JP2006163120A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner excellent in fixing performance, that is, low-temperature fixing property and offset resistance, excellent also in charge stability, having good transferability and fogging property, and giving a high-definition image. <P>SOLUTION: The toner includes at least a binder resin, a colorant and at least one or more of the compounds represented by general formulae (1) and (2) and has two different endothermic peaks P1 and P2 in the temperature range of 55-120°C on a DSC curve when temperature up measured by DSC. In general formulae (1) and (2), R<SB>1</SB>-R<SB>11</SB>are each a 1-6C alkyl and may be the same or different. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a toner used in an image forming method and a toner jet recording method for revealing an electrostatic charge latent image.

  Conventionally, many methods are known as electrophotographic methods. The electrophotographic method generally uses a photoconductive material, forms an electric latent image on an electrostatic image carrier (hereinafter also referred to as a photoreceptor) by various means, and then develops the latent image with toner. To make a visible image. If necessary, the toner image is transferred onto a transfer material such as paper, and then the toner image is fixed on the transfer material by heat, pressure or the like to obtain a copy.

  The fixing device in the electrophotographic image forming apparatus uses unfixed toner formed on the surface of a transfer material by a direct method or an indirect (transfer) method using a toner (developer) made of heat-meltable resin or the like. This is an apparatus for heat-fixing an image as a fixed image on a transfer material surface. Conventionally, a heat roller method or a film heating method has been used as such a fixing device.

  In addition, image forming apparatuses such as LBPs and copiers have become higher in resolution and higher in speed as a technology direction. In general, when image formation is performed at a higher speed, a large amount of heat energy is instantaneously required while applying a higher pressure in the fixing device. For this reason, an unfavorable situation occurs in which the fixing device needs to be large and complicated.

  From these viewpoints, the toner used in the image forming apparatus as described above preferably exhibits high sharp melt property when heated, and attempts have been made to achieve high sharp melt property by improving the binder of the toner. . Such a toner is excellent not only in low-temperature fixability but also in color mixing at the time of full-color image formation, so that the color reproduction range of the obtained fixed image can be expanded.

  As other measures, many methods have been proposed for solving the above-mentioned problems by adding a wax component such as low molecular weight polyethylene or polypropylene to the toner. However, in order to achieve a sufficient effect, it is necessary to add a large amount of the wax component as described above to the toner. In this case, filming on the photosensitive member or the surface of the toner carrier such as a carrier or a sleeve. Contamination may occur and new problems such as image degradation may occur.

  In addition, when the amount of the wax component added is small, it is necessary to newly provide a device for supplying a slight amount of offset preventing liquid or an auxiliary cleaning member such as a winding type cleaning web or a cleaning pad. Produce. In particular, when an OHP film is used as a transfer material during full-color image formation, transparency of the fixed image and haze (cloudiness) are caused due to high crystallization of the wax component and a difference in refractive index from the binder resin. There is still room for consideration in solving the problem of worsening.

  In order to solve these problems, an attempt to improve the fixing property by adding two or more kinds of waxes having different melting points is known (for example, see Patent Documents 1, 2, and 3). . However, it is difficult to improve various properties required of the toner to a high degree by simply including a wax component in the toner.

Further, a technique for reducing the amount of residual monomer in the toner by using a polymerization initiator having a specific structure has been disclosed, but a polymerization initiator having a specific structure generates a specific ether compound, and the presence thereof. It is not disclosed that the image quality is improved (see, for example, Patent Document 4).

Further, although there is a technique disclosed for the presence of a specific ether compound (see, for example, Patent Document 5), there is no discussion about the correlation with the thermal history of the toner. It became clear that it was not satisfactory. Thus, improvement of various properties as a toner is still desired.
JP-A-5-303232 JP-A-10-268559 Japanese Patent Laid-Open No. 10-268560 JP 2002-251037 A JP 7-140701 A

  The problem to be solved by the present invention is to provide a toner excellent in fixing performance, that is, to provide a toner excellent in low-temperature fixability and offset resistance.

  Furthermore, the problem to be solved by the present invention is to provide a toner capable of obtaining a high-definition image having excellent charging stability and excellent transferability and fog characteristics.

  As a result of intensive studies by the present inventors, it is a toner containing at least a binder resin and a colorant, and the toner contains at least one compound represented by the following general formula (1) or (2). The toner has two different endothermic peaks P1 and P2 in the temperature range of 55 to 120 ° C. in the DSC curve at the time of temperature rise measured by DSC, and the endothermic peak P1 is on the lower temperature side than the endothermic peak P2. It has been found that a certain peak is effective for obtaining a toner which is excellent in low-temperature fixability and anti-offset properties and can obtain a high-definition image, and has completed the present invention.

R < ₁ > -R < ₁₁ > in General formula (1) and General formula (2) is a C1-C6 alkyl group, and may mutually be same or different.

According to the present invention, a toner having excellent low-temperature fixability and high-temperature offset resistance can be obtained. Further, it is possible to provide a toner that is excellent in charging stability and that can provide a high-definition image having good transferability and fog characteristics.

  In order to satisfy the fixing performance of the toner, it is indispensable to achieve a high degree of compatibility between the conflicting performances of low-temperature fixability and high-temperature offset resistance. As a result of intensive studies by the present inventors, it has been found that the toner has good fixing performance when a specific ether compound is present in the toner and the toner has a certain thermal history.

  Specifically, the toner contains at least a binder resin, a colorant, and a wax component, and the toner contains at least one compound represented by the following structural formula, and the toner is measured by DSC. In the DSC curve at the time of temperature rise, it is essential to have two different endothermic peaks P1 and P2 (P1 is lower than P2) in the temperature range of 55 to 120 ° C. I was able to find satisfaction.

  R1 to R11 in the general formula (1) and the general formula (2) are alkyl groups having 1 to 6 carbon atoms, and may be the same as or different from each other.

  Here, in the DSC curve of the toner, when there are no two different endothermic peaks P1 and P2 (P1 is at a lower temperature side than P2) in the temperature range of 55 to 120 ° C., both low-temperature fixability and high-temperature offset resistance are obtained. Alternatively, either of them may not be satisfied. Even when the two different peaks are present, if the ether having the structure described above is not present, not only the fixing performance is not satisfied, but also the toner charging performance is insufficient. There is a case.

  Although details about this reason are not clear, two different endothermic peaks in the temperature range of 55 to 120 ° C. contribute to low temperature fixing performance and high temperature offset resistance such as suppression of contamination of the surface heating unit and fixing roller, respectively. Thus, it is considered that both of the performances can be satisfied, but the ether compound having the above structure is involved in expressing the effects in a highly compatible manner.

  That is, it is considered that the ether compound having the above structure is excellent in compatibility with the binder resin by having a hydrophobic part (alkyl group) and a hydrophilic part (oxygen atom). Therefore, when it is contained in the toner, it is considered that it is dispersed in a nearly uniform state. It is considered that this also interacts with the constituent elements resulting from each endothermic peak in the toner, and has a function of making the toner binder composition and various additives uniform without being localized.

Here, when R _{1 to} R ₁₁ in the ether compound (general formula (1) and general formula (2)) are an alkyl group having 7 or more carbon atoms, and when R _{1 to} R ₁₁ are not an alkyl group, The compatibility of the ether compound with the binder resin may be insufficient, or the interaction with each constituent material in the toner may be insufficient, and the effects of the present invention may not be exhibited.

  Examples of the structure of the ether compound include the following structures.

  Among these, a compound represented by the following structural formula is preferable for obtaining the effects of the present invention.

  One or more ether compounds may be contained, and the ether compound having another structure may be included. The content at that time is the total amount of the ether compounds contained.

  Further, the content of the ether compound is preferably 5 to 800 ppm with respect to the toner in order to exhibit the effects of the present invention. When the amount is less than 5 ppm, the fixing performance may be insufficient due to a small addition amount, and when the amount exceeds 800 ppm, the addition performance tends to be excessive and similarly the fixing performance may be insufficient. .

Therefore, the present inventors prefer that the binder composition having these two different endothermic peaks exist in the toner with a certain degree of domain rather than the parts corresponding to various additives being completely compatible. I also think. And the content of the ether compound is more preferably 10 to 500 ppm. The content of the ether compound can be adjusted by, for example, the blending amount of the ether compound at the time of toner production.

  The amount of the ether compound is not particularly limited as long as it is a method capable of quantifying in ppm units, and can be performed using an ordinary instrument capable of quantitatively detecting the ether compound. For example, it can be carried out by gas chromatography provided as a detector such as an FID detector or a mass spectrum, or by liquid chromatography provided with a UV spectrum or a differential refractometer.

  In this example, the amount of the ether compound contained in the toner was measured and evaluated using a multiple headspace extraction method. This method will be described below.

  The multiple headspace extraction method is a method in which a sample is accommodated in an airtight container having a predetermined volume, the airtight container is heated as necessary, and the gas phase in the airtight container is extracted (extracted). The gas phase extraction is performed a plurality of times as necessary.

<Devices and instruments>
HS40XL manufactured by Perkin Elmer Japan Co., Ltd. is used for the headspace sampler, and TRACE GC, TRACE MS manufactured by ThermoQuest Co., Ltd. is used for GC / MS.

  A head vial sampler is equipped with a sample vial which is a sealed container for storing a sample. A sample is stored in the sample vial, and the gas phase in the sample vial is collected under the following conditions. As the sample vial, a glass vial for headspace analysis (22 ml) manufactured by PerkinElmer Japan Co., Ltd. is used.

(1) Headspace sampler conditions / sample amount: 50 mg
・ Vial: 22ml
Sample temperature: 120 ° C
・ Needle temperature: 150 ℃
・ Transfer line temperature: 180 ℃
・ Retention time: 60 min
・ Pressurization time: 0.25 min
・ Injection time: 0.08 min

The sample vial is connected to a gas chromatography, and the gas collected using the multiple headspace extraction method is analyzed, for example, under the following conditions.
(2) GC conditions / column: HP5-MS (0.25 mm, 60 m)
Column temperature: 40 ° C. (3 min), 70 ° C. (2.0 ° C./min), 150 ° C. (5.0 ° C./min), 300 ° C. (10.0 ° C./min)
・ Split ratio 50: 1

  In the determination of the ether compound, a standard sample and a toner sample are prepared, and a multiple headspace extraction method is applied to these samples to detect the ether compound from each sample.

(3) Preparation of standard sample First, as a standard sample for ether compound determination, a methanol solution having an ether compound concentration of 1000 ppm is prepared, and 5 μl of this solution is made of 22 ml of glass using a 10 μl volume microsyringe. Place in a vial and seal quickly with a high-temperature analytical septum.

(4) Preparation of Toner Sample 50 mg of toner is put in a 22 ml glass vial and sealed with a high-temperature analysis septum to prepare a sample.

(5) Measurement and Analysis First, a standard sample of the ether compound is measured using a multiple headspace extraction method for collecting a certain amount of gas phase, and the total peak area per 0.005 μl of the ether compound is obtained. Since the sensitivity of GC varies from day to day, the peak area per 0.005 μl of ether compound needs to be examined for each measurement. Similarly, toner samples are measured using multiple headspace extraction methods.

  Next, in the obtained chromatograph, the volume of the ether compound in the toner sample is obtained by proportional calculation from the total peak area obtained by the multiple headspace extraction method of the toner sample and the total peak area of the standard sample. The calculated value is multiplied by the specific gravity of the ether compound to perform weight conversion, and the concentration of the ether compound in the toner is calculated.

  The calculation of each peak area by the multiple headspace extraction method can be performed using the following approximate expression.

  In the approximate expression, ΣAn represents the total peak area, and An represents the n-th extraction peak area.

  When the structure of the ether compound contained in the toner particles is unknown, the structure is specified by an analysis method such as gas chromatography mass spectrometry (GC-MS) or liquid chromatography mass spectrometry (LC-MS). It is possible to quantify with the above compound by the above-mentioned method.

