WO2010007905A1 - 電子写真用現像剤 - Google Patents
電子写真用現像剤 Download PDFInfo
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- WO2010007905A1 WO2010007905A1 PCT/JP2009/062195 JP2009062195W WO2010007905A1 WO 2010007905 A1 WO2010007905 A1 WO 2010007905A1 JP 2009062195 W JP2009062195 W JP 2009062195W WO 2010007905 A1 WO2010007905 A1 WO 2010007905A1
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- composite oxide
- toner
- oxide particles
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to an electrophotographic developer used in an electrophotographic image forming apparatus.
- Patent Documents 1 and 2 It is known to add a metal titanate represented by calcium titanate or strontium titanate to an electrophotographic developer (Patent Documents 1 and 2). This is because the metal titanate salt not only contributes to the prevention of filming on the surface of the photoreceptor during image formation and improves the cleaning property, but also contributes to the improvement of charging property because it has high dielectric properties.
- the metal titanate has a relatively high resistance, even if the metal titanate is added to the electrophotographic developer, the charge rise is slow and the saturation charge amount is high in a low temperature and low humidity environment. For example, if an image with a high printing rate is output after an image with a low printing rate is continuously displayed, a toner with a high charge amount that has been sufficiently mixed and stirred and a toner with a low charge amount that has been rapidly replenished are likely to exist. The distribution was widened, fogging and scattering occurred, and the image density of the solid image was lowered.
- the present invention is excellent in charging stability and free from fog and density reduction even in a high-temperature and high-humidity environment in which it is difficult to maintain the charging performance of the developer or in a low-temperature and low-humidity environment in which the charge start-up property tends to be low.
- An object of the present invention is to provide an electrophotographic developer capable of obtaining an image over a long period of time.
- the present invention provides a titanate metal salt particle containing titanium as a first metal atom and a second metal atom, and selected from the group consisting of metal atoms belonging to Group 5A of the long-period element periodic table.
- the present invention relates to an electrophotographic developer comprising composite oxide particles containing 0.009 to 0.350 wt% of three metal atoms.
- the toner is obtained by adding an external additive to toner particles, and the toner and the toner particles are used separately.
- the electrophotographic developer of the present invention is excellent in charge rising property and charging stability even in a high-temperature and high-humidity environment or a low-temperature and low-humidity environment. Can be maintained. As a result, an image free from fogging and density reduction can be obtained over a long period of time.
- the electrophotographic developer of the present invention has specific composite oxide particles.
- the composite oxide particle is obtained by containing a predetermined third metal atom in an appropriate amount in a metal salt particle of a titanic acid containing a titanium atom as the first metal atom with the second metal atom. is there.
- a predetermined third metal atom with respect to the metal titanate, when the composite oxide particles come into contact with the toner at the time of development, it acts like a carrier or a capacitor in a pseudo manner.
- the charging stability is considered to be improved.
- the toner acts like a carrier and can charge a predetermined level of image formation to the toner, the initial toner chargeability can be stably maintained.
- the composite oxide particles act like a capacitor to temporarily accumulate the overcharged toner charge and then promptly pass through the third metal atom. Since the toner is discharged, the toner chargeability can be stably maintained.
- the toner charge rising property tends to be low, but the composite oxide particles act like a carrier in the presence of the third metal atom, so that a good charge rising property can be obtained.
- excellent chargeability can be maintained from the beginning for a long period of time, and it is considered that an image free from fogging and density reduction can be obtained for a long period of time even in a high temperature and high humidity environment or a low temperature and low humidity environment.
- the composite oxide particle may have a structure in which a third metal atom is incorporated as a part of a lattice point in a crystal lattice of a metal titanate, or a third between the crystal lattices of the metal titanate. It may have a structure in which metal atoms are contained in an oxide state, or may have a composite structure thereof.
- the metal titanate containing the third metal atom is a metal salt with a second metal atom of titanate containing a titanium atom as the first metal atom.
- the second metal atom is one or more kinds of metal atoms selected from the group consisting of metal atoms belonging to groups 1A and 2A of the long-period element periodic table.
- Specific examples of the metal atom belonging to Group 1A include, for example, Li, Na and K.
- Specific examples of metal atoms belonging to Group 2A include Mg, Ca, Sr, Ba, and the like.
- the second metal atom that is preferable from the viewpoint of further improving the charge rising property and charging stability is a metal atom belonging to Group 2A, and is more preferably selected from Mg, Ca, Sr, and Ba.
- Such a metal titanate is a salt formed from titanium oxide (IV) and an oxide or carbonate of a second metal atom, and is called a so-called metatitanate. Can be represented.
- General formula (I) M I 2 TiO 3 or M II TiO 3 (In the formula, M I represents a group 1A metal atom, and M II represents a group 2A metal atom.)
- the metal titanate containing the third metal atom examples include calcium titanate CaTiO 3 , magnesium titanate MgTiO 3 , strontium titanate SrTiO 3 , barium titanate BaTiO 3 and the like.
- calcium titanate CaTiO 3 and magnesium titanate MgTiO 3 are preferable from the viewpoint of environmental impact and the like, and calcium titanate CaTiO 3 is particularly preferable because the charge amount is maintained at a constant level over a long period of time.
- the third metal atom contained in the metal titanate is one or more metal atoms selected from the group consisting of metal atoms belonging to Group 5A of the long-period element periodic table.
- Specific examples of the metal atom belonging to Group 5A include, for example, vanadium V, niobium Nb, tantalum Ta, and the like, particularly Nb.
- the content of the third metal atom in the composite oxide particles is 0.009 to 0.350% by weight, and preferably 0.03 to 0.30% by weight from the viewpoint of further improving the charge rising property and charge stability. In particular, it is 0.08 to 0.25% by weight. If the content of the third metal atom is too small, the rise of charging is slow in a low temperature and low humidity environment, excessive charging occurs during durability, fogging and scattering occur, and the image density of the solid image decreases. If the content of the third metal atom is too large, the charge retention at a high temperature and high humidity is reduced, causing a decrease in the charge amount and increasing the fog.
- the content of the third metal atom in the composite oxide particle is expressed as a ratio to the total metal atoms contained in the composite oxide particle.
- inductively coupled plasma as schematically shown in FIG. It can be measured by an emission spectroscopic analyzer (ICP-OES).
- ICP-OES is a method in which a sample is excited by a plasma flame generated by irradiating an argon gas with a high frequency, and an element is identified and quantified from an emission spectrum when returning to a ground state.
- the measurement method of the third metal atom specifically, first, 1 g of composite oxide particles to be measured in a dry 200 ml conical beaker is collected. 20 ml of sulfuric acid is added as a decomposition reagent, microwave decomposition is performed with a sealed microwave wet decomposition apparatus (MLS-1200MEGA; manufactured by MILESTONE), and then water cooling is performed. At this time, the microwave decomposition is performed until there is no undissolved material. Transfer the degradation solution to a 100 ml volumetric flask and add distilled water up to the marked line to adjust the sample solution to 100 ml.
- MLS-1200MEGA sealed microwave wet decomposition apparatus
- the sample solution is provided to the ICP-OES described above, the intensity at a wavelength peculiar to the atom is measured, and quantification is performed using a calibration curve.
- the wavelengths peculiar to the third metal atom are, for example, 269.706 nm (Nb), 309.311 nm (V), and 226.230 nm (Ta).
- a calibration curve can be created by the following method.
- Complex oxide particles not containing a third metal atom for example, a metal titanate such as calcium titanate, strontium titanate, magnesium titanate
- the decomposition solution is used as a 100 ml volumetric flask.
- the sample solution is adjusted to 100 ml by adding distilled water up to the marked line. 25 ml of the sample was dispensed into a 100 ml volumetric flask, the third metal atom standard solution was added to 0 ppm, 1 ppm, 2 ppm, and 3 ppm, respectively, and distilled water was added to the marked line to make 100 ml. To do.
- a calibration curve is created from the above four points for each composite oxide particle.
- the composite oxide particles have a number-based average particle size of 30 nm to 3000 nm, particularly preferably 50 nm to 2000 nm, and more preferably 50 nm to 400 nm.
- the composite oxide particles by setting the size of the composite oxide particles in the above range, the excellent charge rising property and charging stability of the toner can be further stabilized. This is because, when the value of the number average particle size of the composite oxide particles is in the above range, the composite oxide particles have an appropriate contact area that facilitates charge transfer between the toner and the toner, and charge exchange is facilitated. It is thought that is formed.
- the composite oxide particles are externally added to the toner particles, if the number-based average particle diameter of the composite oxide particles is within the above range, a state where the composite oxide particles are strongly fixed to the toner particle surface is avoided. At the same time, since separation from the toner particles is avoided, it contributes to the improvement of toner fluidity, and the charge rising property and charging stability of the toner can be further effectively improved.
- the number-based average particle diameter of the composite oxide particles can be calculated from, for example, an electron micrograph. Specifically, it can be calculated by the following procedure. (1) The composite oxide particles isolated from the developer are photographed with a scanning electron microscope at a magnification of 30,000, and the photograph image is captured by a scanner. (2) The composite oxide particles present on the toner surface on the photographic image are binarized by an image processing analyzer “LUZEX AP (manufactured by Nireco)”, and the horizontal ferret diameter is calculated for 100 particles. The average value of the ferret diameter is defined as the average particle diameter.
- the horizontal ferret diameter means a distance between two vertical lines sandwiched between two vertical lines between the composite oxide particles on the photographic image.
- the composite oxide particles preferably have a particle size standard deviation value of 1000 nm or less, particularly 500 nm or less, more preferably 250 nm or less.
- the composite oxide particles in use have no variation in their charge-contributing performance, and any composite oxide particles have the same level of charge performance as the toner. Therefore, it is considered that the toner contributes effectively in realizing uniform charging of the toner.
- the composite oxide particles preferably have a BET specific surface area in the range of 3 m 2 / g to 30 m 2 / g, particularly 5 m 2 / g to 25 m 2 / g.
- the BET specific surface area is the specific surface area of particles calculated by the gas adsorption method.
- the calculation of the specific surface area of particles by the gas adsorption method adsorbs gas molecules whose adsorption occupation area is known, such as nitrogen gas, to the particles.
- the specific surface area of the particles is calculated from the adsorption amount.
- the BET specific surface area can accurately calculate the amount of gas molecules adsorbed directly on the solid surface (monomolecular layer adsorption amount).
- the BET specific surface area can be calculated using a mathematical formula called a BET formula shown below.
- the BET equation shows the relationship between the adsorption equilibrium pressure P when in an adsorption equilibrium state at a constant temperature and the adsorption amount V at that pressure, and is expressed as follows.
- P / V (Po ⁇ P) (1 / VmC) + ((C ⁇ 1) / VmC) (P / Po)
- Po saturation vapor pressure
- Vm monomolecular layer adsorption amount, adsorption amount when gas molecules form a monomolecular layer on the solid surface
- C parameter on heat of adsorption (> 0)
- the BET specific surface area is a value calculated by the following measuring method using an automatic specific surface area measuring device “GEMINI 2360 (manufactured by Shimadzu Micromeritics)”.
- GEMINI 2360 manufactured by Shimadzu Micromeritics
- the second metal atom / first metal atom (titanium atom) in the composite oxide particle, particularly Ca / Ti, is preferably 0.9 to 1.3, more preferably 1.0 to 1.2 in terms of molar ratio. 1 to 1.15 are more preferable.
