WO2007142343A1 - トナー - Google Patents
トナー Download PDFInfo
- Publication number
- WO2007142343A1 WO2007142343A1 PCT/JP2007/061678 JP2007061678W WO2007142343A1 WO 2007142343 A1 WO2007142343 A1 WO 2007142343A1 JP 2007061678 W JP2007061678 W JP 2007061678W WO 2007142343 A1 WO2007142343 A1 WO 2007142343A1
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- WO
- WIPO (PCT)
- Prior art keywords
- toner
- fine powder
- acid
- silica fine
- silica
- Prior art date
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Classifications
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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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09725—Silicon-oxides; Silicates
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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
- G03G9/0802—Preparation methods
- G03G9/0812—Pretreatment of components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0819—Developers with toner particles characterised by the dimensions of the particles
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0825—Developers with toner particles characterised by their structure; characterised by non-homogenuous distribution of components
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/087—Binders for toner particles
- G03G9/08784—Macromolecular material not specially provided for in a single one of groups G03G9/08702 - G03G9/08775
- G03G9/08786—Graft polymers
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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
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09708—Inorganic compounds
- G03G9/09716—Inorganic compounds treated with organic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09783—Organo-metallic compounds
Definitions
- the present invention relates to a toner used in electrophotography, an image forming method for developing an electrostatic image, a toner jet method, and the like.
- an electrophotographic method generally forms an electric latent image on a photoreceptor by various means, and then develops the latent image with toner, and if necessary, transfers toner to a transfer material such as paper. After the image is transferred, the toner image is fixed on the transfer material by heat or pressure to obtain a copy. The toner remaining on the photosensitive member without being transferred is cleaned by various methods, and the above-described steps are repeated.
- the copy-forgery-inhibited pattern printing technology is a technology that simultaneously prints a copy-forgery-inhibited pattern that conceals character strings when printing a document with a copier or printer.
- a character string such as “No copy” is embedded in the “background pattern” in advance so that it is difficult to see, and the character string stands out when copied with a copier.
- the copy-forgery-inhibited pattern printing technology uses the limits of the dot reproducibility when copying with a copier, so density stability (density range), dot reproducibility, line reproducibility, especially line width reproducibility, There is a need for a toner that has good tailing at the rear end.
- QR codes matrix-type two-dimensional codes
- Japanese Patent Laid-Open No. 5-1 4 2 8 Japanese Patent No. 49, Japanese Patent Application Laid-Open No. 5-224456 and Japanese Patent Application Laid-Open No. 2002-287410 propose to improve image stability by adding hydrophobic and spherical force to toner particles.
- high-speed development systems tend to cause embedding and release of the desired silica, resulting in high speed and high speed. In order to achieve fine image formation, there is not enough room for improvement.
- the chargeability of the toner is not sufficient, a long-term durability tends to cause a decrease in image density and fogging.
- Japanese Patent Application Laid-Open No. 2002-003213 proposes to improve the chargeability of the toner and improve the image stability by adding fine amorphous silica powder to the toner particles.
- Japanese Patent Laid-Open No. 2002-108001 proposes adding silica fine powder produced by a so-called sol-gel method to toner particles. According to these methods, an image having a good density and fog can be obtained, but since the pores on the surface of the silica fine powder are not controlled, the physical properties of the surface of the silica fine powder tend to be uneven. Also, in a high humidity environment, moisture in the atmosphere may be adsorbed and the toner charge may be reduced.
- Japanese Patent Laid-Open Nos. 2004-334069 and 6-019190 propose to increase toner chargeability by adding a hydrophobized titanium oxide or alumina to toner particles.
- Japanese Laid-Open Patent Publication No. 20 03-322998 proposes to increase the stability of an image by adding an inorganic fine powder having a prescribed particle size to toner particles.
- an object of the present invention is to provide a toner that eliminates the above-mentioned problems. That is, the object of the present invention is to obtain good density stability, line reproducibility, and dot reproducibility stably over a long period of time, even in a high-speed copying machine or printer.
- the purpose is to provide a toner that provides image quality that can be applied to QR code prints.
- the present invention relates to a toner having toner particles containing at least a binder resin and a colorant and silica fine powder, and the silica fine powder has a volume-based median diameter (D 50) of 0.70. It is characterized in that the total pore volume measured in the range of not less than m and not more than 3.0 m but not less than 1.7 nm and not more than 300 nm is not more than 0.200 cm 3 Zg. It is about Tona. .
- the fine silica powder preferably has an average pore diameter of 50 nm or less.
- the toner preferably further has a hydrophobic inorganic fine powder having a BET specific surface area of 5 Om 2 Zg or more and 30 Om 2 Zg or less.
- the amount of moisture adsorbed in the adsorption process at a relative humidity of 80% RH is in the range of 0.001 to 1.00% by mass. Is preferred.
- the silica fine powder is produced by a gas phase method.
- the present inventors have determined that the toner has toner particles containing at least a binder resin and a colorant and silica fine powder.
- the toner has toner particles containing at least a binder resin and a colorant and silica fine powder.
- a high-definition latent image is formed.
- the silica fine powder in a toner having toner particles containing at least a binder resin and a colorant, and silica fine powder, has a volume-based median diameter (D 50) of 0.70.
- the total pore volume measured in the range of not less than m and not more than 3.0 m and not less than 1.7 nm and not more than 30.0 nm is not more than 0.200 cm 3 Z g. It is characterized by that.
- the inorganic fine powder is required to have a high chargeability, a sharp particle size distribution, and a uniform shape. Satisfies these required performances and is preferably used.
- the silica fine powder used for toner is generally amorphous, and the surface has many submicron order (several nm to several hundred nm) pores, resulting in non-uniform charging. Tend. Especially in a high humidity environment, water molecules in the atmosphere enter the pores, so the charging ability decreases with continued durability. As a result, the chargeability of the toner becomes more non-uniform so that the toner tends to aggregate and the line reproducibility and dot reproducibility may deteriorate. Furthermore, the image density may decrease in the second half of the endurance due to a decrease in charging ability.
- toner In high-speed development systems, toner receives a large share in the developing unit. Therefore, the toner is liable to cause toner deterioration caused by embedding external additives in the developing device.
- the function of the silica fine powder as a spacer is reduced, and therefore the toner is more easily aggregated due to strong influences of non-uniform charging and a decrease in charging ability.
- silica fine powder as a spacer is not sufficient for a high-speed development system, as in the present invention, controlling surface characteristics and optimizing particle size by controlling the surface microstructure. Becomes important.
- the present inventors have added a silica fine powder having a specific pore state to the toner particles, so that a high-definition latent image is formed. It has been found that good density stability, line reproducibility, and dot reproducibility can be stably obtained over a long period of time regardless of environment.
