JP5176562B2 - Method for evaluating abundance of solid surface deposit, and method for evaluating protective agent coating apparatus - Google Patents

Description

The reference means according to the present invention is used in an image forming apparatus provided with an image carrier or a process cartridge equipped in the image carrier, and the surface of the image carrier is subjected to a mechanical force such as a frictional force with a cleaning blade. The present invention relates to a protective agent coating apparatus that applies a protective agent for protecting the image carrier from stress, electrical stress due to charging, etc., and further, a process cartridge equipped with the protective agent coating apparatus, or the protective agent coating. The present invention relates to an image forming apparatus such as a copying machine, a printer, a plotter, a facsimile, or a complex machine including the apparatus or process cartridge.
In addition, the present invention provides a solid surface deposit abundance evaluation method for evaluating the abundance of a very small amount of deposit adhering to a solid surface such as an image carrier, and an image carrier using the evaluation method. The present invention relates to a method for evaluating a protective agent coating apparatus that evaluates the pass / fail of a protective agent coating apparatus that applies a protective agent to the surface.

  It is required in many fields to evaluate the abundance of a very small amount of deposits on a solid surface. For example, the electrical and mechanical properties of the solid surface change, and the wettability and adhesiveness change depending on the evaluation of the thickness of the coating layer in the coating technology field and the amount of deposits that are foreign substances on the solid surface. It is necessary to evaluate the amount of deposits on the solid surface. In particular, the deposit on the surface of the photoreceptor used for image formation or the like may have a great influence on the formed image even if the deposit is very small. In addition, it is very important how much a necessary amount of a substance that exhibits a function of maintaining high image quality due to being thinly present on the photoreceptor, such as a protective agent, is present on the photoreceptor. Therefore, a method for evaluating the amount of thin film deposits on the solid surface is strongly demanded.

  For example, quantitative analysis using ICP (Inductively Coupled Plasma) emission analysis and analysis using XPS (X-ray photoelectron spectroscopy) have been performed as methods for evaluating the amount of deposits on the solid surface. However, since the ICP emission analysis is an elemental analysis, organic substances that do not contain metal elements cannot be quantitatively analyzed. In XPS analysis, only information on the solid surface of a solid having a depth of several nanometers can be obtained. As a result, it was impossible to estimate the abundance of a thick deposit having a thickness of several nm or more.

  In addition, there is an example in which the amount of zinc stearate, which is a protective agent, is estimated in analysis of deposits on the surface of a photoreceptor using XPS (for example, Patent Document 1 (Japanese Patent Laid-Open No. 2005-17469)). 2 (Japanese Unexamined Patent Application Publication No. 2005-249901), Japanese Patent Application Laid-Open No. 2005-004051, Japanese Patent Application Laid-Open No. 2004-198662). However, in the XPS analysis of zinc stearate, a method of evaluating by the ratio of zinc element to all elements was used, and the evaluation of deposits was basically limited to those having indices like metal elements. .

  Alternatively, if the solid does not dissolve in the solvent in which the deposit is dissolved, the deposit is extracted by dissolution, and the deposit is quantified by liquid chromatography, gas chromatography, mass spectrometry, NMR, or the like. However, most of the organophotoreceptors are dissolved in a solvent that dissolves deposits, and this method cannot be used.

  As described above, some deposits cannot use the evaluation method as described above. For example, when a protective agent having a simple structure not containing metal such as paraffin is used, XPS analysis or XRF ( Since no metal was detected in X-ray fluorescence analysis or ICP emission analysis, it was difficult to evaluate the amount adhering to the photoreceptor.

  On the other hand, an ATR (Attenuated Total Reflection) method is known as a method for analyzing organic substances (see, for example, Patent Document 5 (Utility Model Registration No. 2597515)). This ATR method is one of the methods for measuring the infrared absorption spectrum and uses total reflection. An ATR prism having a high refractive index is brought into close contact with the sample, and the sample is irradiated with infrared light through the ATR prism. The light emitted from the ATR prism is spectrally analyzed.

  When infrared light is incident on the prism at a certain angle or more due to the refractive index relationship between the ATR prism and the sample, the infrared light does not exit the ATR prism and causes total reflection at the contact surface between the ATR prism and the sample. However, at that time, infrared light oozes to the sample side by a short distance, so that if the sample absorbs infrared light, the reflected light attenuates and an absorption spectrum of the sample can be obtained.

Since the ATR method can measure the absorption spectrum of a very thin sample portion in contact with the ATR prism, it has the advantage that even a thick sample or a sample with low permeability can be measured if it can be brought into close contact with the ATR prism. I have.
When the ATR method is used, the functional group is known from the wave number at which infrared light absorption occurs. Therefore, the ATR method is often used for qualitative analysis.
However, since the peak intensity of the absorption spectrum changes depending on the pressure with which the sample is pressed, it has not been basically used for quantitative analysis.

  Next, in an image forming apparatus using an electrophotographic process, an image is formed by performing a charging process, an exposure process, a development process, and a transfer process on the photoreceptor. The discharge product generated in the charging process and remaining on the surface of the photoreceptor and the residual toner or toner component remaining on the surface of the photoreceptor after the transfer process are removed through a cleaning process.

As a generally used cleaning method, a rubber blade that is inexpensive, has a simple mechanism, and has excellent cleaning properties is used. However, since the rubber blade is pressed against the photoconductor to remove the residue on the surface of the photoconductor, stress due to friction between the surface of the photoconductor and the cleaning blade is large. Layer wear occurs and shortens the life of rubber blades and organophotoreceptors. In addition, the toner used for image formation in response to the demand for higher image quality has become a small particle size. In an image forming apparatus using small-diameter toner, the rate at which residual toner passes through the cleaning blade increases. In particular, the dimensional accuracy and assembly accuracy of the cleaning blade are insufficient, or the cleaning blade partially vibrates. In such a case, the toner slips through the image and prevents high-quality image formation.
Therefore, in order to extend the life of the organic photoreceptor and maintain high image quality over a long period of time, it is necessary to reduce deterioration of the member due to friction and improve cleaning properties.