- the molar ratio of the second metal atom / first metal atom, particularly Ca / Ti, can be measured by elemental analysis using fluorescent X-rays.
- the content of the composite oxide particles in the developer is not particularly limited as long as the object of the present invention is achieved.
- the content is usually 0.1 to 10.0% by weight with respect to the whole developer.
- the preferable range of such content varies depending on the content of the composite oxide particles, and will be described later.
- the total content may be in the above range.
- the composite oxide particles can be produced by adding a predetermined amount of a third metal atom supply source to these raw materials in a known production method of a metal titanate (titanate of a second metal atom).
- a metal titanate titanium oxide (IV) hydrate (TiO 2 .H 2 O) is obtained through hydrolysis by the so-called sulfuric acid method and taking the form of hydrate called metatitanic acid.
- the second metal atom source, and the third metal atom source are mixed, the mixture is reacted while adding an alkaline aqueous solution at 50 ° C. or higher, and then calcined.
- Composite oxide particles can be produced by the treatment.
- Titanium (IV) oxide is not limited to that produced by the sulfuric acid method, and may be produced by other known methods.
- a hydrolyzate of titanium oxide typified by metatitanic acid obtained by hydrolysis in the sulfuric acid method is also called a mineral acid peptizer and has a liquid form in which titanium oxide particles are dispersed.
- Metatitanic acid obtained by the sulfuric acid method which is one of the representative examples of mineral acid peptizers, has a sulfurous acid SO 3 content of 1.0% by weight or less, preferably 0.5% by weight or less, and has a pH of 0.00 with hydrochloric acid. It is adjusted to 8 to 1.5 and peptized.
- the concentration of the titanium oxide hydrolyzate is 0.05 to 1.0 mol / liter in terms of TiO 2 , and preferably 0.1 to 0.8 mol / liter.
- carbonates, oxides, nitrates and chlorides of metals belonging to Group 1A and Group 2A can be used, and water-soluble ones are particularly preferably used.
- Specific examples include, for example, calcium carbonate, calcium oxide, calcium nitrate, calcium chloride, magnesium carbonate, magnesium oxide, magnesium nitrate, magnesium chloride, strontium carbonate, strontium oxide, strontium nitrate, strontium chloride, barium carbonate, barium oxide, barium nitrate.
- Barium chloride, lithium carbonate, lithium oxide, lithium nitrate, lithium chloride, sodium carbonate, sodium oxide, lithium nitrate, lithium chloride, potassium carbonate, potassium oxide, potassium nitrate, potassium chloride and the like can be used.
- the addition ratio (molar ratio) of the second metal atom supply source is 0.9 to 1.4 with respect to titanium oxide when the second metal atom is a metal atom belonging to Group 2A, and 0.95 To 1.15 is a preferable range.
- the second metal atom is 1.8 to 2.8 with respect to the titanium oxide hydrolyzate, and 1.9 to 2.3 is a preferable range.
- the third metal atom supply source is not particularly limited as long as it is a compound containing a third metal atom, and examples thereof include niobium oxide, niobium hydroxide, vanadium oxide, vanadium hydroxide, tantalum oxide, and tantalum hydroxide.
- the third metal atom supply source may be used in the form of a powder, or may be used in the form of a slurry that is previously dispersed in water.
- the addition ratio (molar ratio) of the third metal atom supply source is not particularly limited as long as the composite oxide particles having the above-described third metal atom content can be obtained.
- the addition ratio is usually 0.0009 to 0.035 mol with respect to 1 mol of the titanium oxide hydrolyzate.
- the addition ratio is based on the addition ratio when the third metal atom is an oxide, based on the addition ratio of the third metal atom in 1 mol of the other compound. What is necessary is just to adjust suitably according to a number. By adjusting such an addition ratio, the content of the third metal atom in the composite oxide particles can be controlled.
- a caustic alkaline aqueous solution represented by an aqueous sodium hydroxide solution is preferably used as the alkaline aqueous solution used in the method for producing composite oxide particles.
- the addition rate of the alkaline aqueous solution tends to affect the particle size of the resulting composite oxide particles. The slower the addition rate, the larger the composite oxide particles, and the faster the addition rate, the smaller the particle size. Tend to form.
- the addition rate of the aqueous alkali solution is 0.001 to 1.0 equivalent / h, preferably 0.005 to 0.5 equivalent / h, relative to the charged raw material, and can be appropriately adjusted according to the desired particle size. is there.
- the addition rate of the alkaline aqueous solution can be changed in the middle depending on the purpose.
- the addition ratio of the second metal atom supply source to the titanium oxide hydrolyzate by adjusting the addition ratio of the second metal atom supply source to the titanium oxide hydrolyzate, the concentration of the titanium oxide hydrolyzate during the reaction, the temperature during the addition of the alkaline aqueous solution, etc. It is possible to control the particle size of the composite oxide particles.
- the reaction step it is preferable to carry out the reaction in a nitrogen gas atmosphere in order to prevent the formation of a carbonic acid compound.
- the obtained composite oxide particles may be used as they are, but it is preferable to subject the composite oxide particles to a hydrophobic treatment in order to adjust the chargeability of the obtained toner and improve the charging environment stability.
- a hydrophobizing agent is used alone or as a dilute solution dissolved in an organic solvent such as tetrahydrofuran (THF), toluene, ethyl acetate, methyl ethyl ketone or acetone, and powdered composite oxide particles
- THF tetrahydrofuran
- ethyl acetate ethyl acetate
- methyl ethyl ketone or acetone acetone
- powdered composite oxide particles Add the hydrophobizing agent or its diluted solution by dripping or spraying it while forcibly stirring it with a blender, etc., and mix it thoroughly or dissolve the hydrophobizing agent in an organic solvent.
- the treatment method is to improve the uniformity of the hydrophobization treatment for the composite oxide particles and to immerse the composite oxide particles by dispersing the hydrophobizing agent in an aqueous medium from the viewpoint of safety and cost.
- the wet method is preferably a wet method in which an aqueous emulsion is used as the hydrophobizing agent, and the hydrophobization treatment is performed in an aqueous medium.
- hydrophobizing agents conventionally used for inorganic oxides such as SiO 2 and Al 2 O 3 are used.
- chlorosilane, alkylsilane, alkoxysilane Silane coupling agents such as silazane, various coupling agents such as titanate, aluminum and zircoaluminate
- silicone oil is particularly preferable.
- water-based emulsions of silicone oil that can be suitably used include dimethylpolysiloxane emulsions such as “SM7036EX”, “SM7060EX”, and “SM8706EX” (above, manufactured by Toray Dow Corning Silicone).
- Amino-modified silicone emulsions such as “SM8704”, “SM8709”, “BY22-819” (manufactured by Toray Dow Corning Silicone); carboxy modification such as “BY22-840” (manufactured by Dow Corning Silicone) Silicone emulsions; Phenylmethyl silicone emulsions such as “SM8627EX” (manufactured by Toray Dow Corning Silicone) and the like.
- the addition ratio of the hydrophobizing agent varies depending on the type of the composite oxide, but is preferably 0.1 to 5.0% by mass, more preferably 0.2 to 3.0% by mass with respect to the composite oxide particles. %.
- the addition ratio of the hydrophobizing agent is less than 0.1% by mass, a sufficient hydrophobizing effect may not be obtained.
- the addition rate of the hydrophobizing agent exceeds 5.0% by mass, The hydrophobizing agent that does not contribute to the hydrophobizing treatment on the surface of the composite oxide particles is discharged together with the dispersion medium, or the hydrophobizing agents aggregate together. May contaminate the manufacturing apparatus or the image forming apparatus.
- the developer may be a two-component developer including a toner and a carrier in which an external additive is externally added to the toner particles, or the external additive is added to the toner particles.
- a one-component developer made of an externally added toner may be used.
- the content of the composite oxide particles in the developer of the present invention is not particularly limited as long as the contact between the composite oxide particles and the toner is ensured.
- the composite oxide when the developer is a two-component developer, the composite oxide The particles are included in at least one form shown below. (A1) Composite oxide particles are externally added to the toner particles; (A2) complex oxide particles are internally added to the toner particles; (A3) Composite oxide particles are internally added to the carrier; (A4) Composite oxide particles are externally added to the carrier; (A5) Composite oxide particles are added as a third component to the developer.
- the composite oxide particles are included in at least one form shown below.
- (B1) Composite oxide particles are externally added to the toner particles;
- (B2) Composite oxide particles are internally added to the toner particles.
- the composite oxide fine particles are contained in the developer in the form of (A1) or (B1) from the viewpoint of efficiently and stably expressing the effect.
- the developer according to Embodiment 1 is a two-component developer in which the composite oxide particles are contained in the form (A1), that is, the composite oxide particles are externally added to the toner particles.
- A1 the composite oxide particles are externally added to the toner particles.
- externally added to toner particles means to be added to and mixed with toner particles once obtained.
- the content of the composite oxide particles is not particularly limited as long as the content relative to the whole developer is within the above range, and is usually 0.1 to 10.0% by weight with respect to the toner particles. 3 to 5.0% by weight is preferred. More preferably, it is 0.4 to 2.0% by weight.
- the method for producing toner particles is not particularly limited, and wet methods such as so-called emulsion polymerization aggregation method, emulsion polymerization method and suspension polymerization method, and dry methods such as pulverization method can be used.
- Such a toner manufacturing method includes the following steps. (1) Production process of resin fine particle dispersion (2) Production process of colorant fine particle dispersion (3) Aggregation / fusion process of resin fine particles, etc. (4) Aging process (5) Cooling process (6) Washing process (7 ) Drying step (8) External additive treatment step Hereinafter, each step will be described.
- This process is a process of forming resin fine particles having a size of about 100 nm by introducing a polymerizable monomer that forms resin fine particles into an aqueous medium and performing emulsion polymerization. is there. It is also possible to form a resin fine particle containing wax. In this case, when the wax is dissolved or dispersed in the polymerizable monomer and polymerized in an aqueous medium, resin fine particles containing the wax are formed.
- Colorant fine particle dispersion preparation step In this step, a colorant is dispersed in an aqueous medium to prepare a colorant fine particle dispersion having a size of about 110 nm.
- aggregation is used based on the concept that at least a plurality of resin fine particles are simply attached.
- aggregation so-called hetero-aggregated particles (groups) are formed in which the constituent particles are in contact with each other, but the bonding due to melting of resin fine particles or the like is not formed.
- a group of particles formed by such “aggregation” is referred to as “aggregated particles”.
- Fusion is a concept that is intended to form a bond as a unit of use and handling by forming a bond due to melting of resin fine particles, etc., at least at a part of the interface of each constituent particle in the aggregated particles.
- the particle group that has undergone such “fusion” is referred to as “fused particles”.
- This step is a step of aging the reaction system until the desired average circularity is achieved by heat-treating the reaction system subsequent to the aggregation / fusion step.
- Cooling step This step is a step of cooling (rapid cooling) the dispersion of the colored particles.
- cooling is performed at a cooling rate of 1 to 20 ° C./min.
- the cooling treatment method is not particularly limited, and examples thereof include a method of cooling by introducing a refrigerant from the outside of the reaction vessel, and a method of cooling by directly introducing cold water into the reaction system.
- Washing step comprises a step of solid-liquid separation of the colored particles from the colored particle dispersion cooled to a predetermined temperature in the above step, and a cake-like aggregate called a wet toner cake that has been solid-liquid separated. It consists of a washing process for removing deposits such as surfactants and flocculants from the colored particles.