- a silica fine powder having a total pore volume measured within a pore diameter range of 1.7 nm or more and 30.0 nm or less and not more than 0.200 cm 3 / g is used.
- 0 7 is 0 cm 3 Z g or less, and more preferably not more than 0. 0 2 5 cm 3 Z g.
- the total pore volume measured in the pore diameter range of 1.7 nm to 30.0 nm is less than 0 ⁇ 200 cm ⁇ g, which means that the number of pores on the surface of the silica fine powder is It represents less and / or a smaller volume of each pore.
- the chargeability of the silica fine powder becomes uniform and the water resistance is greatly improved, so that the chargeability can be stably maintained over a long period of time regardless of the environment. It becomes possible. For this reason, the chargeability of the toner is uniform and stable, so that high-speed Even in photocopiers and printers, it is possible to faithfully reproduce high-definition latent images without toner aggregation. As a result, good density stability, line reproducibility, and dot reproducibility can be stably obtained over a long period of time regardless of the environment.
- the total pore volume is larger than 0.200 cm 3 Zg, it indicates that there are many pores on the surface of the silica fine powder and that the volume of Z or each pore is large.
- the surface fine structure is not uniform, so the chargeability is also not uniform, and furthermore, water molecules in the atmosphere enter the pores, so that the charging ability decreases when the durability is continued.
- the chargeability of the toner becomes non-uniform so that the cohesiveness deteriorates, and the line reproducibility and dot reproducibility tend to deteriorate.
- the decrease in charging ability makes it easy for image density and fogging to deteriorate in the latter half of durability.
- the surface pore state of the fine silica powder can be measured with good reproducibility, and the pore size in which the fine pore state is accurately measured in the long range is in the range of 1.7 nm or more and 30.0 nm or less.
- the pore volume was measured.
- the present inventors use a silica fine powder having a total fine particle volume of 0.20 cm 3 Zg or less measured in a pore diameter range of 1. ⁇ nm or more and 300.0 nm or less. It was found that the silica fine powder can be added to the toner particles.
- the silica fine powder of the present invention has a volume-based median (D50) of 0.7 to ⁇ 3.00 m (preferably 0.70 to 111.50 / m). It is characterized by being.
- toner deterioration due to embedding of the silica fine powder can be achieved even in an environment where the toner receives a large share in the developing device as in a higher-speed image system.
- An image having good density stability, line reproducibility, and dot reproducibility can be stably obtained over a long period of time without depending on the environment.
- Silica fine powder with a median diameter (D 50) smaller than 0.70 m is likely to be embedded in toner particles, resulting in poor toner cohesion in high-speed development systems, and low line reproducibility and dot reproducibility. Become. On the other hand, silica fine powder larger than 3.00 / zm The powder tends to be released from the toner particles, and the image density decreases in the second half of the endurance.
- fine silica powder is measured in a volume-based median diameter (D 50) of 0.70 m or more and 3.00 / im or less and a pore diameter of 1.7 nm or more and 300.0 nm or less.
- D 50 volume-based median diameter
- a means for controlling the total pore volume to 0.200 cm 3 Zg or less it can be achieved by controlling the synthesis concentration, temperature and cooling rate in the production method of silica fine powder.
- the particle shape there is no particular limitation on the particle shape as long as the particle size and pores of the silica fine powder are controlled within the above ranges.
- the pore volume in the present invention is measured by a gas adsorption method in which nitrogen gas is adsorbed on the surface of a sample using a pore distribution measuring apparatus Tristar 3000 (manufactured by Shimadzu Corporation).
- Tristar 3000 manufactured by Shimadzu Corporation.
- the outline of the measurement is described in the operation manual issued by Shimadzu Corporation and is as follows. Prior to measurement of pore distribution, place 1 to 2 g of sample in a sample tube and evacuate at 10 for 24 hours. After evacuation, the sample weight was carefully sought to obtain a sample.
- the total pore volume in the range of pore diameters of 1.7 nm or more and 300.0 nm or less of the obtained sample was determined by the B JH desorption method using the pore distribution measuring apparatus. For the evaluation of the pore distribution, it is preferable to use the total pore volume closest to the measured data as an index.
- the particle size distribution is measured with a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by HOR I BA).
- LA-920 manufactured by HOR I BA.
- a measurement method for example, about 3 Omg of a sample is added to 100 ml of ion-exchanged water as a dispersion medium, and this dispersion is treated with an ultrasonic disperser for 1 minute to obtain a dispersion. This dispersion is dropped into the measuring cell so that the sample concentration is about 80% transmittance.
- the relative refractive index of the measurement sample and water is set according to the type of sample, and the median diameter (D50) is obtained by measuring the particle size distribution on the basis of the volume used with the measurement device.
- the toner such as a high-speed development system receives a large share in the developing device, that is, in a compacted state. It is easy to unravel during development without agglomeration Is the feature.
- a shear scan TS-1 12 (Sci-Te c) was used to evaluate the cohesiveness of the toner in the compacted state.
- Share scan is measured by the principle of Moul Coulomb model described in 'CHARACTER IZI NG POWDER FLOWAB ILI TY (2 0 02 ⁇ . 0 1.24 Announced)' written by Prof. V ire nd ra M. Puri I do.
- measurement was performed in a room temperature environment (2 3 ⁇ :, 60% RH) using a linear shear cell (cylindrical, diameter 80 mm, capacity 140 cm 3 ) that can apply shear force linearly in the cross-sectional direction. Went. Put a toner into this cell, apply a vertical load to 2.5 kPa, and prepare a compacted powder layer so that it becomes the closest packed state at this vertical load.
- the measurement by the shear scan is preferable in that it can be automatically detected and manufactured without individual differences.
- a compacted powder layer with a vertical load of 5. O kPa and 10.0 kPa is formed.
- Uniaxial collapse stress (U) is related to the ease of loosening due to agitation in the toner container and the situation when the toner is coated on the toner carrier through the restriction while receiving the share of the restriction member. To do. Further, the maximum consolidation stress (X) in the present invention represents the stress applied to the toner that is densely packed by the shear received in the developing device.
- the uniaxial collapse stress at the maximum compaction stress of 0.1 kPa is used to discuss the powder characteristics in a state where the share of the toner is relatively small, and the uniaxial collapse stress at the maximum compaction stress of 20.0 kPa is used. It is possible to discuss the powder characteristics when the share of toner is large. Then, by evaluating the transition of the uniaxial collapse stress between these maximum consolidation stresses, the powder characteristics of the toner layer under the compaction state were expressed.
- the toner of the present invention has a uniaxial collapse stress of 1 kPa or less when the maximum compaction stress of the toner is 0.1 kPa, and a uniaxial collapse stress of 2 or less when the maximum compaction stress of the toner is 20.0 kPa.
- It is preferably O kP a or more and 6.0 kP.a or less. By controlling to the above range, it is preferable that it is easy to unravel at the time of development without agglomeration even in a compacted state of light pressure or high pressure.