  In response to this requirement, a method of actually supplying a protective agent including a lubricant to the photoreceptor and forming a protective agent film with a cleaning blade is employed. Since the surface of the photoconductor is protected by the protective agent by applying the protective agent to the photoconductor, the photoconductor wear due to friction between the cleaning blade and the photoconductor or the energy of the discharge caused by charging the photoconductor Degradation is reduced. Also, the application of the protective agent increases the lubricity of the surface of the photoreceptor, so that the phenomenon that the cleaning blade partially oscillates is reduced, and the amount of slip-through toner is reduced. However, if the amount of the protective agent applied is too small, such a lubricity and protective property can not exert sufficient effects on photoconductor wear, photoconductor deterioration due to AC charging, and toner slipping. It was necessary to keep it.

  Regarding the evaluation of the coating amount of the protective agent, when zinc stearate generally used as a protective agent is used, as described above, the amount of zinc stearate applied to the surface of the photosensitive member is determined by the XPS of the photosensitive member surface. A method of evaluating by the ratio of zinc element to all elements detected by analysis has been used (see Patent Documents 1 to 4).

Since XPS analysis detects all elements other than hydrogen on the surface of the sample, analyzing the surface of an organic photoreceptor coated with zinc stearate using XPS analysis increases the coverage of zinc stearate. When the zinc stearate coverage becomes 100%, the element ratio theoretically matches the element ratio of zinc stearate, and the detected amount of zinc is saturated. Resulting in. That is, when zinc stearate (C ₃₆ H ₇₀ O ₄ Zn) covers the entire surface of the photoreceptor, the XPS is calculated from the ratio of elements other than hydrogen in the molecule of zinc stearate (C ₃₆ H ₇₀ O ₄ Zn). The ratio of zinc element to the total element detected by analysis is theoretically 2.44%.

  In recent years, so-called AC charging using a charging roller or the like for charging by superimposing an alternating current (AC) voltage on a direct current (DC) voltage has been used in the charging step. This AC charging has excellent performance such as high uniformity of the charging potential of the photoconductor, less generation of oxidizing gas such as ozone and nitrogen oxide (NOx), and miniaturization of the apparatus. Depending on the frequency of the applied AC voltage, positive and negative discharges of several hundred to several thousand times per second are repeated between the charging member and the photoconductor, so that the photoconductor is subjected to this large number of discharges and the deterioration of the surface layer is accelerated. Is done. For this deterioration, when a protective agent is applied to the photoconductor, the AC charging energy is first absorbed by the protective agent, and the photoconductor is difficult to reach, so that the photoconductor is protected.

  The protective metal soap is decomposed by the AC charging energy, but the metal soap is not completely decomposed and lost, but a fatty acid having a low molecular weight is generated, and the frictional force between the photoconductor and the cleaning blade In addition to the fact that the toner component easily adheres in a film form to the photosensitivity along with the fatty acid, and the resolution of the image tends to be lowered, the photoconductor wears out, and the density tends to be uneven. was there. Therefore, a large amount of metal soap is supplied onto the photoconductor so that the surface of the photoconductor can be immediately covered with metal soap even if fatty acids are generated. However, even if a large amount of metal soap is supplied onto the photoconductor, only a small portion of the metal soap actually adheres to the surface of the photoconductor, and most of the metal soap supplied onto the photoconductor is used together with the toner. Since the toner is transferred or removed together with the waste toner, the metal soap is depleted at an early stage, and the metal soap must be replaced with a new one before the life of the photosensitive member.

  As a protective agent (lubricant) that replaces metal soap, for example, in Patent Document 6 (Japanese Patent Laid-Open No. 2005-274737), a lubricant that supplies a lubricant mainly composed of a higher alcohol having 20 to 70 carbon atoms. By using the supply device, higher alcohol stays at the tip of the blade nip as irregular particles and has appropriate wettability to the surface of the image carrier, so that the durability of the lubricating performance is expressed.

  However, lubricants with higher alcohols tend to get wet on the surface of the photoreceptor and can be expected to be effective as lubricants. However, higher alcohol molecules adsorbed on the image carrier and the occupied area occupied by each molecule tend to be larger. Since the density of molecules adsorbed per unit area of the image bearing member (adsorbed molecule weight per unit area) is small, it is difficult to protect the photoconductor from the above-described electrical stress due to AC charging.

  In Patent Document 7 (Japanese Patent Application Laid-Open No. 2002-97483), a powder of a specific alkylene bisalkyl amide compound is used as a lubricating component, so that the cleaning blade and the image carrier are brought into contact with each other at the pressure contact. Since fine powder particles are present, a smooth lubricating action can be maintained over a long period of time.

  However, a lubricant having a nitrogen atom in the molecule has an ion dissociation property similar to a nitrogen oxide or an ammonium-containing compound as a decomposition product when the lubricant itself is subjected to the above-described electrical stress due to AC charging. A compound may be generated and taken into the lubricating layer, and the lubricating layer may have a low resistance under high humidity, causing image blurring.

  On the other hand, the paraffin-based protective agent protects the photoconductor from electrical stress due to AC charging, can reduce the frictional force between the photoconductor and the cleaning blade, and has an extremely high waste toner cleaning property. It turns out to be good. In particular, a protective agent mainly composed of paraffin is very preferable because even if it is oxidized by stress due to AC charging, the production of fatty acid is small and the change in frictional force between the photoreceptor and the cleaning blade is very small.

  However, when image formation is repeated using a protective agent mainly composed of paraffin, an abnormal image that may be caused by wear of the photoreceptor and the cleaning blade may occur. In particular, the probability of occurrence of an abnormal image may vary greatly depending on the lot for manufacturing the protective agent coating apparatus.

  A detailed investigation of where the abnormal image occurred and where it did not occur revealed that the film thickness of the photoconductor was small in the place where the streaky abnormal image occurred and where no abnormal image occurred. It was found that the toner component was attached and a large amount of the toner component was adhered, but it was not known why this phenomenon occurred.

  As described above, paraffin is effective as a protective agent to replace metal soap. However, when a protective agent with a simple structure not containing metal such as paraffin is used, the metal is not used in XPS analysis or XRF analysis. Since it was not detected, it was difficult to evaluate the amount of protective agent applied on the photoreceptor. In addition, in the case of a protective agent containing a metal such as metal soap, the coating amount can be followed from the metal element by ICP emission analysis as a method for obtaining the coating amount, but a protective agent that does not contain a metal such as paraffin is used. In such a case, the coating amount could not be evaluated by ICP emission analysis.