  The intensity ratio (P1 / P2) between the endothermic peaks P1 and P2 is preferably 0.1-10. If the intensity ratio of the endothermic peak is less than 0.1, the fixing property on the low temperature side may be inferior, and if the intensity ratio of the endothermic peak exceeds 10, contamination of the surface heating unit or the fixing roller may occur. The intensity ratio can be adjusted by, for example, the type and amount of a component in the toner, for example, wax.

  Furthermore, it is a more preferable embodiment that the peak P1 is a peak derived from an ester wax and the endothermic peak P2 is a peak derived from a hydrocarbon wax.

  In the DSC measurement using a differential scanning calorimeter of toner in the present invention, for example, DSC-7 manufactured by PerkinElmer or DSC-2920 manufactured by TA Instruments Japan can be used.

  In the measurement of endothermic peak temperature of toner and wax, when using DSC-2920 manufactured by TA Instruments Japan, an aluminum pan is used as a measurement sample, an empty pan is set for control, and an amplitude is ± 1 from 20 ° C. The temperature is raised to 180 ° C. at a temperature rising rate of 2 ° C./min while applying a modulation of 5 ° C. and a period of 1 / min.

  The intensity of the endothermic peak in the present invention is the height ΔH from the baseline to the peak top per unit mass by using the DSC measurement method (the value obtained by dividing the measured peak height by the mass of the measurement sample). (MW / mg)). The glass transition temperature Tg of a binder resin or a release agent can also be measured by the DSC measurement method.

  Even if the peaks P1 and P2 in the toner of the present invention are overlapped, it is only necessary that the peak top of each other can be confirmed. In this case, the endothermic peak intensity is defined as a peak top at which each peak can be confirmed, and ΔH obtained therefrom.

  Hereinafter, preferred embodiments of the toner of the present invention will be further described.

  In the present invention, in order to obtain good charging performance such as further excellent transferability and fog characteristics, the toner shape is preferably spherical. Specifically, it is preferable that the average circularity of the toner is 0.940 or more, so that the contact area between the toner particles and the photoreceptor is reduced, and the toner is caused by mirror image force, van der Waals force, or the like. Since the adhesion force of the particles to the photoconductor is reduced, the transfer efficiency is high and the toner consumption is reduced.

  In addition, when the toner shape is spherical, when the essential requirements of the present invention are satisfied, each material constituting the toner tends to exist at an equal distance from the toner surface layer. This is a preferred form for expression.

  Furthermore, since the toner with the above average circularity has a high circularity and has a shape close to a sphere, it is easy to uniformly rub the entire surface when compared with an irregular shaped toner having uneven portions. Therefore, it is particularly excellent in charging uniformity.

  At this time, the mode circularity is more preferably 0.99 or more in the circularity distribution of the toner. When the mode circularity is 0.99 or more, it means that most of the toner particles have a shape close to a true sphere, and the above action becomes more remarkable, and the fixing performance and the triboelectric charging characteristics are further improved. .

  Here, the “mode circularity” means that the circularity is 0.40 to 1.00 divided by 61 every 0.01, and the measured circularity of the toner is assigned to each divided range according to the circularity. This is the lower limit value of the division range in which the frequency value is maximum in the circularity frequency distribution.

  If the average circularity of the toner is less than 0.940, it may be difficult to obtain toner charging uniformity, and fogging and uneven density may occur. Further, the fixing performance may be insufficient.

  The average circularity in the present invention is used as a simple method for quantitatively expressing the shape of the particles, and is obtained for each particle according to the following formula (1) for a particle group having a circle equivalent diameter of 3 μm or more. It is a value obtained by dividing the sum of all the particles of circularity (ai) by the total number of particles (m).

  The circularity, the average circularity, and the mode circularity can be obtained from a particle image of toner particles. In the present invention, the measurement can be performed using a flow type particle image analyzer “FPIA-1000” manufactured by Toa Medical Electronics.

  The measurement method is as follows. A dispersion is prepared by dispersing 5 mg of toner in 10 ml of water in which about 0.1 mg of a surfactant is dissolved, and ultrasonic waves (20 kHz, 50 W) are irradiated to the dispersion for 5 minutes, and the dispersion concentration is set to 5000 to 2 The number of particles / μl is measured by the above apparatus, and the average circularity and mode circularity of a particle group having an equivalent circle diameter of 3 μm or more are obtained.

  The average circularity in the present invention is an index of the degree of unevenness of the toner particles, and indicates 1.000 when the toner is a perfect sphere, and the circularity becomes smaller as the surface shape becomes more complicated.

  In this measurement, the reason for measuring the circularity only for the particle group having an equivalent circle diameter of 3 μm or more is as follows. The particle group having an equivalent circle diameter of less than 3 μm includes a large number of particle groups of external additives that exist independently of the toner particles. Therefore, when the object to be measured is expanded to less than 3 μm, the effect of the toner particles This is because the circularity of the group cannot be estimated accurately.

  Next, the particle size of the toner will be described.

  In the present invention, the toner of the present invention preferably has a weight average particle diameter of 3 to 10 μm in order to develop finer latent image dots faithfully in order to further improve the image quality. The toner preferably has a weight average particle diameter of 4 to 8 μm. In a toner having a weight average particle diameter of less than 3 μm, there may be a large amount of toner remaining on the photoreceptor due to a decrease in transfer efficiency. In such a case, it is difficult to suppress the photoconductor scraping and toner fusion in the contact charging step.

  Furthermore, in addition to an increase in the surface area of the entire toner, the fluidity and agitation as a powder decrease, and it becomes difficult to uniformly charge individual toner particles, so that fog and transferability tend to deteriorate. This is not preferable for the toner used in the present invention because it tends to cause non-uniform image unevenness other than scraping and fusing.

  When the weight average particle diameter of the toner exceeds 10 μm, the characters and line images are likely to be scattered and high resolution is difficult to obtain. In order to obtain higher resolution, it is preferable to use a toner of 8 μm or less.

  The weight average particle size and number average particle size of the toner of the present invention can be measured by various known particle size measuring devices such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co.). Specifically, it can be measured as follows.

Using a Coulter Multisizer (manufactured by Coulter), an interface (manufactured by Nikka) and a PC 9801 personal computer (manufactured by NEC) are connected to output the number distribution and volume distribution. As the electrolytic solution, a 1% NaCl aqueous solution prepared using primary sodium chloride can be used. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. The measurement procedure is as follows.

  2 to 20 mg of a measurement sample is added to 100 to 150 ml of the electrolytic solution. The electrolyte in which the sample is suspended is subjected to a dispersion process for about 1 to 3 minutes with an ultrasonic disperser, and the volume and number of toner particles having a size of 2 μm or more are measured with the Coulter Multisizer using a 100 μm aperture. Calculate the distribution. From this, the weight average particle diameter (D4) and the number average particle diameter (D1) are determined.

  Although the toner according to the present invention can be produced by a pulverization method, the toner particles obtained by this pulverization method are generally indefinite shape, and the average circularity which is a preferable requirement of the toner according to the present invention is high. In order to obtain a physical property of 0.940 or more (preferably a mode circularity of 0.99 or more), it is necessary to perform mechanical / thermal or some treatment.

  Therefore, in the present invention, it is preferable to produce toner particles by a polymerization method. Examples of the toner production method by polymerization include a direct polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion association polymerization method, and a seed polymerization method. Among these, the balance between the particle size and the particle shape is balanced. In view of easiness, it is particularly preferable to produce by suspension polymerization.

  In this suspension polymerization method, a colorant (in addition, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) is uniformly dissolved in a polymerizable monomer that forms a binder resin by polymerization. Alternatively, after dispersing to form a polymerizable monomer composition, the polymerizable monomer composition is placed in a continuous layer (for example, an aqueous medium such as an aqueous phase) containing a dispersion stabilizer using a suitable stirrer. The toner is dispersed and polymerized to obtain a toner having a desired particle size. When the toner is produced by this suspension polymerization method, since the individual toner particle shapes are almost spherical, the average circularity is 0.940 or more, especially the mode circularity is 0.99 or more. It is easy to obtain toner, and such toner has a high transferability because the distribution of charge amount is relatively uniform.

  In the present invention, the polymerization initiator used is preferably a polymerization initiator having a 10-hour half-life temperature of 40 ° C. or more and less than 60 ° C. When the 10-hour half-life temperature is less than 40 ° C., it may be difficult to control the polymerization reaction, and the fixing performance tends to deteriorate, for example, the uniform dispersibility in the toner is poor. Further, when the 10-hour half-life temperature is 60 ° C. or higher, the progress of the polymerization reaction tends to be slow, and the low-temperature fixing performance of the toner tends to deteriorate.

  Furthermore, the polymerization initiator has a structure represented by the following general formula (3). It is preferable for expressing the effects of the present invention.

In general formula (3), R ₁₂ is unsubstituted or substituted alkyl having 3 to 8 carbon atoms, unsubstituted or substituted cycloalkyl having 3 to 8 carbon atoms, unsubstituted or substituted having 3 to 8 carbon atoms R ₁₃ , R ₁₄ and R ₁₅ each represent an alkyl group, and the total number of carbon atoms of R ₁₃ , R ₁₄ and R ₁₅ is 3
It is 5 or less.

  The peroxyesters represented by the general formula (3) are particularly effective for suppressing residual monomers and efficiently polymerize, and may cause contamination of the surface heating unit and the fixing roller. Since the production | generation of an ultra-low molecular weight component can be suppressed, it is preferable when expressing the effect of this invention.

In addition, when the carbon number of R ₁₂ is less than 2, it is not preferable because the polymerization in the suspended particles tends to be difficult to proceed, and when the carbon number is 9 or more, it may be difficult to control the polymerization reaction.

Furthermore, it is preferable that the sum total of carbon number of R < ₁₃ >, R <_14> , R < ₁₅ > is 3-5. When the total number of carbon atoms is 6 or more, it is difficult to control the polymerization reaction, the uniform distribution in the toner tends to be insufficient, and the fixing performance may be insufficient.

  Examples of the polymerization initiator used in the present invention include tert-butyl peroxyacetate, tert-butyl peroxylaurate, tert-butyl peroxypivalate, tert-butyl peroxy-2-ethylhexanoate, tert-butylperoxyisobutyrate, tert-butylperoxyneodecanoate, tert-hexylperoxyacetate, tert-hexylperoxylaurate, tert-hexylperoxypivalate, tert-hexylperoxy-2- Ethyl hexanoate, tert-hexylperoxyisobutyrate, tert-hexylperoxyneodecanoate, tert-butylperoxybenzoate, α, α'-bis (neodecanoylperoxy) diisopropylbenze , Cumyl peroxyneodecanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1 -Cyclohexyl-1-methylethylperoxyneodecanoate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, 2,5-dimethyl-2,5 -Bis (benzoylperoxy) hexa Tert-butylperoxy-m-toluoyl benzoate, bis (tert-butylperoxy) isophthalate, tert-butylperoxymaleic acid, tert-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) hexane, tert-amylperoxyneodecanoate, tert-amylperoxypivalate, tert-amylperoxy-2-ethylhexano Peroxyesters such as tert-amyl peroxy normal octoate, tert-amyl peroxyacetate, tert-amyl peroxyisononanoate, tert-amyl peroxybenzoate; benzoyl peroxide, lauroyl peroxide Diacyl peroxide such as dibutyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-sec-butylperoxide Organic peroxides such as peroxydicarbonates such as oxydicarbonate;

Among these, those suitable for the present invention are the peroxyesters described above. If necessary, two or more of these peroxides can be used, or 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, , 1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile, or other azo polymerization initiators alone or in combination It is also possible to use it.

  Furthermore, from the viewpoint of more effectively using the action according to the present invention, the polymerizable monomer preferably contains styrene or styrene having a substituent on the aromatic ring, and (meth) acrylic acid ester as essential components. . When the substance is not contained, the uniform dispersibility of the wax in the toner tends to be impaired, and the fixing performance of the toner tends to deteriorate.

  When the toner of the present invention is produced by a polymerization method, examples of the polymerizable monomer constituting the polymerizable monomer composition include the following.

