 part by mass to 100 parts by mass, and more preferably 25 parts by mass to 70 parts by mass.
  • a solvent is used, it is removed by heating under normal pressure or reduced pressure after the elongation and / or crosslinking reaction.
  • the elongation and / or crosslinking reaction time is the isocyanate group structure and amine of the prepolymer (A).
  • the reaction temperature is usually 0 ° C. to 150 ° C., preferably 40 ° C. to 98 ° C.
  • a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.
  • a method of gradually elevating the temperature of the entire system and / or reducing the pressure to completely evaporate and remove the organic solvent in the droplets can be employed.
  • a dry atmosphere in which the emulsified dispersion is sprayed a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, particularly various air streams heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used are generally used. Sufficient quality can be obtained with a short processing time such as spray dryer, belt dryer, rotary kiln. Further, filtration may be performed.
  • the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classifying into a desired particle size distribution.
  • the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like.
  • the classification operation may be performed after obtaining the powder after drying, but it is preferably performed in a liquid in terms of efficiency.
  • the unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
  • the dispersant used is preferably removed from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.
  • the resulting dried toner powder By mixing the resulting dried toner powder with dissimilar particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or by giving mechanical impact force to the mixed powder By immobilizing and fusing on the surface, it is possible to prevent detachment of the foreign particles from the surface of the resulting composite particle.
  • Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture into a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there.
  • Ong mill manufactured by Hosokawa Micron Co., Ltd.
  • I-type mill manufactured by Nippon Pneumatic Co., Ltd.
  • hybridization system manufactured by Nara Machinery Co., Ltd.
  • kryptron system Kawasaki Heavy Industries, Ltd.
  • the toner of the present invention When the toner of the present invention is used for a two-component developer, it may be used by mixing with a magnetic carrier.
  • the carrier to toner content ratio in the developer is 1 part by weight of toner to 100 parts by weight of carrier. 10 parts by mass is preferred.
  • the magnetic carrier conventionally known ones such as iron powder, ferrite powder, magnetite powder, magnetic resin carrier having a particle diameter of about 20 ⁇ m to 200 ⁇ m can be used.
  • the carrier surface may be coated, and examples of the coating material include amino resins such as urea-formaldehyde resin, melamine resin, benzoguanamine resin, urea resin, polyamide resin, and epoxy resin.
  • Polyvinyl and polyvinylidene resins for example, acrylic resins, polymethyl methacrylate resins, polyacrylonitrile resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyvinyl butyral resins, polystyrene resins and polystyrene resins such as styrene acrylic copolymer resins, Halogenated olefin resins such as polyvinyl chloride, polyester resins such as polyethylene terephthalate resin and polybutylene terephthalate resin, polycarbonate resins, polyethylene resins, polyvinyl fluoride resins, polyvinylidene fluoride resins, polytrifluoroethylene resins, poly Hexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, copolymer of vinylidene fluoride and vinyl fluoride, tetrafluoroethylene and vinylidene fluoride Fluoro such as ter
  • conductive powder examples include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. These conductive powders preferably have an average particle diameter of 1 ⁇ m or less. When the average particle diameter is larger than 1 ⁇ m, it is difficult to control electric resistance.
  • the toner of the present invention can also be used as a one-component magnetic toner that does not use a carrier or a non-magnetic toner.
  • the toner of the present invention even if the toner container made of a flexible member capable of reducing the volume by 60% or more is filled and used, the toner can be supplied with a small amount of toner. Specifically, by filling a toner container made of a flexible member capable of reducing volume by 60% or more with the toner of the present invention, automatic supply from the container to the developing unit can be stably performed. After storage, toner powder packing does not occur in the container, and the remaining amount of toner powder can be further reduced.
  • the toner of the present invention has a low temperature fixability and a small particle diameter, and has excellent toner and fluidity. Therefore, as a toner supply means connected to a toner storage means, a mixture of toner powder and air is used.
  • the flexible toner container automatically reduces its volume when the pump means is used so that the fluid does not flow backward, and the shape around the container changes to give a loosening action, and the remaining amount of toner is reduced. It can be effectively reduced.
  • a gas such as air is jetted into the toner container using a nozzle or the like, and the toner powder layer is allowed to pass through while diffusing, thereby facilitating the fluidization of the toner. Even when a supply member such as an agitator cannot be assembled, the toner can be supplied more stably and the remaining toner can be reduced.
  • FIG. 1 An example of a toner supply method from a toner container that can be used in the present invention will be described below.