- Washing is performed with water until the electrical conductivity of the filtrate reaches about 10 ⁇ S / cm, for example.
- the filtration method include a centrifugal separation method, a vacuum filtration method using Nutsche and the like, and a filtration method using a filter press and the like, and are not particularly limited.
- Drying step This step is a step of drying the washed colored particles to obtain dried toner particles.
- the dryer used in this step include a spray dryer, a vacuum freeze dryer, and a vacuum dryer, and a stationary shelf dryer, a mobile shelf dryer, a fluidized bed dryer, and a rotary dryer. It is preferable to use a stirring dryer or the like.
- the water content of the dried toner particles is preferably 5% by weight or less, and more preferably 2% by weight or less.
- the toner particles subjected to the drying treatment are aggregated by weak interparticle attractive force, the aggregate may be crushed.
- a mechanical crushing apparatus such as a jet mill, a Henschel mixer, a coffee mill, or a food processor can be used.
- External additive treatment step This step is a step of preparing toner by adding external additives such as the composite oxide particles described above to the dried toner particles.
- the external additive mixing device include mechanical mixing devices such as a Henschel mixer and a coffee mill. Through the above steps, a toner can be manufactured.
- the toner preferably has a volume reference median diameter (D50) of 3 ⁇ m or more and 8 ⁇ m or less, and the toner belonging to such a small diameter class is optimal for reproducing a high-definition dot image corresponding to a digital technology described later. It is.
- D50 volume reference median diameter
- the volume-based median diameter (D50) is measured and calculated using, for example, an apparatus in which “Multisizer 3 (manufactured by Beckman Coulter)” is connected to a computer system equipped with data processing software “Software V3.51”. can do.
- a surfactant solution for example, a surfactant solution obtained by diluting a neutral detergent containing a surfactant component 10 times with pure water for the purpose of dispersing the toner. After that, ultrasonic dispersion is performed for 1 minute to prepare a toner dispersion.
- the acid value of the toner particles is not particularly limited, but is preferably 5 KOHmg / g or more and 30 KOHmg / g, more preferably 7 to 25 KOHmg / g. Even with relatively high acid value toner particles, the charging performance can be more stably maintained without being affected by the print production environment. That is, toner particles having an acid value in the above range have stable charge rise and charge stability even in an environment where moisture in the air is adsorbed on the toner particle surface and leakage is more likely to occur, such as in a high temperature and high humidity environment. Is expressed.
- the acid value of toner particles refers to the number of mg of potassium hydroxide required to neutralize polar groups such as carboxyl groups contained in 1 g of resin and toner particles.
- the acid value of the toner particles is calculated from the neutralization amount by dissolving the sample in a benzene-ethanol mixed solvent and titrating with a potassium hydroxide solution having a known titer.
- a specific method for measuring the acid value of the toner for example, the method described in JIS-0070-1992 can be mentioned.
- the acid value of toner particles is controlled by adjusting the composition ratio in the polymerization reaction at the time of toner production, for example, in the resin formed by addition polymerization reaction, for example, the composition ratio of acidic components having carboxyl groups such as acrylic monomers can do.
- the ratio of the acid component to the alcohol component in the polymerization stage is controlled, for example, by introducing a polyfunctional acid such as trimellitic acid to suppress the progress of the crosslinking reaction. It is possible to control by changing the polymerization conditions.
- the binder resin a polymer formed by polymerizing a polymerizable monomer called a vinyl monomer described below can be used.
- the polymer constituting the resin that can be used in the present invention is a polymer obtained by polymerizing at least one polymerizable monomer, and these vinyl monomers are used alone. Or it is the polymer produced combining multiple types.
- Styrene or styrene derivatives Styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, ⁇ -methylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-phenylstyrene, p-ethylstyrene 2,4-dimethylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, etc.
- Methacrylic acid ester derivatives Methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate Lauryl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, and the like.
- Vinyl ketones Vinyl methyl ketone, vinyl ethyl ketone, vinyl hexyl ketone and the like.
- N-vinyl compounds N-vinylcarbazole, N-vinylindole, N-vinylpyrrolidone and the like.
- Others Vinyl compounds such as vinyl naphthalene and vinyl pyridine, acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide.
- the toner may be formed by appropriately using the above-described polymerizable monomer having a polar group or a highly hydrophilic polymerizable monomer.
- Examples of the colorant include known ones. Specific colorants are shown below.
- Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black, and magnetic powder such as magnetite and ferrite.
- C.I. I. Pigment red 2 As colorants for magenta or red, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 48; 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 139, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I.
- colorants can be used alone or in combination of two or more as required.
- the addition amount of the colorant is set in the range of 1 to 30% by weight, preferably 2 to 20% by weight, based on the whole toner.
- wax examples include the following known ones.
- Polyolefin wax Polyethylene wax, polypropylene wax, etc.
- the melting point of the wax is usually 40 to 125 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. By setting the melting point within the above range, the heat-resistant storage stability of the toner is ensured, and stable toner image formation can be performed without causing cold offset or the like even when fixing at a low temperature.
- the wax content in the toner is preferably 1% by weight to 30% by weight, and more preferably 5% by weight to 20% by weight.
- inorganic fine particles or organic fine particles other than the composite oxide particles described above can be used together as an external additive.
- the type of external additive that can be used in combination with the composite oxide particles is not particularly limited, and examples thereof include inorganic fine particles and organic fine particles as described below, and lubricants.
- the inorganic fine particles conventionally known fine particles can be used, and those having an average primary particle size of 4 to 800 nm are preferably used. Specifically, silica, alumina and the like can be preferably used. These inorganic fine particles may be hydrophobized if necessary. Examples of the silica fine particles include commercially available products R-805, R-976, R-974, R-972, R-812, R-809 manufactured by Nippon Aerosil Co., Ltd., HVK-2150, H-200 manufactured by Hoechst, and Cabot. Commercially available products TS-720, TS-530, TS-610, H-5, MS-5 and the like manufactured by the company are listed.
- alumina fine particles examples include commercial products RFY-C and C-604 manufactured by Nippon Aerosil Co., Ltd. and commercial products TTO-55 manufactured by Ishihara Sangyo Co., Ltd.
- organic fine particles spherical organic fine particles having an average primary particle size of about 10 to 2000 nm can be used. Specifically, homopolymers such as styrene and methyl methacrylate and copolymers thereof can be used.
- a metal salt of a higher fatty acid called a so-called lubricant can be used as an external additive.
- the higher fatty acid metal salt include the following. That is, salts of zinc stearate, aluminum, copper, magnesium, calcium, etc., zinc oleate, salts of manganese, iron, copper, magnesium, etc., zinc palmitate, salts of copper, magnesium, calcium, etc., linoleic acid
- salts of zinc, calcium and the like, and zinc and calcium of ricinoleic acid are salts of zinc, calcium and the like, and zinc and calcium of ricinoleic acid.
- the amount of the external additive added to the toner is preferably 0.1 to 10.0% by weight based on the toner particles including the composite oxide particles described above.
- an addition method of an external additive the method of adding using various well-known mixing apparatuses, such as a Turbuler mixer, a Henschel mixer, a Nauta mixer, and a V-type mixer, is mentioned.
- the carrier for example, conventionally known magnetic materials such as metals such as iron, ferrite and magnetite, alloys of these metals with metals such as aluminum and lead may be used as they are, or the magnetic materials may be used as carriers.
- a binder-type carrier dispersed in a binder resin for use may be used, or a coated carrier in which the magnetic material is used as a core material particle and the surface of the core material particle is coated with a resin layer is used. May be. From the viewpoint of increasing electrical resistance, a coated carrier is preferable.
- the coated carrier can be manufactured, for example, by mixing the core material particles and the coat resin with a high-speed mixer and forming a resin layer on the surface of the core material particles by the action of mechanical impact force.
- Coat resins suitable for forming a carrier coating layer include polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene; polyacrylates such as polystyrene and polymethyl methacrylate, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl Polyvinyl and polyvinylidene resins such as butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, and polybiliketones; copolymers such as vinyl chloride-vinyl acetate copolymers and styrene-acrylic acid copolymers; silicones composed of organosiloxane bonds Resin or its modified resin (for example, modified resin by alky
- the binder type carrier can be produced by melting and kneading a carrier binder resin and a magnetic material, cooling, pulverizing and classifying.
- a binder-type carrier by a polymerization method can also be preferably used.
- the carrier binder resin a phenol resin or the like can be used in addition to the coating resin.
- the volume average particle diameter of the carrier is preferably 15 to 100 ⁇ m, more preferably 20 to 60 ⁇ m.
- the mixing ratio of the toner and the carrier is not particularly limited, but usually 3/97 to 10/90 in terms of the weight ratio (toner / carrier), although it depends on the particle diameter of the carrier and the toner. .
- the developer can be produced by thoroughly mixing the toner and carrier added at such a ratio.
- the developer according to Embodiment 2 is a two-component developer in which the composite oxide particles are contained in the form (A2), that is, the composite oxide particles are internally added to the toner particles.
- A2 the composite oxide particles are internally added to the toner particles.
- the contact between the toner particles having the composite oxide particles internally added and the carrier is ensured, and the excellent charge rising property and charge stability of the toner are exhibited.
- internal added to toner particles means that complex oxide particles are added and contained in the toner particles in the production process of the toner particles. As the internal addition state, it is preferable that the composite oxide particles exist in the vicinity of the toner particle surfaces.
- the developer of Embodiment 2 is the same as the developer of Embodiment 1 described above except that the composite oxide particles are internally added to the toner particles instead of the composite oxide particles being externally added to the toner particles. It is.
- the toner particles are the same as the exemplary embodiment except that the composite oxide particles are added in the aggregation / fusion process of the resin fine particles and are aggregated / fused together with the resin fine particles and the colorant particles. This is the same as the toner particles in one developer.
- the toner particles can also be produced by mixing the composite oxide particles together with the binder resin and the colorant in a so-called pulverization method before melting and kneading.
- the content of the composite oxide particles is not particularly limited as long as the content relative to the entire developer is within the above range, and is usually 0.1 to 10% by weight, particularly 0%, based on the entire toner. 5 to 5% by weight is preferred.
- the developer according to Embodiment 3 is a two-component developer in which the composite oxide particles are contained in the form (A3), that is, the composite oxide particles are internally added to the carrier.
- the contact between the composite oxide particles that are internally added to the carrier and exist in the vicinity of the carrier surface and the toner is ensured, and the toner has excellent charge rising property and charge stability.
- “internally added to the carrier” means that composite oxide particles are added and contained inside the carrier during the carrier production process. As an internally added state, it is preferable that the composite oxide particles exist in the vicinity of the carrier surface.
- the developer of Embodiment 3 is the same as the developer of Embodiment 1 described above except that the composite oxide particles are internally added to the carrier instead of the composite oxide particles being externally added to the toner particles. is there.
- the method for producing the carrier is not particularly limited as long as the composite oxide particles are contained inside the carrier.
- the coated carrier used in the developer of Embodiment 3 is prepared by mixing the core material particles, the coat resin, and the composite oxide particles with a high-speed mixer, and by using the mechanical impact force and the heat generated by the core material particles. It can be produced by the same method as that for the coat carrier of the developer of Embodiment 1 except that the composite oxide particles are contained in the resin layer while forming a resin layer on the surface.