- silica fine powder used in the present invention can be used as long as it has the above-mentioned properties, but preferably has the following properties.
- the fine silica powder of the present invention preferably has an average pore size of 50.0 nm or less. If the average pore diameter is greater than 50 nm, the fine pores on the silica fine powder surface are large Indicates that Such a fine silica powder is not preferable because the amount of moisture absorption increases in a high humidity environment and the chargeability tends to decrease.
- the average pore diameter of the silica fine powder in the present invention can be determined by the same measurement method as the pore volume described above.
- the toner according to the present invention preferably further contains a hydrophobic inorganic fine powder having a BET specific surface area of 5 O m 2 Zg or more and 30 O m 2 / g or less.
- the silica fine powder can be uniformly dispersed in the toner.
- the BET specific surface area of the hydrophobic inorganic fine powder is less than 50, it is not preferable because the fine silica powder is not sufficiently dispersed.
- the BET specific surface area of the hydrophobic inorganic fine powder is larger than 300, the toner is charged up, which causes an adverse effect such as a decrease in density.
- hydrophobic inorganic fine powders examples include silicon dioxide (silica), titanium dioxide (titania), aluminum oxide (alumina), zinc oxide, magnesium oxide, cerium oxide, iron oxide, copper oxide, and tin oxide. It is done. Among these, a so-called dry method produced by vapor phase oxidation of a silicon halide or dry silica called fumed silica is preferably used.
- Hydrophobic treatment can be performed by using one or two treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic key compounds, and organic titanium compounds.
- treatment agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic key compounds, and organic titanium compounds. The above can be used in combination.
- the BET specific surface area was measured by adsorbing nitrogen gas to the sample surface using the specific surface area measuring device Jemi 2 2 7 75 (Shimadzu Corporation) according to the BET specific surface area method. Was used to calculate the specific surface area.
- the silica fine powder in the present invention has a moisture absorption / desorption isotherm at 30 ° C.
- the moisture content in the adsorption process at a relative humidity of 80% RH is preferably 0.01% by mass or more and 1.00% by mass or less, more preferably 0.01% by mass or more and 0.50% by mass or less, and particularly preferably 0. It is 10 mass% or more and 0.20 mass% or less. If the amount of adsorbed water at a relative humidity of 80% RH is greater than 1.00% by mass, the amount of adsorbed water is large.
- the amount of moisture adsorbed in the present invention is measured with an adsorption equilibrium measuring device ("EAM-02J" manufactured by JT Toshi Co., Ltd.) This is only the target gas (water in the present invention). It is a device that measures solid weight and vapor pressure at this time by reaching solid-gas equilibrium under the conditions. 'The actual adsorption / desorption isotherm is measured by the following dry matter weight, dissolved air in water Everything from deaeration to the measurement of the adsorption / desorption isotherm is performed automatically by a computer, and the outline of the measurement is described in the operation manual issued by JT Toshi Co., Ltd. In the present invention, water is used as the solvent liquid.
- the temperature of the thermostatic chamber and the temperature of the sample part were set to 30 ° C. After that, open the air valve VI (main valve) and V2 (exhaust valve), operate the evacuation unit, and evacuate the vacuum container to about 0.0 ImmHg to dry the sample. The mass at the time when the mass of the sample ceases to change is the “dry matter amount”. ..
- the pressure in the vacuum chamber does not reach the set pressure, repeat the above operation to set the pressure in the vacuum chamber to the set pressure.
- the pressure and weight in the vacuum vessel become constant, and the pressure, temperature, and sample weight at that time are measured as equilibrium data.
- the adsorption and desorption isotherm can be measured.
- the relative vapor pressure for measuring the adsorption amount is set in advance. For example, when the set pressure is 5%, 10%, 30%, 50%, 70%, 80%, 90%, 95%, the “adsorption process” in the present invention means the amount of moisture adsorbed in order from 5%.
- the “desorption process” is a process that follows the adsorption process, contrary to the adsorption process, while reducing the relative vapor pressure from 95%. The process of measuring the amount of adsorption is shown.
- the pressure is set by the relative vapor pressure (% RH), and the adsorption / desorption isotherm is displayed by the adsorption amount (%) and the relative vapor pressure (% RH).
- the calculation formulas for adsorption amount and relative vapor pressure are shown below.
- the specific surface area of the silica fine powder used in the present invention is 1.0111 2 Roh ⁇ more 20. 0 m 2 or less is preferable Zg, more preferably not more than 2. 0 m 2 Zg least 10. 0 m 2 Zg .
- the specific surface area is larger than 20.0 m 2 Z g, the silica fine powder is embedded in the toner particles, that is, toner deterioration is likely to occur, so that there is a problem such as a decrease in image density in the second half of the durability. Arise.
- the specific surface area is smaller than 1. O mV g, the toner does not have sufficient fluidity, resulting in problems such as a decrease in concentration in the latter half of the durability.
- Silica fine powder having a particle size of 0.220 cm 3 / g or less is preferably produced by a gas phase method.
- the silica fine powder can be produced by a gas phase method in which a metal compound such as metal silicon, octagenated silicon, and a silane compound is reacted in the gas phase, and a silane compound such as alkoxysilane.
- a metal compound such as metal silicon, octagenated silicon
- silane compound such as alkoxysilane.
- wet methods solvent removal from a silica sol suspension obtained by hydrolysis and condensation in a water / organic solvent mixed system, and drying to form particles.
- the silica fine powder can easily control the surface pore state within the above range by optimizing the reaction conditions of the gas phase method.
- the temperature in the reaction system higher than the melting point of silica in the gas phase reaction, it is possible to form silica fine powder with few pores because it is manufactured through a molten state.
- the pore state can be easily controlled by controlling the cooling rate from the molten state. Rapid cooling without controlling the cooling rate is not preferable because pores are likely to be formed.
- a vapor phase oxidation method in which a metal silicon powder raw material is directly oxidized with a chemical flame consisting of oxygen and hydrogen to obtain silica fine powder is preferable.
- the gas phase oxidation method can instantaneously raise the melting point of the silicic force in the reaction system, and is a preferable production method for controlling the surface pore structure and particle size.
- silica fine powder is produced from a silica sol suspension obtained by hydrolysis and condensation reaction of a silane compound, and thus has a structure having numerous pores on the surface.
- the reaction rate is slow compared to the gas phase method and it is difficult to control the pore distribution, it is not preferable as a method for producing fine silica powder with controlled pore state, which is a feature of the present invention.
- the content of the silica fine powder used in the present invention is preferably 0.05 parts by mass or more and 2.00 parts by mass or less with respect to 100 parts by mass of the toner particles.
- the content of the silica fine powder is larger than 2.00 parts by mass, the charge balance of the toner is lost, and problems such as density reduction and capri are likely to occur.