  • air is sent from the air inflow unit 30 to the toner container 23.
  • the air is ejected into the toner container, and the ejected air passes while diffusing the toner layer.
  • the air ejected from the toner container together with the toner into the toner container passes through the toner layer while diffusing.
  • the fluidization of the toner is promoted. Occurrence of a cross-linking phenomenon or the like is prevented, and toner supply is more reliable.
  • a suction type uniaxial eccentric screw pump (commonly known as MONO pump) is preferable. Its configuration consists of a rotor made in the shape of a screw that is eccentric with a rigid material such as metal, a stator that is made of a rubber material and fixed in the shape of a screw with two insides, and wraps these powders It consists of a holder made of a resin material that forms the transfer path. When the rotor rotates, a strong self-priming force is generated in the pump, and it becomes possible to suck in an airflow containing toner. If an air pump is used in addition to the powder pump means 25, fluidization of the toner is promoted by the supplied air, and toner transfer by the powder pump means 25 becomes more reliable.
  • MONO pump suction type uniaxial eccentric screw pump
  • the developing unit 10 includes a developing sleeve 11 disposed opposite to the photosensitive member 1 as a latent image carrier and stirring screws 12 and 13. In the developer circulated between the stirring screws 12 and 13, the supplied toner is subjected to uniform toner concentration and proper charge amount. Further, the developer is transferred to the developing sleeve 11 to develop the electrostatic latent image formed on the photoreceptor 1.
  • this is only an example, and it can be used for other developing devices and developing systems.
  • the toner container that can be used in the present invention includes a bag portion and a connection portion formed of a flexible single layer or laminated sheet.
  • FIG. 2 shows an example of a toner container
  • FIG. 3 shows a form when the volume of the toner container is reduced.
  • the toner container 40 includes a rigid mouth part 41 and a soft and flexible bag part 42.
  • the mouth part 41 can use a normal molding material such as polyethylene, polypropylene, nylon, ABS resin, NBS resin
  • the bag part 42 can use a plastic film or paper such as polyethylene, polypropylene, polyester, polyurethane, In the case of a plastic film, a thickness of about 0.05 mm to 0.5 mm is preferable.
  • FIG. 4 is a schematic diagram of a toner supply device including a toner container, an air supply device, and a powder pump.
  • 2 is a toner container
  • 14 is an air supply nozzle
  • 17 is an air nozzle
  • 20 is an air supply tube
  • 21 is an air pump
  • 22 is a toner supply tube
  • 26 is a powder pump.
  • the toner container is flexible, the volume in the bag is reduced as the toner sucks, and the introduced air causes the occurrence of toner clogging due to local deformation at the time of volume reduction of the bag-like toner container. At the same time, the suction efficiency of the powder pump increases, and the stored toner is discharged without leaving the bag.
  • the toner container 23 and the developing device 10 are connected via a tube 16.
  • the tube 16 is a flexible tube having a diameter of 4 to 10 mm, and is preferably made of a rubber material having toner resistance such as polyurethane, nitrile, EPDM, or silicone.
  • a part is a mass part.
  • the storage elastic modulus G ′, Tfb, and glass transition temperature of the low molecular weight polyester were measured as follows.
  • the number average molecular weight Mn, the weight average molecular weight Mw, and the acid value of the low molecular weight polyester were measured by a known measuring method.
  • ⁇ Measurement method of storage elastic modulus G '> The storage elastic modulus G ′ was measured using a viscoelasticity measuring device (rheometer) RDA-II type (manufactured by Rheometrics). Measurement jig: A parallel plate having a diameter of 7.9 mm was used. Measurement sample: The toner was heated and melted and molded into a cylindrical sample having a diameter of about 8 mm and a height of 3 mm. Measurement frequency: 1Hz Measurement temperature: 50 ° C to 230 ° C Measurement strain setting: The initial value was set to 0.1%, and the measurement was performed in the automatic measurement mode. Sample elongation correction: Adjusted in automatic measurement mode.
  • Ts and Tfb were measured using an elevated flow tester (manufactured by Shimadzu Corporation) according to the method described in JIS K72101. While heating a sample of 1 cm 3 at a heating rate of 6 ° C./min, a load of 10 kg / cm 2 is applied by a plunger, and a nozzle having a diameter of 0.5 mm and a length of 1 mm is pushed out. Draw a volume-temperature curve. The flow curve of this flow tester becomes data as shown in FIG. 5, and each temperature can be read therefrom.
