JP5606280B2 - toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method or a toner jet method.

In recent years, there has been a growing demand to make copying machines or printers inexpensive and small. In response to the above demands, the main body itself is designed to realize a lower price by designing with simpler components. In addition, high image quality is also required in designing with such simple components. That is, the performance required for the toner is required to be higher than ever. Specifically, it is required to realize stable provision of high image quality with minimal control of the main body even in long-term use in high temperature and high humidity environments and low temperature and low humidity environments. .
In response to this requirement, the toner particles have a sharp particle size distribution, rounded shape, and adhesion of inorganic fine particles with a certain size to a certain degree, thereby providing excellent chargeability, developability, charging stability over time, and blade cleaning properties. There is a method for obtaining a toner (for example, Patent Document 1).
However, printers are used in a wider variety of environments than before, and there are some problems in the rise of charging and charging stability under high-temperature and high-humidity environments and low-temperature and low-humidity environments. There is also a problem with respect to contamination of the photoreceptor and charging member due to the release of inorganic fine particles from the toner.
In such a case, in the toner containing polyester and containing a nonionic surfactant and an external additive, the content of the nonionic surfactant is set to an appropriate amount, and the negatively charged inorganic fine particles having a small particle size and a certain amount are used. There is a method in which, by incorporating large positively chargeable organic fine particles, the fixing property is excellent and fog can be improved (for example, Patent Document 2).
In addition, when dispersing the colorant particles in the toner including the core particles formed by aggregating the resin particles, the colorant particles, and the wax particles, a polymer-based dispersant and a nonionic dispersant are used, and the wax particles are When dispersing, by using polypropylene glycol ethylene oxide adduct and nonionic dispersant, it is possible to produce a small particle size toner with sharp particle size distribution, excellent durability and charging stability, fixing property, anti-offset property There is a method for obtaining a toner having excellent properties, storage stability and transferability (for example, Patent Document 3).
However, there are still some problems regarding the contamination of the photosensitive member and the charging member due to the release of the inorganic fine particles from the toner and the fogging in the high temperature and high humidity environment and the low temperature and low humidity environment.

JP 2005-266557 A JP 2008-151950 A JP 2009-077554 A

  An object of the present invention is to provide a toner that solves the above problems. That is, the present invention relates to member contamination of the photoreceptor or charging member by the metal oxide fine powder due to the liberation of the metal oxide fine powder from the toner after long-term use, as well as in a high temperature and high humidity environment and low temperature and low humidity. An object of the present invention is to provide a toner that does not cause fogging in an environment.

The present invention is a binder resin, the toner particles A having containing a coloring agent and a nonionic surface active agent, a toner having a metallic oxide fine powder, the nonionic surfactant, alkylene glycol by weight of the block copolymer, the number average molecular weight measured by gel permeation chromatography of a block copolymer of alkylene glycol is 1,200 to 40,000, wherein the nonionic extracted with methanol from the toner the amount of extracted sexual surfactant and a (ppm), and the theoretical specific surface area determined from the particle size distribution of the toner using the precision particle size distribution measuring apparatus based on a pore electrical resistance method and B (m 2 ^{/ g)} when the value of the ratio of the B of the a (a / B) ^{is, 0.02 × 10 -3 (g /} m 2) or more 9.00 × ¹⁰ -3 (g / ²⁾ or less, the metal oxide fine powder is a median size (D50) of the volume-based, relates to a toner which is characterized in that at least 0.07 .mu.m 2.00 .mu.m or less.

  According to the present invention, due to the release of metal oxide fine powder from the toner after long-term use, the metal oxide fine powder contaminates the photosensitive member, the charging member, etc., as well as in a high temperature and high humidity environment and low temperature and low humidity. A toner that does not cause fogging in an environment can be provided.

The schematic diagram of the methanol dropping transmission light curve in the hydrophobization degree intensity | strength measurement of metal oxide fine powder.

The inventors of the present application have studied repeatedly to solve the above-described problems. As a result, it has been found that it is important to satisfy the following elements, and the present invention has been completed.
That is, the present invention provides a toner having at least a toner particle containing a binder resin, a colorant and a nonionic surfactant, and at least a metal oxide fine powder, wherein the nonionic surfactant is an alkylene. The non-ionic polymer containing a block copolymer of glycol and having a number average molecular weight of 1200 to 40,000 as measured by gel permeation chromatography of the block copolymer of alkylene glycol and extracted from the toner with methanol When the extraction amount of the surfactant is A (ppm) and the theoretical specific surface area obtained from the particle size distribution of the toner using a precision particle size distribution measuring device by the pore electrical resistance method is B (m ² / g) , the ratio B of the a (a / B) is ^{0.02 × 10 -3 (g / m} 2) or more 9.00 × 10 ^- (G / ^{m 2)} or less, the metal oxide fine powder had a volume-based median diameter of (D50) is a toner which is characterized in that at least 0.07 .mu.m 2.00 .mu.m or less.
The details will be described below.
That is, the toner of the present invention is a toner having toner particles containing at least a binder resin, a colorant, and a nonionic surfactant having a specific structure, and a metal oxide fine powder. The effect of the present application can be obtained by using a metal oxide fine powder having a specific particle size within a proper range of the amount of the agent present per unit surface area.
The reason why the effect can be manifested is not necessarily clear, but the present inventors consider as follows. This will be described in detail below.
The metal oxide fine powder having a certain large particle diameter is difficult to be embedded in the toner particles, and is excellent in durability and transferability. On the other hand, there is a problem that the toner particles are easily separated from the surface of the toner particles and the photosensitive member and the charging member are easily contaminated. Therefore, if a metal oxide fine powder having a large particle size is adhered in a state where the nonionic surfactant of the present invention is present at an appropriate concentration on the surface of the toner particle, the fine powder is released from the toner particle. Was suppressed. This is considered to be a result of the combination of the following two effects. (1) An electrostatic interaction between an alkylene glycol structure in a nonionic surfactant existing on the toner particle surface, a metal atom of the metal oxide fine powder, and an oxygen atom bonded to the metal interact. Increased adhesive force. (2) Since the nonionic surfactant is a block copolymer, the block structure portion on the more hydrophobic side in the block copolymer exhibits an anchor effect on the toner particle surface. By these actions, it is considered that contamination of the photoreceptor and the charging member due to the metal oxide fine powder resulting from the liberation of the metal oxide fine powder from the toner is suppressed. As for these effects, the interaction with the metal oxide fine powder and the anchor effect with respect to the toner particles cannot be sufficiently obtained unless the number average molecular weight of the block copolymer is 1200 or more. The effect of the present invention cannot be obtained unless it is a metal oxide fine powder instead of organic fine particles. Compared with organic fine particles mainly composed of resin, metal oxide fine powder has more active movement of electrons. Yes, it is considered that the interaction with the lone pair present in the oxygen atom in the alkylene glycol structure is likely to occur, and the oxygen atom adjacent to the metal atom and the oxygen atom in the alkylene glycol structure have high affinity. .
In addition, since the metal oxide fine powder has a certain large particle diameter, it is difficult to be embedded in the toner particles, and the release of the metal oxide fine powder from the toner particles is suppressed, so that the surface condition of the toner can be improved over a long period of use. Is maintained stably. For this reason, the chargeability and fluidity of the toner are maintained even during long-term use. Further, since a predetermined amount of the metal oxide fine powder and the nonionic surfactant are present on the surface of the toner particles, an appropriate leak site is formed, so that the toner is overcharged in a low temperature and low humidity environment. It is considered that fog is reduced. In a high-temperature and high-humidity environment, the chargeability of the toner is usually reduced by moisture absorption by the nonionic surfactant. In the present invention, the metal oxide fine powder has a somewhat large particle size. Due to the spacer effect, the probability that the water adsorbed on the surface of the toner particles contacts another toner particle is lowered. In addition, since the toner has an appropriate fluidity, the frequency of frictional charging is kept high. With these effects, sufficient chargeability as a toner can be obtained, and fogging can be suppressed. As described above, it is considered that fogging can be suppressed even under long-term use under high temperature and high humidity environment and low temperature and low humidity environment.

The toner of the present invention exhibits the effect by having a nonionic surfactant on the toner surface. Here, the method for retaining the nonionic surfactant on the toner surface includes a method in which a nonionic surfactant is added to and mixed with a dispersion in which toner particles are dispersed in a solvent, and a nonionic interface. A method in which toner particles are dispersed in a dispersion or solution in which an activator is dispersed or dissolved in a solvent such as water or an aqueous methanol solution, and a nonionic surfactant is retained on the toner particles. A highly volatile solvent such as methanol. Any method may be used, such as a method in which a nonionic surfactant is dispersed in and then sprayed and mixed with a spray. However, the nonionic surfactant is preferably dispersed as uniformly as possible on the toner surface. For this purpose, the toner particles used in the present invention are prepared by adding a nonionic surfactant to a dispersion obtained by dispersing toner particles in a solvent (such as an aqueous medium) and mixing the nonionic surfactant into the toner particles. The step of containing, or dispersing the toner particles in a dispersion or solution obtained by dispersing or dissolving the nonionic surfactant in a solvent (aqueous medium or the like) such as water or an aqueous methanol solution, The toner particles and the nonionic surfactant are preferably mixed in the aqueous medium such as the step of adding the toner particles to the toner particles, so that the toner particles contain the nonionic surfactant. Further, in this method, after producing toner particles without using a nonionic surfactant, the above aqueous medium containing a nonionic surfactant is used, and the nonionic interface contained in the aqueous medium is used. By controlling the concentration of the activator and the number of treatments, it is possible to control the abundance of the nonionic surfactant on the toner particle surface.
In view of the step of incorporating the nonionic surfactant into the toner particles, the toner particles are produced by a production method of granulating in an aqueous medium, such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method. It is preferable to obtain.
Further, in order to go through the step of incorporating the nonionic surfactant into the toner particles, the addition timing of the nonionic surfactant is preferably after the toner particle granulation before the toner particle granulation. Adoption of this addition timing makes it easy for a specific amount of nonionic surfactant to be present on the surface of the toner particles, not inside the toner particles, and as a result, effectively suppresses the liberation of the metal oxide fine powder. It becomes possible. In addition, the use of this addition timing is preferable because the charge-related attenuation due to the nonionic surfactant contained in the toner particles is suppressed when the toner is charged, so that the effect on the chargeability of the toner is further increased. .
On the other hand, as the solid-liquid separation method of the toner particles in the step of incorporating the nonionic surfactant into the toner particles, any known method such as filtration, centrifugation, decanting, etc. may be used. It is also a preferred aspect that a washing step is performed after the step of incorporating the nonionic surfactant into the toner particles. In this cleaning step, any method may be used, but a method of cleaning toner particles containing a nonionic surfactant using a belt type filter press or the like is preferable. By adopting the washing step, the abundance of the nonionic surfactant on the toner particle surface can be easily controlled.