JP 2005-17469 A JP 2005-249901 A JP-A-2005-004051 JP 2004-198662 A Utility Model Registration No. 2597515 JP 2005-274737 A JP 2002-97483 A JP 52-36016 A

The reference means according to the present invention has been made in view of the above circumstances, and evaluated the coating amount of the protective agent using an evaluation method for evaluating the existing amount of the protective agent on the image carrier, and the appropriate coating amount. A protective agent coating apparatus capable of supplying a protective agent to prevent the occurrence of an abnormal image, a process cartridge including the protective agent coating apparatus, and an image including the protective agent coating apparatus or the process cartridge It is a technique aimed at providing a forming apparatus .
In addition, the present invention provides a solid surface when a thin film-like deposit is present on a solid surface such as an image carrier, or when a thin film-like deposit containing no metal element is present on the solid surface. It is an object of the present invention to provide an abundance evaluation method for solid surface deposits that evaluates the abundance of deposits, and a method for evaluating a protective agent coating apparatus that evaluates the pass / fail of a protection agent coating apparatus using the evaluation method.

In order to achieve the above object, the following means are employed in the reference means according to the present invention and the present invention .
The first reference means according to the present invention is a protective agent coating apparatus for applying a protective agent to the surface of an image carrier. “In the ATR (Attenuated Total Reflection) method of infrared absorption spectrum method, Ge, red When comparing IR spectrum A of the image carrier before application of the protective agent and IR spectrum B of the image carrier after application of the protective agent with respect to the IR spectrum obtained by measuring under the condition of 45 ° as the external light incident angle, A peak derived from the image carrier existing in both IR spectrum A and IR spectrum B, and of the peaks derived from the image carrier, a peak not overlapping with a peak derived from the protective agent in IR spectrum B Of the two peaks, the peak having the larger wave number in the IR spectrum A is the peak a1, and the peak having the smaller wave number is the peak. Is the peak a2, the peaks in the IR spectrum B corresponding to the wave numbers detected at the same wave numbers as the peaks a1 and a2 are the peaks b1 and b2, and the height of the peak a1 in the IR spectrum A is h. (A1) When the height of the peak b1 in the IR spectrum B is h (b1), the IR spectrum A is multiplied by [h (b1) / h (a1)] (referred to as IR spectrum A ′). ) Is a spectrum obtained by subtracting from IR spectrum B as IR spectrum C, and peaks corresponding to wave numbers detected at the same positions as peaks a 1 and a 2 in IR spectrum C are peaks c 1 and c 2, respectively. When the area of the peak b1 in the IR spectrum B is S (b1) and the area of the peak c2 in the IR spectrum C is S (c2), the ratio of the area S (b1) to the area S (c2) ( S (c2) / S (b1)) as an index, and an evaluation method for evaluating the abundance of the protective agent on the image carrier ”, the peak b1 is 1770 cm ⁻¹ and the peak c2 is 815 cm ⁻¹ . When the amount of the protective agent on the image carrier is evaluated, the value of the index (S (c2) / S (b1)) in the image carrier after the protective agent is applied for 20 minutes is 0. 012 or more, the value of the index (S (c2) / S (b1)) in the image carrier after the protective agent is applied for 100 minutes is 0.10 or less.

According to a second reference means of the present invention , in the protective agent coating apparatus of the first reference means, an index (S (c2) / S (b1)) calculated from the IR spectrum is used on the image carrier. using the evaluation method for evaluating the presence of the protective agent, when the peak b1 is the peak of 1770 cm ^-1, the peak c2 is obtained by evaluating the presence of the protective agent on the image bearing member as a peak of 1250 cm ^-1 The image carrier after the protective agent is applied for 20 minutes and the index (S (c2) / S (b1)) of the image carrier is 0.10 or more and the protective agent is applied for 100 minutes. The value of the index (S (c2) / S (b1)) in the body is 0.35 or less.

According to a third reference means of the present invention , in the protective agent coating apparatus of the first or second reference means, the image carrier to which the protective agent is applied is a photoconductor.
According to a fourth reference means of the present invention , in the protective agent coating apparatus of the third reference means, the photoconductor is an organic photoconductor containing an organic compound having a carbonate bond, and the peak a1 is The peak is derived from a carbonate bond.
The fifth reference means according to the present invention is the protective agent coating apparatus according to any one of the first to fourth reference means, wherein the protective agent contains 50% by weight or more of paraffin. .

According to a sixth reference means of the present invention , in the protective agent coating apparatus according to any one of the first to fifth reference means, the protective agent bar mainly composed of paraffin and the protective agent of the protective agent bar are scraped off. A brush to be supplied to the image carrier, and a blade for fixing the protective agent supplied to the image carrier; the protective agent on the protective agent bar is scraped off by the brush; and the brush is attached to the image carrier. A protective agent mainly composed of paraffin is supplied to the image carrier by pressing, and the protective agent is fixed on the image carrier by pressing the blade.

Seventh reference means according to the present invention is a process cartridge, characterized by comprising an image bearing member, a protective agent applying device of the first to sixth one of the reference means.
Further, reference means 8 according to the present invention is an image forming apparatus, characterized by comprising an image bearing member, a protective agent applying device of the first to sixth one of reference means .
Further ninth reference means according to the present invention is an image forming apparatus, characterized by being equipped with a process cartridge of the seventh reference means detachably.
Furthermore, a tenth reference means according to the present invention is the image forming apparatus of the eighth or ninth reference means, comprising a plurality of the image carriers or the process cartridges, and images having different colors on each image carrier. Then, the image is transferred to a transfer medium to form a multicolor or color image.