  Examples of the polymerizable monomer include styrene monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, and p-ethylstyrene; methyl acrylate, ethyl acrylate, -N-butyl acrylate, isobutyl acrylate, -n-propyl acrylate, -n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate Acrylic acid esters such as methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, methacrylic acid-n-butyl, isobutyl methacrylate, methacrylic acid-n-octyl, dodecyl methacrylate, 2-ethylhexyl methacrylate , Stearyl methacrylate, meta Phenyl acrylic acid, dimethylaminoethyl methacrylate, methacrylic acid esters such as diethylaminoethyl methacrylate; acrylonitrile; methacrylonitrile; acrylamide; monomers, and the like. These monomers can be used as a mixture.

  In the present invention, a crosslinking agent can be used as necessary. As the crosslinking agent used in the present invention, a compound having two or more polymerizable double bonds is mainly used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, and the like; A divinyl compound such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and a compound having three or more vinyl groups are used alone or as a mixture. The amount to be added needs to be adjusted according to the polymerization initiator used, the type of crosslinking agent, and the reaction conditions, but is generally 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer. It is.

  In the toner of the present invention, various known resins can be used as the binder resin for the toner. Examples of such a resin mainly include a polymer of the polymerizable monomer and a polyester resin. The binder resin may be one type of resin or a plurality of types of resins.

  Various known colorants can be used in the present invention. For example, carbon black, a magnetic material, and the one that is toned to black using the following yellow / magenta / cyan colorants are used. In addition, when the toner of the present invention is produced by the above-described polymerization method, it is necessary to pay attention to the polymerization inhibition property and water phase transfer property of the colorant. The colorant is preferably subjected to surface modification (for example, a hydrophobic treatment without polymerization inhibition). In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 74, 83, 93, 94, 95, 109, 110, 111, 128, 129, 147, 1
68, 180, etc. are preferably used.

  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. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 254 are particularly preferred.

  As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like can be used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used.

  These colorants can be used alone or in combination, and further in a solid solution state. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in the toner. The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the resin.

  Further, the toner of the present invention can be used as a magnetic toner containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, hematite and ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium and tin of these metals. And alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, and mixtures thereof.

  The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When the toner of the present invention is produced by a polymerization method, the surface modifying agent, which is a substance that does not inhibit polymerization, Those subjected to hydrophobic treatment are preferred. Examples of such surface modifiers include silane coupling agents and titanium coupling agents.

  These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount to be contained in the toner particles is about 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight with respect to 100 parts by weight of the binder resin.

  When the toner of the present invention is produced by a polymerization method, the polymerization may be performed by adding a resin to the polymerizable monomer composition. For example, hydrophilic functional groups such as amino groups, carboxylic acid groups, hydroxyl groups, sulfonic acid groups, glycidyl groups, and nitrile groups that cannot be used because monomers are water-soluble and dissolve in aqueous suspension to cause emulsion polymerization. When it is desired to introduce a polymerizable monomer component containing styrene into a toner, a random copolymer, a block copolymer, or a graft copolymer of these with a vinyl compound such as styrene or ethylene is formed into a copolymer form. Or in the form of a polycondensate such as polyester or polyamide, or a polyaddition polymer such as polyether or polyimine. When such a high molecular polymer containing a polar functional group is allowed to coexist in the toner, it is possible to phase-separate the above-mentioned wax component, to increase the encapsulation, and to obtain a toner with better blocking resistance and developability. it can.

Among these resins, the effect is particularly great by containing a polyester resin. I think this is because of the following reasons. Since the polyester resin contains many ester bonds which are functional groups having relatively high polarity, the polarity of the resin itself becomes high. Due to its polarity, when a toner is produced by a polymerization method, polyester tends to be unevenly distributed on the surface of the droplets of the polymerizable monomer composition in the aqueous dispersion medium, and the polymerization proceeds while maintaining this state. Become toner. For this reason, when the polyester resin is unevenly distributed on the toner surface, the surface state and the surface composition become uniform. As a result, the chargeability becomes uniform, and a very good developability can be obtained due to a synergistic effect with the good inclusion property of the release agent.

  The toner of the present invention may further contain other components other than the binder resin and the colorant. Examples of such other components include a release agent and a charge control agent.

  Examples of release agents that can be used in the present invention include petroleum waxes such as paraffin wax, microcrystalline wax, petrolatum and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, and polyethylene. Polyolefin waxes and derivatives thereof, natural waxes such as carnauba wax and candelilla wax and derivatives thereof, and the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products.

  In addition, fatty acids such as higher aliphatic alcohols, stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes, silicone oils, etc. are also used. it can.

  Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability.

  The following compounds are mentioned as a preferable ester compound which comprises ester wax. The ester wax suitably used in the present invention preferably has a weight average molecular weight (Mw) of 350 to 1,500 from the viewpoint of improving low-temperature fixability and OHP transmittance. When Mw is less than 350, the fixability on the low temperature side tends not to work effectively, and when it exceeds 1,500, the OHP transmittance tends to deteriorate.

In general formula (IV), a and b are integers of 0 to 4, and a + b is 4. R ₁ and R ₂ are each independently an organic group having 1 to 40 carbon atoms. m and n are integers of 0 to 40, and m and n are not 0 at the same time.

In general formula (V), a and b are integers of 0 to 3, and a + b is 1 to 3. R ₁ and R ₂ are each independently an organic group having 1 to 40 carbon atoms. R ₃ is a hydrogen atom or 1 carbon atom
These are the above organic groups. k is an integer of 1 to 3, and a + b + k = 4. m and n are integers of 0 to 40, and m and n are not 0 at the same time.

In the general formula (VI), R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ represents an organic group having 1 to 40 carbon atoms.

In general formula (VII), R ₁ and R ₃ are organic groups having 1 to 40 carbon atoms, and R ₁ and R ₃ may be the same or different. R ₂ represents an organic group having 1 to 40 carbon atoms.

In general formula (VIII), a is an integer of 1-4, b is an integer of 1-4, and a + b is 4. R ₁ is each independently an organic group having 1 to 40 carbon atoms. m and n are integers of 0 to 40, and m and n are not 0 at the same time.

  Further, hydrocarbon waxes preferable for the present invention include hydrocarbon waxes by the Fischer-Tropsch method, and when the wax is used, the effect of improving the fixing property is further enhanced. These wax components may be added with an antioxidant within a range that does not affect the chargeability of the toner. Moreover, the weight average molecular weight (Mw) of the hydrocarbon wax used suitably is 300-4,000. When Mw is less than 300, the effect as a wax does not tend to work sufficiently, and contamination of the surface heating unit and the fixing roller tends to occur. When Mw exceeds 4,000, the OHP transmittance tends to deteriorate.

  The Mw of the wax can be measured by a known method such as gel permeation chromatography.

  The average molecular weight such as Mw of the wax can be adjusted depending on, for example, the type of wax, the wax production conditions, and the type of monomer used for wax production.

And it is preferable that the said mold release agent contains 1-30 mass% with respect to binder resin. More preferably, it is 3 to 25% by mass. If the content of the release agent is less than 1% by mass, the effect of adding the release agent is not sufficient, and further, the offset suppressing effect may be insufficient. On the other hand, if it exceeds 30% by mass, the long-term storage stability is deteriorated and the dispersibility of the toner material such as the colorant is deteriorated, which may lead to deterioration of the coloring power of the toner and deterioration of image characteristics. In addition, exudation of the release agent is likely to occur, and the durability under high temperature and high humidity may be inferior. Further, since a large amount of the release agent is included, the toner shape tends to become distorted.

  The toner of the present invention may contain a charge control agent in order to further stabilize the charge characteristics. As the charge control agent, a known one can be used, and a charge control agent that has a high charging speed and can stably maintain a constant charge amount is particularly preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous medium is particularly preferable.

  Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfones Examples thereof include a polymer compound having an acid or carboxylic acid group in the side chain, a boron compound, a urea compound, a silicon compound, and a calixarene. Examples of positive charge control agents include quaternary ammonium salts, polymer compounds having the quaternary ammonium salt in the side chain, guanidine compounds, nigrosine compounds, imidazole compounds, and the like.

  As a method for adding the charge control agent to the toner, there are a method of adding the charge control agent inside the toner particles and a method of adding the charge control agent to the toner particles, and either method may be adopted depending on the kind of the charge control agent. The amount of use of these charge control agents is determined primarily by various conditions such as the type of binder resin, the presence or absence of other additives, and the toner production method including the dispersion method, and is uniquely limited. Although it is not a thing, when adding internally, it becomes like this. Preferably it is 0.1-10 mass parts with respect to 100 mass parts of binder resin, More preferably, it is used in 0.1-5 mass parts. In addition, when externally added, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

  In the polymerization method for producing the toner of the present invention, generally, the above-described colorant, magnetic powder, release agent and other toner compositions are appropriately added to the polymerizable monomer to produce a homogenizer, ball mill, colloid mill, A polymerizable monomer composition is obtained by uniformly dissolving or dispersing by a disperser such as an ultrasonic disperser. This is suspended in an aqueous medium containing a dispersion stabilizer. At this time, if a high-speed disperser such as a high-speed stirrer or an ultrasonic disperser is used to make a desired toner particle size at a stretch, the particle size of the obtained toner particle becomes sharp.

  The polymerization initiator may be added at the same time when other additives are added to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous dispersion medium. It can also be added during granulation or immediately after granulation. As the aqueous medium, water or a liquid containing water and a water-soluble component such as a lower alcohol and mainly containing water is usually used.

  After granulation, stirring may be performed using a normal stirrer to such an extent that the particle state is maintained and the particles are prevented from floating and settling.

  When the toner of the present invention is produced by a polymerization method, a known surfactant, organic dispersant, or inorganic dispersant can be used as a dispersion stabilizer. In particular, inorganic dispersants are less likely to produce harmful ultrafine powders, and because of their steric hindrance, dispersion stability is obtained, so even if the reaction temperature is changed, stability is not easily lost, and cleaning is easy and does not adversely affect the toner. Therefore, it can be preferably used.

Examples of such inorganic dispersants include polyvalent metal phosphates such as calcium phosphate, magnesium phosphate, aluminum phosphate and zinc phosphate, carbonates such as calcium carbonate and magnesium carbonate, calcium metasuccinate, calcium sulfate and barium sulfate. Inorganic oxides such as inorganic salts, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, silica, bentonite and alumina can be mentioned.

  When these inorganic dispersants are used, they may be used as they are, but in order to obtain finer particles, the inorganic dispersant particles may be generated and used in an aqueous medium. For example, in the case of calcium phosphate, it is possible to produce a water-insoluble calcium phosphate by mixing a sodium phosphate aqueous solution and a calcium chloride aqueous solution under high-speed agitation, which enables more uniform and fine dispersion of calcium phosphate.

  At the same time, a water-soluble sodium chloride salt is produced as a by-product. However, if a water-soluble salt is present in the aqueous medium, dissolution of the polymerizable monomer in water is suppressed, and an ultrafine toner based on emulsion polymerization is produced. Since it becomes difficult to generate | occur | produce, it is more convenient. The inorganic dispersant can be almost completely removed by dissolution with an acid or alkali after the polymerization.

  These inorganic dispersants are desirably used alone in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer. In some cases, 0.001 to 0.1 parts by mass of a surfactant may be used in combination.

  Examples of the surfactant include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium stearate, potassium stearate and the like.

  After the polymerization is completed, the polymerized toner particles are filtered, washed and dried by a known method, and if necessary, inorganic fine powder is mixed and adhered to the surface, whereby the toner of the present invention can be obtained. Moreover, it is one of the desirable forms of this invention to put a classification process in a manufacturing process and to cut coarse powder and fine powder.

  In the present invention, the toner is preferably added with inorganic fine powder having a number average primary particle size of 4 to 100 nm as a fluidizing agent. The inorganic fine powder is added to improve the fluidity of the toner and to further improve the uniform charge of the toner particles. By adjusting the charge amount of the toner by a treatment such as hydrophobizing the inorganic fine powder, It is also a preferable form to provide functions such as improvement of environmental stability.