The amount of the nonionic surfactant per unit surface area of the toner necessary for exhibiting the effects of the present invention will be described. The condition can be obtained from the extraction amount of the nonionic surfactant extracted from the toner with methanol and the theoretical specific surface area obtained from the particle size distribution of the toner. Specifically, the extraction amount of the nonionic surfactant extracted from the toner with methanol is defined as A (ppm), and it is obtained from the particle size distribution of the toner using a precise particle size distribution measuring apparatus by the pore electrical resistance method. When the theoretical specific surface area is B (m ² / g), the ratio of A to B (A / B) is 0.02 × 10 ⁻³ (g / m ² ) or more and 9.00 × 10 ⁻³ (g / M ² ) or less. The (A / B) is preferably 0.40 × 10 ⁻³ (g / m ² ) or more and 2.00 × 10 ⁻³ (g / m ² ) or less.
This is an approximation of the amount of the surfactant present on the toner surface and expresses the amount of the surfactant necessary in the present invention. In the present invention, since the amount of the nonionic surfactant on the toner surface is discussed, the extraction of the nonionic surfactant hardly causes the resin toner to swell or penetrate into the toner. Methanol with strong hydrophilicity was used. Details of the extraction conditions and the like will be described later.
When the above (A / B) is less than 0.02 × 10 ⁻³ (g / m ² ), a sufficient amount of nonionic surfactant is not present in the toner surface. Toner that does not cause contamination of the photosensitive member or charging member due to the release of the metal oxide fine powder from the toner during use, and fogging in a high-temperature, high-humidity environment and a low-temperature, low-humidity environment. Providing the effect of the present invention is difficult. On the other hand, when (A / B) is larger than 9.00 × 10 ⁻³ (g / m ² ), the excessive amount of the surfactant increases the hygroscopicity of the toner, and the metal oxide fine powder and the non-powder. Since the water molecules adsorbed on the toner surface inhibit the interaction of the ionic surfactant, the effect of the present invention is not exhibited. Further, when the toner is stored for a long period of time, the toner tends to be easily blocked. This is because plasticization occurs due to the interaction between the resin component inside the toner and the nonionic surfactant, and the plasticized resin is easily oozed out to the toner surface.

<Measurement of Extraction Amount of Nonionic Surfactant Extracted from Toner Surface>
The extraction amount of the nonionic surfactant extracted from the toner surface is determined as follows using ¹ H-NMR (nuclear magnetic resonance) measurement.
First, 50 ml of methanol and 5 g of toner are precisely weighed in a sample bottle, mixed well, and then a desktop ultrasonic cleaner (trade name “B2510J-MTH”, manufactured by Branson) with an oscillation frequency of 42 kHz and an electrical output of 125 W. Irradiate with ultrasound for 30 minutes. Thereafter, filtration is performed using a solvent-resistant membrane filter “Maysho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm. After removing methanol from the filtrate by an evaporator, the filtrate is dissolved with 10 mg of trichlorosilane (TMS) in deuterated chloroform (1% TMS) and analyzed by ¹ H-NMR.
Extraction amount of nonionic surfactant extracted from the toner surface using a calibration curve based on TMS intensity obtained using the same surfactant as the surfactant already contained in the toner ( A) is calculated. The calibration curve is prepared from the TMS intensity and the peak intensity ratio derived from hydrogen of the oxyalkylene group near 3.0 to 5.0 ppm.
The measurement apparatus and measurement conditions are as follows.
Apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement temperature: 40 ° C

<Measurement of theoretical specific surface area (B) determined from particle size distribution of toner>
The theoretical specific surface area (B) obtained from the particle size distribution of the toner is calculated as follows.
As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. The measurement conditions are set and measured in the same manner as in the measurement conditions and the measurement method (6) in the measurement of the weight average particle diameter (D4) and number average particle diameter (D1) of the toner described later.
The measurement data obtained by the measurement method (6) is analyzed with the dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter) attached to the apparatus, and the theoretical specific surface area is calculated as follows. calculate. First, the result of the next 16 channels is calculated on the “analysis / number statistical value (arithmetic mean)” screen when the graph / number% is set in the dedicated software. Specifically, in the measurement result of the particle size distribution (number statistical value) of the measured toner sample, it is divided into the following 16 channels and the number% of the particle size within each range is calculated.

Number CH range DIF%
1 1.587-2.000 μm N ₁
2 2.000 to 2.520 μm N ₂
3 2.520-3.175 μm N ₃
4 3.175 to 4.000 μm N ₄
5 4.000-5.040 μm N ₅
6 5.040-6.350 μm N ₆
7 6.350-8.000 μm N ₇
8 8.000-10.079 μm N ₈
9 10.079-12.699 μm N ₉
10 12.699-16.000 μm N ₁₀
11 16.000-20.159 μm N ₁₁
12 20.159-25.398 μm N ₁₂
13 25.398-32.000 μm N ₁₃
14 32.000-40.317 μm N ₁₄
15 40.317-50.797 μm N ₁₅
16 50.797 to 64.000 μm N ₁₆

Next, the particles in the range of the particle size of each range are all assumed to be true spherical particles having a specific gravity of 1.00 (g / cm ³ ) having a particle size just in the middle of each range (for example, 1.587 to 2.000 μm). The theoretical specific surface area (m ² / g) of the measured toner is calculated from the surface area per particle of the particles in each range and the number% of the particles in each range. . In other words, assuming that the radius of the particle diameter in the middle of a certain range is Rn (m) and the number% of the range is Nn (number%), the calculation is performed for all the corresponding ranges. The specific surface area (B) is calculated as follows.
Theoretical specific surface area (B: m ² / g)
= {Σ (4πRn ² × Nn)} / [Σ {(4/3) πRn ³ × Nn × 1.00 × 10 ⁻⁶ }]
(N = 1-16)

The nonionic surfactant used in the present invention contains an alkylene glycol block copolymer, and the number average molecular weight measured by gel permeation chromatography of the alkylene glycol block copolymer is from 1200 to 40000. Yes, preferably 2000 or more and 30000 or less, more preferably 2000 or more and 22000 or less, and particularly preferably 3000 or more and 18000 or less.
When the number average molecular weight (Mn) is less than 1200, member contamination of the photoreceptor or charging member due to the metal oxide fine powder caused by the liberation of the metal oxide fine powder from the toner during long-term use, and It is difficult for the effect of the present invention to provide a toner that does not cause fogging in a high temperature and high humidity environment and a low temperature and low humidity environment. On the other hand, when the number average molecular weight (Mn) exceeds 40000, the viscosity of the block copolymer is increased, and it is difficult to uniformly disperse on the toner surface, resulting in unevenness of the effect, which is not preferable.

<Calculation of number average molecular weight (Mn) of block copolymer of alkylene glycol in nonionic surfactant>
The number average molecular weight (Mn) of the block copolymer of alkylene glycol in the nonionic surfactant in the present invention is measured by gel permeation chromatography (GPC) as follows.
First, a nonionic surfactant (alkylene glycol block copolymer) is dissolved in tetrahydrofuran (THF) over 24 hours at room temperature. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, the number average molecular weight (Mn) of the alkylene glycol block copolymer is determined under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml
In calculating the molecular weight of the sample, standard polystyrene resin (trade names “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F-10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

  In the present invention, the alkylene glycol block copolymer is preferably a composition represented by the following structural formula (1).

［構造式中、ａ、ｂ及びｃは整数であって、ａ＞０、ｂ≧１５、ｃ≧０、ａ＋ｃ≧４である。］

[In the structural formula, a, b and c are integers, and a> 0, b ≧ 15, c ≧ 0, a + c ≧ 4. ]

As described above, the block copolymer of alkylene glycol is preferably an ethylene oxide adduct (PEG-PPG-PEG type) of polypropylene glycol (PPG) represented by the structural formula (1). In the above composition, the polyethylene glycol (PEG) chain has a high affinity for the metal oxide fine powder, and the polypropylene glycol (PPG) chain has a good affinity for the toner particle surface. The interaction between the nonionic surfactant and the metal oxide fine powder continues even during long-term use without the copolymer being released from the toner surface. If the structure of the block copolymer of alkylene glycol is a propylene oxide adduct of polyethylene glycol (that is, the PEG chain and the PPG chain are reversed in the structural formula (1) [PPG-PEG-PPG type]), this effect is obtained. Is not desirable because of its weakness. This is an anchor to the toner surface because the polypropylene glycol (PPG) chain has strong rigidity and is more hydrophobic than the polyethylene glycol (PEG) chain. Therefore, the polyethylene glycol chain located in the center is difficult to move due to the rigid and large anchor glycol effect on both sides, and the flexibility is weakened. As a result, it is difficult to come into contact with the metal oxide fine powder, and the interaction is weakened. As a result, if the block copolymer of alkylene glycol is an ethylene oxide adduct of polypropylene glycol represented by the structural formula (1), the toner has excellent chargeability and transferability.
“A + c” indicating the total number of added moles of ethylene oxide in the structural formula (1) is preferably 4 or more, more preferably 8 or more and 600 or less, and further preferably 10 or more and 550 or less. . When “a + c” is smaller than 4, the interaction with the metal oxide fine powder surface tends to be weak.
Further, the number average molecular weight (Mn) of the polypropylene glycol (PPG) chain is preferably 1000 or more and 3600 or less, and when it is within this range, the balance between the adhesion force to the toner particle surface and the adhesion force (interaction) to the metal oxide fine powder. Is good. If it is less than 1000, the hydrophobicity is weakened and the affinity for the toner particle surface is weakened, so that the anchor effect tends to be difficult to obtain. Conversely, when it exceeds 3600, the rigidity of the molecule increases and the flexibility decreases, so that the adhesion of the block copolymer of the alkylene glycol to the curved surface of the toner particle surface decreases. The more preferable range of the number average molecular weight of the polypropylene glycol (PPG) chain is 2000 or more and 3400 or less, and the affinity to the toner particle surface is more stable and has an appropriate rigidity. Therefore, it is also desirable in terms of stress resistance.
That is, “b” indicating the added mole number of propylene oxide in the structural formula (1) is preferably 15 or more and 64 or less, and more preferably 32 or more and 60 or less.
The ratio of the polyethylene glycol structure and the polypropylene glycol structure is preferably 0.045 mol% or more and 0.400 mol% or less of polypropylene glycol structure / (polyethylene glycol structure + polypropylene glycol structure). This is because when the polypropylene glycol structure part is a hydrophobic part and the polyethylene glycol structure part is a hydrophilic part, the hydrophilic / hydrophobic balance of the block copolymer of alkylene glycol is good. A ratio of polypropylene glycol structure / (polyethylene glycol structure + polypropylene glycol structure) of 0.045 mol% or more is desirable in terms of stress resistance since the nonionic surfactant is excellent in rigidity.
On the other hand, when the ratio of polypropylene glycol structure / (polyethylene glycol structure + polypropylene glycol structure) is 0.400 mol% or less, the molecular chain of the nonionic surfactant has an appropriate flexibility, and the three-dimensional structure of the polypropylene glycol structure. Obstacles are also desirable because they do not affect the interaction with the metal oxide fine powder.
A rough standard for the amount of the nonionic surfactant used in the present invention is preferably 0.05 parts by mass or more and 0.50 parts by mass or less, more preferably 0.10 parts by mass with respect to 100 parts by mass of the toner particles. The amount is 0.40 parts by mass or less, more preferably 0.15 parts by mass or more and 0.35 parts by mass or less.

<Calculation of the number of moles added in the block copolymer of alkylene glycol>
In the present invention, the number of added moles of ethylene oxide and propylene oxide in the block copolymer of alkylene glycol represented by the structural formula (1) is calculated by ¹ H-NMR measurement and gel permeation chromatography (GPC).
Molar number of addition of ethylene oxide and propylene oxide is first weighed accurately block copolymer 10mg of alkylene glycol, dissolved in trimethylsilane 10mg (TMS) containing deuterochloroform (1% ^TMS), in 1 H-NMR analyse. ^{In the 1} H-NMR spectrum, the hydrogen signal of the ethylene group adjacent to the oxygen atom of the oxyethylene group in the vicinity of 3.5 ppm to 3.7 ppm and the oxypropylene group in the vicinity of 3.4 ppm to 3.5 ppm. The peak intensity ratio of the methine hydrogen adjacent to the oxygen atom (equivalent to 1H each) and the hydrogen of the methyl group adjacent to the methine group of the oxypropylene group in the vicinity of 1.1 ppm to 1.2 ppm (equivalent to 3H each) By confirming, the composition ratio of ethylene oxide and propylene oxide is calculated.
(Measurement of ¹ H-NMR (nuclear magnetic resonance) spectrum)
Measuring apparatus: FT NMR apparatus JNM-EX400 (manufactured by JEOL Ltd.)
Measurement frequency: 400MHz
Pulse condition: 5.0μs
Frequency range: 10500Hz
Integration count: 1024 times Measurement temperature: 60 ° C
Next, the number average molecular weight (Mn) of the block copolymer of alkylene glycol is measured using gel permeation chromatography (GPC). The measurement conditions by gel permeation chromatography (GPC) are as described above. The added mole number is calculated from the measured number average molecular weight (Mn) and the composition ratio of ethylene oxide and propylene oxide calculated from the 1H-NMR spectrum described above.