  • A is a measurement start temperature
  • B Ts (softening temperature)
  • C Tfb (outflow start temperature)
  • D is a 1/2 outflow temperature
  • E is a measurement end temperature.
  • ⁇ Glass transition temperature Tg> A TG-DSC system TAS-100 manufactured by Rigaku Corporation was used as an apparatus for measuring the glass transition temperature (Tg). First, about 10 mg of a sample was placed in an aluminum sample container, placed on a holder unit, and set in an electric furnace. First, after heating from room temperature to 150 ° C. at a temperature rising rate of 10 ° C./min, the sample was allowed to stand at 150 ° C. for 10 minutes, the sample was cooled to room temperature and left for 10 minutes, and the temperature rising rate was again increased to 150 ° C. under a nitrogen atmosphere. DSC measurement is performed with heating at min. The glass transition temperature Tg was calculated from the tangent line of the endothermic curve near the Tg and the base line using the analysis system in the TAS-100 system.
  • Aqueous vinyl resin (a copolymer of styrene-methacrylic acid-butyl acrylate-methacrylic acid ethylene oxide adduct sulfate sodium salt)
  • a dispersion [fine particle dispersion 1] was obtained.
  • the volume average particle diameter of the obtained [fine particle dispersion 1] measured with a particle size distribution analyzer (LA-920, manufactured by Horiba Seisakusho) was 0.10 ⁇ m.
  • a part of the obtained [fine particle dispersion 1] was dried to isolate the resin component.
  • the resin content had a Tg of 57 ° C. and a weight average molecular weight of 121,000.
  • aqueous phase 990 parts of water, 80 parts of [fine particle dispersion 1], 40 parts of a 48.5% aqueous solution of sodium dodecyl diphenyl ether disulfonate (Eleminol MON-7, manufactured by Sanyo Chemical Industries), and 90 parts of ethyl acetate were mixed and stirred. A liquid was obtained. This is designated as [Aqueous Phase 1].
  • G ′ (Tfb) 9,800, and an SP value.
  • Low molecular weight polyester 12 has a number average molecular weight of 2,600, a weight average molecular weight of 6,400, Tg of 48 ° C, an acid value of 20.2 mgKOH / g, T1 of 59.2 ° C, T2 of 68.3 ° C, and a resin softening coefficient.
  • G ′ (Tfb) 4,500, SP value was 11.1.
  • Table 1 shows the physical properties of low molecular weight polyesters 1-16.
  • ⁇ Synthesis of crystalline polyester 2 > 1260 g of 1,4-butanediol, 120 g of ethylene glycol, 1400 g of stearic acid, 350 g of trimellitic anhydride, 3.5 g of tin octylate, and 1.5 g of hydroquinone
  • Into a 5 liter four-necked flask equipped with a reaction mixture reacted at 160 ° C. for 5 hours, heated to 200 ° C. and reacted for 1 hour, and further reacted at 8.3 kPa for 1 hour to produce crystalline polyester.
  • the obtained crystalline polyester (2) had a melting point of 89 ° C. and an SP value of 9.5.
  • [Intermediate polyester 1] had a number average molecular weight of 2,100, a weight average molecular weight of 9,500, Tg of 55 ° C., an acid value of 0.5 mgKOH / g, and a hydroxyl value of 49 mgKOH / g.
  • 411 parts of [Intermediate polyester 1], 89 parts of isophorone diisocyanate, and 500 parts of ethyl acetate are placed in a reaction vessel equipped with a cooling pipe, a stirrer, and a nitrogen introduction pipe, and reacted at 100 ° C. for 5 hours.
  • [Prepolymer 1] was obtained.
  • [Prepolymer 1] had a free isocyanate mass% of 1.53%.
  • Example 1 ⁇ Production of toner> -Preparation of oil phase- A container equipped with a stir bar and a thermometer was charged with 378 parts of [Low molecular polyester 1], 110 parts of carnauba wax, 220 parts of [Crystalline polyester 1], and 947 parts of ethyl acetate, and the temperature was raised to 80 ° C. with stirring. The mixture was kept at 80 ° C. for 5 hours, and then cooled to 30 ° C. in 1 hour to obtain [Raw material solution 1].
  • [Emulsified slurry 1] was put into a container equipped with a stirrer and a thermometer, allowed to stand at 15 ° C for 1 hour, and then desolvated at 30 ° C for 1 hour to obtain [Dispersed slurry 1].
  • the obtained [Dispersion Slurry 1] had a volume average particle size of 5.95 ⁇ m and a number average particle size of 5.45 ⁇ m (measured with Multisizer II).