  When the number average primary particle size of the inorganic fine powder is larger than 100 nm, or when the inorganic fine powder of 100 nm or less is not added, good toner fluidity cannot be obtained, and charge imparting to the toner particles is not possible. Unevenness tends to occur, and problems such as an increase in fog, a decrease in image density, and toner scattering may occur. When the number average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration of the inorganic fine powder is strengthened. Image defects due to development of aggregates, damage to the image carrier or toner carrier, and the like. In order to make the charge distribution of the toner particles more uniform, the number average primary particle size of the inorganic fine powder is preferably 6 to 70 nm.

  In the present invention, the method for measuring the number average primary particle size of the inorganic fine powder is a photograph of the toner magnified by a scanning electron microscope, and further an inorganic fine powder by an elemental analysis means such as XMA attached to the scanning electron microscope. Measure 100 or more primary particles of inorganic fine powder adhering to or liberating from the toner surface while comparing photographs of the toner mapped with the elements contained in It can be measured by determining the average primary particle size.

As the inorganic fine powder used in the present invention, silica, titanium oxide, alumina and the like can be used, and they may be used alone or in combination of two or more. As the silica, for example, both a so-called dry method produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and so-called wet silica produced from water glass or the like can be used. Further, dry silica having less silanol groups on the surface and inside of the silica fine powder and less production residue such as Na ₂ O, SO ₃ ²⁻ is more preferable.

  In dry silica, it is also possible to obtain composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halide compounds in the production process. Yes, the silica also includes them.

  The amount of inorganic fine powder having a number average primary particle size of 4 to 100 nm is preferably 0.1 to 3.0% by mass with respect to the toner particles. If the addition amount is less than 0.1% by mass, the effect may not be sufficient, and if it exceeds 3.0% by mass, the fixability may be deteriorated. The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  In the present invention, the inorganic fine powder is preferably a hydrophobized product in view of characteristics in a high temperature and high humidity environment. When the inorganic fine powder added to the toner absorbs moisture, the charge amount of the toner particles is remarkably reduced, and the toner is easily scattered.

  Examples of the treating agent used for the hydrophobizing treatment include treating agents such as silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organic silicon compounds, and organic titanium compounds. These treatment agents can be used alone or in combination.

  Among them, those treated with silicone oil are preferable, and more preferably, the inorganic fine powder is treated with silicone oil at the same time as or after hydrophobizing with a silane compound. It is sufficient to keep the charge amount high and prevent toner scattering.

  As a method for treating such inorganic fine powder, for example, as a first-stage reaction, a silanization reaction is performed with a silane compound and silanol groups are eliminated by chemical bonding, and then a hydrophobic reaction is performed on the surface with silicone oil as a second-stage reaction. The method of forming the thin film of this is mentioned.

The silicone oil preferably has a viscosity at 25 ° C. of 10 to 200,000 mm ² / s, more preferably 3,000 to 80,000 mm ² / s. When the viscosity is less than 10 mm ² / s, there is no stability in the inorganic fine powder, and the image quality tends to deteriorate due to heat and mechanical stress. If it exceeds 200,000 mm ² / s, uniform processing tends to be difficult.

  As the silicone oil used, for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like are particularly preferable.

  As a method of treating the inorganic fine powder with silicone oil, for example, the inorganic fine powder treated with the silane compound and the silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the inorganic fine powder may be mixed. Alternatively, a method of spraying silicone oil may be used. Alternatively, after dissolving or dispersing silicone oil in an appropriate solvent, an inorganic fine powder may be added and mixed, and then the solvent may be removed. A method using a sprayer is more preferable in that the production of inorganic fine powder aggregates is relatively small.

  The treatment amount of the silicone oil is 1 to 40 parts by mass, preferably 3 to 35 parts by mass with respect to 100 parts by mass of the inorganic fine powder. If the amount of silicone oil is too small, good hydrophobicity tends to be not obtained, and if it is too large, problems such as fogging tend to occur.

The inorganic fine powder used in the present invention is preferably silica, alumina or titanium oxide in order to impart good fluidity to the toner, and silica is particularly preferred among them. Further, silica having a specific surface area of 20 to 350 m ² / g measured by the BET method by nitrogen adsorption is preferable, and more preferably 25 to 300 m ² / g.

  The specific surface area is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method and calculating the specific surface area using the BET multipoint method. Can do.

The toner of the present invention further has a primary particle size of more than 30 nm (preferably a specific surface area of less than 50 m ² / g), more preferably a primary particle size of 50 nm or more (preferably a specific surface area) for the purpose of improving cleaning properties. It is also one of the preferable modes to add inorganic or organic fine particles having a spherical shape of less than 30 m ² / g). For example, spherical silica particles and spherical resin particles are preferably used.

  The toner used in the present invention may further contain other additives, for example, a lubricant powder such as a polyfluorinated ethylene powder, a zinc stearate powder, a polyvinylidene fluoride powder, or a cerium oxide powder within a range that does not substantially adversely affect the toner. Abrasives such as silicon carbide powder and strontium titanate powder, and organic fine particles having opposite polarity and inorganic fine particles can also be used in small amounts as developability improvers. These additives can also be used after hydrophobizing the surface.

  As a method for externally adding the fine powder to the toner, the toner and the fine powder are mixed and stirred. Specific examples include mechanofusion, I-type mill, hybridizer, turbo mill, Henschel mixer and the like. From the viewpoint of preventing the generation of coarse particles, it is particularly preferable to use a Henschel mixer.

  The toner of the present invention can be used as a toner for a non-magnetic one-component developer, and can also be used as a toner for a two-component developer having carrier particles. When used as a non-magnetic toner, in a developing device for developing an electrostatic latent image, a blade or a roller in contact with the developing sleeve for carrying the toner is used to forcibly frictionally charge the developing sleeve, There is a method of transporting toner by adhering it onto the developing sleeve.

  When used as a two-component developer, a carrier is used as a developer together with the toner of the present invention. The magnetic carrier is composed of an element consisting of iron, copper, zinc, nickel, cobalt, manganese, chromium elements alone or in a composite ferrite state.

  The magnetic carrier has a spherical shape, a flat shape, or an indeterminate shape. Furthermore, it is preferable to control the fine structure (for example, surface unevenness) of the surface state of the magnetic carrier particles. In general, a method is used in which a magnetic carrier core particle is generated in advance by firing and granulating the magnetic inorganic oxide as described above, and then coated on a resin.

  In order to reduce the load on the toner of the magnetic carrier, a method of obtaining a low-density dispersion carrier by kneading and classifying the magnetic inorganic oxide and the resin, and further kneading the magnetic inorganic oxide and the monomer It is also possible to use a method in which a product is directly suspension-polymerized in an aqueous dispersion medium to obtain a true spherical magnetic carrier.

  A coated carrier in which the carrier obtained as described above is used as carrier core particles and the surface thereof is coated with a resin is particularly preferable. As the method, a resin is dissolved or suspended in a solvent, this suspension is applied to the surface of the carrier core particles, and the resin is adhered to the carrier core particles, or simply a resin powder and carrier core particles. A method of mixing and adhering can be applied.

  The substance fixed to the surface of the carrier core particles varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide , Polyvinyl butyral, aminoacrylate resin and the like. These may be used alone or in plural.

The magnetic properties of the carrier are as follows. The magnetization intensity (σ _79.6 ) at 79.57 kA / m (1000 oersted) after magnetic saturation is preferably 3.77 to 37.7 μWb / cm ³ . Further, in order to achieve higher image quality, it is preferably 12.6 to 31.4 μWb / cm ³ . When it is larger than 37.7 μWb / cm ^3, it becomes difficult to obtain a high-quality toner image. When it is less than 3.77 μWb / cm ³ , the magnetic binding force is also reduced, so that carrier adhesion is likely to occur.

  When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is usually 2 to 15% by mass, preferably 4 to 13% by mass, as the toner concentration in the developer. Good results are obtained.

  The toner of the present invention can be applied to various known developing means depending on the form of the developer to be applied, and can be applied to various known image forming apparatuses and image forming methods. An image forming method to which the toner of the present invention can be applied will be described below with reference to the accompanying drawings.

  The toner of the present invention can be mixed with a magnetic carrier and developed using, for example, developing means 37 in an image forming apparatus as shown in FIG.

  The image forming apparatus includes a photosensitive drum 33 as an electrostatic image holding member, a charging unit (not shown) for charging the photosensitive drum 33, and a photosensitive drum 33 charged with light corresponding to an image to be formed. And an exposure means (not shown) for forming an electrostatic latent image on the photosensitive drum 33 by irradiating the photosensitive drum 33, and developing the electrostatic latent image formed on the photosensitive drum 33 with a developer to form a toner image Means 37; transfer means 43 for transferring the formed toner image onto the transfer material; heating and pressure fixing means for heating and pressurizing the toner image transferred onto the transfer material to fix it on the transfer material; and photoconductor after transfer. And cleaning means 44 for removing toner remaining on the drum 33 from the photosensitive drum 33.

  As the photosensitive drum 33, a known drum-shaped photosensitive member such as an OPC photosensitive member is used.

  The developing means 37 includes a developer container that contains a developer, a developing sleeve 31 that is a developer carrying member rotatably provided in an opening of the developer container, and a developer carried on the developing sleeve 31. A developer regulating member 32 that regulates and regulates the layer thickness of the developer on the developing sleeve 31, stirring means 35 and 36 that stir the developer in the developer container, and the developer container should be replenished A toner chamber in which the toner 41 is accommodated.

Inside the developing sleeve 31, there is provided a fixed magnet 34 fixed in the developing sleeve 31 so as to form a plurality of predetermined magnetic poles. The developing sleeve 31 is connected to a power source. The developer container contains a two-component developer containing the toner of the present invention, and the toner of the present invention is used as the toner 41. The developing means 37 is provided at a position where the surface of the photosensitive drum 33 and the surface of the developing sleeve 31 are separated by a predetermined distance B.

  The transfer means 43 is connected to a power source, and a known transfer means such as a corona charger is used. As the cleaning unit 44, for example, a unit having an elastic cleaning blade that comes into contact with the photosensitive drum 33 is used. For the heat and pressure fixing means, for example, a means comprising a heating roller 46 incorporating a heater and a pressure roller 45 provided so as to press the surface of the heating roller 46 is used.

  In the developing unit 37, it is preferable to perform development in a state where the magnetic brush is in contact with the photosensitive drum 33 while applying an alternating electric field. The distance B between the developing sleeve 31 and the photosensitive drum 33 (SD distance) B is preferably 100 to 1,000 μm in terms of preventing carrier adhesion and improving dot reproducibility. If the distance B is less than 100 μm, the supply of the developer to the photosensitive drum 33 tends to be insufficient, and the image density may be lowered. When the distance B exceeds 1,000 μm, the lines of magnetic force from the magnetic pole S1 spread, the density of the magnetic brush becomes low, the dot reproducibility is inferior, the carrier restraining force is weakened, and carrier adhesion is likely to occur.

  The toner 41 is sequentially supplied to the developing device, mixed with the carrier by the stirring means 35 and 36, and conveyed to the developing sleeve 31 including the fixed magnet 34.

  The voltage between the peaks of the alternating electric field is preferably 500 to 5,000 V, the frequency is 500 to 10,000 Hz, preferably 500 to 3,000 Hz, and can be appropriately selected depending on the process. In this case, various waveforms such as a triangular wave, a rectangular wave, a sine wave, or a waveform with a changed duty ratio can be selected and used as the waveform of the applied voltage. When the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and the fog toner in the non-image area may not be recovered satisfactorily. If it exceeds 5,000 V, the electrostatic image may be disturbed via the magnetic brush, resulting in a reduction in image quality.

  By using a two-component developer having a well-charged toner, the anti-fogging voltage (Vback) can be lowered, and the primary charge of the photoreceptor can be lowered, thereby extending the life of the photoreceptor. Life can be extended. Vback is 150 V or less, more preferably 100 V or less, although it depends on the development system.

  The contrast potential is preferably 200 to 500 V so that a sufficient image density can be obtained.

  When the frequency is lower than 500 Hz, although related to the process speed, carrier injection may occur due to charge injection to the carrier, or the image quality may be deteriorated by disturbing the latent image. If the frequency exceeds 10,000 Hz, the toner cannot follow the electric field and the image quality is likely to deteriorate.