The metal oxide fine powder used in the present invention is not particularly limited as long as it is used as a metal oxide fine powder having charge controllability in the technical field, but tin oxide, titania, zinc oxide, silica A fine powder of metal oxide such as alumina can be suitably exemplified. Of these, titania and alumina are more preferable, and alumina is particularly preferable.
The manufacturing method of these metal oxide fine powder is not limited, A well-known method can be used. In the case of alumina, it can be produced under known conditions using a vapor phase method or the like. In addition, titania can be produced under known conditions using a wet method or the like. In the case of hydrophobizing these metal oxide fine powders, the method is not particularly limited. Examples of the treatment agent used include non-modified silicone varnishes, various modified silicone varnishes, unmodified silicone oils, various types. Modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds are exemplified. These treatment agents may be used alone or in combination.
The metal oxide fine powder used in the present invention has a volume-based median diameter (D50) of 0.07 μm or more and 2.00 μm or less, preferably 0.07 μm or more and 1.00 μm or less. This is because when the volume-based median diameter (D50) of the metal oxide fine powder is less than 0.07 μm, the metal oxide fine powder is likely to be embedded in the toner surface, and the durability and transferability of the toner can be improved over a long period of use. It tends to cause a decline. On the other hand, when the volume-based median diameter (D50) of the metal oxide fine powder exceeds 2.00 μm, the nonionic surfactant of the present invention is used and the metal oxide fine powder and the nonionic surfactant are used. Even with the interaction effect, the metal oxide fine powder is easily released from the toner surface.
The content of the metal oxide fine powder is preferably 0.02 parts by mass or more and 2.00 parts by mass or less, and 0.02 parts by mass or more and 0.80 parts by mass or less with respect to 100 parts by mass of the toner particles. More preferred. When the content of the metal oxide fine powder is less than 0.02 parts by mass with respect to 100 parts by mass of the toner particles, the effect of the present invention tends to be reduced. There is a tendency for the ability to suppress the release of fine powder from the toner particle surface to decrease.

<Measurement method of volume-based median diameter (D50) of metal oxide fine powder>
The volume-based median diameter (D50) of the metal oxide fine powder used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows. As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.
The measurement procedure is as follows.
(1) A batch type cell holder is attached to LA-920.
(2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.
(3) The inside of the batch cell is stirred using a dedicated stirrer chip.
(4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).
(5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.
(6) After performing warm-up operation for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.
(7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.
(8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.
(9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.
(10) In a state where ultrasonic waves are applied to the aqueous solution in the beaker of (9), about 1 mg of metal oxide fine powder is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. At this time, the metal oxide fine powder may be hardened and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the solid is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.
(11) The aqueous solution in which the metal oxide fine powder prepared in (10) is dispersed is immediately added little by little to a batch type cell, taking care not to introduce bubbles, and the transmittance of the tungsten lamp is 90% or more. Adjust to 95% or less. Then, the particle size distribution is measured. The volume-based median diameter (D50) is calculated based on the obtained volume-based particle size distribution data.

The metal oxide fine powder used in the present invention has a degree of hydrophobicity measured by a methanol titration method of preferably 35.0 or less, and more preferably 15.0 or less. This means that the surface property of the metal oxide fine powder has the property of being familiar with methanol. That is, the property is similar to that of a nonionic surfactant extracted from toner using methanol. Therefore, since the affinity of both substances is high, the interaction between the nonionic surfactant and the metal oxide fine powder becomes stronger. Further, when the degree of hydrophobicity of the metal oxide fine powder satisfies the above range, the charge-up tends to be suppressed in a low temperature and low humidity environment, and the image density is excellent.
The measurement of the degree of hydrophobicity in the present invention uses a powder wettability tester WET-100P (manufactured by Reska Co., Ltd.) and uses a methanol drop transmitted light intensity curve measured under the following conditions and procedures.
First, 50 ml of water is placed in a flask and the transmitted light intensity (T) is measured. At this time, the transmitted light intensity (T) is set to 100, and the transmitted light intensity (T) in a state where no light is transmitted is set to 0, and the transmitted light intensity is measured. However, when measuring metal oxide fine powder as used in the present invention, depending on the sample, transmitted light is detected even in a suspension state completely wetted with methanol, and the transmitted light intensity does not become zero completely. Can also occur. In the present invention, since it is necessary to strictly control, in consideration of the above case, when the suspension is completely suspended and the slope of the tangent line of the transmitted light curve becomes −0.02 (T / vol%) or more. The transmitted light intensity (T) is defined as 0. The methanol concentration (vol%) when the transmitted light intensity (T) becomes 0 is defined as the degree of hydrophobicity of the metal oxide fine powder.
The transmitted light intensity (T) is measured according to the following procedure.
A magnetic stirrer is put into a beaker containing 50 ml of water (methanol concentration 0%). Then, 0.30 g of the metal oxide fine powder is precisely weighed and put in a state where the metal oxide fine powder is suspended in the beaker.
Next, stirring was started with a magnetic stirrer at a stirring speed of 300 rpm (5 rotations / second), and methanol was continuously added to the measurement sample solution at a rate of 1.4 ml / min through a glass tube while the wavelength was 780 nm. The transmitted light intensity of the light is measured, and a methanol dropping transmitted light curve as shown in FIG. 1 is created.
In this measurement, a beaker with a diameter of 5 cm and a glass with a diameter of 1.75 mm was used, and a magnetic stirrer had a spindle shape with a length of 25 mm and a maximum diameter of 8 mm and was coated with Teflon (registered trademark). Use what was done.
Under the above conditions, the initial methanol concentration of wettability is set to 0%, but the methanol concentration at the point where the transmitted light intensity starts to drop from 100 (the point at which the metal oxide fine powder begins to get wet) is quite high. In this case, the measurement starting concentration is appropriately selected, and the methanol concentration that becomes T (0) of the present invention is accurately obtained.
In addition, the definition of the methanol concentration (vol%) in the water / methanol mixed solvent in the present invention follows the following formula for the convenience of the measuring apparatus.
Methanol concentration (vol%) = [methanol volume (vol) / {methanol volume (vol) + water volume (vol)}] × 100
For example, when adjusting 60 ml of a solution with a methanol concentration of 65 (vol%), it is defined as the sum of 21 ml of pure water using a measuring cylinder and 39 ml of methanol using another measuring cylinder. Is done.
In addition, the degree of hydrophobicity of the metal oxide fine powder measured by the methanol titration method can be adjusted by adjusting the production conditions (for example, temperature) of the metal oxide fine powder to determine the amount of hydroxyl groups present on the surface of the metal oxide fine powder. It is possible to adjust to the above range by using the method of adjusting, the method of surface treatment using various coupling agents such as silane coupling agent and titanium coupling agent, and the method of surface treatment with oil such as silicone oil. It is.

The metal oxide fine powder used in the present invention is the amount of adsorbed moisture in the adsorption process at a relative vapor pressure of 80% RH on the isotherm of moisture absorption / desorption at a temperature of 28 ° C. measured using an adsorption equilibrium measuring device. However, it is preferable that they are 0.01 mass% or more and 4.00 mass% or less, and it is more preferable that they are 0.01 mass% or more and 1.50 mass% or less. This is because when the adsorbed moisture content of the metal oxide fine powder is less than 0.01% by mass, the toner tends to be charged up in a low temperature and low humidity environment. On the other hand, when the amount of adsorbed moisture of the metal oxide fine powder exceeds 4.00% by mass, the influence of the moisture adsorbed on the metal oxide fine powder becomes large, and the nonionic surfactant and the metal oxide fine powder are increased. Tend to weaken the interaction.
In the present invention, the amount of adsorbed moisture of the metal oxide fine powder is measured by an adsorption equilibrium measuring device (“EAM-02” manufactured by JT Toshi). This is a device that reaches solid-gas equilibrium under conditions where only the target gas (water in the present invention) exists, and measures the solid mass and vapor pressure at this time.
The actual absorption / desorption isotherm is automatically measured by the computer, from the measurement of dry matter amount and degassing of dissolved air in water to the measurement of absorption / desorption isotherm. The outline of the measurement is described in the operation manual issued by JT Toshi Co., Ltd. and is as follows. In the present invention, water is used as the solvent liquid.
First, about 5 g of metal oxide fine powder is filled in the sample container in the adsorption tube, and then the thermostat temperature and the sample part temperature are set to 28 ° C. Thereafter, the air valves V1 (main valve) and V2 (exhaust valve) are opened to operate the evacuation unit, and the vacuum vessel is evacuated to about 0.01 mmHg to dry the sample. The mass when the mass change of the sample ceases is defined as “dry matter amount”.
Since air is dissolved in water as a solvent solution, it is necessary to deaerate. First, water is put into a liquid reservoir, the evacuation unit is operated, and the air valves V2 and V3 (liquid reservoir valves) are alternately opened and closed to remove dissolved air. The above operation is repeated several times, and the deaeration ends when no more bubbles are seen in the water.
Following the measurement of the amount of dry matter and deaeration of dissolved air in water, water vapor is introduced from the reservoir by closing the air valves V1, V2 and opening the air valve V3 while keeping the inside of the vacuum vessel under vacuum, Close the air valve. Next, the solvent vapor is introduced into the vacuum vessel by opening the air valve V1, and the pressure is measured by the pressure sensor. When the pressure in the vacuum vessel does not reach the set pressure, the above operation is repeated to set the pressure in the vacuum vessel to the set pressure. When the equilibrium is reached, the pressure and mass in the vacuum vessel become constant, and the pressure and temperature at that time and the sample mass are measured as equilibrium data.
By operating as described above and changing the pressure of water vapor, the isotherm of adsorption / desorption can be measured. In actual measurement, a relative vapor pressure for measuring the amount of adsorption is set in advance. For example, when the set pressure is 5%, 10%, 30%, 50%, 70%, 80%, 90%, and 95%, the “adsorption process” in the present invention refers to the amount of moisture adsorbed in order from 5%. Is the process of measuring the isotherm, and the “desorption process” is the process that follows the adsorption process. In contrast to the adsorption process, the amount of adsorbed water is measured while decreasing the relative vapor pressure from 95%. Show the process of going.
In this apparatus, the pressure is set by the relative vapor pressure (% RH), and the adsorption / desorption isotherm is displayed by the adsorbed moisture amount (% by mass) and the relative vapor pressure (% RH). The formula for calculating the amount of adsorbed water and the relative vapor pressure is shown below.
M = {(Wk−Wc) / Wc} × 100
Pk = (Q / Q0) × 100
(Where M is the amount of adsorbed water (% by mass), Pk is the relative vapor pressure (% RH), Wk (mg) is the sample mass, Wc (mg) is the amount of dry matter in the sample, and Q0 (mmHg) is the (The saturated vapor pressure of water determined by the Antoine equation from the temperature Tk (° C.) at the time of desorption equilibrium, and Q (mmHg) indicates the pressure measured as the equilibrium data.)
In addition, as the method for adjusting the amount of adsorbed moisture, a method for adjusting the production conditions (for example, temperature) of the metal oxide fine powder to adjust the amount of hydroxyl groups present on the surface of the metal oxide fine powder, a silane coupling agent And a surface treatment using various coupling agents such as a titanium coupling agent and a surface treatment using oil such as silicone oil. In addition, the amount of adsorbed moisture can be adjusted by changing the particle diameter and shape of the metal oxide fine powder according to the production method and production conditions.