- the binder type carrier used for the developer of Embodiment 3 is the same as the binder type carrier of the developer of Embodiment 1 except that the carrier binder resin, magnetic material, and composite oxide particles are melted and kneaded. It can be manufactured by the method.
- the content of the composite oxide particles is not particularly limited as long as the content relative to the whole developer is within the above range, and is usually 0.1 to 10% by weight, particularly 0%, based on the whole carrier. 5 to 5% by weight is preferred.
- the developer according to Embodiment 4 is a two-component developer in which the composite oxide particles are contained in the form (A4), that is, the composite oxide particles are externally added to the carrier.
- A4 the composite oxide particles are externally added to the carrier.
- contact between the toner particles and the composite oxide particles externally added to the carrier is ensured, and by adjusting the surface resistance of the carrier, it is possible to adjust the charge rising property and charge level of the toner. Stability is more reliably expressed.
- the developer of Embodiment 4 is the same as the developer of Embodiment 1 described above except that the composite oxide particles are externally added to the carrier instead of the composite oxide particles being externally added to the toner particles. is there.
- the carrier is the same as the carrier in the developer of Embodiment 1 except that the composite oxide particles are mainly attached to the carrier surface.
- the toner particles contact between the toner particles and the composite oxide particles externally added to the carrier is ensured, and by adjusting the surface resistance of the carrier, the toner has excellent charge rising property, charge level adjustment and charge stability. It is expressed more reliably.
- the content of the composite oxide particles is not particularly limited as long as the content with respect to the whole developer is within the above range, and is usually 0.0001 to 1% by weight, particularly 0.001% with respect to the carrier. 0005 to 0.1% by weight is preferred.
- the developer according to Embodiment 5 is a two-component developer in which the composite oxide particles are contained in the form (A5), that is, the composite oxide particles are added as a third component to the developer. .
- the composite oxide particles are added as a third component to the developer, and the third component is interposed between the toner and the carrier, so that the excellent charge rising property and charge stability of the toner are expressed.
- the composite oxide particles are interposed between the carrier and the toner, so that improvement in charge rising property and charge stability of the toner is expressed.
- the developer of Embodiment 5 is the same as the developer of Embodiment 1 described above except that the composite oxide particles are externally added to the toner and the carrier instead of the composite oxide particles being externally added to the toner particles. It is the same.
- the developer of Embodiment 5 can be produced by the same method as that of the developer of Embodiment 1 except that in the toner and carrier mixing step, the composite oxide particles are added and mixed together with the toner and the carrier.
- the content of the composite oxide particles is not particularly limited as long as the content with respect to the entire developer is within the above range, and is usually 0.001 to 5% by weight, particularly with respect to the entire developer. 0.01 to 3% by weight is preferred.
- the developer according to Embodiment 6 is a one-component developer in which the composite oxide particles are contained in the form (B1), that is, the composite oxide particles are externally added to the toner particles.
- the contact between the toner particles and the composite oxide particles externally added to the toner particles is ensured, and the excellent charge rising property and charge stability of the toner are more reliably ensured.
- the developer of Embodiment 6 is the same as the developer of Embodiment 1 described above, except that no carrier is contained.
- the content of the composite oxide particles is not particularly limited as long as the content relative to the entire developer is within the above range, and is usually 0.1 to 10% by weight, particularly 0.3 to 5% by weight is preferred. More preferably, it is 0.5 to 2% by weight.
- the developer according to Embodiment 7 is a one-component developer in which the composite oxide particles are contained in the form (B2), that is, the composite oxide particles are internally added to the toner particles.
- the contact between the adjacent oxide and the composite oxide particles that are internally added to the toner particles and exposed from the surface of the toner particles is ensured, and the toner has excellent charge rising properties. In addition, charging stability is exhibited.
- the developer of Embodiment 7 is the same as the developer of Embodiment 2 described above, except that no carrier is contained.
- the content of the composite oxide particles is not particularly limited as long as the content relative to the whole developer is within the above range, and is usually 0.1 to 10% by weight, particularly 0%, based on the whole toner. 5 to 5% by weight is preferred.
- the developer according to the present invention is a two-component developer
- the two-component developer is mounted and used in a known image forming apparatus adopting a so-called two-component development method.
- the developer according to the present invention is a one-component developer
- the one-component developer is mounted and used in a known image forming apparatus that employs a so-called one-component development system.
- These image forming apparatuses may be for monochrome image formation or for full color image formation.
- the temperature of the dispersion was adjusted to 35 ° C., and stirred at this temperature for 1 hour to peptize the metatitanic acid dispersion.
- Metatitanic acid corresponding to 0.156 mol in terms of titanium oxide TiO 2 was collected from the metatitanic acid dispersion that had been subjected to the peptization treatment and charged into a reaction vessel, followed by calcium carbonate CaCO 3 aqueous solution and niobium oxide aqueous solution. was charged into the reaction vessel. Thereafter, a reaction system was prepared so that the titanium oxide concentration was 0.156 mol / liter.
- Nitrogen gas is supplied into the reaction vessel, and the reaction vessel is left in a nitrogen gas atmosphere by allowing it to stand for 20 minutes, and then a mixed solution of metatitanic acid, calcium carbonate, and niobium oxide is heated to 90 ° C. did. Subsequently, an aqueous sodium hydroxide solution was added over 24 hours until the pH reached 8.0, and then stirring was continued at 90 ° C. for 1 hour to complete the reaction. After completion of the reaction, the inside of the reaction vessel was cooled to 40 ° C., and the supernatant was removed under a nitrogen atmosphere. Then, 2500 parts by weight of pure water was put into the reaction vessel, and decantation was repeated twice.
- the reaction system was filtered with Nutsche to form a cake, and the obtained cake was heated to 110 ° C. and dried in air for 8 hours.
- the obtained dried calcium titanate was put into an alumina crucible, dehydrated at 930 ° C. and fired. After the firing treatment, calcium titanate is put into water, wet-grinded with a sand grinder to obtain a dispersion, 6.0 mol / liter hydrochloric acid aqueous solution is added to adjust the pH to 2.0, Excess calcium carbonate was removed.
- a wet hydrophobization treatment was performed on calcium titanate using a silicone oil emulsion (dimethylpolysiloxane emulsion) “SM7036EX (manufactured by Toray Dow Corning Silicone Co., Ltd.)”.
- silicone oil emulsion dimethylpolysiloxane emulsion
- S7036EX manufactured by Toray Dow Corning Silicone Co., Ltd.
- volume-based particle size, particle size standard deviation (SD value), and BET specific surface area of the produced “inorganic particles 1” were measured by the above-described methods, the volume-based particle size was 198 nm, and the particle size standard deviation ( SD value) was 108 nm, and the BET specific surface area was 15.4 m 2 / g.
- KPS potassium persulfate
- a surfactant solution in which 1.6 parts by weight of sodium lauryl sulfate was dissolved in 2700 parts by weight of ion-exchanged water was prepared in a reaction vessel equipped with a stirrer, a temperature sensor, a cooling pipe, and a nitrogen introduction device. Heated to 98 ° C. After adding 28 parts by weight of the above-mentioned “resin particle dispersion 1H” in terms of solid content to the surfactant solution, the mixture 1B was charged. Further, a dispersion (emulsion) was prepared by mixing and dispersing for 8 hours using a mechanical dispersion device “CLEARMIX” (manufactured by M Technique Co., Ltd.) having a circulation path.
- CLEARMIX mechanical dispersion device
- an initiator solution prepared by dissolving 5.1 parts by weight of potassium persulfate (KPS) in 240 parts by weight of ion-exchanged water and 750 parts by weight of ion-exchanged water are added to the dispersion (emulsion). Polymerization was carried out by stirring at 98 ° C. for 12 hours. In this manner, a dispersion of “resin particle 1HM” having a composite structure in which the surface of “resin particle 1H” was coated with resin was prepared.
- KPS potassium persulfate
- reaction system was cooled to 28 ° C. to prepare a dispersion of “resin particle 1HML” having a composite structure in which the surface of “resin particle 1HM” was coated with resin.
- the obtained resin particles had a particle size of about 150 nm.
- toner particles A (aggregation / fusion) Into a reaction vessel equipped with a stirrer, temperature sensor, cooling pipe, nitrogen introduction device, and stirrer, the following were charged, the inside of the reaction vessel was adjusted to 30 ° C., and 5 mol / liter sodium hydroxide was further added. The aqueous solution was added to adjust the pH to 10.6.
- Resin particle dispersion 1HML 200 parts by weight (solid content conversion) 3000 parts by weight of ion-exchanged water 71 parts by weight of “colorant dispersion 1” (in terms of solid content)
- an aqueous solution prepared by dissolving 52.6 parts by weight of magnesium chloride hexahydrate in 72 parts by weight of ion-exchanged water was added over 10 minutes while stirring the reaction system at a temperature of 30 ° C. After the addition, the reaction system was left for 3 minutes. Thereafter, the temperature of the reaction system was started, and the temperature of the system was raised to 75 ° C. over 60 minutes to start aggregation of the particles.
- aggregation was continued while measuring the particle size of the aggregated particles using “Multisizer 3 (manufactured by Beckman Coulter)”.
- Multisizer 3 manufactured by Beckman Coulter
- an aqueous solution in which 115 parts by weight of sodium chloride was dissolved in 700 parts by weight of ion-exchanged water was added to stop particle growth.
- the liquid temperature was set to 90 ° C., and the heating and stirring treatment was performed for 6 hours to continue the fusion of the particles. Thereafter, the reaction system was cooled to 30 ° C., hydrochloric acid was added to adjust the pH to 2.0, and stirring was stopped.
- the colored particles produced through aggregation and fusion are solid-liquid separated, repeatedly washed with ion exchange water at 45 ° C., and then dried with hot air at 40 ° C. Particle A "was produced.
- the acid value of “toner particle A” was measured by the method prescribed in JIS-0070-1992 to be 15.
- Resin particle dispersion 2HM was prepared in the same manner as described above except that “mixture 2B” made of the following compound was used instead of “mixture 1B” in the production process of “resin particle 1HM”.
- toner particles F ⁇ Manufacture of toner particles F>
- the toner particle A except that 6 parts by weight of the inorganic particle dispersion shown below was also charged when the resin particle dispersion 1HML, the ion exchange water and the colorant dispersion 1 were charged into the reaction vessel.
- Toner particles F were manufactured by the same method as that described above.
- the acid value of “toner particles F” was 15 KOH mg / g.
- An inorganic particle dispersion was prepared by the following method. 90 parts by weight of anionic surfactant sodium lauryl sulfate was put into 1600 parts by weight of ion-exchanged water, and stirred to prepare a surfactant solution. While stirring the surfactant solution, 1600 parts by weight of inorganic particles 2 were gradually added. Thereafter, dispersion treatment was performed using a mechanical dispersion device “CLEARMIX (manufactured by M Technique Co., Ltd.)” to prepare an “inorganic particle dispersion”.
- CLEARMIX manufactured by M Technique Co., Ltd.
- toner 1 ⁇ Manufacture of toner 1> The following were added as external additives to the toner particles A.
- “Inorganic particles 1” 2.0% by weight Hydrophobic silica (particle size 17nm, hexamethyldisilazane treated product) 1.0% by weight Hydrophobic silica (particle size 21 nm, hexamethyldisilazane treated product) 1.0% by weight
- the external addition process is performed using a Henschel mixer “FM10B (Mitsui Miike Chemical Co., Ltd.)” at a temperature of 30 ° C., setting the peripheral speed of the stirring blade to 35 m / sec and a processing time of 20 minutes. Coarse particles were removed using an open sieve to produce “Toner 1”.