From the viewpoint of developing a sufficient image density, excellent dot reproducibility, and development without carrier adhesion, the contact width (development nip C) of the magnetic brush on the developing sleeve 31 with the photosensitive drum 33 is preferably 3 to 3. It is preferable to make it 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to satisfactorily satisfy a sufficient image density and dot reproducibility. If the developing nip C is larger than 8 mm, developer packing occurs and the operation of the machine is stopped. It becomes difficult to sufficiently suppress adhesion. Examples of the method for adjusting the developing nip include a method for adjusting the distance A between the developer regulating member 32 and the developing sleeve 31 and a method for adjusting the distance B between the developing sleeve 31 and the photosensitive drum 33.

  In the output of a full color image in which halftone is particularly important, three or more developing units for magenta, cyan, and yellow are used, and the developer and the developing method of the present invention are used. By combining with the formed development system, it is possible to develop the dot latent image faithfully without being affected by the magnetic brush and without disturbing the latent image. Also in the transfer step, a high transfer rate can be achieved by using the toner of the present invention. Therefore, high image quality can be achieved in both the halftone part and the solid part.

  Furthermore, the effect of the present invention that the image quality is not deteriorated can be sufficiently exhibited even when a large number of copies are made by using the toner of the present invention together with the improvement of the initial image quality.

  The toner image on the photosensitive drum 33 is transferred to a transfer material by the transfer unit 43, and the toner image on the transfer material is fixed by a heat and pressure fixing unit having a heating roller 46 and a pressure roller 45. Transfer residual toner on the photosensitive drum 33 is removed from the photosensitive drum 33 by the cleaning blade of the cleaning unit 44.

  In order to obtain a good full-color image, it is preferable to have a developing device for magenta, cyan, yellow, and black, and a black image can be developed last, so that a tight image can be obtained. .

  An example of an image forming apparatus that can satisfactorily implement a multi-color or full-color image forming method will be described with reference to FIG.

  The color electrophotographic apparatus shown in FIG. 2 includes a transfer material conveyance system I provided from the right side of the apparatus main body to a substantially central portion of the apparatus main body, and the transfer material conveyance system I at a substantially central portion of the apparatus main body. The latent image forming unit II provided in the vicinity of the transfer drum 415 and the developing means (that is, the rotary developing device) III provided in the vicinity of the latent image forming unit II are roughly divided. Is done.

The transfer material transport system I has the following configuration.
An opening is formed in the right wall (right side in FIG. 2) of the apparatus main body, and transfer material supply trays 402 and 403 which are detachable from the opening are partly projected outside the apparatus. Feed rollers 404 and 405 are disposed substantially directly above the trays 402 and 403. The feed rollers 404 and 405 and a transfer drum 415 that is arranged on the left and is rotatable in the direction of arrow D are provided. A paper feed roller 406 and paper feed guides 407 and 408 are provided so as to be linked. Near the outer peripheral surface of the transfer drum 415, a contact roller 409, a gripper 410, a transfer material separation charger 411, and a separation claw 412 are sequentially arranged from the upstream side to the upstream side in the rotation direction.

  A transfer charger 413 and a transfer material separation charger 414 are disposed on the inner peripheral side of the transfer drum 415. A transfer sheet (not shown) made of a polymer such as polyvinylidene fluoride is attached to a portion of the transfer drum 415 around which the transfer material is wound, and the transfer material is electrostatically placed on the transfer sheet. Affixed in close contact with. At the upper right side of the transfer drum 415, a conveyance belt means 416 is disposed in the vicinity of the separation claw 412. A fixing device 418 is disposed at the end (right side) of the conveyance belt means 416 in the transfer material conveyance direction. Has been.

The fixing device 418 includes a heating roller 429 for heating the conveyed transfer material, and a pressure roller 430 that presses the conveyed transfer material toward the heating roller 429. The heating roller 429 is a sleeve having heat conductivity, and a heater 436 is provided therein. The pressure roller 430 is an elastic roller, and includes, for example, a cored bar 437 and an elastic layer that covers the peripheral surface of the cored bar 437.

  Further downstream of the fixing device 418 in the transport direction, the transfer roller 452 for feeding the transfer material on which the image has been fixed by the fixing device 418 and the discharge roller 452 to the outside are extended to the outside of the device main body 401. A discharge tray 417 detachably attached to 401 is disposed.

  Next, the configuration of the latent image forming unit II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 419 which is a latent image carrier that can rotate in the direction of the arrow in FIG. 2 is disposed with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 415. Above the photosensitive drum 419 and in the vicinity of the outer peripheral surface thereof, a static elimination charger 420, a cleaning unit 421 and a primary charger 423 are sequentially arranged from the upstream side to the downstream side in the rotation direction of the photosensitive drum 419. An image exposure means 424 such as a laser beam scanner for forming an electrostatic latent image and an image exposure reflection means 425 such as a mirror are provided on the outer peripheral surface of the photosensitive drum 419.

The configuration of the rotary developing device III is as follows.
A rotatable housing (hereinafter referred to as “rotating body”) 426 is disposed at a position facing the outer peripheral surface of the photosensitive drum 419, and four types of developing devices are provided in the rotating body 426 at four positions in the circumferential direction. The electrostatic latent image formed on the outer peripheral surface of the photosensitive drum 419 is visualized (that is, developed). The four types of developing devices include a yellow developing device 427Y, a magenta developing device 427M, a cyan developing device 427C, and a black developing device 427BK, respectively.

  The sequence of the entire image forming apparatus configured as described above will be described by taking the case of the full color mode as an example.

  When the photosensitive drum 419 described above rotates in the direction of the arrow in FIG. 2, the photosensitive drum 419 is charged by the primary charger 423. In the apparatus of FIG. 2, the peripheral speed (hereinafter referred to as process speed) of the photosensitive drum 419 is 100 mm / sec or more (for example, 130 to 250 mm / sec). When the photosensitive drum 419 is charged by the primary charger 423, image exposure is performed by the laser beam E modulated by the yellow image signal of the document 428, and an electrostatic latent image is formed on the photosensitive drum 419, and rotated. The yellow latent image is developed by the yellow developing device 427Y previously placed at the developing position by the rotation of the body 426, and a yellow toner image is formed.

  The transfer material conveyed via the paper feed guide 407, the paper feed roller 406, and the paper feed guide 408 is held by the gripper 410 at a predetermined timing, and the contact roller 409 and the contact roller 409 It is wound around the transfer drum 415 electrostatically by the facing electrode. The transfer drum 415 is rotated in the direction of arrow D in FIG. 2 in synchronization with the photosensitive drum 419. The yellow toner image formed by the yellow developing device 427Y is the outer peripheral surface of the photosensitive drum 419 and the transfer drum 415. The image is transferred onto the transfer material by the transfer charger 413 at a portion where the outer peripheral surface of the image is in contact. The transfer drum 415 continues to rotate to prepare for the transfer of the next color (magenta in FIG. 2).

The photosensitive drum 419 is neutralized by the static elimination charger 420 and cleaned by the cleaning unit 421 having a cleaning member such as a cleaning blade or a brush, and then charged again by the primary charger 423, and the image is generated by the next magenta image signal. Exposure is performed to form an electrostatic latent image. The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 419 by image exposure based on a magenta image signal, so that the magenta developing device 427M is disposed at the predetermined developing position described above. Develop with magenta toner.

  Subsequently, the above-described processes are performed for cyan and black colors, respectively, and when the transfer of the four-color toner images is completed, the three-color visible images formed on the transfer material are transferred to the chargers 422 and 414, respectively. The transfer material is discharged by the gripper 410, and the transfer material is released from the transfer drum 415 by the separation claw 412, sent to the fixing device 418 by the conveyance belt 416, and fixed by heat and pressure. Is done. In this way, a series of full-color print sequences is completed, and a required full-color print image is formed on one surface of the transfer material.

  Next, another image forming method will be described more specifically with reference to FIG.

In the apparatus system shown in FIG. 3, a developer having cyan toner, a developer having magenta toner, a developer having yellow toner, and a black are respectively added to the developers 54-1, 54-2, 54-3, and 54-4. A developer having toner is introduced, and the electrostatic image formed on the photoconductor 51 is developed by a magnetic brush development method or a non-magnetic one-component development method, and each color toner image is formed on the photoconductor 51. The photoreceptor 51 is a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, Cds, ZnO ₂ , OPC, or a-Si. The photoreceptor 51 is rotated in the direction of the arrow by a driving device (not shown).

  As the photoreceptor 51, an amorphous silicon photosensitive layer or a photoreceptor having an organic photosensitive layer is preferably used. The photoconductor 51 has a conductive substrate and a photosensitive layer formed on the conductive substrate.

  The organic photosensitive layer may be a single layer type in which the photosensitive layer contains a charge generation material and a substance having charge transport performance in the same layer, or a functional separation type photosensitive layer having the charge generation layer as a component. There may be. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one preferred example.

  The binder resin of the organic photosensitive layer is preferably a polycarbonate resin, a polyester resin, or an acrylic resin, particularly from the viewpoint of transferability and cleaning properties, and poor cleaning, fusion of toner to the photoreceptor, external additives Filming hardly occurs.

  In the charging process, there are a non-contact method using the corona charger 51 and a contact type method using a roller or the like, and either method is used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 3 is preferably used.

  The charging roller 52 is basically composed of a central core metal 52b and a conductive elastic layer 52a that forms the outer periphery thereof. The charging roller 52 is pressed against the surface of the photoconductor 51 with a pressing force, and is driven to rotate as the photoconductor 51 rotates.

  As a preferable process condition when using the charging roller, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 g / cm), and when the AC voltage is superimposed on the DC voltage, The voltage is 0.5 to 5 kVpp, the AC frequency is 50 Hz to 5 kHz, the DC voltage is ± 0.2 to ± 1.5 kV, and when the DC voltage is used, the DC voltage is ± 0.2 to ± 5 kV.

  Other charging means include a means using a charging blade and a means using a conductive brush. These contact charging means are effective in that a high voltage is unnecessary and generation of ozone is reduced.

  The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) and the like are applicable.

  The toner image on the photosensitive member is transferred to the intermediate transfer member 55 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The surface of the photoreceptor after the transfer is cleaned by a cleaning unit 59 having a cleaning blade 58.

  The intermediate transfer member 55 includes a pipe-shaped conductive core 55b and a medium-resistance elastic layer 55a formed on the outer peripheral surface thereof. The cored bar 55b may be a plastic pipe with conductive plating.

Medium resistance elastic layer 55a is made of elastic material such as silicone rubber, fluororesin rubber, chloroprene rubber, urethane rubber, EPDM (ethylene propylene diene terpolymer), carbon black, zinc oxide, tin oxide, carbonized carbon. It is a solid or foamed meat layer in which a conductivity imparting material such as silicon is blended and dispersed to adjust the electric resistance value (volume resistivity) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm.

  The intermediate transfer member 55 is disposed in parallel with the photosensitive member 51 and is in contact with the lower surface of the photosensitive member 51, and rotates in the counterclockwise direction indicated by the arrow at the same peripheral speed as the photosensitive member 51.

  In the process in which the first color toner image formed and supported on the surface of the photoconductor 51 passes through the transfer nip where the photoconductor 51 and the intermediate transfer body 55 are in contact with each other, the transfer nip region is applied with the transfer bias applied to the intermediate transfer body 55. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer member 55 by the electric field formed on the intermediate transfer member 55.

  If necessary, the surface of the intermediate transfer member 55 is cleaned by the removable cleaning unit 500 after the transfer of the toner image onto the transfer material. When the toner image is present on the intermediate transfer member, the cleaning unit 500 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

  On the lower surface portion of the intermediate transfer member 55, a transfer unit is disposed so as to be in contact with the intermediate transfer member 55 in parallel. The transfer means 57 is, for example, a transfer roller or a transfer belt, and rotates in the clockwise direction indicated by an arrow at the same peripheral speed as that of the intermediate transfer body 55. The transfer unit 57 may be disposed so as to be in direct contact with the intermediate transfer member 55, or a belt or the like may be disposed between the intermediate transfer member 55 and the transfer unit 57.