The metal oxide fine powder used in the present invention has a degree of hydrophobicity measured by methanol titration of 15.0 or less, and the adsorbed water content is 0.01% by mass or more and 1.50% by mass or less. It is more preferable. Here, the metal oxide fine powder is preferably not hydrophobized by a hydrophobizing agent. This seems to be because in the interaction between the nonionic surfactant and the metal oxide fine powder, the hydrophobic treatment agent does not interfere with the electron and electron distribution related to the interaction. That is, the metal oxide fine powder is preferably a metal oxide fine powder that has a small number of polar groups such as hydroxyl groups and a small amount of adsorbed moisture and has not been hydrophobized by the hydrophobizing agent.

The total pore volume measured in the range of the pore diameter of 1.7 to 300.0 nm of the metal oxide fine powder used in the present invention is preferably 0.200 cm ³ / g or less, and 0.070 cm ³ / G or more and 0.200 cm ³ / g or less is more preferable. This is because the contact area of the metal oxide fine powder on the toner particle surface is wide, and the nonionic surfactant present on the toner particle surface and the metal oxide fine powder are easily in contact with each other, and the interaction is strengthened. Conceivable. That is, of the convex portions and concave portions on the surface of the metal oxide fine powder, only the convex portions come into contact with the nonionic surfactant present on the toner particle surface. As a result, it is excellent in fog and filming.
The total pore volume measured in the range of the pore diameter of the metal oxide fine powder of 1.7 nm or more and 300.0 nm or less is measured using a pore distribution measuring device Tristar 3000 (manufactured by Shimadzu Corporation) with nitrogen gas on the sample surface. It is measured by the gas adsorption method to adsorb. The outline of the measurement is described in the operation manual issued by Shimadzu Corporation and is as follows.
Before measuring the pore distribution, about 1 g of sample is put in a sample tube and evacuated at 100 ° C. for 24 hours. After evacuation, the sample mass is precisely weighed to obtain a sample. For the obtained sample, the total pore volume in the range of the pore diameter of 1.7 nm or more and 300.0 nm or less is determined by the BJH desorption method using the pore distribution measuring apparatus. For evaluation of the pore distribution, the total pore volume closest to the measurement data information is preferably used as an index.
In addition, the total pore volume is based on the metal oxide fine powder production method (gas phase method, wet method, etc.) and production conditions (in the case of the gas phase method, the gas flow rate of LPG, oxygen, nitrogen, etc., and the raw metal powder. It is possible to adjust to the above-mentioned range by controlling the supply amount.

The toner particles used in the present invention are manufactured through a step of mixing toner particles and a nonionic surfactant in an aqueous medium after the toner particles are granulated, and adding the nonionic surfactant to the toner particles. The nonionic surfactant used is a composition represented by the above structural formula (1), and the degree of hydrophobicity measured by methanol titration of the metal oxide fine powder used is 35. Of the adsorption process at a relative vapor pressure of 80% RH on an isotherm of moisture absorption / desorption at a temperature of 28 ° C. measured using an adsorption equilibrium measuring apparatus for the metal oxide fine powder used. When the water content is 0.01% by mass to 4.00% by mass, the following effects can be obtained.
This is because the extraction amount (A) of the nonionic surfactant in (A / B) is the amount of the nonionic surfactant extracted from the toner with methanol, and the nonionic surfactant has a high affinity with methanol. It is considered to represent the amount of ionic surfactant. In addition, when the degree of hydrophobicity of the metal oxide fine powder measured by the methanol titration method is 35.0 or less, the metal oxide fine powder also has high affinity with methanol. The exact reason is unknown, but the nonionic surfactant having a high affinity for methanol and the metal oxide fine powder both come into contact with each other on the toner particle surface to cause a stronger interaction. It is considered to be. Usually, a nonionic surfactant is a substance that easily absorbs moisture if not as much as an ionic surfactant. Moreover, the metal oxide fine powder having a low degree of hydrophobicity has high hygroscopicity. For this reason, although the amount of moisture adsorbed is too large, the interaction is likely to be hindered, although the combination is likely to interact strongly. Therefore, the nonionic surfactant is a composition represented by the structural formula (1) so that the interaction is sufficiently developed, and the adsorbed water content of the metal oxide fine powder is 0.01 mass. % Or more and 4.00% by mass or less is a more preferable embodiment, but has been clarified by the present invention.
Although the exact reason is unknown, a metal oxide fine powder having a high affinity for methanol but a low amount of adsorbed moisture with a nonionic surfactant (composition represented by structural formula (1)) extracted with methanol. Water adsorption on the surface of the toner particle is suppressed by the interaction of the combination of the bodies (a strong interaction occurs due to similar properties) to cap the water adsorption site. In addition, an action such as an unshared electron pair existing in each other's oxygen atom is added, and thus the charge is hardly leaked and the charge-up is also suppressed. Therefore, the occurrence of fog in a high temperature and high humidity environment is further reduced, and the image density is more excellent by suppressing charge-up in a low temperature and low humidity environment. This effect is particularly prominent when the metal oxide fine powder is alumina. This is considered to be due to the influence of the electronic state and resistance of alumina in combination with the nonionic surfactant (composition represented by the structural formula (1)). As a result, it is excellent due to poor regulation and solid image uniformity.

Further, the toner particles used in the present invention undergo a process of mixing the toner particles and the nonionic surfactant in the aqueous medium after the toner particles are granulated, and adding the nonionic surfactant to the toner particles. The produced non-ionic surfactant is a composition represented by the above structural formula (1), and the number average of the polypropylene glycol structure of the block copolymer of alkylene glycol in the nonionic surfactant The molecular weight is 1000 or more and 3600 or less, and the ratio of polypropylene glycol structure and polyethylene glycol structure is 0.045 mol% or more and 0.400 mol% or less of polypropylene glycol structure / (polyethylene glycol structure + polypropylene glycol structure). / B) of ^{0.40 × 10 -3 (g / m} 2) or more 2 00 × and at 10 -3 ^{(g /} m ²⁾ or less, a metal oxide fine powder alumina, the hydrophobic degree of the metal oxide fine powder is 15.0 or less, the metal oxide fine powder When the adsorbed water content is 0.01% by mass or more and 1.50% by mass or less, and the volume-based median diameter (D50) of the metal oxide fine powder is 0.07 μm or more and 1.00 μm or less, it is further in a low temperature and low humidity environment. The effect that the blotch in is suppressed. This optimizes the adhesion state between the toner particles and the metal oxide fine powder and optimizes not only the chargeability of the toner but also the fluidity of the toner, thereby suppressing the blotch in a low-temperature and low-humidity environment. It is thought that it will be. At this time, since the release of the nonionic surfactant and the metal oxide fine powder from the toner particles is suppressed, the effect is particularly sustained even during long-term use.
In particular, in the case of use in an image forming method and apparatus in which a latent image carrier is brought into contact with a rubber blade or the like to collect transfer residual toner, the influence on the cleaning property is remarkable. One cause of defective cleaning is that toner with a small particle diameter is overcharged and passes through the regulation by the cleaning blade. On the other hand, if a nonionic surfactant having a specific adhesion, polarity and electron distribution that satisfies the above conditions is used at a specific concentration, the particle size dependency of the charging property is suppressed and the particle size is large. This is desirable because it exerts an effect of suppressing the difference in chargeability between a small one and a small one to some extent, and provides an appropriate fluidity to suppress the occurrence of defective cleaning.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 3.0 μm or more and 9.0 μm or less. When the weight average particle size is less than 3.0 μm, the specific surface area of the toner is large, and thus there is a tendency that problems are likely to occur in durability and heat resistance during long-term use. On the other hand, when the weight average particle diameter (D4) exceeds 9.0 μm, the resolution of the toner image tends to be inferior.

<Measurement of Weight Average Particle Size (D4) and Number Average Particle Size (D1) of Toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. The measurement is performed with 25,000 effective measurement channels.
As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.
Prior to measurement and analysis, the dedicated software is set as follows.
On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.
In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.
The specific measurement method is as follows.
(1) About 200 ml of the electrolytic solution is placed in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rpm. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.
(2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.
(3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dispersion System Tetora 150” (manufactured by Nikkaki Bios) with an electrical output of 120 W is prepared. A predetermined amount of ion-exchanged water is placed in a water tank of an ultrasonic disperser, and about 2 ml of the contamination N is added to the water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . Measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set in the dedicated software, the “average diameter” on the “Analysis / volume statistics (arithmetic average)” screen is the weight average particle diameter (D4), and the graph / number% is set. The “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

Hereinafter, the method for producing the toner of the present invention will be described.
The toner particles used in the present invention can be produced by a suspension polymerization method, an emulsion polymerization method, an interfacial polymerization method such as a microcapsule production method, or agglomeration of at least one kind of fine particles to obtain a desired particle size. Examples thereof include an association polymerization method, a dispersion polymerization method, and a suspension granulation method in which a raw material dissolved and dispersed in an organic solvent is granulated in an aqueous medium to form a toner. Of these, production of toner particles by suspension polymerization is preferred. This is because the target toner particles can be easily obtained because the manufacturing process is simple. In particular, as compared with the association polymerization method and the suspension granulation method, it is not necessary to use an extra ionic surfactant or nonionic surfactant at the time of toner granulation or aggregation process. This is because there is no inhibition of the effect. In addition, it is desirable to use the organic solvent as compared with the suspension granulation method because the effect of the present invention is not hindered due to the seepage of the solvent to the toner surface during the solvent removal step. In addition, by using a water-soluble polymerization initiator as compared with the emulsion polymerization method, it is due to the influence of a strongly polar functional group in the water-soluble polymerization initiator residue or the polymer terminal that will be present at the polymer end. This is because the effect of the present invention is not hindered. As a result, a toner having excellent chargeability can be obtained. Further, it is excellent in rising of charge and excellent in initial image density.
Hereinafter, a suspension polymerization method will be exemplified to describe a method for producing toner particles, but the present invention is not limited thereto. The toner particles using the suspension polymerization method are prepared by adding a polymerizable monomer, a colorant, and other additives as necessary depending on a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. Dissolve or disperse uniformly, dissolve the polymerization initiator in this, and prepare a polymerizable monomer composition. Next, toner particles are produced by dispersing the polymerizable monomer composition in an aqueous medium, granulating, and polymerizing the polymerizable monomer. The binder resin constituting the toner particles is not particularly limited, but styrene-acrylic copolymer, styrene-methacrylic copolymer, epoxy resin, styrene-butadiene copolymer generally used as a resin for toner. Coalescence is mentioned. Therefore, as the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.
Examples of the polymerizable monomer include the following. Styrene; Styrenic monomers such as o- (m-, p-) methylstyrene, m- (p-) ethylstyrene; methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, Propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, Acrylic acid ester monomers such as 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate and diethylaminoethyl methacrylate, Ether-based monomers; butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, such as ene-based monomers methacrylamide.
In addition, in the method of obtaining toner particles using the suspension polymerization method, it is particularly preferable to add the polar resin simultaneously from the viewpoint of allowing the polymerization reaction of the polymerizable monomer to be carried out without hindrance. Examples of polar resins used in the present invention include copolymers of styrene and (meth) acrylic acid, copolymers of styrene and unsaturated carboxylic acid esters, nitrile monomers such as acrylonitrile, and vinyl chloride. Polymers such as halogen monomers, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, or nitro monomers, or monomers thereof A copolymer of styrene monomer and the like, a maleic acid copolymer, a polyester resin, and an epoxy resin are preferably used. The polar resin is particularly preferably one containing no unsaturated group capable of reacting with a polymerizable monomer in the molecule. As addition amount of these polar polymers and / or copolymers, 0.1-30 mass% is preferable with respect to a polymerizable monomer, and it is especially preferable in it being 0.5-20 mass%. The polar resin has an acid value of 5.0 (mgKOH / g) to 30.0 (mgKOH) from the viewpoint of environmental stability and from the viewpoint of not inhibiting the interaction between the metal oxide fine powder and the nonionic surfactant. / G) The following is preferable.
When the toner of the present invention contains a polyester resin as a polar resin, the polyester resin is produced by, for example, a method utilizing a dehydration condensation reaction from a carboxylic acid compound and an alcohol compound, or a transesterification reaction. The catalyst may be a general acidic or alkaline catalyst used in the esterification reaction, such as zinc acetate or a titanium compound. Thereafter, it may be highly purified by a recrystallization method, a distillation method or the like.