- a toner was manufactured by the same method as that of toner 1 except that the toner particles and inorganic particles listed in Table 2 were used.
- a toner was produced by the same method as the production method of the toner 1 except that the toner particles F were used and an external additive other than the inorganic particles 1 was externally added.
- a toner was produced by the same method as that for toner 1 except that external additives other than inorganic particles 1 were externally added.
- Mn—Mg ferrite particles having a volume average diameter of 60 ⁇ m and a saturation magnetization of 10.7 ⁇ 10 ⁇ 5 Wb ⁇ m / kg were prepared. 100 parts by weight of Mn—Mg ferrite particles and 3.8 parts by weight of copolymer resin fine particles of styrene / methyl methacrylate (copolymerization ratio 2/8) were put into a high-speed mixer equipped with stirring blades and heated at 120 ° C. for 60 minutes. By stirring and mixing, a resin layer was formed on the surface of the ferrite particles by the action of a mechanical impact force to obtain a carrier 1 coated with the resin layer. The thickness of the resin layer of the carrier 1 was 2500 nm. The volume average particle diameter of the carrier 1 was 65 ⁇ m.
- Mn—Mg ferrite particles having a volume average diameter of 60 ⁇ m and a saturation magnetization of 10.7 ⁇ 10 ⁇ 5 Wb ⁇ m / kg were prepared. 100 parts by weight of Mn—Mg ferrite particles, 3.8 parts by weight of copolymer resin fine particles of styrene / methyl methacrylate (copolymerization ratio 2/8) and 5 parts by weight of inorganic particles 2 were added to a high-speed mixer equipped with stirring blades. The mixture was stirred and mixed at 120 ° C. for 60 minutes, and a resin layer was formed on the surface of the ferrite particles by the action of mechanical impact force. Thus, carrier 2 containing inorganic particles 2 in the resin layer was obtained. The thickness of the resin layer of this carrier 2 was 2540 nm. The volume average particle diameter of the carrier 2 was 65 ⁇ m.
- a developer was produced by the same method as the developer 1 except that the toner and carrier shown in Table 3 were used in combination.
- Example 1 Two-Component Developer >> ⁇ Example / comparative example>
- the developer described in Table 4 is mounted on a two-component image forming apparatus (bizhub Pro C450; manufactured by Konica Minolta), and the image forming apparatus is placed in a high temperature and high humidity environment (30 ° C., 80% RH) for 24 hours. After standing, 3000 sheets were continuously printed in the above environment, and image quality evaluation was performed at the start and after the continuous printing. Similarly, after leaving the image forming apparatus in a low-temperature, low-humidity environment (10 ° C., 15% RH) for 24 hours, 3000 sheets are continuously printed in the environment, and image quality evaluation is performed at the start and after the continuous printing. It was.
- a fine line image with a pixel rate of 6% consisting of three types: 4 lines / mm, 5 lines / mm, and 6 lines / mm), a halftone image (image density 0.40), a white background image, and a solid image
- An image an A4-size original image in which the image density is 1.30 is divided into 1 ⁇ 4 equal parts. The evaluation was performed with respect to fogging and image density fluctuations on the photosensitive member and the image.
- the fog on the photoreceptor is visually observed on the surface of the photoreceptor after continuous printing of 3000 sheets. After the visual observation, the photoreceptor surface is coated with a 30 mm wide book tape “Amenity B Coat T (manufactured by Kihara)”. After peeling, the peeled tape was stuck on a white paper and visually observed.
- Evaluation was performed in four stages as follows, and ⁇ to ⁇ were regarded as acceptable.
- X Occurrence of fog was observed over the entire surface of the photoconductor, and it was determined from the peeled tape that there was a practically problematic fog generation state.
- the fog of the image was evaluated by the following method. With respect to the white background image on the printed matter produced at the start of continuous printing, the density at 20 locations was measured using a reflection density meter “RD-918” manufactured by Macbeth Co., Ltd., and this average value was defined as the white background density. Next, with respect to the white background portion of the 3000th continuous print, the density at 20 locations was measured in the same manner to obtain an average value, which was set as the 3000th white background density. The value obtained by subtracting the white background density at the start from the 3000th white background density was defined as the fog density. A fog density of 0.010 or less was accepted. ⁇ ; Less than 0.003; ⁇ : 0.003 or more and less than 0.006; ⁇ : 0.006 or more and 0.010 or less; X: Value exceeding 0.010.
- Image density The density of the solid image portion on the start of continuous printing and on the 3000th printed material was measured and evaluated. Specifically, 12 points on the solid image area on the 3000th printed matter at the start of print production were measured using a reflection densitometer “RD-918 (manufactured by Macbeth)”, and the average value was obtained. This was taken as the image density. Then, evaluation was performed by calculating a difference in image density between the start of continuous printing and the 3000th sheet. Those having an image density difference of 0.04 or less were regarded as acceptable. ⁇ ; less than 0.01; ⁇ : 0.01 or more and less than 0.02; ⁇ : 0.02 to 0.04; X: Value exceeding 0.04.