- the silica fine powder content is less than 0.05 parts by mass, the addition amount is small with respect to the toner, and the effect of charging up due to the addition of the silica fine powder cannot be obtained.
- the weight average particle diameter (D 4) of the toner particles is preferably 4.0 m or more and 9.0 m or less.
- D50 volume-based median diameter
- the weight average particle diameter (D4) of the toner particles is less than 4, the balance of the particle diameter with the silica fine powder will be lost, so the toner will not have sufficient fluidity and the concentration will decrease in the second half of the endurance. Occurs.
- the weight average diameter (D 4) of the toner particles is larger than 9.0 zm, the reproducibility to a higher-definition electrostatic latent image is remarkably lowered, which is not preferable from the viewpoint of dealing with the security image quality.
- the toner of the present invention has an acid value of 5. OmgKOHZg or more and 50. OmgKOH or less, more preferably 10. OmgKOHZg or more and 40. OmgKOHZg or less.
- the acid value of the toner within this range, the force loxyl group on the toner particle surface and The affinity with the fine silica powder is improved, and the fine silica powder can be surely present on the surface of the toner particles.
- the toner particles of the present invention preferably have negative chargeability.
- silica fine powder with strong negative chargeability to the negatively chargeable toner particles, the surface of the toner becomes uniform and the electrostatic cohesion between the toners caused by uneven charge is reduced. The effect is obtained.
- toner agglomerates can be easily broken when an electric field is applied, so even a high-definition latent image formed by a small particle size laser spot can be reproduced faithfully without protruding the latent image. This is possible and is preferable from the viewpoint of security image quality.
- binder resins used in the present invention include styrene resins, styrene copolymer resins, polyester resins, polyol resins, polyvinyl chloride resins, phenol resins, natural modified phenol resins, and natural resin modified maleic acids.
- Resin Acrylic resin, Methacrylic resin, Polyvinyl acetate, Silicone resin, Polyurethane resin, Polyamide resin, Furan resin, Epoxy resin, Xylene resin, Poly-bipropylyl, Terbene resin, Coumarone indene resin, Petroleum Resin.
- resins preferably used include styrene copolymer resins, polyester resins, polyester resins and vinyl resins, or a hybrid resin in which both have partially reacted.
- a binder resin containing a polyester resin having a force loxyl group at the terminal is used.
- the silica fine powder having a controlled surface fine structure which is a feature of the present invention, has a higher chargeability and can be started up early, and can be used preferably because a stable image density can be obtained over a long period of time.
- polyester monomer used for the polyester resin used in the binder resin according to the present invention or the polyester unit of the above-mentioned hybrid resin include the following compounds.
- the alcohol components include ethylene glycol, propylene glycol, 1,3 monobutanediol, 1,4 monobutanediol, 2,3-butanediol, jetylene glycol, triethylene glycol, 1,5 monopentanediol, 1 , 6-Hexanediol, Neopentyl glycol, 2-Ethyl-1,3 Hexanediol, Bisphenol hydride 8, Bisphenol derivative represented by the following formula (I-1) and Formula (I-12) The diols indicated by
- the acid component examples include benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isofuric acid, and phthalic anhydride, or anhydrides thereof; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof; Further, succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydrous product thereof; unsaturated dicarboxylic acid such as fumearliest acid, maleic acid, citraconic acid, itaconic acid, or an anhydride thereof; Can be mentioned.
- benzene dicarboxylic acids such as phthalic acid, terephthalic acid, isofuric acid, and phthalic anhydride, or anhydrides thereof
- alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, or anhydrides thereof
- the polyester resin or polyester unit according to the present invention is preferably a polyester resin having a crosslinked structure of trivalent or higher polyvalent rubonic acid or anhydride thereof and Z or trivalent or higher polyhydric alcohol.
- the trivalent or higher polyvalent carboxylic acids or anhydrides thereof include 1,2,4_benzenetricarboxylic acid, 1,2,4,4-hexane hexanetricarboxylic acid, 1,2,4 mononaphthalenetricarboxylic acid, and the like. Acid, pyromellitic acid and acid anhydrides or lower alkyl esters thereof.
- the trihydric or higher polyhydric alcohol include 1, 2, 3_propanetriol, trimethylolpropane, hexanetriol. Penyu erythritol.
- aromatic alcohols having high stability due to environmental fluctuations are particularly preferable, and examples thereof include 1,2,4 monobenzenetricarboxylic acid and anhydrides thereof.
- Examples of the vinyl monomer constituting the vinyl polymer unit of the vinyl resin or the hybrid resin used in the binder resin according to the present invention include the following compounds.
- Styrene ⁇ -methyl styrene, m-methyl styrene, p-methyl styrene, p-methoxy styrene, p-phenyl styrene, p-chloro styrene, 3,4-dichlorostyrene, ethyl styrene, 2,4 dimethyl styrene, p- Styrene such as n-butyl styrene, p-tert-butyl styrene, p- n-hexyl styrene, p- n-octyl styrene, 1 n-nonyl styrene, p- n-decyl styrene, p- n-dodecyl styrene, and Derivatives thereof; ethylene, propylene, butylene, Sty
- Acrylic acid esters such as vinyl; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and biisobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; ⁇ -vinyl pyrrole, ⁇ ⁇ -Pinyl compounds such as vinyl carbazol, ⁇ -vinyl indole, ⁇ -vinyl pyrrolidone; Biernaphthol derivatives; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide.
- unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, alkenyl succinic acid anhydride
- the vinyl resin or vinyl polymer unit used for the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups.
- the crosslinking agent used include aromatic dibier compounds such as divinylbenzene and dipinylnaphthalene; dialkylate compounds linked by an alkyl chain such as ethylene glycol diacrylate, 1, 3-butylene glycol diacrylate, 1,4 monobutanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate And acrylates of the above compounds in place of methacrylates; di-chains connected by alkyl chains containing ether linkages.
- diethylene glycol diacrylate triethylene glycol diacrylate, tetraethylene..lene glycol diacrylate, poly: t-ethylene glycol # 4 0 0 diacrylate, polyethylene glycol # 6 0 Diacrylate, dipropylene glycol diacrylate, and compounds in which the acrylate relays of the above compounds are replaced by methacrylates;
- diacrylate compounds bound by a chain containing an aromatic group and an ether bond include ..
- polyester-type diacrylate compounds examples include “MANDA” manufactured by Nippon Kayaku Co., Ltd.
- Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds Instead of methacrylate; Triali ⁇ / Cyanurate, Triaryl® Limelite
- crosslinking agents can be used in an amount of 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the other monomer component.
- cross-linking agents those which are preferably used for the binder resin, from the viewpoint of fixing property and offset resistance, are aromatic divinyl compounds (particularly divinylbenzene), chains containing aromatic groups and ether bonds. Examples thereof include ligated diacrylate compounds.