The acid value of the polar resin can be measured as follows.
The number of mg of potassium hydroxide required to neutralize free fatty acids, resin acids and the like contained in 1 g of a sample is referred to as an acid value. The acid value of the resin is measured according to JIS K 0070-1992. Specifically, it is measured according to the following procedure.
(1) Preparation of Reagent 1.0 g of phenolphthalein is dissolved in 90 ml of ethyl alcohol (95 vol%), and ion exchanged water is added to make 100 ml to obtain a phenolphthalein solution.
7 g of special grade potassium hydroxide is dissolved in 5 ml of water, and ethyl alcohol (95 vol%) is added to make 1 l. In order not to touch carbon dioxide, etc., put in an alkali-resistant container and let stand for 3 days, then filter to obtain a potassium hydroxide solution. The obtained potassium hydroxide solution is stored in an alkali-resistant container. The factor of the potassium hydroxide solution was as follows: 25 ml of 0.1 mol / l hydrochloric acid was placed in an Erlenmeyer flask, a few drops of the phenolphthalein solution were added, titrated with the potassium hydroxide solution, and the hydroxide required for neutralization. Determined from the amount of potassium solution. As the 0.1 mol / l hydrochloric acid, one prepared according to JIS K 8001-1998 is used.
(2) Operation (A) Main test A 2.0 g sample of the pulverized resin is precisely weighed into a 200 ml Erlenmeyer flask, and 100 ml of a toluene / ethanol (2: 1) mixed solution is added and dissolved over 5 hours. Subsequently, several drops of the phenolphthalein solution is added as an indicator, and titration is performed using the potassium hydroxide solution. The end point of titration is when the light red color of the indicator lasts for about 30 seconds.
(B) Blank test Titration is performed in the same manner as above except that no sample is used (that is, only a mixed solution of toluene / ethanol (2: 1) is used).
(3) The acid value is calculated by substituting the obtained result into the following formula.
A = [(C−B) × f × 5.61] / S
Here, A: acid value (mgKOH / g), B: addition amount (ml) of a potassium hydroxide solution in a blank test, C: addition amount (ml) of a potassium hydroxide solution in this test, f: potassium hydroxide Solution factor, S: sample (g).

The toner of the present invention contains a colorant. As the black colorant, carbon black, which is toned to black using the yellow, magenta and cyan colorants shown below, is used.
As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. A known dye may be used as the yellow colorant.
As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used.
As the cyan colorant, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used.
These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The amount of the colorant added is preferably 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the binder resin.
The toner of the present invention may contain a wax. In that case, at least one of the waxes preferably has a melting point (a temperature corresponding to the maximum endothermic peak of the DSC endothermic curve in the temperature range of 20 to 200 ° C.) of 30 ° C. or more and 120 ° C. or less, more preferably 50 ° C. It is 100 degreeC or less, More preferably, it is 50 degreeC or more and 80 degrees C or less. Further, a solid wax that is solid at room temperature is preferable, and a solid wax having a melting point of 50 ° C. or higher and 80 ° C. or lower is particularly preferable in terms of toner blocking resistance, durability of a large number of sheets, low-temperature fixability, and offset resistance.
Examples of waxes include polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer-Tropsch wax, amide waxes, higher fatty acids, long chain alcohols, ester waxes, ketone waxes, and derivatives such as graft compounds and block compounds. Known waxes can be used. In the toner of the present invention, the wax content is preferably 5 to 30 parts by mass, more preferably 5 to 20 parts by mass, and still more preferably 8 to 15 parts by mass. If the amount of wax added is less than the lower limit, the effect of preventing offset tends to be lowered, and if the amount exceeds the upper limit, the anti-blocking effect is lowered and the anti-offset effect tends to be affected. In addition, when obtaining the physical properties as described above, when the wax needs to be extracted from the toner, the extraction method is not particularly limited, and any method can be used. For example, a predetermined amount of toner is Soxhlet extracted with toluene, and after removing the solvent from the obtained toluene-soluble component, a chloroform-insoluble component is obtained. Thereafter, identification analysis is performed by IR method or the like. In addition, quantitative analysis is performed by DSC or the like.
A known charge control agent may be used for the toner of the present invention. The content of the charge control agent is preferably 0.01 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the binder resin in the toner. .
In the toner of the present invention, various known inorganic and organic external additives can be used for the purpose of imparting various properties within a range that does not impair the effects of the present invention. The external additive used is preferably smaller than the volume-based median diameter of the metal oxide fine powder used in the present invention. The particle size of the external additive means the number average particle size obtained by observing the surface of the toner particles with a scanning electron microscope.
The amount of these external additives added is preferably 0.01 parts by mass or more and 5 parts by mass or less, and more preferably 0.02 parts by mass or more and 3.00 parts by mass or less with respect to 100 parts by mass of the toner particles. . These external additives may be used alone or in combination. These external additives are preferably hydrophobized.
As a method for the hydrophobization treatment, various coupling agents such as a silane coupling agent and a titanium coupling agent can be used. By increasing the degree of hydrophobicity with silicone oil, external addition under high humidity is possible. Since moisture adsorption of the agent (particularly inorganic fine powder) is suppressed, and further, contamination of the regulating member and the charging member is suppressed, a high-quality image is obtained, which is preferable. Examples of the silicone oil include dimethyl silicone oil, alkyl-modified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxylic acid-modified silicone oil, alcohol-modified silicone oil, α-methylstyrene-modified silicone oil, methylphenyl silicone oil, Examples thereof include chlorophenyl silicone oil and fluorine-modified silicone oil, but are not limited to the above. The silicone oil preferably has a viscosity at a temperature of 25 ° C. of 50 mm ² / s to 1000 mm ² / s. If it is less than 50 mm ² / s, part of it is exerted by application of heat, and the charging characteristics are likely to deteriorate. When it exceeds 1000 mm ² / s, handling becomes difficult in terms of processing work. A known technique can be used as a method for treating the silicone oil. For example, silicate fine powder and silicone oil are mixed using a mixer. Silicone oil is sprayed into the silicate fine powder using a sprayer. Or the method of mixing a silicic acid fine powder after dissolving silicone oil in a solvent is mentioned. The processing method is not limited to this.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but this does not limit the present invention in any way. In addition, “parts” in the following examples and the like are “parts by mass”.
First, the polyalkylene glycol (PAG) used in the present invention will be described.
<Method for producing polyalkylene glycol 1>
A container containing 2000 g of polypropylene glycol 2000 (35 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 13000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 1. The physical properties of the resulting polyalkylene glycol 1 are shown in Table 1.
<Method for producing polyalkylene glycol 2>
A container containing 1000 g of polypropylene glycol 1000 (18 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 9000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 2. The physical properties of the resulting polyalkylene glycol 2 are shown in Table 1.
<Method for producing polyalkylene glycol 3>
A container containing 1000 g of polypropylene glycol 1000 (18 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 1500 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 3. The physical properties of the resulting polyalkylene glycol 3 are shown in Table 1.
<Method for producing polyalkylene glycol 4>
A container containing 1000 g of polypropylene glycol 1000 (18 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Then, polyalkylene glycol 4 was obtained by adding 24000 g of ethylene oxide under pressure and performing an addition reaction. The physical properties of the resulting polyalkylene glycol 4 are shown in Table 1.
<Method for producing polyalkylene glycol 5>
A container containing 1000 g of polypropylene glycol 1000 (18 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Then, polyalkylene glycol 5 was obtained by adding 500 g of ethylene oxide under pressure and performing an addition reaction. The physical properties of the resulting polyalkylene glycol 5 are shown in Table 1.
<Method for producing polyalkylene glycol 6>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 22000 g of ethylene oxide was added under pressure to cause addition reaction, whereby polyalkylene glycol 6 was obtained. The physical properties of the resulting polyalkylene glycol 6 are shown in Table 1.
<Method for producing polyalkylene glycol 7>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 4000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 7. The physical properties of the resulting polyalkylene glycol 7 are shown in Table 1.
<Method for producing polyalkylene glycol 8>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 3000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 8. The physical properties of the resulting polyalkylene glycol 8 are shown in Table 1.
<Method for producing polyalkylene glycol 9>
A container containing 4000 g of polypropylene glycol 4000 (70 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 11,000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 9. The physical properties of the resulting polyalkylene glycol 9 are shown in Table 1.
<Method for producing polyalkylene glycol 10>
A container containing 400 g of polypropylene glycol 400 (7 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 1100 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 10. The physical properties of the resulting polyalkylene glycol 10 are shown in Table 1.
<Method for producing polyalkylene glycol 11>
A container containing 1500 g of polyethylene glycol 1540 (34 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 1200 g of propylene oxide was added under pressure to cause addition reaction, thereby obtaining polyalkylene glycol 11. The physical properties of the resulting polyalkylene glycol 11 are shown in Table 1.
<Method for producing polyalkylene glycol 12>
A container containing 400 g of polyethylene glycol 400 (9 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 300 g of propylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 12. The physical properties of the resulting polyalkylene glycol 12 are shown in Table 1.
<Method for producing polyalkylene glycol 13>
Polyalkylene glycol 13 was obtained by adding 2000 g of propylene oxide and 13000 g of ethylene oxide, heating the container containing 1 g of sodium hydroxide to 150 ° C. while stirring, and reacting. The physical properties of the resulting polyalkylene glycol 13 are shown in Table 1.
<Method for producing polyalkylene glycol 14>
A container containing 400 g of polypropylene glycol 400 (7 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 400 g of ethylene oxide was added under pressure to cause addition reaction, whereby polyalkylene glycol 14 was obtained. The physical properties of the resulting polyalkylene glycol 14 are shown in Table 1.
<Method for producing polyalkylene glycol 15>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 29000 g of ethylene oxide was added under pressure to cause addition reaction to obtain polyalkylene glycol 15. The physical properties of the resulting polyalkylene glycol 15 are shown in Table 1.
<Method for producing polyalkylene glycol 16>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Thereafter, 35,000 g of ethylene oxide was added under pressure to cause addition reaction, thereby obtaining polyalkylene glycol 16. The physical properties of the resulting polyalkylene glycol 16 are shown in Table 1.
<Method for producing polyalkylene glycol 17>
A container containing 3000 g of polypropylene glycol 3000 (53 mol adduct, Kishida Chemical Co., Ltd.) and 1 g of sodium hydroxide is heated to 150 ° C. while stirring. Then, polyalkylene glycol 17 was obtained by adding 39000 g of ethylene oxide under pressure and performing an addition reaction. The physical properties of the obtained polyalkylene glycol 17 are shown in Table 1.

表中、「ａ」、「ｂ」及び「ｃ」は、上記構造式（１）に記載の付加モル数を意味する。また、ＰＡＧは、ポリアルキレングリコールを、ＰＰＧは、ポリプロピレングリコールを意味する。

In the table, “a”, “b”, and “c” mean the added mole number described in the structural formula (1). PAG means polyalkylene glycol, and PPG means polypropylene glycol.