The first means of the present invention is an evaluation method for evaluating the abundance of deposits on a solid surface. The IR of a solid surface without deposits measured by the ATR (Attenuated Total Reflection) method of infrared absorption spectroscopy. When comparing the spectrum A and the IR spectrum B of the solid surface to which the deposit is attached, the solid-derived peak that exists in both the IR spectrum A and the IR spectrum B, and of the solid-derived peaks, the IR There are at least two peaks that do not overlap with the peaks derived from the deposits in the spectrum B. Of the two peaks, the peak having the larger wave number in the IR spectrum A is the peak a1, and the peak having the smaller wave number is the peak. Is the peak a2, and the peaks in the IR spectrum B corresponding to the wave numbers detected at the same wave numbers as the peaks a1 and a2 are the peaks b1 and b2. When the height of the peak a1 in the IR spectrum A is h (a1) and the height of the peak b1 in the IR spectrum B is h (b1), the IR spectrum A is [h (b1) / h. (A1)] The spectrum obtained by subtracting the multiplied spectrum (referred to as IR spectrum A ′) from the IR spectrum B is referred to as IR spectrum C, and the IR spectrum C is detected at the same wave number as the peaks a1 and a2. When the peaks corresponding to wave numbers are peaks c1 and c2, the area of the peak b1 in the IR spectrum B is S (b1), and the area of the peak c2 in the IR spectrum C is S (c2), From the ratio (S (c2) / S (b1)) of the area S (b1) of the peak b1 in the IR spectrum B and the area S (c2) of the peak c2 in the IR spectrum C on the solid surface Presence of deposits Characterized in that it evaluated.

According to a second means of the present invention, in the method for evaluating the amount of solid surface deposits of the first means, the peak a1 is detected as the penetration depth at the wave number of the infrared light from which the peak a2 is detected. It is characterized by being 130% or more of the penetration depth at the wave number of infrared light.

A third means of the present invention is characterized in that, in the solid surface deposit abundance evaluation method of the first or second means, the solid for evaluating the solid surface deposit abundance is a photoconductor. To do.
According to a fourth means of the present invention, in the method for evaluating the amount of solid surface deposits of the third means, the photoreceptor is an organic photoreceptor containing an organic compound having a carbonate bond, and the peak a1 Is a peak derived from the carbonate bond.

The fifth means of the present invention is a protective agent having a function of protecting the photoreceptor by the deposit on the surface of the photoreceptor in the method for evaluating the amount of the deposit on the solid surface of the third or fourth means. It is characterized by that.
According to a sixth means of the present invention, in the method for evaluating the abundance of solid surface deposits according to the fifth means, the protective agent contains 50% by weight or more of paraffin.

The seventh means of the present invention is a method for evaluating a protective agent coating apparatus for applying a protective agent to the surface of an image carrier, wherein the amount of solid surface deposits is evaluated according to any one of claims 1 to 6. When the protective agent is applied to the image carrier by the protective agent coating apparatus using the method, the amount of deposits in the abundance evaluation method is an index within the predetermined application time. The ratio (S (c2) / S (b1)) of the area S (b1) of the peak b1 in the IR spectrum B and the area S (c2) of the peak c2 in the IR spectrum C is within a predetermined standard. When the value is reached, the protective agent coating apparatus is passed.

According to the reference means of the present invention , even when a protective agent containing no metal such as paraffin is used, an evaluation method capable of evaluating the amount of the protective agent applied on an image carrier such as a photoreceptor. By using the protective agent coating apparatus, it is possible to satisfactorily apply the protective agent to the image carrier and prevent the occurrence of abnormal images, and a process including the protective agent coating apparatus. A cartridge and an image forming apparatus can be provided.
Further, according to the present invention, there is provided an evaluation method capable of evaluating the abundance of the protective agent applied to the solid surface even when a protective agent containing no metal such as paraffin is applied to the solid surface such as an image carrier. Yes, by using this evaluation method, the quality of the protective agent coating apparatus can be determined.

[ Reference Form 1]
First, the reference embodiment according to the first to tenth reference means according to the present invention.
In the image forming apparatus using a photoconductor as an image carrier, the present inventors investigate the cause of the occurrence of an abnormal image. The surface observation was performed using a scanning electron microscope (SEM). As a result of surface observation, it was possible to observe the appearance of the protective agent adhering to the photoconductor, but from the SEM observation, the amount of the protective agent could not be estimated, and the cause of abnormal image generation was I didn't understand.

Next, the present inventors considered that the generation mechanism of the abnormal image differs depending on the image to be imaged, and observed the location where the abnormal image is generated in more detail by SEM. As a result, the image area of the image to be imaged When the amount of toner is small, the toner component often adheres to the photoreceptor and the resolution of the image is often lowered. When the image area of the image to be formed is large, the photoreceptor is partially worn and an abnormal image is likely to occur. I understood. As described above, the method of generating an abnormal image differs depending on the image to be formed. Therefore, the image is not formed and only the protective agent is applied on the photoconductor, that is, depending on the protective agent application capability of the protective agent application device. Considering that an abnormal image may or may not appear, an attempt was made to estimate the coating amount of the protective agent on the photoreceptor.
Here, as described in the above background art, when a protective agent containing no metal such as paraffin is used as the protective agent, the amount of the protective agent applied on the photoreceptor is estimated by a conventional method. Is difficult. Therefore, an attempt was made to use the FT-IR ATR method, which is used for analysis of organic substances, as a method for analyzing a protective agent not containing a metal.

Here, the IR spectrum obtained by FT-IR looks at how the intensity distribution with respect to the wave number (wavelength) of light possessed by the infrared light source changes depending on the specimen sample, and is usually the reciprocal of the wavelength. The wave number (unit: cm ⁻¹ ) is taken as a horizontal axis, and the vertical axis is drawn as a curve with transmittance (T) and absorbance (A). The transmittance is the ratio of the energy transmitted through the sample to the energy incident on the sample, and the absorbance is a common logarithm of the reciprocal of the transmittance. It is well known that the absorbance and the sample concentration are in a proportional relationship (Lambert-Beer's law), and when performing a quantitative calculation, the peak intensity of the absorbance spectrum is generally used. The peak intensity of the IR spectrum is preferably not a transmittance but an absorbance with good quantitativeness.

  Devices for measuring IR spectra are broadly divided into dispersive infrared spectrophotometers and Fourier transform infrared spectrophotometers, and because of their high time efficiency, light usage rate, wave number resolution, and wave number accuracy, Fourier transform red Outer spectrophotometers (FT-IR) are the current mainstream. As a measurement method, there are various measurement accessories in addition to the normal transmission method, and the measurement method can be selected according to the form of the sample and information to be known. Among various measurement accessories, the ATR (Attenuated Total Reflection) method is capable of measuring an IR spectrum with almost no sample processing, and has recently become quite popular as a measurement accessory for FT-IR.