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Abstract
Description
本発明において複合酸化物粒子は、第1金属原子としてチタン原子を含むチタン酸の、第2金属原子との金属塩粒子中に、所定の第3金属原子が適正量で含有されてなるものである。チタン酸金属塩に対して所定の第3金属原子を適正量で含有することにより、複合酸化物粒子が現像時にトナーと接触すると、擬似的にキャリアやコンデンサのように作用するので、帯電立ち上がり性および帯電安定性が向上するものと考えられる。例えば、電荷のリークが起こり易い高温高湿環境下では、複合酸化物粒子に第3金属原子が存在していても、その含有量が適正な範囲であればリークをおこすことなく適正な帯電性を維持することができる。また擬似的にキャリアの様に作用し、所定レベルの画像形成が行える電荷をトナーに供給するため、初期のトナー帯電性を安定して維持できる。また例えば、トナーが過剰帯電し易い低温低湿環境下では、複合酸化物粒子は擬似的にコンデンサの様に作用して過剰帯電したトナー電荷を一旦蓄積した後、速やかに第3金属原子を介して放出させるため、トナー帯電性を安定して維持できる。低温低湿環境下ではトナーの帯電立ち上がり性が低くなる傾向があるが、複合酸化物粒子は第3金属原子の存在により擬似的にキャリアの様に作用するので、良好な帯電立ち上がり性が得られる。それらの結果、優れた帯電性を初期から長期にわたって維持できるので、高温高湿環境下や低温低湿環境下においても、カブリや濃度低下のない画像を長期にわたって得ることができるものと考えられる。
そのようなチタン酸金属塩は、酸化チタン(IV)と第2金属原子の酸化物または炭酸塩とから生成される塩のことをいい、いわゆるメタチタン酸塩と呼ばれ、一般式(I)で表すことができる。
一般式(I);MI 2TiO3またはMIITiO3
(式中、MIは1A族の金属原子、MIIは2A族の金属原子を表す。)
(1)現像剤より単離した複合酸化物粒子に対して走査電子顕微鏡にて倍率3万倍の写真撮影を行い、この写真画像をスキャナにて取り込む。
(2)画像処理解析装置「LUZEX AP(ニレコ社製)」にて、写真画像上のトナー表面に存在する複合酸化物粒子を2値化処理し、100個について水平フェレ径を算出し、水平フェレ径の平均値を平均粒径とする。ここで、水平フェレ径とは、写真画像上の複合酸化物粒子を2本の垂直線ではさみ、はさんだ2本の垂直線間の距離のことをいう。
粒径標準偏差(SD値)
=〔個数基準84%粒径(D84)-個数基準16%粒径(D16)〕/2
で表されるものである。
式1:
P/V(Po-P)=(1/VmC)+((C-1)/VmC)(P/Po)
ただし、Po:飽和蒸気圧
Vm:単分子層吸着量、気体分子が固体表面で単分子層を形成した時の吸着量
C :吸着熱などに関するパラメータ(>0)
上式より単分子吸着量Vmを算出し、これにガス分子1個の占める断面積を掛けることにより、粒子の表面積を求めることができる。
先ず、複合酸化物粒子2gをストレートサンプルセルに充填し、前処理として窒素ガス(純度99.999%)にて2時間セル内を置換する。置換後、測定装置本体にて前処理した複合酸化物粒子に窒素ガス(純度99.999%)を吸脱着させて、多点法(7点法)により算出する。
反応工程では炭酸化合物の生成を防ぐために窒素ガス雰囲気下で反応を行うことが好ましい。
また、シリコーンオイルの水系エマルションとして好適に使用できるものとしては、具体的には、「SM7036EX」,「SM7060EX」,「SM8706EX」(以上、東レ・ダウコーニングシリコーン社製)などのジメチルポリシロキサン系エマルション;「SM8704」,「SM8709」,「BY22-819」(以上、東レ・ダウコーニングシリコーン社製)などのアミノ変性シリコーンエマルション;「BY22-840」(東レ・ダウコーニングシリコーン社製)などのカルボキシ変性シリコーンエマルション;「SM8627EX」(東レ・ダウコーニングシリコーン社製)などのフェニルメチルシリコーンエマルションなどが挙げられる。
疎水化剤の添加割合は、複合酸化物の種類によって異なるが、複合酸化物粒子に対して0.1~5.0質量%であることが好ましく、より好ましくは0.2~3.0質量%である。
疎水化剤の添加割合が0.1質量%未満である場合は、十分な疎水化の効果が得られないおそれがあり、一方、疎水化剤の添加割合が5.0質量%を超える場合は、処理すべき複合酸化物粒子に対して過剰に存在する状態となり、複合酸化物粒子表面の疎水化処理に寄与しない疎水化剤が、分散媒体と共に排出されたり、当該疎水化剤同士が凝集したりすることにより、製造装置内や画像形成装置を汚染してしまうおそれがある。
本発明に係る現像剤は複合酸化物粒子を有する限り、トナー粒子に外添剤が外添されたトナーおよびキャリアを含む二成分現像剤であってもよいし、またはトナー粒子に外添剤が外添されたトナーからなる一成分現像剤であってもよい。
(A1)複合酸化物粒子がトナー粒子に外添されている;
(A2)複合酸化物粒子がトナー粒子に内添されている;
(A3)複合酸化物粒子がキャリアに内添されている;
(A4)複合酸化物粒子がキャリアに外添されている;
(A5)複合酸化物粒子が現像剤に第3成分として添加されている。
(B1)複合酸化物粒子がトナー粒子に外添されている;
(B2)複合酸化物粒子がトナー粒子に内添されている。
実施形態1に係る現像剤は複合酸化物粒子が前記(A1)の形態で含有されるものであり、すなわち複合酸化物粒子がトナー粒子に外添されている二成分現像剤である。本実施形態においては、トナー粒子と当該トナー粒子に外添された複合酸化物粒子との接触が確保され、トナーの優れた帯電立ち上がり性および帯電安定性がより確実に発現される。
(1)樹脂微粒子分散液の作製工程
(2)着色剤微粒子分散液の作製工程
(3)樹脂微粒子等の凝集・融着工程
(4)熟成工程
(5)冷却工程
(6)洗浄工程
(7)乾燥工程
(8)外添剤処理工程
以下、各工程について説明する。
この工程は樹脂微粒子を形成する重合性単量体を水系媒体中に投入して乳化重合を行うことにより100nm程度の大きさの樹脂微粒子を形成する工程である。なお、樹脂微粒子中にワックスを含有させたものを形成することも可能である。この場合、ワックスを重合性単量体に溶解あるいは分散させておき、これを水系媒体中で重合させると、ワックスを含有してなる樹脂微粒子が形成される。
水系媒体中に着色剤を分散させ、110nm程度の大きさの着色剤微粒子分散液を作製する工程である。
この工程は、水系媒体中で樹脂微粒子と着色剤粒子を凝集させ、凝集させたこれらの粒子を融着させ、着色粒子を作製する工程である。この工程では、樹脂微粒子と着色剤粒子とが存在している水系媒体中に、塩化マグネシウム等に代表されるアルカリ金属塩やアルカリ土類金属塩等の凝集剤を添加し、次いで、前記樹脂微粒子のガラス転移点以上であって、かつ前記混合物の融解ピーク温度(℃)以上の温度に加熱することで凝集を進行させると同時に樹脂微粒子同士の融着を行う。凝集を進行させて粒子の大きさが目標になった時に、食塩等の塩を添加して凝集を停止させる。
この工程は、上記凝集・融着工程に引き続き、反応系を加熱処理することにより着色粒子の形状を所望の平均円形度になるまで熟成する工程である。
この工程は、前記着色粒子の分散液を冷却処理(急冷処理)する工程である。冷却処理条件としては、1~20℃/minの冷却速度で冷却する。冷却処理方法としては特に限定されるものではなく、反応容器の外部より冷媒を導入して冷却する方法や、冷水を直接反応系に投入して冷却する方法を例示することができる。
この工程は、上記工程で所定温度まで冷却された着色粒子分散液から着色粒子を固液分離する工程と、固液分離されてウェットのトナーケーキと呼ばれるケーキ状集合体となった着色粒子より界面活性剤や凝集剤等の付着物を除去するための洗浄工程からなる。
この工程は、洗浄処理された着色粒子を乾燥処理し、乾燥されたトナー粒子を得る工程である。この工程で使用される乾燥機としては、スプレードライヤ、真空凍結乾燥機、減圧乾燥機などを挙げることができ、静置棚乾燥機、移動式棚乾燥機、流動層乾燥機、回転式乾燥機、撹拌式乾燥機などを使用することが好ましい。
この工程は、乾燥されたトナー粒子に前述した複合酸化物粒子をはじめとする外添剤を添加し、トナーを作製する工程である。外添剤の混合装置としては、ヘンシェルミキサー、コーヒーミル等の機械式の混合装置が挙げられる。
以上の工程を経て、トナーを作製することが可能である。
測定手順としては、トナー0.02gを、界面活性剤溶液20ml(トナーの分散を目的として、例えば界面活性剤成分を含む中性洗剤を純水で10倍希釈した界面活性剤溶液)で馴染ませた後、超音波分散を1分間行い、トナー分散液を作製する。このトナー分散液を、サンプルスタンド内のISOTON II(ベックマン・コールター社製)の入ったビーカーに、測定濃度5~10%になるまでピペットにて注入し、測定機カウントを25000個に設定して測定する。なお、マルチサイザー3のアパチャー径は50μmのものを使用する。
(1)スチレンあるいはスチレン誘導体
スチレン、o-メチルスチレン、m-メチルスチレン、p-メチルスチレン、α-メチルスチレン、p-クロロスチレン、3,4-ジクロロスチレン、p-フェニルスチレン、p-エチルスチレン、2,4-ジメチルスチレン、p-tert-ブチルスチレン、p-n-ヘキシルスチレン、p-n-オクチルスチレン、p-n-ノニルスチレン、p-n-デシルスチレン、p-n-ドデシルスチレン等。
(2)メタクリル酸エステル誘導体
メタクリル酸メチル、メタクリル酸エチル、メタクリル酸n-ブチル、メタクリル酸イソプロピル、メタクリル酸イソブチル、メタクリル酸t-ブチル、メタクリル酸n-オクチル、メタクリル酸2-エチルヘキシル、メタクリル酸ステアリル、メタクリル酸ラウリル、メタクリル酸フェニル、メタクリル酸ジエチルアミノエチル、メタクリル酸ジメチルアミノエチル等。
(3)アクリル酸エステル誘導体
アクリル酸メチル、アクリル酸エチル、アクリル酸イソプロピル、アクリル酸n-ブチル、アクリル酸t-ブチル、アクリル酸イソブチル、アクリル酸n-オクチル、アクリル酸2-エチルヘキシル、アクリル酸ステアリル、アクリル酸ラウリル、アクリル酸フェニル等。
(4)オレフィン類
エチレン、プロピレン、イソブチレン等。
(5)ビニルエステル類
プロピオン酸ビニル、酢酸ビニル、ベンゾエ酸ビニル等。
(6)ビニルエーテル類
ビニルメチルエーテル、ビニルエチルエーテル等。
(7)ビニルケトン類
ビニルメチルケトン、ビニルエチルケトン、ビニルヘキシルケトン等。
(8)N-ビニル化合物類
N-ビニルカルバゾール、N-ビニルインドール、N-ビニルピロリドン等。
(9)その他
ビニルナフタレン、ビニルピリジン等のビニル化合物類、アクリロニトリル、メタクリロニトリル、アクリルアミド等のアクリル酸あるいはメタクリル酸誘導体等。
黒色の着色剤としては、たとえば、ファーネスブラック、チャンネルブラック、アセチレンブラック、サーマルブラック、ランプブラック等のカーボンブラック、更にマグネタイト、フェライト等の磁性粉も用いられる。
(1)ポリオレフィン系ワックス
ポリエチレンワックス、ポリプロピレンワックス等
(2)長鎖炭化水素系ワックス
パラフィンワックス、サゾールワックス等
(3)ジアルキルケトン系ワックス
ジステアリルケトン等
(4)エステル系ワックス
カルナウバワックス、モンタンワックス、トリメチロールプロパントリベヘネート、ペンタエリスリトールテトラミリステート、ペンタエリスリトールテトラステアレート、ペンタエリスリトールテトラベヘネート、ペンタエリスリトールジアセテートジベヘネート、グリセリントリベヘネート、1,18-オクタデカンジオールジステアレート、トリメリット酸トリステアリル、ジステアリルマレエート等
(5)アミド系ワックス
エチレンジアミンジベヘニルアミド、トリメリット酸トリステアリルアミド等。
シリカ微粒子としては、例えば日本アエロジル社製の市販品R-805、R-976、R-974、R-972、R-812、R-809、ヘキスト社製のHVK-2150、H-200、キャボット社製の市販品TS-720、TS-530、TS-610、H-5、MS-5等が挙げられる。