- Examples of the polymerization initiator used for the polymerization of the vinyl resin or the vinyl polymer unit include 2, 2′-azobisisoptyronitrile, 2, 2, monoazobis (4-methoxy-2, 4- Dimethylvaleronyl), 2,2, -azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), dimethyl-2,2'-azobisisoptylate, 1 , 1 '-azobis (1-cyclohexanecarbonitryl), 2- (carbamoylazo) monoisoptyronitrile, 2, 2' -azobis (2, 4, 4 trimethylpentane), 2-phenazol 2, 4-dimethyl-1-methoxyvaleronitryl, 2,2-azobis (2-methylpropan), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone peroxide Such Ketonpa one oxides, 2, 2-bis (t tert-butyl peroxide)
- the vinyl resin and the Z or polyester resin component contain a monomer ⁇ "component capable of reacting with both resin components.
- monomers that can react with the vinyl resin among the monomers constituting the component include unsaturated dicarboxylic acids such as fuuric acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof.
- the monomers constituting the vinyl resin component it can react with the polyester resin component Examples thereof include those having a strong loxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.
- a method of obtaining a reaction product of a vinyl resin and a polyester resin there is a polymer containing a monomer component capable of reacting with each of the vinyl resin and the polyester resin mentioned above.
- a method obtained by subjecting the resin to a polymerization reaction is preferred.
- the mass ratio of the polyester-based monomer to the vinyl-based monomer is preferably 50 0 5 0 to 90 0 Z l 0, and preferably 60 0 4 0 to 8 5 Z It should be 1-5.
- the chargeability of the silica fine powder with a polyester-based unit of less than 50% is impaired, and if it exceeds 90%, not only the balance of chargeability is lost, but also the storage stability and the state of release agent dispersion. This is not preferable because of the influence.
- the binder resin should contain 30% by mass or more of a low molecular weight component having a molecular weight of 10,000 or less, as measured by GPC soluble in tetrahydrofuran (TH F). Is preferred.
- the glass transition temperature of the binder resin is preferably 53 ° C. or more and 62 ° C. or less from the viewpoint of fixability and storage stability.
- '' Binder resin as described above may be used alone, but in the present invention, two types of high softening point resin (A) and low softening point resin (B) having different softening points are used. You may mix and use in the range of 1 0-10 0/90. Such a system is preferable because the molecular weight distribution of the toner can be designed relatively easily and a wide fixing area can be provided.
- the dressing and coloring agent of the present invention is preferably magnetic iron oxide.
- magnetic iron oxide which is a dielectric
- toner agglomerates can be easily removed when an electric field is applied, so even in a high-definition latent image formed by a small particle size laser spot. Therefore, it is possible to faithfully reproduce the latent image without protruding, and this is preferable from the viewpoint of security image quality.
- magnetic properties are also used from the viewpoint of durability and stability in high-speed machines. It is preferable to use ferrous iron oxide.
- magnetic iron oxides iron oxides such as magnetite, maghemite, and ferrite are used.
- the magnetic iron oxide of the present invention is preferably subjected to a treatment for temporarily loosening the magnetic iron oxide by applying shear to the slurry during production for the purpose of improving the fine dispersibility in the toner particles.
- the amount of magnetic iron oxide contained in the toner is preferably 20 parts by weight or more and 20 parts by weight or less, more preferably 30 parts by weight or more 15 parts by weight with respect to 100 parts by weight of the binder resin. 0 parts by mass or less.
- a wax can be used as necessary to impart releasability to the toner.
- the wax low dispersion due to toner and high releasability can be used.
- Hydrocarbon waxes such as molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, and paraffin wax are preferably used, but one or two or more kinds of waxes may be used in a small amount as required. The following are examples.
- Oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; waxes based on fatty acid esters such as carnauba wax, sazol wax, and montanic acid esterx; and deoxidation Examples include fatty acid esters such as carnauba wax that are partially or fully deoxidized.
- saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid
- unsaturated fatty acids such as brassic acid, eleostearic acid, and phosphoric acid
- stearyl alcohol, aralkyl alcohol behenyl alcohol, carnubi Saturated alcohols such as alcohol, ceryl alcohol, and melyl alcohol
- long chain alkyl alcohols polyhydric alcohols such as sorbitol
- fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide
- Saturated fatty acid bisamides such as acid amides, ethylene bis-power puramides, ethylene bislauric acid amides, hexamethylene bis-stearic acid amides
- Unsaturated fatty acid amides such as tylene bisoleic acid amide, hexamethylene bisoleic acid amide, N, N '— dioleyl adipic acid amide,
- Examples of the release agent particularly preferably used in the present invention include aliphatic hydrocarbon series.
- Such aliphatic hydrocarbon waxes include, for example, low molecular weight alkylene polymers obtained by radical polymerization of alkylene under high pressure or using a tidy catalyst under low pressure; high molecular weight alkylene polymers.
- An alkylene polymer obtained by thermally decomposing one a synthetic hydrogenated wax obtained from the distillation residue of a hydrocarbon obtained by a coal method from a synthesis gas containing carbon monoxide and hydrogen, and a synthetic carbonized product obtained by hydrogenating it Hydrogen wax; those aliphatic hydrocarbon waxes separated by the press sweat method, solvent method, vacuum distillation, or fractional crystallization method.
- hydrocarbon as the matrix of the aliphatic hydrocarbon wax examples include those synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often a multi-component system of two or more types).
- a metal oxide catalyst for example, the Gintoll method, Hydrocol method (using a fluidized catalyst bed), hydrocarbon compounds synthesized by);
- the Wager method using an identified catalyst bed
- hydrocarbons obtained by polymerizing alkylene such as ethylene with a Ziegler catalyst.
- a hydrocarbon synthesized by a method not based on polymerization of alkylene is particularly preferred from the molecular weight distribution.
- Specific examples that can be used include Biscol (registered trademark) 330-P, 550-P, 660-P, TS-200 (Sanyo Chemical Industries), High Wax 400P, 200mm, 100mm, 410mm, 420mm, 320 ⁇ , 220 ⁇ > 210 ⁇ , 110 ⁇ (Mitsui Chemicals), Sazol HI, H2, C80, C 105, C 77 (Schwemann-Sazol), HNP-1, HNP_3, HNP-9, HNP — 10, HNP—1 1, HNP-12 (Nippon Seiki Co., Ltd.), Unilin (registered trademark) 350, 425, 550, 700, Unicid (registered trademark), Unicid (registered trademark) 350, 42 5, 550, 700 (Toyo Petrolite Co., Ltd.), wood wax, beeswax, rice wax, candelilla wax, caulirena wax (available from Celerica NODA).
- the timing of adding the release agent may be added at the time of melt-kneading during toner production, or may be at the time of binder resin production, and is appropriately selected from existing methods. These mold release agents may be used alone or in combination.