The ATR method is a method for measuring an infrared absorption spectrum, which uses total reflection. An ATR prism having a high refractive index is closely attached to a sample, and the sample is irradiated with infrared light through the ATR prism. The light emitted from the ATR prism is spectrally analyzed.
Due to the relationship between the refractive index of the ATR prism and the sample, when infrared light is incident on the prism at a certain angle or more, the infrared light does not come out of the ATR prism and is totally reflected at the contact surface between the ATR prism and the sample. At this time, since the infrared light oozes out to the sample side by a small distance, if the sample absorbs the infrared light, the reflected light is attenuated and an absorption spectrum of the sample can be obtained.

Since the ATR method can measure the absorption spectrum of a very thin sample portion in contact with the ATR prism, it has the advantage that even a thick sample or a sample with low permeability can be measured if it can be brought into close contact with the ATR prism. I have.
In addition, when the ATR method is used, since the functional group is known from the wave number at which infrared light absorption occurs, the ATR method is often used for qualitative analysis, but the peak intensity of the absorption spectrum changes depending on the pressure with which the sample is pressed. It was not basically used for quantitative analysis.

The present inventors think that it is difficult to perform a quantitative analysis using the ATR method, but it may be a rough amount. The ATR measurement was performed on the obtained photoreceptor under various conditions, and the spectra were compared and analyzed.
As a result, in the ATR method, the penetration depth of infrared light changes depending on the crystal used and the incident angle condition. Therefore, even if the same sample is measured, the spectrum obtained is different. Only the peak derived from the photocatalyst was detected, only the peak of only the protective agent was detected, and both the peak derived from the photoconductor and the peak derived from the protective agent were detected. Applying the protective agent on the photoconductor from the spectrum obtained under various conditions where both the crystal used and the incident angle are finely changed to detect both the photoconductor-derived peak and the protective agent-derived peak. We eagerly investigated whether the amount could be evaluated.

  Here, in the ATR method, the intensity ratio changes depending on the pressure with which the sample is pressed, so the intensity of the spectrum cannot be followed directly. Therefore, when setting the sample during measurement, if the gap between the jig for fixing the sample and the crystal can be kept constant, or if the pressing pressure is constant, an IR spectrum can be obtained under certain conditions. Therefore, when setting the sample, the gap between the jig for pressing the sample and the crystal could be kept constant, and the sample with the coating time varied by a protective agent coating apparatus was measured. As a result, the spectrum of the photoconductor not coated with the protective agent was subtracted from the obtained spectrum so that the reference peak was zero, and the resulting difference spectrum was derived from the photoconductor. The peak on the lower wavenumber side than the reference peak tended to be stronger as the protective agent application time was longer.

Therefore, when the difference spectrum was taken with respect to the polycarbonate, the area of the peak that remained without being subtracted from the photoreceptor existing on the lower wave number side than the peak of the polycarbonate in the difference spectrum was calculated, and was further used as the reference. When divided by the area of the polycarbonate peak (the spectrum used for calculating the area of the polycarbonate peak was the spectrum where the protective agent was applied), it was found that the area ratio gradually increased as the coating time increased.
Next, using the area ratio obtained above, it was investigated whether a good state of the coating amount of the protective agent on the photoreceptor after applying the protective agent with the protective agent coating apparatus could be defined. It was found that the image forming with high image quality can be realized by setting it within the preferable range, and the present invention has been achieved.

That is, the reference means of the present invention is used in a process cartridge or an image forming apparatus, and in a protective agent coating apparatus that applies paraffin as a protective agent to the surface of a photoconductor as an image carrier, the “ATR of infrared absorption spectrum method” is used. In the method, for the IR spectrum obtained by measurement under the conditions of Ge as the ATR prism and 45 ° as the incident angle of infrared light, the IR spectrum A of the photoconductor before applying the protective agent and the IR spectrum of the photoconductor after applying the protective agent When B is compared, it is a peak derived from the photoreceptor existing in both IR spectrum A and IR spectrum B, and does not overlap with a peak derived from the protective agent in IR spectrum B among the peaks derived from the photoreceptor. There are at least two peaks, and the peak with the larger wave number in IR spectrum A is the peak of the two peaks. 1. The peak with the smaller wave number is the peak a2, the peak in the IR spectrum B corresponding to the wave number detected at the same position as the peaks a1 and a2 is the peak b1, b2, and the peak in the IR spectrum A A spectrum obtained by multiplying IR spectrum A by [h (b1) / h (a1)] (IR spectrum, where h1 is the height of a1 and h (b1) is the height of peak b1 in IR spectrum B A ′) is subtracted from IR spectrum B as IR spectrum C, and the peak corresponding to wave number detected at the same position as peaks a 1 and a 2 in IR spectrum C is peak c 1. The ratio of the area S (b1) to the area S (c2) where c2 is the area of the peak b1 in the IR spectrum B is S (b1) and the area of the peak c2 in the IR spectrum C is S (c2). (S (c2) / Using an evaluation method for evaluating the abundance of the protective agent on the photoreceptor using S (b1)) as an index, the peak b1 is 1770 cm ⁻¹ and the peak c2 is 815 cm ⁻¹ on the photoreceptor. When the abundance of the protective agent was evaluated, the value of (S (c2) / S (b1)) in the photoreceptor after applying the protective agent for 20 minutes was 0.012 or more and in the photoreceptor after 100 minutes of application. The value of (S (c2) / S (b1)) is 0.12 or less.

  Here, the infrared light does not reflect at the sample interface, but enters the sample side by a certain depth and then totally reflects, but the penetration depth of the infrared light irradiates the sample with infrared light. At this time, the intensity of the infrared light is defined as a distance that is 1 / e of the intensity on the sample surface, and is expressed by the following formula 1. From Equation 1, the depth at which the infrared light enters the sample varies depending on the incident angle and the refractive index and wavelength (wave number) of the ATR crystal. As the incident angle θ increases and the refractive index of the ATR crystal increases, the measurement wavelength increases. The shorter the is, the smaller the depth of penetration, and information closer to the surface is reflected in the spectrum.

dp = λ / 2πn ₁ [sin ² θ− (n ₂ / n ₁ ) ² ] ^1/2 (Formula 1)
However,
dp: penetration depth n ₂ and n ₁ : refractive index of crystal and sample θ: incidence angle λ: wavelength.