キャリアの被覆層形成に好適なコート樹脂は、ポリエチレン、ポリプロピレン、塩素化ポリエチレン、クロルスルホン化ポリエチレン等のポリオレフィン系樹脂;ポリスチレン、ポリメチルメタクリレート等のポリアクリレート、ポリアクリロニトリル、ポリビニルアセテート、ポリビニルアルコール、ポリビニルブチラール、ポリ塩化ビニル、ポリビニルカルバゾール、ポリビニルエーテル、ポリビリケトン等のポリビニル及びポリビニリデン系樹脂;塩化ビニル-酢酸ビニル共重合体やスチレン-アクリル酸共重合体等の共重合体;オルガノシロキサン結合からなるシリコーン樹脂またはその変成樹脂(例えば、アルキッド樹脂、ポリエステル樹脂、エポキシ樹脂、ポリウレタン等による変成樹脂);ポリテトラクロルエチレン、ポリフッ化ビニル、ポリフッ化ビニリデン、ポリクロルトリフルロルエチレン等のフッ素樹脂;ポリアミド;ポリエステル;ポリウレタン;ポリカーボネート;尿素-ホルムアルデヒド樹脂等のアミノ樹脂;エポキシ樹脂等である。
樹脂層の平均厚さhは、キャリアの耐久性と低抵抗化の両立の観点より50~4000nmが好ましく、更には200~3000nmが好ましい。
キャリア用バインダー樹脂としては、上記コート樹脂に加えてフェノール樹脂なども使用可能である。
実施形態2に係る現像剤は複合酸化物粒子が前記(A2)の形態で含有されるものであり、すなわち複合酸化物粒子がトナー粒子に内添されている二成分現像剤である。本実施形態においては、複合酸化物粒子が内添されたトナー粒子とキャリアとの接触が確保され、トナーの優れた帯電立ち上がり性および帯電安定性が発現される。
内添状態としては、トナー粒子表面近傍に複合酸化物粒子を存在させることが好ましい。
実施形態3に係る現像剤は複合酸化物粒子が前記(A3)の形態で含有されるものであり、すなわち複合酸化物粒子がキャリアに内添されている二成分現像剤である。本実施形態においては、キャリアに内添されてキャリア表面近傍に存在する複合酸化物粒子と、トナーとの接触が確保され、トナーの優れた帯電立ち上がり性および帯電安定性が発現される。
内添状態としては、キャリア表面近傍に複合酸化物粒子を存在させることが好ましい。
例えば、実施形態3の現像剤に使用されるコート型キャリアは、芯材粒子とコート樹脂と複合酸化物粒子を高速混合機で混合して、機械的衝撃力と発熱の作用で芯材粒子の表面に樹脂層を形成しつつ当該樹脂層内に複合酸化物粒子を含有させること以外、実施形態1の現像剤のコート型キャリアと同様の方法によって製造できる。
実施形態4に係る現像剤は複合酸化物粒子が前記(A4)の形態で含有されるものであり、すなわち複合酸化物粒子がキャリアに外添されている二成分現像剤である。本実施形態においては、トナー粒子とキャリアに外添された複合酸化物粒子との接触が確保され、キャリアの表面抵抗を調整することにより、トナーの優れた帯電立ち上がり性および帯電レベルの調整と帯電安定性がより確実に発現される。
実施形態5に係る現像剤は複合酸化物粒子が前記(A5)の形態で含有されるものであり、すなわち複合酸化物粒子が現像剤に第3成分として添加されている二成分現像剤である。本実施形態においては、現像剤に第3成分として複合酸化物粒子を添加し、トナーとキャリアの間に第3成分が介在することにより、トナーの優れた帯電立ち上がり性および帯電安定性が発現される。
実施形態6に係る現像剤は複合酸化物粒子が前記(B1)の形態で含有されるものであり、すなわち複合酸化物粒子がトナー粒子に外添されている一成分現像剤である。本実施形態においては、実施形態1においてと同様に、トナー粒子と当該トナー粒子に外添された複合酸化物粒子との接触が確保され、トナーの優れた帯電立ち上がり性および帯電安定性がより確実に発現される。
実施形態7に係る現像剤は複合酸化物粒子が前記(B2)の形態で含有されるものであり、すなわち複合酸化物粒子がトナー粒子に内添されている一成分現像剤である。本実施形態においては、実施形態2においてと同様に、トナー粒子に内添されてトナー粒子表面から露出した複合酸化物粒子と、隣接するトナーとの接触が確保され、トナーの優れた帯電立ち上がり性および帯電安定性が発現される。
本発明に係る現像剤が一成分現像剤である場合、当該一成分現像剤はいわゆる一成分現像方式を採用した公知の画像形成装置に搭載されて使用される。
それらの画像形成装置は、モノクロ画像形成用であってもよいし、またはフルカラー画像形成用であってもよい。
硫酸法により作製したメタチタン酸分散液に、4.0モル/リットルの水酸化ナトリウム水溶液によりpHを9.0に調整して脱硫処理を行った後、6.0モル/リットルの塩酸水溶液を添加してpHを5.5に調整して中和処理した。その後、メタチタン酸分散液をろ過、水洗処理して作製したメタチタン酸のケーキ物に水を加え、酸化チタンTiO2換算で1.25モル/リットルに相当する分散液に調製した後、6.0モル/リットルの塩酸水溶液でpH1.2に調整した。そして、分散液の温度を35℃に調整して、この温度下で1時間撹拌を行ってメタチタン酸分散液を解膠処理した。
上記解膠処理を行ったメタチタン酸分散液より、酸化チタンTiO2換算で0.156モルに相当するメタチタン酸を採取して反応容器に投入し、続いて、炭酸カルシウムCaCO3水溶液と酸化ニオブ水溶液を反応容器に投入した。その後、酸化チタン濃度が0.156モル/リットルとなる様に反応系を調製した。ここで、炭酸カルシウムCaCO3は、酸化チタンに対しモル比で1.15となる様(CaCO3/TiO2=1.15/1.00)添加し、酸化ニオブは、酸化チタンに対してモル比で0.001になる様に添加した(Nb2O5/TiO2=0.001/1.00)。
反応終了後、反応容器内を40℃まで冷却し、窒素雰囲気下で上澄み液を除去した後、純水2500重量部を反応容器内に投入してデカンテーションを繰り返し2回行った。デカンテーション実施後、反応系をヌッチェでろ過処理してケーキ物を形成し、得られたケーキ物を110℃に加熱して大気中で8時間の乾燥処理を行った。
得られたチタン酸カルシウムの乾燥物をアルミナ性るつぼに投入し、930℃で脱水するとともに焼成処理した。焼成処理後、チタン酸カルシウムを水中に投入し、サンドグラインダで湿式粉砕処理を行い分散液とした後、6.0モル/リットルの塩酸水溶液を添加してpHを2.0に調整して、過剰分の炭酸カルシウムを除去した。前記除去処理後、シリコーンオイルエマルジョン(ジメチルポリシロキサン系エマルジョン)「SM7036EX(東レ・ダウコーニングシリコーン(株)製)」を用いてチタン酸カルシウムに対して湿式の疎水化処理を行った。前記疎水化処理は、チタン酸カルシウム固形分100重量部に対して前記シリコーンオイルエマルジョンを0.7重量部添加して、30分間撹拌処理を行ったものである。
作製した「無機粒子1」について、ICP分析法によりニオブ原子の含有量を測定したところ0.010重量%であった。また、作製した「無機粒子1」の体積基準粒径、粒径標準偏差(SD値)、BET比表面積を前述の方法で測定したところ、体積基準粒径が198)nm、粒径標準偏差(SD値)が108nm、BET比表面積が15.4m2/gであった。
表1に記載の第2金属原子を用いたこと、表1に記載の第3金属原子を用いるために所定の添加材料を所定の添加量で用いたこと以外、無機粒子1の製造方法と同様の方法により、無機粒子を製造した。
第2金属原子としてSrを用いる場合は炭酸ストロンチウムを、Mgを用いる場合は炭酸マグネシウムを、Baを用いる場合は炭酸バリウムを用いた。
(1)「樹脂粒子1H」の作製
撹拌装置、温度センサ、冷却管、窒素導入装置を取り付けた反応容器に、アニオン系界面活性剤ラウリル硫酸ナトリウム7.08重量部をイオン交換水3010重量部に溶解させて界面活性剤溶液(水系媒体)を作製した。そして、前記界面活性剤溶液を窒素気流下で230rpmの速度で撹拌しながら、反応容器内の温度を80℃に昇温させた。
前記界面活性剤溶液に、重合開始剤である過硫酸カリウム(KPS)9.2重量部をイオン交換水200重量部に溶解させた重合開始剤溶液を投入し、反応容器内の温度を75℃にした。その後、下記化合物よりなる「混合液1A」を1時間かけて滴下し、
スチレン 69.4重量部
n-ブチルアクリレート 28.3重量部
メタクリル酸 2.3重量部
さらに、75℃の温度下で撹拌を2時間行うことにより重合を行い、「樹脂粒子分散液1H」を作製した。
撹拌装置を取り付けたフラスコ内に、下記化合物を投入し、
スチレン 97.1重量部
n-ブチルアクリレート 39.7重量部
メタクリル酸 3.22重量部
n-オクチル-3-メルカプトプロピオン酸エステル 5.6重量部
さらに、
ペンタエリスリトールテトラベヘネート 98.0重量部
を添加し、90℃に加温して化合物Aを溶解させて、上記化合物よりなる「混合液1B」を調製した。
前記「樹脂粒子1HML」の分散液に、過硫酸カリウム(KPS)7.4重量部をイオン交換水200重量部に溶解させた開始剤溶液を添加して、温度を80℃に調整した。その後、下記化合物よりなる「混合液1C」を1時間かけて滴下した。すなわち、
スチレン 277重量部
n-ブチルアクリレート 113重量部
メタクリル酸 9.21重量部
n-オクチル-3-メルカプトプロピオン酸エステル 10.4重量部
滴下終了後、前記温度下で2時間にわたり加熱、撹拌して重合を行い、その後、反応系を28℃に冷却して、「樹脂粒子1HM」表面に樹脂を被覆した複合構造を有する「樹脂粒子1HML」の分散液を作製した。得られた樹脂粒子の粒径は約150nmであった。
アニオン性界面活性剤ラウリル硫酸ナトリウム90重量部をイオン交換水1600重量部中に投入し、撹拌を行って界面活性剤溶液を作製した。前記界面活性剤溶液を撹拌しながら、着色剤である下記カーボンブラックを徐々に添加した。すなわち、
「リーガル330R(キャボット社製)」 400重量部
上記カーボンブラックを添加後、機械式分散装置「クレアミックス(CLEARMIX)(エム・テクニック(株)製)」を用い、カーボンブラックの粒子径が200nmになるまで分散処理を行うことにより、「着色剤分散液1」を調製した。
撹拌装置、温度センサ、冷却管、窒素導入装置、撹拌装置を取り付けた反応容器に、下記のものを投入した後、反応容器内を30℃に調整し、さらに、5モル/リットルの水酸化ナトリウム水溶液を添加してpHを10.6に調整した。すなわち、
「樹脂粒子分散液1HML」 200重量部(固形分換算)
イオン交換水 3000重量部
「着色剤分散液1」 71重量部(固形分換算)
上記調整の後、塩化マグネシウム・6水和物52.6重量部をイオン交換水72重量部に溶解させた水溶液を温度30℃の下で反応系を撹拌させた状態で10分間かけて添加し、添加後、反応系を3分間放置した。
その後、反応系の昇温を開始し、この系を60分間かけて75℃まで昇温させ、上記粒子の凝集を開始した。ここでは、「マルチサイザー3(ベックマン・コールター社製)」を用いて凝集粒子の粒径を測定しながら凝集を継続させた。
凝集粒子の体積基準メディアン径が6.5μmになった時に、塩化ナトリウム115重量部をイオン交換水700重量部に溶解した水溶液を添加して粒子成長を停止させた。さらに、熟成処理として液温度90℃にし、加熱撹拌処理を6時間にわたり行って、粒子の融着を継続させた。その後、反応系を30℃に冷却し、塩酸を添加してpHを2.0に調整した後、撹拌を停止した。
上記の様に、凝集と融着を経て作製された着色粒子を固液分離し、45℃のイオン交換水による洗浄を繰り返し行った後、40℃の温風で乾燥処理することにより、「トナー粒子A」を作製した。「トナー粒子A」の酸価をJIS-0070-1992で規定される方法で測定したところ15であった。
(1)「樹脂粒子2H」の作製
前述の「樹脂粒子1H」の製造工程で「混合液1A」に代えて、下記化合物よりなる「混合液2A」を用いた他は同様の手順により、「樹脂粒子分散液2H」を作製した。
スチレン 70.3質量部
n-ブチルアクリレート 28.7質量部
メタクリル酸 1.0質量部
前述の「樹脂粒子1HM」の製造工程で「混合液1B」に代えて、下記化合物よりなる「混合液2B」を用いた他は同様の手順により、「樹脂粒子分散液2HM」を作製した。
スチレン 98.3質量部
n-ブチルアクリレート 40.2質量部
メタクリル酸 1.51質量部
n-オクチル-3-メルカプトプロピオン酸エステル 5.6質量部
ペンタエリスリトールテトラベヘネート 98質量部
前述の「樹脂粒子1HML」の製造工程で「混合液1C」に代えて、下記化合物よりなる「混合液2C」を用いた他は同様の手順で、「樹脂粒子分散液2HML」を作製した。
スチレン 283質量部
n-ブチルアクリレート 115質量部
メタクリル酸 4.3質量部
n-オクチル-3-メルカプトプロピオン酸エステル 10.4質量部
前記「トナー粒子A」の作製において、「樹脂粒子分散液1HML」を「樹脂粒子分散液2HML」に変更した他は同様の手順により、酸価が7の「トナー粒子B」を作製した。
(1)「樹脂粒子3H」の作製
前述の「樹脂粒子1H」の製造工程で「混合液1A」に代えて、下記化合物よりなる「混合液3A」を用いた他は同様の手順により、「樹脂粒子分散液3H」を作製した。
スチレン 74.5質量部
n-ブチルアクリレート 21.6質量部
アクリル酸 1.93質量部