- the release agent is preferably added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.
- the amount is less than 1 part by mass, the desired release effect cannot be obtained sufficiently.
- the amount exceeds 20 parts by mass, the dispersion in the toner is poor, and the toner adheres to the photosensitive member, and the developing member / cleaning member. Surface contamination of the toner occurs, and problems such as deterioration of the toner image are likely to occur.
- the following pigments or dyes can be used as colorants.
- colorant carbon black and other conventionally known pigments and dyes can be used, or one or more of them can be used.
- the dyes are CI Direct Red 1, C.I. Direct Red 4, C. I. Acid Red 1, CI Basic Red 1, C. I. Modern Red 30, CI Direct Blue 1, CI Direct Bull 1, C. .1. Acid Blue 9, CI Acid Blue 5, CI Basic Blue 3, CI Basic Blue 5, CI Modern Blue 7, CI Direct Lean 6, CI Basic Green 4, CL Basic Green 6, etc.
- the toner of the present invention When the toner of the present invention is used as a full-color image forming toner, the following colorants can be mentioned.
- magenta pigment may be used alone, but it is more preferable from the viewpoint of the image quality of a full-color image to improve the clarity by using a dye and a pigment together.
- a dye and a pigment For magenta evening dyes, C. I. Solvent Red 1, 3, 8, 23, 24, 25, 27, 3 0, 49, 81, 82, 83, 84, 100, 109, 121, CI disperse thread 9, CI solvent violet 8, 13, 14, 21, 27, C.
- Oil-soluble dyes such as Disperse Violet 1, C.I.Basic Red 1,
- cyan pigments examples include CI Pigment Bull 1, 2, 3, 15, 16, 17, CI Bat Blue 6, CI Acid Bull 45, or a phthalocyanine skeleton having the following structure with 1 to 5 substituted phthalimidomethyl groups. Copper phthalocyanine pigments.
- the colorant is preferably 0.1 parts by weight or more and 60 parts by weight or less, more preferably 0.5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the resin component.
- a charge control agent is used in order to stabilize the charging property.
- the charge control agent varies depending on the type and physical properties of other toner particle constituent materials, generally, it is contained in the toner particles in an amount of 0.1 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the binder resin. More preferably, the content is 0.1 parts by mass or more and 5 parts by mass or less.
- charge control agents there are known ones that control the toner to be negatively charged, and those that control the toner to be positively charged.
- One or two of various types are used depending on the type and use of the toner. More than one species can be used.
- an organometallic complex or a chelate compound is effective.
- organometallic complex or a chelate compound examples thereof include a monoazo metal complex; a acetylacetone metal complex; an aromatic group, a hydroxycarponic acid or an aromatic group.
- Metal complexes or metal salts of dicarboxylic acids examples include aromatic mono- and poly-ruccinic acid and their metal salts and water; esters and phenol derivatives such as bisphenol; etc. Is mentioned.
- a metal complex or a metal salt of aromatic hydroxycarponic acid that can provide stable charging performance is particularly preferably used.
- negatively chargeable toner particles are preferably used, a negatively chargeable control agent or a negatively chargeable control resin is preferably used.
- Quaternary ammonium salts such as tetrafluoroborate and their analogs such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents) , Phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanic acid, ferrocyan compound, etc.);, metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, dicyclo Diorganotinoxides such as hexyltinoxide; dibutyl And diorganotin borates such as dipole tin borates, dicyclohexyl tin borates, and the like.
- charge control agents such as digrosine compounds and quaternary ammonium salts are particularly preferably used for controlling the toner to be positively charged.
- charge control agents such as digrosine compounds and quaternary ammonium salts are particularly preferably used for controlling the toner to be positively charged.
- Specific examples that can be used include Spi 1 on Blac TRH, T-77, T-95 (Hodogaya Chemical), BONTRON (registered trademark) S-34, S-44, S-54, ⁇ —84, ⁇ —88, ⁇ —89 (Orient Chemical Co., Ltd.), and preferred for positive charging are TP-302, TP-415 (Hodogaya Kagaku), BONTRON (registered trademark) ) N-01, N-04, N-07, P-51 (Orient Chemical), Copy Blue PR (Clariant).
- a charge control resin can be used, and it can be used in combination with the above-described charge control agent.
- external additives may be added to the toner of the present invention.
- external additives include charging aids, conductivity-imparting agents, fluidity-imparting agents, anti-caking agents, release agents at the time of heat roller fixing, lubricants, abrasives, resin fine particles and inorganic fine particles. is there.
- examples of the lubricant include polyfluorinated styrene powder, zinc stearate powder, polyvinylidene fluoride powder, and the like. Among these, polyvinylidene fluoride powder is preferable.
- examples of the abrasive include cerium oxide powder, silicon carbide powder, and strontium titanate powder. These external additives can be sufficiently mixed using a mixer such as a Henschel mixer to obtain the toner of the present invention.
- a binder resin, a colorant, other additives, etc. are sufficiently mixed by a mixer such as a Henschel mixer or a pole mill, and then heated rolls, kneaders, extractors, etc.
- the mixture is melt-kneaded using a suitable heat kneader, cooled and solidified, pulverized and classified, and if necessary, desired additives are sufficiently mixed by a mixer such as a Henschel mixer to obtain the toner of the present invention. I can do it.
- Henschel mixer Mitsubishi Co., Ltd.
- Supermixer I Rotaryu Yusha
- Lipocorn Okawara Seisakusho
- Now Yuichi Mixer, Yuichi View Riser cyclomix (manufactured by Hosokawa Micron Co.), spiral pin mixer (manufactured by Taihei Machine Co., Ltd.), radige mixer (manufactured by Matsupo Co., Ltd.), KRC kneader (manufactured by Kurimoto Iron Works Co., Ltd.) ); Bus ⁇ Ko ⁇ 21 (made by Buss); T EM type extruder (made by Toshiba Machine); TEX twin-screw kneader (made by Nippon Steel Works); PCM kneader (made by Ikekai Iron Works) ); Three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); kneedex (manufactufact
- the physical property measuring method according to the present invention is as follows. Examples described later are also based on this method.
- the particle size distribution can be measured by various methods. This was done using a multisizer with a freta counter.
- a multisizer IIE type manufactured by Coulter Co., Ltd.
- a Cole evening counter is connected, connected to an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution, and a computer for analysis.
- 0.1 to 5 ml of a surfactant preferably alkylbenzene sulfonate
- a dispersant is added as a dispersant to 100 to 150 ml of the above electrolytic aqueous solution, and further 2 to 2 Omg of a measurement test is added.
- an ultrasonic disperser for measuring the particle size of the toner as an aperture using the Multisizer Type II of the Coulter Counter.
- the volume and number of toner were measured, and the volume distribution and number distribution were calculated.