In the reference means according to the present invention, the ATR method is used for analyzing the protective agent on the photoconductor, and Ge having a large refractive index and capable of obtaining information closer to the surface is used as the ATR prism. In addition, the incident angle of infrared light to the sample is 45 °. In the evaluation of the coating apparatus of the present invention, an index with higher accuracy can be obtained by setting the infrared light incident angle to 45 °. A combination of these ATR prisms and infrared light incident angles can express a preferable state as the coating amount of the protective agent on the photoreceptor.

In the reference means according to the present invention, the peak a1 (b1, c1) is a peak derived from a carbonate bond, and since the carbonate bond is a stable bond, the deterioration is unlikely to occur and the influence on the spectrum is small. Since it has sufficient peak intensity, it is preferable as a standard peak when taking a difference spectrum. The peak area in the reference means according to the present invention is calculated using an absorbance spectrum with good quantitativeness.

In the reference means according to the present invention , the peak of a2 (b2, c2) used for index calculation has sufficient intensity and does not overlap with other peaks, or deformation of the peak of a2 due to overlap is small. preferable. Further, the penetration depth of infrared light at the wave number at which a2 is detected is preferably in the range of 130% to 300% of the penetration depth at the wave number at which a1 is detected. When the penetration depth at the wave number at which the peak a2 is detected is 130% or less and 300% or more of the penetration depth at the wave number at which the peak a1 is detected, the index (S (c2) / S (b1)) Since sensitivity becomes small, it is not preferable.

From these, if you choose the peak derived from a carbonate bond to a peak a1, as the peak a2, it is preferable to use a peak derived from the photosensitive member to be detected by the 600cm ^-1 ~1380cm ^-1, at 815 cm ^-1 The peak to be detected can be selected.
When a peak detected at 815 cm ⁻¹ is selected as a 2, the value of (S (c 2) / S (b 1)) in the photoreceptor after applying the protective agent for 20 minutes is 0.012 or more, preferably 0 .015 to 0.070. When the value of (S (c2) / S (b1)) does not become 0.012 or more within 20 minutes of the application time of the protective agent, the protective agent does not sufficiently protect the photoreceptor in the initial use of the image forming apparatus. Therefore, it is not preferable.

  The value of (S (c2) / S (b1)) in the photoreceptor after 100 minutes of application of the protective agent is 0.12 or less, preferably 0.020 to 0.075. When the value of (S (c2) / S (b1)) is 0.12 or more within 100 application times of the protective agent, the application amount of the protective agent becomes excessive when the image forming apparatus is used extensively. Further, it is not preferable because the photosensitive member is not sufficiently charged or is blurred.

In the reference means according to the present invention , the peak used as a2 may be a peak detected at 1250 cm ⁻¹ .
When a peak detected at 1250 cm ⁻¹ is selected as a 2, the value of (S (c 2) / S (b 1)) in the photoreceptor after applying the protective agent for 20 minutes is 0.10 or more, preferably 0 .10 to 0.3. When the value of (S (c2) / S (b1)) does not become 0.10 or more within 20 minutes of the application time of the protective agent, the protective agent does not sufficiently protect the photoreceptor in the initial use of the image forming apparatus. Therefore, it is not preferable.

The value of (S (c2) / S (b1)) in the photoreceptor after 100 minutes of application of the protective agent is 0.35 or less, preferably 0.15 to 0.32. When the value of (S (c2) / S (b1)) is 0.35 or more within 100 minutes of the coating time of the protective agent, the coating amount of the protective agent becomes excessive when the image forming apparatus is used up. Therefore, the photosensitive member is not sufficiently charged or undesirably blurred.
Thus, the upper and lower limits of the index for maintaining high image quality need to be determined as appropriate depending on the peak to be selected.

In the protective agent coating apparatus of the reference means according to the present invention, the protective agent contains 50% by weight or more, preferably 50 to 95% by weight of paraffin.
The ratio of paraffin in the protective agent in the reference means according to the present invention indicates the ratio to all organic components contained in the protective agent, and when the protective agent contains an inorganic component, the inorganic component Represents the ratio of paraffin to the total organic components excluded.
Further, the threshold value of the index (S (c2) / S (b1)) varies slightly depending on the ratio of paraffin in the protective agent, but the coating amount of the protective agent on the photoreceptor is good regardless of the ratio of paraffin. As described above, the condition is that the value of (S (c2) / S (b1)) in the photoreceptor after applying the protective agent for 20 minutes is 0.012 or more (c2 is a peak at 815 cm ⁻¹ ), 100 minutes. It has been found that the value of (S (c2) / S (b1)) in the photoreceptor after coating is well within the threshold value of 0.12 or less (c2 is a peak at 815 cm ^-1 ).

The protective agent used in the protective agent coating apparatus of the reference means according to the present invention is mainly paraffin.
Examples of the paraffin used as the protective agent for the reference means according to the present invention include normal paraffin and isoparaffin. The paraffin may be used by mixing not only one kind but also different kinds of paraffin.
The proportion of paraffin in the protective agent used as the protective agent of the reference means according to the present invention is 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. When the proportion of paraffin is 50% by weight or less, the function as a protective agent is low, and the photoconductor is easily worn by image formation, which is not preferable. Further, if the ratio of paraffin is 95% by weight or more, it is difficult and difficult for paraffin to cover the surface of the photoreceptor. In the case of paraffin alone, it is indispensable to mix with other substances because it is thin on the photoconductor and hardly spreads in a film form only by the pressure of the brush or blade.