  In the case where the transfer means is a transfer roller, this transfer roller basically has a central core metal 57b and a conductive elastic layer 57a that forms the outer periphery thereof.

  Common materials can be used for the intermediate transfer member and the transfer roller. By setting the volume resistivity of the elastic layer of the transfer roller to be smaller than the volume resistivity of the elastic layer of the intermediate transfer member, the voltage applied to the transfer roller can be reduced and a good toner image can be formed on the transfer material. It can be formed and the transfer material can be prevented from being wrapped around the intermediate transfer member. In particular, the volume specific resistance value of the elastic layer of the intermediate transfer member is particularly preferably 10 times or more than the volume specific resistance value of the elastic layer of the transfer roller.

The transfer means 57 is rotated with a difference in speed or peripheral speed from the intermediate transfer body 55. The transfer material 56 is conveyed between the intermediate transfer body 55 and the transfer means 57, and at the same time, a bias having a reverse polarity to the frictional charge of the toner is applied to the transfer means 57 from the transfer bias means. The upper toner image is transferred to the surface side of the transfer material 56.

  As the material of the transfer rotator (transfer roller), the same material as the charging roller can be used. As a preferable transfer process condition, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 g). DC voltage is ± 0.2 to ± 10 kV.

For example, the conductive elastic layer 57b of the transfer roller has an elastic volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm, such as polyurethane in which a conductive material such as carbon is dispersed, ethylene-propylene-diene terpolymer (EPDM), or the like. Consists of the body. A bias is applied to the metal core 57a by a constant voltage power source. The bias condition is preferably ± 0.2 to ± 10 kV.

  Next, the transfer material 56 is conveyed to a fixing device 501 having a heating roller incorporating a heating element such as a halogen heater and an elastic pressure roller pressed against it with a pressing force. By passing between the pressure rollers, the toner image is fixed to the transfer material by heating and pressing. For fixing the image on the transfer material, a method of fixing with a heater through a film may be used.

  Next, a one-component development method will be described. The toner of the present invention can be applied to a one-component development method such as a magnetic one-component development method or a non-magnetic one-component development method.

  A magnetic one-component developing method will be described with reference to FIG.

  In FIG. 4, the substantially right half circumferential surface of the developing sleeve 73 is always in contact with the toner reservoir in the toner container 74 containing the toner T, and the toner in the vicinity of the developing sleeve 73 surface is in contact with the developing sleeve surface. It is attached and held by the magnetic force of the magnetic generating means 75 and / or by electrostatic force.

  When the developing sleeve 73 is driven to rotate, the magnetic toner layer on the sleeve surface is layered as a magnetic toner thin layer T1 having a substantially uniform thickness in the process of passing the position of the regulating member 76. The magnetic toner is charged mainly by frictional contact between the sleeve surface accompanying the rotation of the developing sleeve 73 and the magnetic toner in the toner reservoir in the vicinity thereof.

  The magnetic toner thin layer surface on the developing sleeve 73 rotates toward the latent image holding body 77 as the developing sleeve rotates, and passes through the developing area F that is the closest portion between the latent image holding body 77 and the developing sleeve 73. . In this passing process, the magnetic toner of the magnetic toner thin layer on the surface of the developing sleeve 73 is applied by the power source 78 between the latent image holding member 77 and the developing sleeve 73 by the direct current and alternating current by the direct current and the alternating voltage. Then, it reciprocates between the surface of the latent image holding member 77 in the developing area F and the surface of the developing sleeve 73 (gap α).

  Finally, the magnetic toner on the developing sleeve 73 side is selectively transferred and attached to the surface of the latent image holding body 77 according to the potential pattern of the latent image, so that toner images T2 are sequentially formed.

  The developing sleeve surface in which the magnetic toner has been selectively consumed after passing through the developing area portion F is re-rotated to the toner reservoir of the toner container 74, thereby receiving the magnetic toner again and developing the developing area portion F. The surface of the magnetic toner thin layer T1 of the sleeve 73 is transferred, and the development process is repeated.

The regulating member 76 as the toner thinning means used in FIG. 4 is a doctor blade such as a metal blade or a magnetic blade arranged with a certain gap from the sleeve. Alternatively, a roller made of metal, resin, or ceramic may be used instead of the doctor blade. Furthermore, an elastic blade or an elastic roller that comes into contact with the surface of the developing sleeve (toner carrier) with an elastic force may be used as the toner thinning regulating member.

  As a material for forming the elastic blade or the elastic roller, a rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel, steel or phosphor bronze can be used. Moreover, those composites may be sufficient. Preferably, the sleeve contact portion is a rubber elastic body or a resin elastic body.

  An example of using an elastic blade is shown in FIG.

  The base which is the upper side of the elastic blade 80 is fixedly held on the developer container side, and the lower side is bent in the forward or reverse direction of the developing sleeve 89 against the elasticity of the blade 80, The inner surface of the blade (or the outer surface in the case of the reverse direction) is brought into contact with the surface of the sleeve 89 with an appropriate elastic pressure. According to such an apparatus, a thin and dense toner layer can be obtained more stably with respect to environmental changes.

  When an elastic blade is used, the toner easily adheres to the sleeve and blade surface. However, since the toner of the present invention is excellent in releasability and stable in triboelectric chargeability, an elastic blade is preferably used as the regulating member. .

  In the case of the magnetic one-component development method, the contact pressure between the blade 80 and the sleeve 89 is 0.98 N / m (0.1 kg / m) or more, preferably 2.94 to as the linear pressure in the central axis direction of the sleeve. 245 N / m (0.3 to 25 kg / m), more preferably 4.9 to 117.6 N / m (0.5 to 12 kg / m) is effective.

  A gap α between the latent image holding member 88 and the sleeve 89 is set to 50 to 500 μm, for example. The layer thickness of the magnetic toner layer on the sleeve 89 is most preferably thinner than the gap α between the latent image holding member 88 and the sleeve 89, but in some cases among the many ears of the magnetic toner constituting the magnetic toner layer, The thickness of the magnetic toner layer may be regulated so that a part thereof is in contact with the latent image holding member 88.

  The developing sleeve 89 is rotated at a peripheral speed of 100 to 200% with respect to the latent image holding member 88.

  The alternating bias voltage by the bias applying means 86 is preferably 0.1 kV or more, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 kV, peak-to-peak. The alternating bias frequency is 0.5 to 5.0 kHz, preferably 1.0 to 3.0 kHz, and more preferably 1.5 to 3.0 kHz. As the alternating bias waveform, a rectangular wave, a sine wave, a sawtooth wave, a triangular wave, or the like can be applied. Also, asymmetrical AC bias with different forward and reverse voltages and time can be used. It is also preferable to superimpose a DC bias.

  As an image forming apparatus in which the toner of the present invention is preferably used, an image forming apparatus shown in FIG. 6 is further exemplified.

The image forming apparatus shown in FIG. 6 corresponds to a photosensitive drum 100 as an image carrier, a charging roller 117 arranged in contact with the photosensitive drum 100 to charge the photosensitive drum 100, and an image to be formed on the charged photosensitive drum. A laser generator 121 that irradiates the laser beam 123 to form an electrostatic latent image, a developer 140 that develops the electrostatic latent image formed on the photosensitive drum 100 with toner to form a toner image, and a photosensitive drum The transfer roller 114 that transfers the toner image formed on the transfer material to the transfer material, and the toner remaining on the photosensitive drum 100 after transfer are transferred to the photosensitive drum 1.
A cleaner 116 for removing the toner image from the 00, a fixing device 126 for fixing the toner image onto the transfer material having the transferred toner image, a register roller 124 for feeding the transfer material to the transfer roller 114, and a post-transfer And a conveying belt 125 for feeding the transfer material to the fixing device 126.

  The photosensitive drum 100 is, for example, an OPC (organic photosensitive member). The photosensitive drum 100 has, for example, a configuration in which an aluminum base, and a conductive coating layer, an undercoat layer, a charge generation layer, and a charge transport layer are sequentially stacked on the base.

  The charging roller 117 is composed of a conductive support such as a cored bar and a resin layer formed thereon and having conductivity and elasticity, and charging for applying a bias to the conductive support by charging. A bias power supply is connected.

  The developing device 140 includes a developing container that accommodates toner, a toner carrier 102 that is rotatably provided in an opening of the developing container, a magnet roller that is fixedly disposed inside the toner carrier 102 and has a plurality of magnetic poles, and a toner carrier. An elastic blade that regulates the amount of toner on the body 102 and a stirring member 141 that stirs the toner in the developing container.

  The transfer roller 114 is a roller member that is conductive and elastic like the charging roller 117, and includes a cored bar and a conductive elastic layer that covers the cored bar.

  The fixing device 126 includes a heating roller and a pressure roller arranged to be biased toward the heating roller. The cleaner 116 includes a cleaning blade that is an elastic plate-like member that contacts the photosensitive drum 100 and a waste toner container that has the cleaning blade in an opening and stores transfer residual toner removed by the cleaning blade.

  Hereinafter, the present invention will be specifically described with reference to production examples and examples, but this does not limit the present invention in any way. In the examples and comparative examples, all parts and% are based on mass unless otherwise specified.

<Example 1>
First, a toner was prepared by the following procedure (polymerization method). To 900 parts of ion-exchanged water heated to 60 ° C., 3 parts of tricalcium phosphate is added, and stirred at 10,000 rpm using a TK homomixer (high speed stirrer, manufactured by Tokushu Kika Kogyo Co., Ltd.). A dispersion medium was prepared.

In addition, the following materials were put into a container equipped with a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.), heated to 60 ° C., stirred at 9,000 rpm using a TK homomixer, dissolved, Distributed.
-Styrene 160 parts-n-butyl acrylate 40 parts-C.I. I. Pigment Blue 15: 3 14 parts / Polyester resin 10 parts (polycondensation product of propylene oxide modified bisphenol A and terephthalic acid, Tg: 65 ° C., Mw: 10,000, Mn: 6,000)
-Stearyl stearate wax (DSC main peak: 60 ° C) 22 parts-Hydrocarbon wax (Nippon Seiki Co., Ltd .; HNP-10, DSC main peak: 75 ° C)
8 parts Aluminum salicylate compound (Bontron E-88; manufactured by Orient Chemical Co., Ltd.) 4 parts Divinylbenzene 0.5 part Di-tert-butyl ether 0.03 part

  In this, 5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

  The polymerizable monomer composition was put into the aqueous dispersion medium, and granulated by stirring at 8,000 rpm using a TK homomixer at 60 ° C. in a nitrogen atmosphere.

  Thereafter, the suspension obtained was heated to 70 ° C. over 1 hour while being transferred to a propeller stirrer and stirred, and further 5 hours later, the temperature was raised to 80 ° C. at a temperature increase rate of 40 ° C./hr. Then, the reaction was carried out at 80 ° C. for 5 hours to produce polymer particles. After the completion of the polymerization reaction, the slurry containing the particles was cooled, washed with 10 times the amount of water as the slurry, filtered and dried, and then adjusted for particle size by classification to obtain cyan toner particles.

  To 100 parts of the cyan toner particles, 1.5 parts of silica (R972 manufactured by Aerosil Co., Ltd.) was mixed with a Henschel mixer (mixer, manufactured by Mitsui Miike Co., Ltd.) to obtain the cyan toner 1 of the present invention.

  6 parts of this cyan toner 1 are mixed with 94 parts of an acrylic coated ferrite carrier to prepare a developer, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. The following image evaluation and durability evaluation were performed. As for cyan toner 1, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that cyan toner 1 contained di-tert-butyl ether. The physical properties of cyan toner 1 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

  The toner image evaluation method in this embodiment will be described below.

-Image evaluation-
Image evaluation and durability evaluation were performed as follows.
Using a commercially available digital full-color copier (CLC500, manufactured by Canon) as shown in Fig. 2, images are formed in a room temperature and normal humidity (23.5 ° C, 60% RH) environment, and image evaluation is performed. It was. Thereafter, a durability test for printing 15,000 horizontal line images with a printing area ratio of 1% was performed, and then image evaluation was performed again. Evaluation items and evaluation methods are as follows.