前記「樹脂粒子1HM」の製造工程で「混合液1B」に代えて、下記化合物よりなる「混合液3B」を用いた他は同様の手順により、「樹脂粒子分散液3HM」を作製した。
スチレン 104質量部
n-ブチルアクリレート 30.2質量部
アクリル酸 2.7質量部
n-オクチル-3-メルカプトプロピオン酸エステル 5.6質量部
ペンタエリスリトールテトラベヘネート 98質量部
前記「樹脂粒子1HML」の製造工程で「混合液1C」に代えて、下記化合物よりなる「混合液3C」を用いた他は同様の手順で、「樹脂粒子分散液3HML」を作製した。
スチレン 306質量部
n-ブチルアクリレート 88.5質量部
アクリル酸 17.4質量部
n-オクチル-3-メルカプトプロピオン酸エステル 10.4質量部
前記「トナー粒子A」の作製において、「樹脂粒子分散液1HML」を「樹脂粒子分散液3HML」に変更した他は同様の手順により、酸価が25の「トナー粒子C」を作製した。
(1)「樹脂粒子4H」の作製
前記「樹脂粒子1H」の製造工程で「混合液1A」に代えて、下記化合物よりなる「混合液4A」を用いた他は同様の手順により、「樹脂粒子分散液4H」を作製した。
スチレン 70.7質量部
n-ブチルアクリレート 28.9質量部
アクリル酸 0.386質量部
前記「樹脂粒子1HM」の製造工程で「混合液1B」に代えて、下記化合物よりなる「混合液4B」を用いた他は同様の手順により、「樹脂粒子分散液4HM」を作製した。
スチレン 99質量部
n-ブチルアクリレート 40.4質量部
アクリル酸 0.54質量部
n-オクチル-3-メルカプトプロピオン酸エステル 5.6質量部
ペンタエリスリトールテトラベヘネート 98質量部
前記「樹脂粒子1HML」の製造工程で「混合液1C」に代えて、下記化合物よりなる「混合液4C」を用いた他は同様の手順で、「樹脂粒子分散液4HML」を作製した。
スチレン 281質量部
n-ブチルアクリレート 114.8質量部
アクリル酸 1.54質量部
n-オクチル-3-メルカプトプロピオン酸エステル 10.4質量部
前記「トナー粒子A」の作製において、「樹脂粒子分散液1HML」を「樹脂粒子分散液4HML」に変更した他は同様の手順により、酸価が3の「トナー粒子D」を作製した。
(1)「樹脂粒子5H」の作製
前記「樹脂粒子1H」の製造工程で「混合液1A」に代えて、下記化合物よりなる「混合液5A」を用いた他は同様の手順により、「樹脂粒子分散液5H」を作製した。
スチレン 67.8質量部
n-ブチルアクリレート 27.7質量部
メタクリル酸 4.5質量部
前記「樹脂粒子1HM」の製造工程で「混合液1B」に代えて、下記化合物よりなる「混合液5B」を用いた他は同様の手順により、「樹脂粒子分散液5HM」を作製した。
スチレン 94.1質量部
n-ブチルアクリレート 38.4質量部
メタククリル酸 7.53質量部
n-オクチル-3-メルカプトプロピオン酸エステル 5.6質量部
ペンタエリスリトールテトラベヘネート 98質量部
前記「樹脂粒子1HML」の製造工程で「混合液1C」に代えて、下記化合物よりなる「混合液5C」を用いた他は同様の手順で、「樹脂粒子分散液5HML」を作製した。
スチレン 269質量部
n-ブチルアクリレート 110質量部
メタクリル酸 21.5質量部
n-オクチル-3-メルカプトプロピオン酸エステル 10.4質量部
前記「トナー粒子A」の作製において、「樹脂粒子分散液1HML」を「樹脂粒子分散液5HML」に変更した他は同様の手順により、酸価が35の「トナー粒子E」を作製した。
トナー粒子Aの製造において、反応容器に、樹脂粒子分散液1HML、イオン交換水および着色剤分散液1を投入する際、以下に示す無機粒子分散液も6重量部投入したこと以外、トナー粒子Aの製造方法と同様の方法により、トナー粒子Fを製造した。「トナー粒子F」の酸価は15KOHmg/gであった。
アニオン性界面活性剤ラウリル硫酸ナトリウム90重量部をイオン交換水1600重量部中に投入し、撹拌を行って界面活性剤溶液を作製した。前記界面活性剤溶液を撹拌しながら、無機粒子2を1600重量部徐々に添加した。その後、機械式分散装置「クレアミックス(CLEARMIX)(エム・テクニック(株)製)」を用いて分散処理を行い、「無機粒子分散液」を調製した。
トナー粒子Aに対して、以下のものを外添剤として添加した。
「無機粒子1」 2.0重量%
疎水性シリカ(粒径17nm、ヘキサメチルジシラザン処理品) 1.0重量%
疎水性シリカ(粒径21nm、ヘキサメチルジシラザン処理品) 1.0重量%
外添処理は、ヘンシェルミキサー「FM10B(三井三池化工社製)」を用い、30℃の温度下で、撹拌羽根の周速を35m/秒、処理時間20分に設定して行い、90μmの目開きのふるいを用いて粗大粒子を除去して「トナー1」を製造した。
表2に記載のトナー粒子および無機粒子を用いたこと以外、トナー1の製造方法と同様の方法により、トナーを製造した。
トナー粒子Fを用いたこと、および無機粒子1以外の外添剤を外添処理したこと以外、トナー1の製造方法と同様の方法により、トナーを製造した。
無機粒子1以外の外添剤を外添処理したこと以外、トナー1の製造方法と同様の方法により、トナーを製造した。
トナー粒子Aに対して、以下のものを外添剤として添加した。
「無機粒子17」 2.0重量%
「酸化ニオブ粒子」(粒径200nm、比表面積8m2/g) 1.0重量%
疎水性シリカ(粒径17nm、ヘキサメチルジシラザン処理品) 1.0重量%
疎水性シリカ(粒径21nm、ヘキサメチルジシラザン処理品) 1.0重量%
外添処理は、ヘンシェルミキサー「FM10B(三井三池化工社製)」を用い、30℃の温度下で、撹拌羽根の周速を35m/秒、処理時間20分に設定して行い、90μmの目開きのふるいを用いて粗大粒子を除去してトナーを製造した。
体積平均径が60μm、飽和磁化が10.7×10-5Wb・m/kgのMn-Mgフェライト粒子を準備した。Mn-Mgフェライト粒子100重量部とスチレン/メチルメタクリレート(共重合比2/8)の共重合体樹脂微粒子を3.8重量部を、撹拌羽根付き高速混合機に投入し、120℃で60分間撹拌混合して機械的衝撃力の作用でフェライト粒子の表面に樹脂層を形成し、樹脂層が被覆されたキャリア1を得た。このキャリア1の樹脂層の厚みは2500nmであった。キャリア1の体積平均粒径は65μmであった。
体積平均径が60μm、飽和磁化が10.7×10-5Wb・m/kgのMn-Mgフェライト粒子を準備した。Mn-Mgフェライト粒子100重量部とスチレン/メチルメタクリレート(共重合比2/8)の共重合体樹脂微粒子を3.8重量部、無機粒子2を5重量部を、撹拌羽根付き高速混合機に投入し、120℃で60分間撹拌混合して機械的衝撃力の作用でフェライト粒子の表面に樹脂層を形成し、樹脂層に無機粒子2が含有されたキャリア2を得た。このキャリア2の樹脂層の厚みは2540nmであった。キャリア2の体積平均粒径は65μmであった。
キャリア1を100重量部、トナー1を6重量部とをV型混合機で混合し、現像剤1を製造した。
表3に記載のトナーとキャリアとを組み合わせて用いたこと以外、現像剤1の製造方法と同様の方法により現像剤を製造した。
キャリア1を100重量部、トナー26を6重量部および無機粒子2を1重量部をV型混合機で混合し、現像剤を製造した。
<実施例/比較例>
表4に記載の現像剤を二成分方式の画像形成装置(bizhub Pro C450;コニカミノルタ社製)に搭載し、当該画像形成装置を高温高湿環境下(30℃、80%RH)に24時間放置後、前記環境下で3000枚の連続プリントを実施し、連続プリント開始時および実施後の画質評価を行った。
同様に、画像形成装置を低温低湿環境下(10℃、15%RH)に24時間放置後、前記環境下で3000枚の連続プリントを実施し、連続プリント開始時および実施後の画質評価を行った。
評価は、感光体上及び画像上でのカブリ、画像濃度の変動について行った。
感光体上のカブリは、3000枚の連続プリント実施後の感光体表面を目視観察するとともに、目視観察の後、感光体表面を30mm幅のブックテープ「アメニティBコートT(キハラ社製)」で剥離し、剥離したテープを白紙上に貼り付けて目視観察した。
◎:感光体上及び剥離したテープのいずれもでカブリの発生は認められなかった;
○:感光体上でカブリの発生がわずかに認められたが、剥離したテープからはカブリの発生は認められなかった;
△:感光体上でカブリの発生が局所的に認められたが、剥離したテープの状態から実用上問題ないレベルと判断した;
×:感光体全面にわたりカブリの発生が認められ、剥離したテープからも実用上問題のあるカブリの発生状態と判断した。
画像像のカブリは以下の方法により評価した。連続プリント開始時に作製したプリント物上の白地画像について、マクベス社製反射濃度計「RD-918」を用いて、20カ所の濃度を測定し、この平均値を白地濃度とした。次いで、連続プリント3000枚目の白地部分についても、同様に20カ所の濃度を測定して平均値を求めて3000枚目の白地濃度とした。3000枚目の白地濃度から開始時の白地濃度を差し引いた値をカブリ濃度とした。カブリ濃度が0.010以下のものを合格とした。
◎;0.003未満;
○;0.003以上0.006未満;
△;0.006以上0.010以下;
×;0.010を超える値。
連続プリント開始時と3000枚目のプリント物上のベタ画像部の濃度を測定して評価した。具体的には、プリント作製開始時と3000枚目のプリント物上のベタ画像部上の任意の12点を反射濃度計「RD-918(マクベス社製)」を用いて測定し、その平均値をとって、これを画像濃度とした。そして、連続プリント開始時と3000枚目の画像濃度の差を算出して評価を行った。両者の画像濃度差が0.04以下のものを合格とした。
◎;0.01未満;
○;0.01以上0.02未満;
△;0.02以上0.04以下;
×;0.04を超える値。
<実施例/比較例>
表4に記載のトナーを、そのまま一成分現像剤として、非磁性1成分方式のフルカラープリンタ「magicolor2300DL」(コニカミノルタビジネステクノロジーズ(株)製)に搭載し、実験例1における二成分現像剤の評価方法と同様の方法により評価を行った。
Claims (11)
- 第1金属原子としてのチタンと、第2金属原子とを含有するチタン酸金属塩粒子中に、長周期型元素周期表の5A族に属する金属原子からなる群から選択される第3金属原子が0.009~0.350重量%含有された複合酸化物粒子を有することを特徴とする電子写真用現像剤。
- 第3金属原子がV、NbおよびTaからなる群から選択される請求項1に記載の電子写真用現像剤。
- チタン酸金属塩を構成する第2金属原子が、長周期型元素周期表の1A族および2A族に属する金属原子からなる群から選択される金属原子である請求項1または2に記載の電子写真用現像剤。
- 第2金属原子がMg、Ca、SrおよびBaからなる群から選択される請求項3に記載の電子写真用現像剤。
- 複合酸化物粒子の個数基準平均粒径が30nm以上3000nm以下であり、かつ、粒径標準偏差の値が1000nm以下であることを特徴とする請求項1~4のいずれかに記載の電子写真用現像剤。
- 第3金属原子が、Nbである、請求項1~5いずれかに記載の電子写真用現像剤。
- 第2金属原子がMgまたはCaである、請求項1~6いずれかに記載の電子写真用現像剤。
- 複合酸化物粒子の個数基準平均粒径が、50nm以上2000nm以下である、請求項1~7いずれかに記載の電子写真用現像剤。
- 電子写真用現像剤がトナー粒子に外添剤が外添されたトナーおよびキャリアを含む二成分現像剤であり、複合酸化物粒子が以下に示す少なくとも1つの形態で含まれる請求項1~8のいずれかに記載の電子写真用現像剤;
(A1)複合酸化物粒子がトナー粒子に外添されている;
(A2)複合酸化物粒子がトナー粒子に内添されている;
(A3)複合酸化物粒子がキャリアに内添されている;
(A4)複合酸化物粒子がキャリアに外添されている;
(A5)複合酸化物粒子が現像剤に第3成分として添加されている。 - 電子写真用現像剤がトナー粒子に外添剤が外添されたトナーからなる一成分現像剤であり、複合酸化物粒子が以下に示す少なくとも1つの形態で含まれる請求項1~8のいずれかに記載の電子写真用現像剤;
(B1)複合酸化物粒子がトナー粒子に外添されている;
(B2)複合酸化物粒子がトナー粒子に内添されている。 - トナー粒子の酸価が5KOHmg/g以上30KOHmg/g以下であることを特徴とする請求項9または10に記載の電子写真用現像剤。
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US20120009515A1 (en) | 2012-01-12 |
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