Substances other than paraffin used as the protective agent of the reference means according to the present invention include amphiphilic organic compounds, aliphatic unsaturated hydrocarbons, alicyclic saturated hydrocarbons, alicyclic unsaturated hydrocarbons and aromatic carbonization. In addition to hydrocarbons classified as hydrogen, polytetrafluoroethylene (PTFE), polyperfluoroalkyl ether (PFA), perfluoroethylene-perfluoropropylene copolymer (FEP), polyvinylidene fluoride (PVdF) , Fluorine-based resins such as ethylene-tetrafluoroethylene copolymer (ETFE), fluorine-based waxes, silicone resins such as polymethylsilicone and polymethylphenylsilicone, silicone-based waxes, mica and other inorganic compounds having lubricity Although not limited to these, among others, amphiphilic organic compounds When the alicyclic saturated hydrocarbon is contained in the protective agent, the coating property of the protective agent is improved. In particular, the alicyclic saturated hydrocarbon such as cyclic polyolefin can be coated on the photoreceptor in the form of a film. Particularly preferred. These compounds other than paraffin may be used not only in one kind but also in a mixture of many kinds.
Examples of the alicyclic saturated hydrocarbon include cycloparaffin and cyclic polyolefin.

Amphiphilic organic compounds are classified into anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and composites thereof. Since the protective agent forms a protective agent layer on the image carrier as described above and undergoes an image forming process, it is necessary not to adversely affect the electrical characteristics of the image carrier.
By using a nonionic surfactant as an amphiphilic organic compound, the surfactant itself does not dissociate, so even if the usage environment, especially humidity, changes significantly, air discharge etc. Therefore, the image quality can be maintained at a high level.

Further, the nonionic surfactant is preferably an esterified product of an alkyl carboxylic acid of the following chemical formula 1 and a polyhydric alcohol.
C _n H _{2n + 1} COOH (Chemical Formula 1)
However, n in a formula shows the integer of 15-35.

  By using a linear alkyl carboxylic acid as the alkyl carboxylic acid of Formula 1, the hydrophobic portion of the amphiphilic organic compound can be easily arranged on the surface of the image carrier on which the amphiphilic organic compound is adsorbed. This is a preferred mode because the adsorption density on the surface is particularly high.

The alkyl carboxylic acid ester in one molecule is hydrophobic, and the larger the number, the more the dissociable substances generated by air discharge are prevented from adsorbing on the surface of the image carrier, and the surface of the image carrier in the charged region. It is effective to reduce the electrical stress on. However, if the proportion of the alkyl carboxylic acid ester is too large, the portion of the polyhydric alcohol that exhibits hydrophilicity is obscured and sufficient adsorption performance may not be exhibited depending on the surface state of the image carrier. .
Therefore, the average number of ester bonds per molecule of the amphiphilic organic compound is preferably 1 to 3.

The average number of ester bonds per molecule of these amphiphilic organic compounds can be adjusted by selecting one or more from a plurality of amphiphilic organic compounds having different numbers of ester bonds.
Examples of the amphiphilic organic compound include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant as described above.

  Examples of anionic surfactants include alkylbenzene sulfonate, α-olefin sulfonate, alkane sulfonate, alkyl sulfate, alkyl polyoxyethylene sulfate, alkyl phosphate, long chain fatty acid salt, α -Anion (anion) at the end of the hydrophobic site, such as sulfo fatty acid ester salt and alkyl ether sulfate, and alkali metal ions such as sodium and potassium, and alkaline earth metal ions such as magnesium and calcium , Compounds in which metal ions such as aluminum and zinc, ammonium ions, and the like are bonded.

Examples of cationic surfactants include a cation (cation) at the end of a hydrophobic site, such as alkyltrimethylammonium salt, dialkylmethylammonium salt, alkyldimethylbenzylammonium salt, etc., and chlorine, fluorine , Bromine and the like, and compounds in which phosphate ions, nitrate ions, sulfate ions, thiosulfate ions, carbonate ions, hydroxide ions, and the like are bonded.
Examples of amphoteric surfactants include dimethylalkylamine oxide, N-alkylbetaines, imidazoline derivatives, alkyl amino acids and the like.

  Examples of nonionic surfactants include alcohol compounds such as long-chain alkyl alcohols, alkyl polyoxyethylene ethers, polyoxyethylene alkyl phenyl ethers, fatty acid diethanolamides, alkyl polyglucooxides, polyoxyethylene sorbitan alkyl esters, Examples include ether compounds and amide compounds. In addition, long-chain alkyl carboxylic acids such as lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, and melicic acid, and polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, and hexitol And ester compounds with these partial anhydrides are also preferred.

  More specific examples of the ester compound include glyceryl monostearate, glyceryl distearate, glyceryl monopaltimate, glyceryl dilaurate, glyceryl trilaurate, glyceryl dipaltimate, glyceryl tripartinate, glyceryl dimyristate, and glyceryl trimistate. Glyceryl stearate, glyceryl monopartate, glyceryl monoarachidate, glyceryl diarachidate, glyceryl monobehenate, glyceryl behenate stearate, glyceryl stearate stearate, glyceryl monomontanate, glyceryl monomelinate, and its substitutes, Sorbitan monostearate, sorbitan tristearate, sorbitan monopartitic acid, sorbitan dipartitic acid, Sorbitan palmitate, sorbitan dimyristate, sorbitan trimistate, sorbitan palmitate, sorbitan monoarachidate, sorbitan diarachidate, sorbitan dibehenate, sorbitan monobehenate, sorbitan stearate, sorbitan monostearate, sorbitan monomontanate, monomelicic acid Examples include, but are not limited to, sorbitans of alkylcarboxylic acids such as sorbitan, and their substitutes.

Moreover, these amphiphilic organic compounds may use a single kind, and may use multiple types together.
Furthermore, you may make a protective agent contain fillers, such as a metal oxide, a silicic acid compound, and a mica, depending on the case.

A specific reference form of the reference means according to the present invention will be described below with reference to the drawings.
FIG. 1 is a schematic configuration diagram showing a main part of an example of the configuration of an image forming apparatus provided with a protective layer forming apparatus as a reference means according to the present invention.
The protective agent coating apparatus 2 disposed opposite to the drum-shaped photosensitive member 1 serving as an image carrier is a protective agent that protects the photosensitive member into a rod-like shape (cylindrical, quadrangular, hexagonal, etc.). A protective agent supply member 22 that has a bar 21, a brush-like member (brush) 22 a that contacts the protective agent bar 21, and supplies the protective agent transferred from the protective agent bar 21 to the brush 22 a to the photoreceptor 1; A pressing force applying mechanism 23 for pressing the bar 21 against the brush 22a of the protective agent supply member 22 to transfer the protective agent to the brush 22a of the protective agent supply member 22, and protection supplied to the photosensitive member by the protective agent supply member 22 It is mainly composed of a protective layer forming mechanism 24 for thinning the agent.