<Production of hydrophobic silica 1>
Silica (AEROSIL 200CF, manufactured by Nippon Aerosil Co., Ltd.) was treated with 10 parts by mass of hexamethyldisilazane and then further treated with 20 parts by mass of chlorophenyl silicone oil to obtain hydrophobic silica 1. The number average particle diameter of the primary particles was 12 nm, and the degree of hydrophobicity was 97. <Production of hydrophobic titanium oxide 1>
Titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was treated with 20 parts by mass of γ-mercaptopropyltrimethoxysilane in toluene, filtered and dried to obtain hydrophobic titanium oxide 1. The number average particle diameter of the primary particles was 25 nm, and the degree of hydrophobicity was 60.

<Production example of metal oxide fine powder 1>
Oxygen was supplied to the combustor at 180 Nm ³ / Hr and LPG (Liquid Petroleum gas) was supplied at 2.0 Nm ³ / Hr to form a flame for ignition of aluminum powder. Next, aluminum powder (average particle size of about 60 μm, supply amount: 18 kg / Hr) was supplied from the aluminum powder supply apparatus to the reactor along with nitrogen gas (supply amount: 1.8 Nm ³ / Hr) through a combustor. In the reactor, the aluminum powder was burned by a flame and oxidized to obtain a metal oxide fine powder 1.
<Production example of metal oxide fine powder 2>
A metal oxide fine powder 2 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the supply amount of the aluminum powder was 6 kg / Hr.
<Production example of metal oxide fine powder 3>
A metal oxide fine powder 3 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the flow rate of nitrogen gas was 1.9 Nm ³ / Hr and the supply amount of aluminum powder was 29 kg / Hr.
<Production example of metal oxide fine powder 4>
A metal oxide fine powder 4 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the flow rate of nitrogen gas was 2.0 Nm ³ / Hr and the supply amount of aluminum powder was 40 kg / Hr.
<Production example of metal oxide fine powder 5>
A metal oxide fine powder 5 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the flow rate of nitrogen gas was 2.3 Nm ³ / Hr and the supply amount of aluminum powder was 70 kg / Hr.
<Production example of metal oxide fine powder 6>
100 parts by mass of metal oxide fine powder 1 was put into a Henschel mixer and stirred at 100 ° C. at a rotational speed of 1600 rpm, while hexamethyldisilazane (Silane coupling agent Z-6079 (trade name) manufactured by Toray Dow Corning) The metal oxide fine powder 1 is sprayed onto the metal oxide fine powder 1 while spraying 1.0 part by mass of a 1: 1 liquid mixture of toluene and toluene using an air spray, and the hydrophobized surface treatment of the metal oxide fine powder 1 is performed. It was. Furthermore, after the said processing mixture was stirred for 15 minutes at the rotational speed of 1500 rpm, the metal oxide fine powder 6 was obtained by drying at 120 degreeC for 3 hours.
<Production example of metal oxide fine powder 7>
A metal oxide fine powder 7 was obtained in the same manner as the metal oxide fine powder 6 except that the mixed solution with toluene at a mass ratio of 1: 1 was changed to 2.2 parts by mass.
<Production example of metal oxide fine powder 8>
A metal oxide fine powder 8 was obtained in the same manner as the metal oxide fine powder 6 except that the mixed liquid with toluene at a mass ratio of 1: 1 was changed to 3.0 parts by mass.
<Production example of metal oxide fine powder 9>
A metal oxide fine powder 9 was obtained in the same manner as the metal oxide fine powder 6 except that the mixed liquid with toluene at a mass ratio of 1: 1 was changed to 3.9 parts by mass.
<Production example of metal oxide fine powder 10>
A metal oxide fine powder 10 was obtained in the same manner as the metal oxide fine powder 6 except that the mixed liquid with toluene at a mass ratio of 1: 1 was 4.8 parts by mass.
<Production Example of Metal Oxide Fine Powder 11>
LPG (Liquid Petroleum gas) was supplied at 1.0 Nm ³ / Hr to form a flame for igniting aluminum powder, and then aluminum powder (average particle size of about 60 μm, supply amount 18 kg / Hr) A metal oxide fine powder 11 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the metal oxide fine powder 1 (feed amount: 10 kg / Hr) was used.
<Example of production of metal oxide fine powder 12>
Metal oxide except that the oxygen flow rate is supplied at 60 Nm ³ / Hr to form a flame for igniting aluminum powder, the flow rate of nitrogen gas is 2.3 Nm ³ / Hr, and the supply amount of aluminum powder is 5 kg / Hr Metal oxide fine powder 12 was obtained in the same manner as in the production example of fine powder 1 <Production example of metal oxide fine powder 13>
A metal oxide fine powder 13 was obtained in the same manner as the metal oxide fine powder 6 except that the mixed solution with a mass ratio of 1: 1 with toluene was 32.0 parts by mass.
<Production Example of Metal Oxide Fine Powder 14>
Hydrous titanium oxide obtained by hydrolyzing a titanyl sulfate aqueous solution was washed with pure water until the supernatant had an electric conductivity of 1150 μS / cm to obtain a slurry. Next, an aqueous sodium hydroxide solution was added to adjust the pH of the slurry to 9.0, and the mixture was stirred for 30 minutes. After completion of the stirring, hydrochloric acid was added to adjust the pH to 7, and the supernatant was washed with pure water until the electrical conductivity of the supernatant became 250 μS / cm. Thereafter, hydrochloric acid was added to adjust the pH to 1.5 to obtain 1 L of titania sol having anatase type crystal structure of 120 g / l as TiO ₂ . After adding 22.0 ml of 250 g / l zirconium oxychloride aqueous solution as ZrO ₂ , the mixture was stirred for 1 hour. Thereafter, an aqueous sodium hydroxide solution was added to adjust the pH to 7.2. The supernatant was washed with pure water until the electric conductivity of the supernatant reached 120 μS / cm, filtered and dried. The dried product was fired at 800 ° C. for 1 hour to obtain a metal oxide fine powder 14.
<Example of production of metal oxide fine powder 15>
The oxygen flow rate ^{50Nm 3 / Hr, LPG (Liquefied} petroleum gas) to be supplied in 1.7 nm ³ / Hr to form flame for ignition of aluminum powder, flow rate of 15.0 nm ³ / Hr of nitrogen gas, the aluminum powder A metal oxide fine powder 15 was obtained in the same manner as in the production example of the metal oxide fine powder 1 except that the supply amount was 10 kg / Hr.
<Production Example of Metal Oxide Fine Powder 16>
Metal oxide fine powder 16 was obtained in the same manner as in the production example of metal oxide fine powder 1 except that the flow rate of nitrogen gas was 2.6 Nm ³ / Hr and the supply amount of aluminum powder was 100 kg / Hr.
<Production Example of Metal Oxide Fine Powder 17>
Metal oxide except that oxygen flow is supplied at 30 Nm ³ / Hr to form a flame for igniting aluminum powder, the flow rate of nitrogen gas is 2.8 Nm ³ / Hr, and the supply amount of aluminum powder is 3 kg / Hr In the same manner as in the production example of the fine powder 1, a metal oxide fine powder 17 was obtained.
<Production Example of Metal Oxide Fine Powder 18>
Metal except that oxygen flow is supplied at 15 Nm ³ / Hr to form a flame for igniting aluminum powder, the flow rate of nitrogen gas is 3.3 Nm ³ / Hr, and the supply amount of aluminum powder is 1.5 kg / Hr In the same manner as in the production example of oxide fine powder 1, metal oxide fine powder 18 was obtained.
<Production Example of Metal Oxide Fine Powder 19>
A metal oxide fine powder 19 was obtained in the same manner as in the production example of the metal oxide fine powder 17 except that LPG (Liquid Petroleum gas) was supplied at 1.8 Nm ³ / Hr.
The physical property values of the metal oxide fine powders 1 to 19 are shown in Table 2.

<Toner Production Example 1>
To 1000 parts by mass of ion-exchanged water in the reaction vessel, 15.3 parts by mass of sodium phosphate and 4.9 parts by mass of 10% hydrochloric acid were added, and kept at 65 ° C. for 60 minutes while purging with N ₂ . Using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), while stirring at 12,000 rpm, an aqueous solution of calcium chloride in which 8.5 parts by weight of calcium chloride is dissolved is added to 10 parts by weight of ion-exchanged water to stabilize dispersion. An aqueous medium containing the agent was prepared.
Styrene 48 parts by mass Colorant 7 parts by mass (CI Pigment Red 122 / CI Pigment Red 57 = 1/1)
-Charge control agent (Orient: Bontron E-88) 0.20 parts by mass-Charge control agent (Orient: Bontron E-89) 0.20 parts by mass Subsequently, the above materials are added to an attritor disperser (Mitsui Miike Chemical Co., Ltd.) ) And further dispersed at 220 rpm for 5 hours using 1.7 mm diameter zirconia particles to obtain a polymerizable monomer composition.
In the polymerizable monomer composition,
Styrene 16 parts by mass n-butyl acrylate 20 parts by mass Amorphous polyester resin (Mw = 10000, acid value = 10.0) 2.5 parts by mass Synthetic wax 12 parts by mass (manufactured by Schumann-Sazol) , Trade name = “Sasol SPRAY30”, melting point = 98 ° C.
, Was added.
The above material was kept at 69 ° C. in a separate container, and uniformly dissolved and dispersed at 500 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). In this, 2.5 parts by mass of a polymerization initiator t-hexyl peroxypivalate (manufactured by NOF Corporation, trade name “Perhexyl PV”, molecular weight: 202, 10 hour half-life temperature: 53.2 ° C.) are dissolved, A polymerizable monomer composition was prepared.
The polymerizable monomer composition was charged into the aqueous medium in the reaction vessel, stirred at 10,000 rpm for 5 minutes with a TK homomixer at 65 ° C. under N ₂ purge, and granulated at pH 5.5. . Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 65 ° C. for 6 hours, further to 90 ° C., and reacted for 6 hours. After completion of the polymerization reaction, the reaction vessel was cooled to obtain a dispersion of toner particles 1.
Thereafter, an aqueous surfactant solution in which 0.200 parts by mass of nonionic surfactant 1 is dissolved in 10 parts by mass of ion-exchanged water is added to the dispersion of toner particles 1, and stirring is further continued for 1 hour. 1 surface treatment was performed.
The dispersion was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a cake of toner particles treated with the nonionic surfactant 1. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This washing operation was repeated once more, followed by drying and air classification to obtain magenta colored toner particles.
First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 1.5 parts by mass of hydrophobic silica 1 is added. Then, 0.30 parts by mass of metal oxide fine powder 1 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain toner 1 having an external additive. The composition and physical properties of the obtained toner 1 are shown in Table 3.

<Toner Production Examples 2 to 25, 30 to 33, 37, 38, 39, 40, 41, 44, and 45>
Toners 2 to 25 and 30 having external additives in the same manner as in Toner Production Example 1 except that the types and addition amounts of the nonionic surfactant and metal oxide fine powder are changed as shown in Table 3. ˜33, 37, 38, 39, 40, 41, 44, and 45 were obtained. The physical properties of the obtained toners 2 to 25, 30 to 33, 37, 38, 39, 40, 41, 44, and 45 are shown in Table 3.