- the weight-based weight average particle diameter (D4) obtained from the volume distribution is obtained.
- oxidation can be measured by the following method. 'Basic operation conforms to JI S K-0070.
- the softening point of the binder resin is measured by a descent type flow tester according to the measurement method shown in JISK 7210. A specific measurement method is shown below.
- Measuring device Differential scissor calorimeter (DSC), MDSC-2920 (manufactured by TAI Instr ume nts)
- the column is stabilized in a heat chamber at 40 ° C, and THF is flowed through the column at this temperature as a solvent at a flow rate of lm 1 per minute, and about 100 1 of the THF sample solution is injected and measured.
- the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of a calibration curve prepared with several types of monodisperse polystyrene standard samples.
- a standard polystyrene sample for preparing a calibration curve for example, one having a molecular weight of about 10 2 to 10 7 manufactured by Toso Corporation or Showa Denko is used, and a standard polystyrene sample having at least about 10 points is used.
- the detector is RI Use a detector.
- As the column it is preferable to combine a plurality of commercially available polystyrene diol columns.
- shode x GPC KF—801, 802, 803, 804, 805, 806, 807, 800 P made by Showa Denko TS kge 1 G 100 OH (H XL ), G200 OH (H XL ), G 300 OH (H XL ), G400 OH (H XL ), G 500 OH (H XL ), G600 OH (H XL ), G700 OH (H XL ), TS.kgu rdco 1 umn can be listed.
- the sample is prepared as follows. .
- the sample that passed through the sample processing filter (pore size 0.2 to 0.5 m, such as MYISHI DISK —-25-2 (manufactured by Tosoh Corporation) was used as the GPC sample. . Also, adjust the sample concentration so that the fat component is 0.5 to 5 mgZml.
- the above acid component and alcohol component and tin 2-ethylhexanoate as a catalyst are charged into a four-necked flask, and a decompressor, water separator, nitrogen gas inlet, temperature measurement
- a styrene-acrylic resin shown below is added to 100 parts by mass of the monomer component for producing the above polyester unit while stirring at 130 ° C. in a nitrogen atmosphere.
- a mixture of 25 parts by mass of a monomer for producing a unit together with a polymerization initiator (benzoyl peroxide) was dropped from a dropping funnel over 4 hours.
- the above-mentioned acid component and alcohol component and 2-ethyl hexyl hexanoate as a catalyst are charged into a four-necked flask, and the pressure is reduced.
- 2-Ethylhexyl acrylate 14% by mass Acrylic acid 2% by mass Aging was carried out for 3 hours while maintaining this at 130 ° C, and the reaction was carried out by raising the temperature to 230 ° C.
- the product is taken out from the container and powdered, and contains a polyester resin component, a vinyl polymer component, and a hybrid resin component in which the polyester unit and styrene-acrylic resin unit are chemically bonded, and softens.
- a binder resin 1 (L) with a point of 99 was obtained.
- Binder resin 1 (H) 60 parts by mass and binder resin 1 (L) 40 parts by mass were mixed with a Henschel mixer to obtain binder resin 1.
- This binder resin 1 had a glass transition temperature of 59 t: a softening point of 128 ° C. and contained 37% by mass of a component having a molecular weight of 10,000 or less in GPC.
- the acid and alcohol components shown above and the esterification catalyst are charged into a 4-neck flask.
- a pressure reducing device, a water separation device, a nitrogen gas introducing device, a temperature measuring device, and a stirring device were attached, and the reaction was performed by raising the temperature to 230 ° C under a nitrogen atmosphere.
- the product was taken out from the vessel, cooled and ground to obtain Binder Resin 2 (H) having a softening point of 142 ° C.
- Binder resin 2 (H) 70 parts by mass and binder resin 2 (L) 30 parts by mass were mixed with a Henschel mixer to obtain binder resin 2.
- This binder resin 2 had a glass transition temperature of 56 ° C. and a softening point of 134 ° C., and contained 36% of a component having a molecular weight of 10,000 or less in GP.
- the monomer composition was mixed with 200 parts by mass of xylene raised to the reflux temperature. Solution polymerization was completed in 6 hours under reflux of xylene to obtain a low molecular weight resin solution.
- the following monomer composition was mixed, suspended and dispersed in 200 parts by mass of deaerated water and 0.2 part by mass of polyvinyl alcohol.
- This suspension dispersion was heated and kept at 80 ° C. for 24 hours under a nitrogen atmosphere to complete the polymerization, dehydrated and dried to obtain a high molecular weight resin.
- this high molecular weight resin is put into the above-mentioned low molecular weight resin solution (containing 23 parts by weight of resin), dissolved completely in the solution and mixed, and then distilled under reduced pressure at a high temperature (180 ° C) And the solvent was removed to obtain a binder resin 3.
- This binder resin 3 had a glass transition temperature of 60 ° C and a softening point of 128 ° C, and contained 38% of a component having a molecular weight of 10,000 or less in GPC.
- a fine silica powder B-2 was obtained in the same manner as in Production Example B-1, except that the carrier gas pressure was 12 kgZcm 3 in Production Example B-1.
- a fine silica powder B-5 was obtained in the same manner as in Production Example B-1, except that the content was 5 ° CZ.
- a fine silica powder B-6 was obtained in the same manner as in Production Example B-1, except that in Production Example B-1, the carrier gas pressure was 1 kgZcm 3 and the cooling rate was 10 ° CZ.
- the pressure of the carrier gas was 1 k gZcm 3 Production Example B- 4, a cooling rate of 2
- a fine silica powder B-7 was obtained in the same manner as in Production Example B_4 except that the content was 0 ° CZ.
- a mixture of 1,130 g and 63 g of 3-aminopropyltriethoxysilane as a silane compound was dropped while maintaining the temperature in the reaction vessel at 20 ° C. to effect hydrolysis to obtain a suspension of silica fine particles. It was. Further, the fine particles were calcined at 250 ° C to obtain fine silica powder B-8 Got.
- Silica fine powder B-10 was obtained in the same manner as in Production Example B-1, except that the pressure of the carrier gas was 16 kgZcm 3 in Production Example B-1.
- Table 1 shows the physical properties of the fine silica powders (B-1) to (B-10).
- Binding resin 1 100 parts by mass ⁇ Magnetic iron oxide particles 60 parts by mass
- the obtained kneaded product is cooled, coarsely pulverized with a hammer mill, and then pulverized with a turbo mill, and the resulting fine pulverized pulverized powder is classified using a multi-division classifier utilizing the Coanda effect, and the weight average particle size is 5. 8 ⁇ m toner particles were obtained.