  The modified machine is an apparatus that is set to a process speed of 250 mm / sec except for the oil application mechanism of the fixing device of the CLC 500, and is modified to form an image with a more unfavorable fixing condition by increasing the process speed. Device.

a) Image Density For the image density, a “Macbeth reflection densitometer” (reflection densitometer, manufactured by Macbeth Co., Ltd.) was used to measure the relative density with respect to the printout image of the white background portion having an original density of 0.00. Evaluated by criteria.
A: Image density is 1.45 or more B; Image density is 1.30 or more and less than 1.45 C; Image density is 1.15 or more and less than 1.30 D; Image density is 1.00 or more and less than 1.15 E; Image density is less than 1.00

b) Fog For the measurement of the fog, the reflectance of the non-image part of the standard paper and the printout image was measured using a reflection densitometer manufactured by Tokyo Denshoku Co., Ltd. and REFECTECTOMER MODEL TC-6DS. As a filter used in the measurement, amber light was used for cyan, blue was used for yellow, and green filters were used for magenta and black. The fog was calculated from the measurement results by the following formula and evaluated according to the following criteria.

[Equation 4]
Fog (reflectance:%) = reflectance on standard paper (%) − reflectance of sample non-image area (%)

A: Fog (reflectance) is 1.0% or less B: Fog (reflectance) is more than 1.0 to 2.0% C: Fog (reflection) is more than 2.0 to 3.0% D ; Fog (reflectance) is more than 3.0 to 4.0% or less E; fog (reflectance) is more than 4.0 to 5.0% or less F; fog (reflectance) is more than 5.0

c) Transferability Regarding transfer efficiency, the transfer residual toner on the photoconductor after solid black image transfer was taped off with Mylar tape and pasted on paper, the Macbeth density value was C, and the toner before transfer and fixing The Macbeth concentration of the Mylar tape affixed on the placed paper was E, and the Macbeth concentration of the Mylar tape affixed on the unused paper was D, calculated approximately by the following formula, and evaluated according to the following criteria.

A: Transfer efficiency (%) is 98% or more B: Transfer efficiency (%) is 96% or more and less than 98% C: Transfer efficiency (%) is 94% or more and less than 96% D: Transfer efficiency (%) is 92% or more Less than 94% E; Transfer efficiency (%) is 90% or more and less than 92% F; Transfer efficiency (%) is less than 90%

d) Charging stability The charging stability of the toner was evaluated by measuring the maximum density difference in the solid black image when a single solid black image was output, and using this as an index of charging stability and evaluating it according to the following criteria: . The method a) described above was used for measuring the image density.
A: Image density difference is less than 0.05 B: Image density difference is 0.05 or more and less than 0.1 C: Image density difference is 0.1 or more and less than 0.2 D: Image density difference is 0.2 or more

e) Fixing rubbing test For the fixing rubbing test, the toner weight per unit area was adjusted to 1.0 mg / cm ² on A4 copying machine plain paper (105 g / m ² ), and 10 mm for density measurement. An image having a large number of x10 mm solid images is output, and the obtained fixed image is rubbed five times with sylbon paper applied with a load of 50 g / cm ² , and then evaluated based on the following rate of decrease in image density did.
A: Decreasing rate (%) is less than 2% B: Decreasing rate (%) is 2% or more and less than 5% C: Decreasing rate (%) is 5% or more and less than 10% D: Decreasing rate (%) is 10% or more

For d) high-temperature offset resistance high-temperature offset resistance, with 64 g / m ² recycled paper test transfer paper, 5 cm entire halftone image density 0.5 from the tip, the other print images that solid white The contamination on the image due to the high temperature offset phenomenon was visually confirmed, and the temperature at which the contamination occurred was defined as the high temperature offset resistance. The higher this temperature, the better the high temperature offset resistance.

  In this test, the heating and fixing apparatus in which the heater temperature of the fixing heating roller (member) can be arbitrarily controlled is used.

f) Gloss measurement After a solid image having a toner weight of 0.7 mg / cm ² was placed on the transfer paper and fixed, GLOSS SENSER PG-3D (gloss meter, NIPPON DENSHOKU IND. CO., LTD) was used. The solid image was measured at an angle of 75 °. The gross value is an average value obtained by measuring the center of each block of the solid output image by dividing it into three parts vertically and horizontally (total of 9 parts).

<Example 2>
Cyan toner 2 was prepared in the same manner as in Example 1 except that 8 parts of tert-hexyl peroxypivalate (“Perhexyl PV” manufactured by NOF Corporation) was used as a polymerization initiator without adding di-tert-butyl ether. Manufactured. In this example, tert-butyl-tert-hexyl ether was produced by the reaction during the polymerization. This compound was identified by mass spectrum.

  The physical properties of the cyan toner 2 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 3>
A cyan toner 3 was produced in the same manner as in Example 1 except that the ether compound to be added was changed to iso-butyl-tert-butyl ether.

  Regarding the cyan toner 3, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 3 contained iso-butyl-tert-butyl ether. The physical properties of the cyan toner 3 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 4>
As a colorant, C.I. I. Instead of using 14 parts of Pigment Blue 15: 3, C.I. I. A yellow toner 4 was produced in the same manner as in Example 1 except that 10 parts of Pigment Yellow 17 was used.

Regarding the yellow toner 4, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the yellow toner 4 contained di-tert-butyl ether. The physical properties of the yellow toner 4 are shown in Tables 1 to 3, and Example 1
Table 4 and Table 5 show the evaluation results performed in the same manner as above.

<Example 5>
As a colorant, C.I. I. Instead of using 14 parts of Pigment Blue 15: 3, C.I. I. Magenta toner 5 was produced in the same manner as in Example 1 except that 16 parts of Pigment Red 122 were used.

  Regarding the magenta toner 5, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the magenta toner 5 contained di-tert-butyl ether. The physical properties of the magenta toner 5 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 6>
As a colorant, C.I. I. Pigment Blue 15: Instead of using 3 14 parts of carbon black (DBP oil ^absorption: 42cm 3/100 g, a specific surface area: ^{60 m} 2 / g), except that the use 16 parts by mass, black in the same manner as in Example 1 Toner 6 was produced.

  Regarding the black toner 6, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the black toner 6 contained di-tert-butyl ether. The physical properties of the black toner 6 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 7>
(Production of hydrophobic iron oxide 1)
An aqueous solution containing ferrous hydroxide was prepared by mixing 1.0 to 1.1 equivalents of a caustic soda solution with respect to iron ions in an aqueous ferrous sulfate solution.

  While maintaining the pH of the aqueous solution at around 9, air was blown and an oxidation reaction was performed at 80 to 90 ° C. to produce seed crystals, thereby preparing a slurry liquid.

  Subsequently, after adding ferrous sulfate aqueous solution to this slurry liquid so that it may become 0.9-1.2 equivalent with respect to the original alkali amount (sodium component of caustic soda), the slurry liquid is maintained at about pH 8, and air The magnetic iron oxide particles produced after the oxidation reaction were washed, filtered, and once taken out. At this time, a small amount of water-containing sample was collected and the water content was measured.

Next, the water-containing sample was re-dispersed in another aqueous medium without drying, and then the pH of the re-dispersed liquid was adjusted to about 6, and the silane coupling agent (n-C ₆ H _{13 was} thoroughly stirred. 3.0 parts of Si (OCH ₃ ) ₃ ) was added to 100 parts of magnetic iron oxide (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample), and a coupling treatment was performed. The produced hydrophobic iron oxide particles were washed, filtered and dried by a conventional method, and then the slightly agglomerated particles were pulverized to obtain hydrophobic iron oxide 1 having an average particle size of 0.19 μm.

(Manufacture of magnetic toner 7)
(Preparation of aqueous dispersion medium)
To 900 parts of ion-exchanged water, 3 parts of tricalcium phosphate was added and stirred at 10,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare an aqueous dispersion medium.

Further, the following formulation was heated to 60 ° C., and uniformly dissolved and dispersed at 9,000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo).
・ Styrene 160 parts ・ n-butyl acrylate 40 parts ・ hydrophobic iron oxide 1 90 parts ・ saturated polyester resin 20 parts (polycondensate of propylene oxide-modified bisphenol A and terephthalic acid, Tg: 65 ° C., Mw: 10,000 )
-Stearyl stearate wax (DSC peak: 60 ° C) 30 parts-Hydrocarbon wax (Nippon Seiki Co., Ltd .; HNP-10, DSC main peak: 75 ° C)
10 parts aluminum salicylate compound (Bontron E-88; manufactured by Orient Chemical Co., Ltd.)
4 parts divinylbenzene 0.6 parts di-tert-butyl ether 0.03 parts

  In this, 5 parts of a polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

  Next, the polymerizable monomer composition is put into the aqueous dispersion medium in a reaction vessel, tert-butyl alcohol (0.6 parts) is further added as an alcohol component, and TK is added at 60 ° C. in a nitrogen atmosphere. The mixture was stirred at 6000 rpm and granulated.

  Thereafter, the resulting suspension was transferred to a propeller type stirring device and stirred, and the temperature was raised to 65 ° C. in 1 hour. After 4 hours, the temperature was raised to 85 ° C. at a heating rate of 40 ° C./hr. Reacted for hours. After completion of the polymerization reaction, the mixture was cooled and diluted hydrochloric acid was added to dissolve the dispersant. Thereafter, solid-liquid separation was performed, and the magnetic toner base particles were obtained by washing with 10 times the amount of water of the slurry, filtering, and drying.

  The magnetic toner 7 of the present invention was obtained by mixing 1.5 parts of silica (R972, manufactured by Aerosil Co., Ltd.) with 100 parts of the above magnetic toner base particles using a Henschel mixer (manufactured by Mitsui Miike).

  Using this magnetic toner 7, image evaluation and durability evaluation were performed in the same manner as in Example 1 using a magnetic one-component developing device (LBP-1760 (manufactured by Canon)) as shown in FIG.

  Regarding the magnetic toner 7, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the magnetic toner 7 contained di-tert-butyl ether. The physical properties of the toner are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 8>
Cyan toner 8 was produced in the same manner as in Example 1 except that the ether compound to be added was changed to iso-butyl-tert-butyl ether and the addition amount was changed to 0.001 part.

  Regarding the cyan toner 8, when the content of the ether compound according to the present invention was measured by gas chromatography, the cyan toner 8 contained 3 ppm of iso-butyl-tert-butyl ether. The physical properties of the cyan toner 8 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 9>
A cyan toner 9 was produced in the same manner as in Example 1 except that the amount of di-tert-butyl ether added was changed to 0.003 part.

  Regarding the cyan toner 9, the content of the ether compound according to the present invention was measured by gas chromatography. As a result, the cyan toner 9 contained 8 ppm of di-tert-butyl ether. The physical properties of the cyan toner 9 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 10>
A cyan toner 10 was produced in the same manner as in Example 1 except that the amount of di-tert-butyl ether added was changed to 0.23 part.

  Regarding the cyan toner 10, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 10 contained di-tert-butyl ether. The physical properties of the cyan toner 10 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 11>
A cyan toner 11 was produced in the same manner as in Example 1 except that the ether compound to be added was changed to the compound of the following structural formula (1) and the addition amount was changed to 0.20 part.

  Regarding the cyan toner 11, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 11 contained the ether compound having the above structure. The physical properties of the cyan toner 11 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 12>
A cyan toner 12 was produced in the same manner as in Example 1 except that the number of wax parts to be added was changed to 18.5 parts for ester wax and 10 parts for hydrocarbon wax.

  When the content of the ether compound according to the present invention was measured for the cyan toner 12 by gas chromatography, the cyan toner 12 contained 110 ppm of di-tert-butyl ether. The physical properties of the cyan toner 12 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 13>
A cyan toner 13 was produced in the same manner as in Example 1 except that the number of wax parts to be added was changed to 25 parts of ester wax and 3 parts of hydrocarbon wax.