<Toner Production Examples 26 and 27>
When preparing an aqueous medium containing a dispersion stabilizer, sodium phosphate is changed to 20.3 parts by mass, 10% hydrochloric acid is changed to 6.5 parts by mass, and calcium chloride is changed to 11.5 parts by mass. Thus, toners 26 and 27 having external additives were obtained in the same manner as in Toner Production Example 1 except that the types and addition amounts of the nonionic surfactant and metal oxide fine powder were changed. The physical properties and the like of the obtained toners 26 and 27 are shown in Table 3.
<Toner Production Examples 28 and 29>
When preparing an aqueous medium containing a dispersion stabilizer, sodium phosphate is changed to 10.3 parts by mass, 10% hydrochloric acid is changed to 3.3 parts by mass, and calcium chloride is changed to 6.5 parts by mass. Thus, toners 28 and 29 having external additives were obtained in the same manner as in Toner Production Example 1 except that the types and addition amounts of the nonionic surfactant and metal oxide fine powder were changed. The physical properties and the like of the obtained toners 28 and 29 are shown in Table 3.

<Toner Production Example 34>
(Toner binder synthesis)
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 660 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 100 parts by mass of bisphenol A propylene oxide 2 mol adduct, 290 parts by mass of terephthalic acid and tetrabutoxy titanate 2 .5 parts by mass, reacted at 220 ° C. under normal pressure for 12 hours, and further reacted at a reduced pressure of 10 to 15 mmHg for 6.5 hours, cooled to 190 ° C., and 32 parts by mass of phthalic anhydride was added thereto. In addition, it reacted for 2 hours. Subsequently, it cooled to 80 degreeC and reacted with 180 mass parts of isophorone diisocyanate in ethyl acetate for 2 hours, and the isocyanate containing prepolymer (1) was obtained. Next, 267 parts by mass of prepolymer (1) and 14 parts by mass of isophoronediamine were reacted at 50 ° C. for 2 hours to obtain a urea-modified polyester resin (A) having a weight average molecular weight of 65,000. 624 parts by mass of bisphenol A ethylene oxide 2 mol adduct, 100 parts by mass of bisphenol A propylene oxide 2 mol adduct, 138 parts by mass of terephthalic acid, 138 parts by mass of isophthalic acid, and 2.5 parts by mass of tetrabutoxy titanate in the same manner as above. The mixture was subjected to polycondensation at 230 ° C. for 5 hours under normal pressure, and then reacted for 5.5 hours at a reduced pressure of 10 to 15 mmHg to obtain an unmodified polyester resin (a) having a peak molecular weight of 6300. 250 parts by mass of urea-modified polyester (A), 730 parts by mass of unmodified polyester resin (a) and 20 parts by mass of styrene are dissolved and mixed in 2000 parts by mass of an ethyl acetate solvent, and an ethyl acetate solution of toner binder (1). Got.
(Create toner)
In a beaker, 240 parts by mass of an ethyl acetate solution of the toner binder (1), C.I. I. Pigment Red 122 pigment 4 parts by mass, 3,5-di-tert-butylsalicylic acid aluminum compound [Bontron E88 (manufactured by Orient Chemical Co., Ltd.)] 1.0 part by mass, release agent [purified carnauba wax 1 powder ( Nippon Wax Co., Ltd.)] (melting point = 83 ° C.) 15 parts by mass, 1-cyclohexyl-1-methylethylperoxyneodecanoate (manufactured by NOF Corporation, trade name “PercycloND”, molecular weight: 313, (10 hours half-life temperature: 41.4 ° C., active oxygen content: 3.58%) 1.0 part by mass was added and stirred at 12000 rpm at 55 ° C. with a TK homomixer, and uniformly dissolved and dispersed. . In a beaker, 706 parts by mass of ion-exchanged water, 294 parts by mass of a 10% hydroxyapatite suspension (Superite 10 manufactured by Nippon Chemical Industry Co., Ltd.) and 0.17 parts by mass of sodium dodecylbenzenesulfonate were uniformly dissolved. Next, the temperature was raised to 55 ° C., and the toner material solution was added and stirred for 3 hours while stirring at 12000 rpm with a TK homomixer. Subsequently, this mixed liquid was transferred to a Kolben equipped with a stirring bar and a thermometer, and the temperature was raised to 98 ° C. to remove the solvent. The aqueous medium was cooled to obtain a dispersion of toner particles 1. Thereafter, an aqueous surfactant solution in which 0.200 parts by mass of nonionic surfactant 1 is dissolved in 10 parts by mass of ion-exchanged water is added to the dispersion of toner particles 1, and stirring is further continued for 1 hour. 1 surface treatment was performed.
The dispersion was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a cake of toner particles treated with the nonionic surfactant 1. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This washing operation was repeated once more, followed by drying and air classification to obtain magenta colored toner particles.
First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 1.5 parts by mass of hydrophobic silica 1 is added. Then, 0.30 part by mass of metal oxide fine powder 1 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner 34 having an external additive. The physical properties of the obtained toner 34 are shown in Table 3.

<Toner Production Example 35>
<Preparation of resin particle dispersion 1>
-Styrene 75 parts by mass-n-Butyl acrylate 25 parts by mass-Acrylic acid 3 parts by mass The above mixture was dissolved, and the nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd .: Nonipol 400) 1.5 parts by mass Parts and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by mass dissolved in 120 parts by mass of ion-exchanged water, dispersed in a flask, emulsified, and slowly for 10 minutes 10 parts by mass of ion-exchanged water in which 1.5 parts by mass of ammonium persulfate was dissolved and mixed with nitrogen, followed by nitrogen substitution, and then 1-cyclohexyl-1-methylethylperoxyneodecanoate (Japan) A product name "Percyclo ND-40E", manufactured by Yufu Co., Ltd., 2.5 parts by mass of 5 parts by weight is slowly stirred for 5 minutes. Molecular weight: 313, 10-hour half-life temperature: 41.4 ° C, active oxygen content: 2.05% It was further added while stirring. Thereafter, while stirring the inside of the flask, the contents are heated in an oil bath until the temperature reaches 70 ° C., and emulsion polymerization is continued for 4 hours to disperse resin particles having an average particle diameter of 0.29 μm. Dispersion 1 was prepared.
<Preparation of resin particle dispersion 2>
-Styrene 73 parts by mass-n-Butyl acrylate 25 parts by mass-Divinylbenzene 0.25 part by mass-Acrylic acid 3 parts by mass The above mixture was dissolved and a nonionic surfactant (manufactured by Sanyo Chemical Co., Ltd.) : Nonipol 400) 1.5 parts by weight and anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) 2.2 parts by weight were dissolved in 120 parts by weight of ion-exchanged water and dispersed in a flask. The mixture was emulsified and slowly mixed for 10 minutes. Then, 10 parts by mass of ion-exchanged water in which 1.9 parts by mass of ammonium persulfate was dissolved was added, and the atmosphere was replaced with nitrogen. The product was heated in an oil bath until the product reached 70 ° C., and emulsion polymerization was continued for 4 hours to prepare resin particle dispersion 2 in which resin particles having an average particle size of 0.31 μm were dispersed. .
<Preparation of Colorant Particle Dispersion 1>
・ C. I. Pigment Red 122 20 parts by mass / Anionic surfactant 3 parts by mass (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in the colorant particle dispersion 1 was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the contained colorant particles was 0.2 μm and 1 μm. No coarse particles exceeding were observed.
<Preparation of release agent particle dispersion>
・ 50 parts by weight of release agent [refined carnauba wax 1 powder (manufactured by Nippon Wax Co., Ltd.)] (melting point = 83 ° C.)
・ 7 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
・ Ion-exchanged water 200 parts by mass The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer, and the average particle size was 0.5 μm. A release agent particle dispersion was prepared by dispersing the release agent.
<Preparation of charge control particle dispersion>
-Di-alkyl salicylic acid metal compound 5 parts by mass (charge control agent, Bontron E-88, manufactured by Orient Chemical Industries)
-3 parts by weight of anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
-Ion exchange water 78 mass parts The above was mixed and it disperse | distributed using the sand grinder mill. When the particle size distribution in this charge control particle dispersion was measured using a particle size measuring device (LA-700, manufactured by Horiba, Ltd.), the average particle size of the charge control particles contained was 0.2 μm, and 1 μm No larger coarse particles were observed.
<Preparation of liquid mixture>
-Resin particle dispersion 1 380 parts by mass-Colorant particle dispersion 1 40 parts by mass-Release agent particle dispersion 70 parts by mass The above was placed in a 1 liter separable flask equipped with a stirrer, a condenser, and a thermometer. Charged and stirred. The mixture was adjusted to pH = 5.2 using 1N potassium hydroxide.
<Agglomerated particle formation>
As a flocculant, 150 parts by mass of an 8% aqueous sodium chloride solution was added dropwise to the mixed solution, and the flask was heated to 55 ° C. while stirring the inside of the flask. At this temperature, 3 parts by mass of the resin particle dispersion 2 and 10 parts by mass of the charge control particle dispersion were added. After maintaining at 55 ° C. for 2 hours, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 3.3 μm were formed.
<Fusion process>
Then, after adding 3 parts by mass of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC), the mixture was heated to 95 ° C. while continuing stirring using a magnetic seal in a stainless steel flask. Hold for 12.5 hours. Then, the aqueous medium was cooled to obtain a dispersion of toner particles. Thereafter, an aqueous surfactant solution in which 0.200 parts by mass of nonionic surfactant 1 is dissolved in 10 parts by mass of ion-exchanged water is added to the dispersion of toner particles 1, and stirring is further continued for 1 hour. 1 surface treatment was performed.
The dispersion was subjected to solid-liquid separation with a pressure filter under a pressure of 0.4 Mpa to obtain a cake of toner particles treated with the nonionic surfactant 1. Thereafter, ion-exchanged water was added to the pressure filter until the water became full, and washing was performed at a pressure of 0.4 Mpa. This washing operation was repeated once more, followed by drying and air classification to obtain magenta colored toner particles.
First, 0.3 part by mass of hydrophobic titanium oxide 1 is added to 100 parts by mass of the obtained magenta colored toner particles, mixed with a Henschel mixer (manufactured by Mitsui Miike), and then 1.5 parts by mass of hydrophobic silica 1 is added. Then, 0.30 part by mass of metal oxide fine powder 1 was added and mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) to obtain a toner 35 having an external additive. The physical properties and the like of the obtained toner 35 are shown in Table 3.

<Toner Production Example 36>
0.35 parts by weight of nonionic surfactant 1 was added to the polymerizable monomer composition, and after the reaction was completed, the toner particle dispersion was filtered and dried without being treated with the nonionic surfactant aqueous solution. In the same manner as in Toner Production Example 1, a toner 36 having an external additive was obtained. The physical properties and the like of the obtained toner 36 are shown in Table 3.
<Toner Production Example 42>
When preparing an aqueous medium containing a dispersion stabilizer, sodium phosphate is changed to 9.3 parts by mass, 10% hydrochloric acid is changed to 2.8 parts by mass, and calcium chloride is changed to 5.8 parts by mass. A toner 42 having an external additive was obtained in the same manner as in Toner Production Example 1 except that the types and addition amounts of the nonionic surfactant and metal oxide fine powder were changed as described above. The physical properties and the like of the obtained toner 42 are shown in Table 3.
<Toner Production Example 43>
After completion of the reaction, a toner 43 having an external additive was obtained in the same manner as in Toner Production Example 1 except that the toner particle dispersion was not treated with a nonionic surfactant aqueous solution but filtered and dried. The physical properties and the like of the obtained toner 43 are shown in Table 3.

<Examples 1-36>
The toners 1 to 36 were subjected to various image evaluations shown below using the following evaluation machines. The evaluation results are shown in Tables 4-7.
<Comparative Examples 1-9>
Each of the toners 37 to 45 was subjected to various image evaluations shown below using the following evaluation machines. The evaluation results are shown in Tables 4-7.