  • Example 2 Toner 2 was obtained in the same manner as in Example 1 except that [Low molecular polyester 2] was used instead of [Low molecular polyester 1] in Example 1.
  • Example 3 Toner 3 was obtained in the same manner as in Example 1, except that [Low molecular polyester 1] was used instead of [Low molecular polyester 1] in Example 1.
  • Example 4 Toner 4 was obtained in the same manner as in Example 1 except that [Low molecular polyester 4] was used instead of [Low molecular polyester 1] in Example 1.
  • Example 5 Toner 5 was obtained in the same manner as in Example 1 except that [Low molecular polyester 5] was used instead of [Low molecular polyester 1] in Example 1.
  • Toner 6 was obtained in the same manner as in Example 1, except that [Low Molecular Polyester 1] was used instead of [Low Molecular Polyester 1].
  • Toner 8 was obtained in the same manner as in Example 1, except that [Low molecular polyester 8] was used instead of [Low molecular polyester 1] in Example 1.
  • a developer composed of 5% by mass of toner subjected to external additive treatment and 95% by mass of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle diameter of 40 ⁇ m can be prepared, and 45 sheets of A4 size paper can be printed per minute.
  • an image forming apparatus manufactured by Ricoh Co., Ltd., imgioNeo450
  • continuous printing was performed and evaluation was performed according to the following criteria. The results are shown in Table 2.
  • volume average particle diameter Dv, number average particle diameter Dn, and particle size distribution (Dv / Dn) of the toner were measured using a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics Co., Ltd., with an aperture diameter of 100 ⁇ m.
  • ⁇ Average circularity of toner> As a method for measuring the average circularity of the toner, there is an optical detection zone method in which a suspension containing particles is passed through an imaging unit detection zone on a flat plate, and a particle image is optically detected and analyzed by a CCD camera. Is appropriate.
  • the circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected area obtained by this method by the perimeter of the actual particle. This value was measured as an average circularity by a flow type particle image analyzer FPIA-2100 (manufactured by Toa Medical Electronics Co., Ltd.).
  • 0.1 ml to 0.5 ml of a surfactant (alkylbenzene sulfonate) is added as a dispersant to 100 ml to 150 ml of water from which impure solids have been removed in advance, and a measurement sample is further added. About 0.1 to 0.5 g was added. The suspension in which the sample was dispersed was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape of the toner was measured with the above apparatus with a dispersion concentration of 3000 to 10,000 / ⁇ l.
  • a surfactant alkylbenzene sulfonate
  • ⁇ Fixability (fixing lower limit temperature, fixing width)>
  • a solid image and a thick paper transfer paper (type 6200 manufactured by Ricoh Co., Ltd. and copy printing paper ⁇ 135> manufactured by NBS Ricoh Co., Ltd.) are solid images of 1.0 ⁇ 0.1 mg / cm 2.
  • the toner was developed so as to be developed, and the temperature of the fixing belt was adjusted to be variable, and the temperature at which no offset occurred on plain paper and the fixing lower limit temperature on thick paper were measured.
  • the minimum fixing temperature was the fixing roll temperature at which the residual ratio of the image density after rubbing the obtained fixed image with a pad was 70% or more, and the low temperature fixing property was evaluated according to the following criteria.
  • Example 6 Example 1 [Emulsification, modification, and solvent removal] was changed as follows, and [Low molecular weight polyester 9] was used instead of [Low molecular weight polyester 1], in the same manner as in Example 1. Toner 9 was obtained.
  • [Emulsification, modification, and solvent removal] [Oil phase dispersion 1] 800 parts and [ketimine compound 1] 6.6 parts are put in a container, mixed with TK homomixer (manufactured by Tokushu Kika) at 5,000 rpm for 1 minute, 1] 1,200 parts were added and mixed with a TK homomixer at a rotational speed of 13,000 rpm for 3 minutes to obtain [Emulsion slurry 1].
  • [Emulsion slurry 1] was put into a container in which a stirrer and a thermometer were set, and allowed to stand at 15 ° C. for 1 hour, followed by desolvation at 30 ° C. for 1 hour to obtain [Dispersion slurry 1].
  • the obtained [Dispersion Slurry 1] had a volume average particle size of 5.95 ⁇ m and a number average particle size of 5.45 ⁇ m (measured with Multisizer II).
  • Example 7 Toner 10 was obtained in the same manner as in Example 6 except that [Low molecular polyester 9] was used instead of [Low molecular polyester 9] in Example 6.