  Regarding the cyan toner 13, when the content of the ether compound according to the present invention was measured by gas chromatography, the cyan toner 13 contained 110 ppm of di-tert-butyl ether. The physical properties of the cyan toner 13 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 14>
Regarding the wax species to be added, distearyl adipate wax (DSC main peak: 65 ° C.) instead of stearyl stearate wax, and hydrocarbon instead of hydrocarbon wax (Nippon Seiki Co., Ltd .; HNP-10) A cyan toner 14 was produced in the same manner as in Example 1 except that wax (manufactured by Nippon Seiki Co., Ltd .; FT100) (DSC main peak: 89 ° C.) was used.

  Regarding the cyan toner 14, the content of the ether compound according to the present invention was measured by gas chromatography. As a result, the cyan toner 14 contained 110 ppm of di-tert-butyl ether. The physical properties of the cyan toner 14 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Example 15>
Styrene / butyl acrylate copolymer produced by solution polymerization method (glass transition temperature: 65 ° C., weight average molecular weight: 12500, Mw / Mn: 2.4) 100 parts Styrene produced by suspension polymerization method -Acrylic acid copolymer (glass transition temperature: 59 ° C, weight average molecular weight: 573,000, Mw / Mn: 2.0) 100 parts-Aluminum salicylate compound
(Bontron E-88; manufactured by Orient Chemical Co., Ltd.) 4 parts C.I. I. Pigment Blue 15: 3 7 parts, di-tert-butyl ether 0.03 parts The above materials are mixed in a blender, melt-kneaded with a biaxial extruder heated to 110 ° C, and the cooled kneaded material is coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product was subjected to air classification to obtain cyan toner particles.

  The cyan toner 15 of the present invention was obtained by mixing 1.5 parts of silica (R972, manufactured by Aerosil Co., Ltd.) with 100 parts of the cyan toner particles using a Henschel mixer (manufactured by Mitsui Miike).

  A developer is prepared by mixing 94 parts of an acrylic-coated ferrite carrier with 6 parts of the cyan toner 15, and the above-mentioned modified machine of a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. The image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 15, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 1 contained di-tert-butyl ether. The physical properties of the cyan toner 15 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 16>
Styrene / n-butyl acrylate copolymer (mass ratio: 80/20) 200 parts Aluminum salicylate compound (Bontron E-88; manufactured by Orient Chemical Co.) 4 parts Stearyl stearate wax (DSC main peak: 60 ° C) ) 22 parts hydrocarbon wax (Nippon Seiki Co., Ltd .; HNP-10, DSC main peak: 75 ° C.)
8 parts I. Pigment Blue 15: 3 7 parts, di-tert-butyl ether 0.03 parts The above materials are mixed in a blender, melt-kneaded with a biaxial extruder heated to 110 ° C, and the cooled kneaded material is coarsely pulverized with a hammer mill. The coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product was subjected to air classification to obtain cyan toner particles.

  The cyan toner 16 of the present invention was obtained by mixing 1.5 parts of silica (R972, manufactured by Aerosil Co., Ltd.) with 100 parts of the cyan toner particles using a Henschel mixer (manufactured by Mitsui Miike).

  A developer is prepared by mixing 94 parts of an acrylic-coated ferrite carrier with 6 parts of the cyan toner 16, and the modified machine of a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. The image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 16, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 16 contained di-tert-butyl ether. The physical properties of the cyan toner 16 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 17>
A cyan toner 17 having a weight average particle diameter of 2.8 μm was obtained by performing the same operation as in Example 1 except that the amounts of ion-exchanged water and tricalcium phosphate in Example 1 were changed. Using this cyan toner 17, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 17, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 17 contained di-tert-butyl ether. The physical properties of the cyan toner 17 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 18>
Except for changing the amounts of ion-exchanged water and tricalcium phosphate in Example 1, the same operation as in Example 1 was performed to obtain cyan toner 18 having a weight average particle diameter of 10.5 μm. Using this cyan toner 18, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 18, the content of the ether compound according to the present invention was measured by gas chromatography. As a result, it was confirmed that the cyan toner 18 contained di-tert-butyl ether. Further, in the image printed out with the toner of the present embodiment, there is no practical problem, but some scattering was confirmed in the characters and line images. The physical properties of the cyan toner 18 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 19>
A cyan toner 19 was obtained in the same manner as in Example 1 except that tert-hexyl peroxypivalate in Example 2 was changed to tert-butyl peroxyneodecanoate. Using this cyan toner 19, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 19, the content of the ether compound according to the present invention was measured by gas chromatography, and it was confirmed that the cyan toner 19 contained the ether compound represented by the following structural formula (2). It was done. The physical properties of the cyan toner 19 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 20>
A cyan toner 20 was obtained in the same manner as in Example 1 except that 2,2′-azobis (2,4-dimethylvaleronitrile) in Example 1 was changed to isobutyl peroxide. Using this cyan toner 20, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 20, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 20 contained di-tert-butyl ether. The physical properties of the cyan toner 20 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 21>
A cyan toner 21 was obtained in the same manner as in Example 1 except that 2,2′-azobis (2,4-dimethylvaleronitrile) in Example 1 was changed to tert-butyl peroxyisobutyrate. . Using this cyan toner 21, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 21, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 21 contained di-tert-butyl ether. The physical properties of the cyan toner 21 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Example 22>
The cyan toner 22 was prepared in the same manner as in Example 1 except that 2,2′-azobis (2,4-dimethylvaleronitrile) in Example 1 was changed to tert-butylperoxy-2-ethylhexanoate. Got. Using this cyan toner 22, image evaluation and durability evaluation were performed in the same manner as in Example 1.

  Regarding the cyan toner 22, when the content of the ether compound according to the present invention was measured by gas chromatography, it was confirmed that the cyan toner 22 contained di-tert-butyl ether. The physical properties of the cyan toner 22 are shown in Tables 1 to 3, and the evaluation results are shown in Tables 4 and 5.

<Comparative Example 1>
A cyan toner 23 was produced in the same manner as in Example 1 except that di-tert-butyl ether was not added.

  Regarding the cyan toner 23, the ether compound content was measured by gas chromatography. As a result, no corresponding ether compound was present in the cyan toner 23. The physical properties of the cyan toner 23 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Comparative example 2>
A cyan toner 24 was produced in the same manner as in Example 1 except that di-tert-butyl ether was changed to diethyl ether having the following structural formula (3).

  Regarding the cyan toner 24, the content of the ether compound was measured by gas chromatography. As a result, the cyan toner 24 contained 130 ppm of the ether compound having the above structure. The physical properties of the cyan toner 24 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Comparative Example 3>
A cyan toner 25 was produced in the same manner as in Example 1 except that the ether compound to be added was changed to the compound of the following structural formula (4).

  Regarding the cyan toner 25, the ether compound content was measured by gas chromatography. As a result, the cyan toner 25 contained 2000 ppm of the ether compound having the above structure. The physical properties of the cyan toner 25 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

<Comparative example 4>
A cyan toner 26 was produced in the same manner as in Example 1 except that no hydrocarbon wax was added. Regarding the cyan toner 26, the content of the ether compound was measured by gas chromatography. As a result, it was confirmed that the cyan toner 26 contained di-tert-butyl ether. The physical properties of the cyan toner 26 are shown in Tables 1 to 3, and the evaluation results obtained in the same manner as in Example 1 are shown in Tables 4 and 5.

FIG. 2 is a diagram schematically illustrating a configuration of an example of an image forming apparatus to which the toner of the present invention is applied. FIG. 6 is a diagram schematically showing a configuration of another example of an image forming apparatus to which the toner of the present invention is applied. FIG. 6 is a diagram schematically showing a configuration of another example of an image forming apparatus to which the toner of the present invention is applied. FIG. 2 is a diagram schematically showing a configuration of an example of a developing device to which the toner of the present invention is applied. It is a figure which shows schematically the structure of the other example of the image development apparatus to which the toner of this invention is applied. 1 is a diagram schematically showing a configuration of an image forming apparatus used in an embodiment of the present invention.

Explanation of symbols

31, 73, 89 Developing sleeve 32 Developer control member 33 Photoconductor drum 34 Fixed magnet 35, 36 Agitation means 37 Developing means 41, T toner 43, 57 Transfer means 44, 59, 421, 500 Cleaning means 45, 430 Pressure Roller 46, 429 Heating roller 51 Photoconductor 52, 117 Charging roller 52a, 57a Conductive elastic layer 52b, 55b, 57b, 437 Core metal 54-1, 54-2, 54-3, 54-4, 140 Developer 55 Intermediate transfer member 55a Elastic layer 56 Transfer material 58 Cleaning blade 74 Toner container 75 Magnetic generating means 76 Restricting member 77, 88 Latent image holding body 78 Power supply 80 Elastic blade 86 Bias applying means 100, 419 Photosensitive drum 102 Toner carrier 114 Transfer Roller 116 Cleaner 121 Laser generation 123, E Laser light 124 Register roller 125 Conveying belt 126, 418 Fixing device 141 Stirring member 402, 403 Transfer material supply tray 404, 405 Feed roller 407, 408 Feed guide 409 Contact roller 410 Gripper 411 Transfer Material separation charger 412 Separation claw 413 Transfer charger 414 Transfer material separation charger 415 Transfer drum 416 Conveyor belt means 417 Ejection tray 420 Charger 423 Primary charger 422 Charger 424 Image exposure means 425 Image exposure reflection Means 426 Case (Rotating body)
427Y Yellow developing device 427M Magenta developing device 427C Cyan developing device 427BK Black developing device 428 Document 436 Heater 452 Ejecting roller 501 Fixing device I Transfer material conveying system I
II Latent image forming section III Developing means (rotary developing device)
A Distance between the developer regulating member 32 and the developing sleeve 31 B Distance between the developing sleeve 31 and the photosensitive drum 33 C Contact width of the magnetic brush on the developing sleeve 31 with the photosensitive drum 33 (developing nip)
D Arrow indicating the rotation direction of the transfer drum 415 F Development area T1 Magnetic toner thin layer T2 Toner image

Claims (11)

A toner containing at least a binder resin and a colorant,
The toner contains at least one compound represented by the following general formula (1) or (2),
The toner has two different endothermic peaks P1 and P2 in the temperature range of 55 to 120 ° C. in the DSC curve at the time of temperature rise measured by DSC.
The toner, wherein the endothermic peak P1 is on a lower temperature side than the endothermic peak P2.

(R _{1 to} R ₁₁ in the general formula (1) and the general formula (2) are alkyl groups having 1 to 6 carbon atoms and may be the same or different from each other.)   The toner according to claim 1, wherein the content of the compound is 5 to 800 ppm.   The toner according to claim 1, wherein the content of the compound is 10 to 500 ppm.   4. The toner according to claim 1, wherein an intensity ratio (P1 / P2) between the endothermic peak P2 and the endothermic peak P1 is 0.1 to 10. 5.   The toner according to any one of claims 1 to 4, wherein the endothermic peak P1 is a peak derived from an ester wax, and the endothermic peak P2 is a peak derived from a hydrocarbon wax.   6. The toner according to claim 1, wherein the toner has an average circularity of 0.940 or more and a weight average particle diameter (D4) of 3 to 10 μm.   The toner according to any one of claims 1 to 6, wherein the mode circularity is 0.99 or more.   The toner according to claim 1, wherein the toner is produced by a polymerization method.   The toner is obtained by suspension polymerization in which a polymerizable monomer composition containing a polymerizable monomer and a colorant is dispersed in an aqueous medium, and the polymerizable monomer is polymerized using a polymerization initiator. The toner according to claim 8, wherein the toner is manufactured.   10. The toner according to claim 9, wherein the polymerization initiator has a 10-hour half-life temperature of 40 ° C. or more and less than 60 ° C. 10. The toner according to claim 9, wherein the polymerization initiator is a compound represented by the following general formula (3).

(In the general formula (3), R ₁₂ is unsubstituted or substituted alkyl having 3 to 9 carbon atoms, unsubstituted or substituted cycloalkyl having 3 to 8 carbon atoms, unsubstituted or substituted cycloalkyl having 3 to 8 carbon atoms, or Any one selected from the group consisting of substituted aryl, R ₁₃ , R ₁₄ and R ₁₅ each independently represent an alkyl group, and the total number of carbon atoms of R ₁₃ , R ₁₄ and R ₁₅ is 3; It is 5 or less.)

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