Various image evaluations were performed as follows.
<Fog>
For the measurement of fog, an evaluation machine, which will be described later, is used as an image forming apparatus, in a normal temperature and normal humidity environment (N / N: temperature 25.0 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature 32). .5 ° C, humidity 85% RH) and low temperature and low humidity environment (L / L: temperature 10 ° C, humidity 10% RH). After the printing of 13,000 durable sheets from the beginning, it was left for 6 days in each environment, and then the fog amount of the first image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. Calculated from the formula. The smaller the value, the less fog. A fogging amount of 2% or less was regarded as no practical problem. As a transfer material used for the durability test, A4 size CLC paper (manufactured by Canon, 80 g / m ² ) was used.
Fog amount (%) = (Whiteness before printout) − (Whiteness of non-image forming portion (white background portion) of recording material after printing)
<Blotch>
The blotch is used in the normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature and low humidity environment (L / L: temperature 10 ° C., humidity 10% RH) using an evaluation machine described later. A durability test was conducted by a method of pausing for 1 minute every time two sheets were printed at a printing rate of 1%. After printing 13,000 sheets from the beginning, the sheets were left in each environment for 6 days, and then the first image sample was visually observed. Evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly present on the image, but practically no problem C: Slightly present on the image, but practically no problem D: Present on the image, practically problematic < Image density reduction>
Image density reduction is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). A durability test was conducted by using a test machine with a printing rate of 1% and a pause of 1 minute every time two sheets were printed. From the beginning, the 5,000th and 8000th endurance image samples were REFECT manufactured by Tokyo Denshoku Co., Ltd. METER
The concentration was measured using MODELTC-6DS, and the concentration difference was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Density reduction is 0.02 or less B: Density reduction is 0.03 or more and 0.06 or less C: Density reduction is 0.07 or more and 0.10 or less D: Density reduction is 0.11 or more <Solid Image Uniformity>
Solid image uniformity is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). Using a printing machine, endurance tests were performed with continuous printing at a printing rate of 1%. Immediately after printing the 10th and 4000th images and after leaving them in each environment for 7 days after printing 4000 sheets, a full solid chart respectively. Was printed and image evaluation was performed. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
The image samples were evaluated as follows: A: The toner was uniformly transferred and colored on the entire surface. B: A portion having a low density partially existed after 50 mm from the image leading edge. C: The toner was observed after 50 mm from the image leading edge. There is a part where the background of the paper is not transferred to the paper. <Initial image density>
The initial image density is an evaluation machine described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a low temperature low humidity environment (L / L: temperature 15 ° C., humidity 10% RH). , The durability test was performed with continuous printing at a printing rate of 1%, and before printing the durability test and immediately after printing the 10th and 100th images of the durability test, a single solid chart was printed on each image. The image density of was measured. The density of the image sample was measured using REFECT METER MODELTC-6DS manufactured by Tokyo Denshoku Co., Ltd. When the image density is 1.20 or more, there is no practical problem. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Density 1.30 or more B: Density 1.20 or more and 1.29 or less C: Density 1.10 or more and 1.19 or less <Fixability>
Fixing property is in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity 10% RH), and in a very low temperature and low humidity environment ( (SL / L: temperature 0 ° C., humidity 10% RH) Using an evaluation machine, which will be described later, the machine and the toner-filled cartridge are in an environment-friendly state (after being left in the environment for 24 hours) and then turned on. Immediately after the image was printed, a 200 μm wide horizontal line pattern (width 200 μm, interval 200 μm) was printed out, and the 50th printed image was used for evaluation of the fixing property. The fixing property was evaluated by rubbing the image with Sylbon paper at a load of 100 g for 5 reciprocations, and peeling of the image was evaluated by the average of the reduction rate (%) of the reflection density.
For the evaluation, bond paper having a surface smoothness of 10 [sec] or less was used. The evaluation criteria are shown below.
A: Density reduction rate less than 3% B: Density reduction rate 3% or more and less than 5% C: Density reduction rate 5% or more and less than 10% D: Density reduction rate 10% or more and less than 15% E: Density reduction rate 15% or more 20 <% <Offset resistance>
Offset resistance is described below in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using this evaluation machine, 100 sheets of solid images were printed out immediately after turning on the power and waiting for the machine and toner-filled cartridges to become familiar with the environment (after being left in the environment for 24 hours). Was evaluated. For the evaluation, an OHP film (CG3700, manufactured by Sumitomo 3M Limited) was used. The evaluation criteria are shown below.
A: No offset is generated at all B: Offset is very slight, but there is no practical problem (and the number of generated sheets is 1)
C: Offset occurred very slightly, but there was no practical problem (and 2 sheets were generated)
D: Offset occurred very slightly, but there was no practical problem (and 3 to 4 sheets generated)
E: Offset occurs and there is a problem in practical use <Fusion and fixing of toner to the development carrier and the toner layer regulating member>
The toner is fused and fixed to the developing carrier and the toner layer regulating member in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a high temperature and high humidity environment (H / H: temperature). Using an evaluation machine described later at 32.5 ° C. and humidity 80% RH), a durability test was performed by a method of pausing for 1 minute every time two sheets were printed at a printing rate of 1%. Samples were evaluated visually. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all on the image B: Slightly generated on the image, but no problem in practical use (1 to 3 slight streaks at the end)
C: Appears on the image and has practical problems (4 or more streaks at the end)
<Contamination of the latent image carrier with metal oxide fine powder (filming)>
Contamination of the latent image carrier with the metal oxide fine powder is performed in a normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), and in a low temperature and low humidity environment (L / L: temperature 15 ° C., humidity). 10% RH), a durability test was performed by continuous printing at a printing rate of 1% using an evaluation machine described later, and the 2000th durability image sample from the beginning was visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material.
A: Not generated at all B: Slightly generated, but no problem in practical use C: Generated, there is a problem in practical use <Cleaning failure>
The cleaning failure is normal temperature and humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH), low temperature low humidity environment (L / L: temperature 15 ° C., humidity 10% RH), extremely low temperature low humidity environment ( (SL / L: Temperature 0 ° C., Humidity 10% RH) Using an evaluation machine described later, 4000 sheets were continuously printed out at a printing rate of 2%, and the cleaning property and image quality were visually evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. (A with good cleaning, A, poor, ie, the elasticity of the blade is reduced, and the toner slips through, so that black horizontal streaks appear in the image. (C) occurred when there was no problem in practical use, and D was generated when there was a problem in practical use.)
<Transfer efficiency>
The transfer efficiency is described below in a normal temperature and normal humidity environment (N / N: temperature 23.5 ° C., humidity 60% RH) and in a high temperature and high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH). Using an evaluator, a durability test was performed in such a manner that every time two sheets were printed at a printing rate of 1%, the durability test was performed for 1 minute. After printing 13,000 sheets from the beginning, the latent image carrier was left for 3 days in each environment. To the intermediate transfer member (primary transfer) was measured. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. The transfer efficiency is calculated as follows.
[Transfer efficiency]
A solid image of 10 cm ² is formed on the photoconductor, and the amount of toner on the photoconductor (W1) and the amount of toner on the paper after transfer (W2) are used, and the ratio between them: W2 / W1 × 100 (% ).
A: 92% or more B: 88% or more and less than 92% C: 84% or more and less than 88% D: Less than 84% <Evaluation of toner blocking properties>
The toner blocking property was evaluated by weighing 10 g of toner in a 100 ml polycup and leaving it in a constant temperature layer at 50 ° C. for 3 days, and then evaluating the 200 mesh (aperture) sieving property. As a measuring apparatus, a powder tester (manufactured by Hosokawa Micron Corporation) having a digital vibrometer (manufactured by DEGITAL VIBRATION METERMODEL 1332 SHOWA SOKKI CORPORATION) was used.
As a measuring method, a blocking evaluation toner is put on a set 200 mesh sieve (aperture 75 μm), and the displacement value of the digital vibrometer is adjusted to 0.50 mm (peak-to-peak). Vibration was applied for 30 seconds. Thereafter, the blocking property was evaluated from the state of agglomerates of toner remaining on each sieve.
A: The remaining amount of toner on the mesh is 0.5 g or less, and the fluidity is excellent. B: The remaining amount of toner on the mesh is 0.5 g or more and 1.0 g or less, and some small aggregates are observed. C: The remaining amount of toner on the mesh is 1.0 g or more and 2.5 g or less, and even if there is an aggregate, it is easily loosened. D: The remaining amount of toner on the mesh is 2.5 g or more or there is an aggregate. Cannot be loosened <Image unevenness / Poor regulation>
Image irregularities / poor regulations are under normal temperature and humidity conditions (N / N: temperature 23.5 ° C., humidity 60% RH), high temperature high humidity environment (H / H: temperature 32.5 ° C., humidity 80% RH) Using an evaluation machine described later in a low temperature and low humidity environment (L / L: temperature 10 ° C., humidity 10% RH), after printing 8000 sheets at a printing rate of 1%, leave it in each environment for 2 days. Thereafter, the first solid black image was evaluated. A4 size CLC paper (Canon, 80 g / m ² ) was used as the transfer material. As the evaluation image, an image having a 100% density solid black image printed on the entire surface was used. The image samples were evaluated as follows.
A: There is no trace of poor regulation on the toner carrier and on the image. B: There is toner that could not be regulated on the toner carrier due to poor regulation of the toner layer regulating member and the toner carrier. Defects on the image are minor and have no practical problems C: Defects exist on the image and have practical problems (evaluator)
Using a commercially available LBP-2710 (manufactured by Canon Inc.) modified to a process speed of 220 mm / s, the product toner is extracted from the commercially available magenta cartridge, the interior is cleaned by air blow, and the toner of the present invention In the case of other cyan, yellow and black cartridges, the product toner was removed and inserted into each station for evaluation.

Claims (7)

Toner particles A having containing a binder resin, a colorant, and a nonionic surfactant,
A toner having a <br/> the metallic oxide fine powder,
The nonionic surfactant contains a block copolymer of alkylene glycol,
Number average molecular weight measured by gel permeation chromatography of a block copolymer of alkylene glycol is 1,200 to 40,000,
The extraction amount of the nonionic surfactant is extracted with methanol from the toner and A (ppm), the theoretical ratio obtained from the particle size distribution of the toner using the precision particle size distribution measuring apparatus based on a pore electrical resistance method when the surface area B ^(m 2 / g), the value of the ratio of the B of the a (a / B) ^{is, 0.02 × 10 -3 (g /} m 2) or more 9.00 × 10 ^{- 3} (g / m ² ) or less,
The toner according to claim 1, wherein the metal oxide fine powder has a volume-based median diameter (D50) of 0.07 μm or more and 2.00 μm or less. The toner according to the composition der Ru請 Motomeko 1 represented by the block copolymers of the alkylene glycol is represented by the following general formula (1).

[In Formula (1), a, b and c are integers, a a> 0, a b ≧ 15, a c ≧ 0, it is a + c ≧ 4. ] The metal hydrophobicity as measured by methanol titration method of the oxide fine powder, the toner according to 請 Motomeko 1 or 2 Ru der 15.0. The metal oxide fine powder is measured using an adsorption equilibrium measuring apparatus in isotherms of adsorption and desorption of water at temperature of 28 ° C., the amount of adsorbed water adsorption process at a relative vapor pressure 80% RH, 0. the toner according to any one of 01 mass% to 1.50 mass% der Ru請 Motomeko 1-3. Total pore volume measured by 300.0nm following ranges pore diameter 1.7nm or more of the metal oxide fine powder, any one of 0.200 cm ³ / g Ru der following 請 Motomeko 1-4 The toner described in 1. The toner particles A is toner according to any one of Der Ru請 Motomeko 1-5 those produced by a suspension polymerization method. The toner particles A are in an aqueous medium .
Toner particles B before containing the nonionic surfactant ;
Any said mixing <br/> nonionic surfactant, the nonionic surfactant said toner particles Ru der and produced by the steps of incorporating the B 請 Motomeko 1-6 The toner according to claim 1 .

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