  • Example 8 The same procedure as in Example 6 was performed except that [Low molecular polyester 9] was used instead of [Low molecular polyester 9] in Example 6, and [Crystalline polyester 2] was used instead of [Crystalline polyester 1]. Thus, toner 11 was obtained.
  • Example 9 Toner 12 was obtained in the same manner as in Example 1, except that [Low molecular polyester 1] was used instead of [Low molecular polyester 1] in Example 1.
  • Example 10 Toner 13 was obtained in the same manner as in Example 9, except that the amount of [Prepolymer 1] added in Example 9 was changed to 288 parts.
  • Toner 15 was obtained in the same manner as in Example 1, except that [Low Molecular Polyester 9] was used instead of [Low Molecular Polyester 9] in Example 6.
  • Toner 16 was obtained in the same manner as in Example 9, except that [Low molecular polyester 15] was used instead of [Low molecular polyester 12] in Example 9.
  • Example 12 The same as Example 9 except that [Low molecular polyester 12] was used instead of [Low molecular polyester 12] in Example 9 and [Crystalline polyester 3] was used instead of [Crystalline polyester 1]. Thus, toner 17 was obtained.
  • a developer consisting of 5% by mass of external additive-treated toner and 95% by mass of a copper-zinc ferrite carrier coated with a silicone resin and having an average particle size of 40 ⁇ m is prepared, and 45 sheets of A4 size paper are printed per minute.
  • a continuous image was printed using an image forming apparatus (manufactured by Ricoh Co., Ltd., imagio Neo 450), and the low-temperature fixability and the storage stability were evaluated according to the above criteria.
  • spent property was evaluated according to the following criteria. The results are shown in Table 3.
  • ⁇ Spent property> Using a tandem color image forming apparatus (imagio Neo450, manufactured by Ricoh Co., Ltd.), while controlling the toner density so that the image density is 1.4 ⁇ 0.2 mg / cm 2 on a chart with a 20% image area, The amount of change in the developer charge amount ( ⁇ c / g) after output of 200,000 sheets (the amount of decrease in charge amount after 200,000 sheet run / charge amount at the beginning of the run) is compared with the initial value before output. Evaluation was made according to the following criteria. The charge amount was measured by a blow-off method. ⁇ Evaluation criteria ⁇ ⁇ : Less than 15% ⁇ : 15% or more and less than 30% ⁇ : 30% or more and less than 50% ⁇ : 50% or more

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  • General Physics & Mathematics (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

L'invention concerne un toner comprenant une résine liante, un agent colorant et un agent de démoulage, la résine liante comprenant un composant de résine à faible poids moléculaire, le composant de résine à faible poids moléculaire ayant un coefficient de ramollissement de résine (A) représenté par la formule (1) supérieur à 0,165 et un module de conservation (dyne/cm2) (G'(Tfb)) inférieur ou égal à 1×104 quand la température de départ d'écoulement (°C) mesurée dans un appareil d'essai d'écoulement élevé est exprimée comme Tfb. A = |(lnG'(r1)-lnG'(r2))/(T1-T2)| formule (1) (Dans la formule, T1 représente la température (°C) à laquelle le module de conservation (G'(r1) devient 1×105 (dyne/cm2) et T2 représente la température (°C) à laquelle le module de conservation (G'(r2)) devient 1×103 mesuré au moyen d'un appareil de mesure de viscoélasticité dans les conditions d'une fréquence de mesure de 1 Hz et d'une déformation de mesure de 1 degré ; et « | | » signifie une valeur absolue.)
PCT/JP2011/073449 2010-03-02 2011-10-12 Toner pour développement à charge électrostatique WO2012101875A1 (fr)

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US13/637,774 US8778588B2 (en) 2010-03-02 2011-10-12 Toner for electrostatic charge development
EP11857117.3A EP2546698A4 (fr) 2011-01-27 2011-10-12 Toner pour développement à charge électrostatique
CN201180016458.0A CN102834782B (zh) 2011-01-27 2011-10-12 静电荷显影用调色剂

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JP6728778B2 (ja) * 2016-03-02 2020-07-22 富士ゼロックス株式会社 光輝性トナー、静電荷像現像剤、トナーカートリッジ、プロセスカートリッジ、画像形成装置、及び画像形成方法
JP6672893B2 (ja) * 2016-03-03 2020-03-25 富士ゼロックス株式会社 光輝性トナー、静電荷像現像剤、トナーカートリッジ、プロセスカートリッジ、画像形成装置、及び画像形成方法

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