- Hydrophobic inorganic fine powder a (silica, BET140m 2 Zg, hexamethyldisilazane (HMD S) Hydrophobic treatment with 30 parts by weight and 10 parts by weight of dimethyl silicone oil) 1.0 part by weight, 0.2 part by weight of silica fine powder B-1 and 3.0 parts by weight of strontium titanate Sieve with a mesh of 150 // m of mesh opening, a toner 1 was obtained.
- Table 4 shows the toner prescriptions and Table 5 shows the physical properties.
- Toner 1 is evaluated under higher speed and higher definition conditions.
- the reflection density of a 5 mm round image was measured with a Macbeth densitometer (manufactured by Macbeth) using an SPI filter.
- Capri is measured using a reflection densitometer (Reflectometer Ichiichi model TC-1 6DS manufactured by Tokyo Denshoku Co., Ltd.), the white background reflection density worst value after image formation is D s, and the transfer material before image formation Capri was evaluated using Dr as the average reflection density and D s-Dr as the amount of capri. Therefore, the smaller the value, the better the capri suppression. This evaluation was performed in each test environment at the initial stage and when printing 500,000 sheets. The evaluation results are shown in Tables 6, 7, and 8.
- Line width change rate (%) I ⁇ line ⁇ out ⁇ —line width of the image I X! 0 0
- Rate of change exceeds 5% and 10% or less
- Rate of change exceeds 10% and 20% or less
- Standard deviation is more than 15 and less than 25
- Toners 2 to 5 were obtained in the same manner as in Example 1 except that the formulation shown in Table 4 was used (Table 3 for hydrophobic inorganic fine powder, Table 1 for silica fine powder, and Table 2 for wax). Table 5 shows the physical property values of the toner thus obtained. Tables 6, 7 and 8 show the results of the same tests as in Example 1.
- Example 1 except that the formulation shown in Table 4 (Table 3 for hydrophobic inorganic fine powders, Table 1 for silica fine powders, Table 2 for waxes) was increased by 10%. In the same manner, Toner 6 was obtained. Table 5 shows the physical property values of the toner thus obtained. Tables 7 and 8 show the results of tests similar to those in Example 1.
- Table 4 Table 3 for hydrophobic inorganic fine powder, Table 1 for silica fine powder, and Table 2 for wax
- Example 1 The formulation shown in Table 4 (Table 3 for hydrophobic inorganic fine powder, Table 1 for silica fine powder, and Table 2 for wax) is the same as Example 1 except that the rotational speed of evening pomil was reduced by 20%. Toner 7 was obtained.
- Table 5 shows the physical property values of the toner thus obtained.
- Tables 6, 7, and 8 show the results of the same tests as in Example 1.
- Table 4 Table 3 for hydrophobic inorganic fine powder, Table 1 for silica fine powder, and Table 2 for wax
- Table 5 shows the physical property values of the toner thus obtained.
- Tables 6, 7, and 8 show the results of the same tests as in Example 1.
- Toner 10 was obtained in the same manner as in Example 1 except that the formulation shown in Table 4 was used (Table 3 for hydrophobic inorganic fine powder and Table 2 for wax), and no silica fine powder was added.
- Table 5 shows the physical property values of the toner thus obtained.
- Tables 6, 7 and 8 show the results of the same tests as in Example 1.
- Toners 11 to 14 were obtained in the same manner as in Example 1 except that the formulation shown in Table 4 was used (Table 3 for hydrophobic inorganic fine powder, Table 1 for silica fine powder, and Table 2 for wax).
- Table 5 shows the physical property values of the toner thus obtained.
- Tables 6, 7 and 8 show the results of tests similar to those in Example 1.
- alumina TM10, manufactured by Daimei Chemical Co., Ltd. was used instead of silica fine powder.
- AAAAA Example 2 1.45 '1.45 0.45 0.58 AAAAAA Example 3 1.45 1.43 0.50 0.63 AAAAAA Example 4 1.45 1.43 0.47 0.55 AA' ABAA Example 5 1.43 1.41 0.75 0.74 ABAAAB Example 6 1.44 1.41 0.47 0.60 AAAAAA Example 7 1.45 1.45 0.43 0.56 AAAAAB Example 8 1.44 1.42 0.74 0.88 ABABAB Example 9 ⁇ 1.40 1.39 1.10 1.06 BCBBBC Comparative Example 1 1.36 1.35 2.05 2.22 DDDDDD Comparative Example 2 1.36 1.32 2.11 2.41 CDCCCD Comparative Example 3 1.35 1.33 2.35 2.65 CDCCCD Comparative Example 4 1.35 1.31 2.14 2.41 CCCDDD Comparative Example 5 1.301.29 2.26 2.56, DDCCCD
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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BRPI0710265-8A BRPI0710265A2 (pt) | 2006-06-08 | 2007-06-04 | toner |
JP2008520643A JP5047170B2 (ja) | 2006-06-08 | 2007-06-04 | トナー |
EP07744970A EP2031451B1 (en) | 2006-06-08 | 2007-06-04 | Toner |
CN2007800182120A CN101449213B (zh) | 2006-06-08 | 2007-06-04 | 调色剂 |
US11/947,523 US7537877B2 (en) | 2006-06-08 | 2007-11-29 | Toner used in electrophotography having toner particles and silica powder |
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JP2006159343 | 2006-06-08 | ||
JP2006-159343 | 2006-06-08 |
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US11/947,523 Continuation US7537877B2 (en) | 2006-06-08 | 2007-11-29 | Toner used in electrophotography having toner particles and silica powder |
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EP (1) | EP2031451B1 (ja) |
JP (1) | JP5047170B2 (ja) |
KR (1) | KR101014991B1 (ja) |
CN (1) | CN101449213B (ja) |
BR (1) | BRPI0710265A2 (ja) |
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JP2011048159A (ja) * | 2009-08-27 | 2011-03-10 | Canon Inc | トナー及び画像形成方法 |
US8582691B2 (en) | 2008-09-26 | 2013-11-12 | Ntt Docomo, Inc. | Receiving apparatus and receiving method |
JP2014232316A (ja) * | 2013-05-01 | 2014-12-11 | キヤノン株式会社 | 現像剤補給カートリッジ及び現像剤補給方法 |
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Also Published As
Publication number | Publication date |
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RU2386158C1 (ru) | 2010-04-10 |
EP2031451A1 (en) | 2009-03-04 |
US7537877B2 (en) | 2009-05-26 |
EP2031451A4 (en) | 2011-03-23 |
KR20090023469A (ko) | 2009-03-04 |
CN101449213B (zh) | 2012-01-18 |
EP2031451B1 (en) | 2012-06-13 |
BRPI0710265A2 (pt) | 2011-08-09 |
KR101014991B1 (ko) | 2011-02-16 |
US20080124643A1 (en) | 2008-05-29 |
JP5047170B2 (ja) | 2012-10-10 |
CN101449213A (zh) | 2009-06-03 |
JPWO2007142343A1 (ja) | 2009-10-29 |
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