The protective agent bar 21 by the reference means according to the present invention is pressed against the brush 22a of the protective agent supply member 22 by a pressing force from a pressing force applying mechanism 23 formed of a pressing member such as a spring or a spring, and the protective agent bar 21 To the brush 22a. The protective agent supply member 22 rotates with a linear velocity difference with the photosensitive member 1 and rubs the surface of the photosensitive member with the tip of the brush 22a. At this time, the protective agent held on the surface of the brush 22a of the protective agent supply member 22 is removed. , And supplied to the surface of the photoreceptor 1.
Further, the protective agent supplied to the surface of the photoreceptor 1 may not be a sufficient protective layer at the time of supply depending on the selection of the material type. For this reason, in order to form a more uniform protective layer, the photosensitive agent surface protective agent is, for example, a blade-like member 24a and a pressure such as a spring or a spring that presses the blade-like member 24a against the surface of the photosensitive drum 1. It is thinned by the protective layer forming mechanism 24 having the member 24b and becomes a protective layer on the surface of the photoreceptor. As described above, by supplying an appropriate amount of the protective agent to the photosensitive member 1 and thinning it by the protective layer forming mechanism 24, the protective agent is easily held as a protective film on the photosensitive member. As a result, it is possible to realize an image forming apparatus that does not cause an abnormal image due to dirt or the like of the charging unit (for example, the charging roller) 3 and can output a high-quality image over a long period of time with less frequent replacement of consumables. .

  The material of the blade-like member 24a used for the protective layer forming mechanism 24 is not particularly limited. For example, an elastic body such as urethane rubber, hydrin rubber, silicone rubber, or fluorine rubber, which is generally known as a cleaning blade material, is used alone. Or it can be blended and used. In addition, these rubber blades may be coated or impregnated with a low friction coefficient material at the contact portion with the photoreceptor 1. Further, in order to adjust the hardness of the elastic body, fillers represented by other organic fillers and inorganic fillers may be dispersed.

These blade-like members 24a are fixed to the blade support 24c by an arbitrary method such as adhesion or fusion so that the tip portion can be pressed against the surface of the photoreceptor (note that the blade tip contact direction) Is not limited to the illustrated example, but may be in the counter direction). The thickness of the blade-like member 24a is not uniquely defined in consideration of the force applied by pressing, but is preferably about 0.5 to 5 mm, more preferably about 1 to 3 mm. Can be used.
Further, the length of the blade-like member 24a that protrudes from the support 24c and can bend, that is, the so-called free length, is not uniquely defined in consideration of the force applied by pressing in the same manner. If it is about ~ 15mm, it can be preferably used, and if it is about 2-10mm, it can be used still more preferably.

  As another configuration of the blade-like member 24a for forming the protective layer, the surface of the elastic metal blade such as a spring plate is coated with a layer of resin, rubber, elastomer or the like, if necessary, via a coupling agent or a primer component, It may be formed by a method such as dipping, heat-cured or the like if necessary, and further subjected to surface polishing if necessary.

The thickness of the elastic metal blade is preferably about 0.05 to 3 mm, and more preferably about 0.1 to 1 mm.
Moreover, in an elastic metal blade, in order to suppress the twist of a blade, you may perform processes, such as a bending process, in the direction substantially parallel to a spindle after attachment.
As a material for forming the surface layer, fluororesins such as PFA, PTFE, FEP, PVdF, and silicone elastomers such as fluoro rubber and methylphenyl silicone elastomer can be used together with a filler if necessary. It is not limited to.

  Further, the force for pressing the blade-like member 24a against the photoconductor by the pressing member 24b of the protective layer forming mechanism 24 is sufficient as the force that the protective agent on the surface of the photoconductor extends to form a protective layer or a protective film, The linear pressure is preferably 5 gf / cm or more and 80 gf / cm or less, and more preferably 10 gf / cm or more and 60 gf / cm or less.

In addition, a brush-like member 22a is preferably used as the protective agent supply member 22. In this case, the brush fiber is preferably flexible in order to suppress mechanical stress on the surface of the photoreceptor.
As a specific material of the flexible brush fiber, one or more kinds can be selected and used from generally known materials. Specifically, polyolefin resins (for example, polyethylene, polypropylene); polyvinyl and polyvinylidene resins (for example, polystyrene, acrylic resin, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether and Polyvinyl chloride); vinyl chloride-vinyl acetate copolymer; styrene-acrylic acid copolymer; styrene-butadiene resin; fluorine resin (for example, polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene); Polyester; Nylon; Acrylic; Rayon; Polyurethane; Polycarbonate; Phenol resin; Amino resin (eg urea-formaldehyde resin, melamine) Fat, benzoguanamine resins, urea resins, polyamide resins); Among such, may be a resin having flexibility.
Also, in order to adjust the degree of bending, diene rubber, styrene-butadiene rubber (SBR), ethylene propylene rubber, isoprene rubber, nitrile rubber, urethane rubber, silicone rubber, hydrin rubber, norbornene rubber, etc. are used in combination. Also good.

The support 22b of the protective agent supply member 22 includes a fixed type and a rotatable roll. As the roll-shaped supply member, for example, there is a roll brush in which a tape having brush fibers piled is wound around a metal core in a spiral shape. The brush fiber has a fiber diameter of about 10 to 500 μm, the length of the brush fiber is 1 to 15 mm, and the brush density is 10,000 to 300,000 per square inch (1.5 × 10 ^{7 to} 4.5 × 10 per square meter). ⁸ ) are preferably used.

  The protective agent supply member 22 is preferably made of a material having a high brush density as much as possible from the viewpoint of supply uniformity and stability, and one fiber is made from several to several hundreds of fine fibers. Is also preferable. For example, bundling 50 fine fibers of 6.7 decitex (6 denier), such as 333 decitex = 6.7 decitex × 50 filament (300 denier = 6 denier × 50 filament), and implanting as one fiber Is also possible.

  In addition, a coating layer may be provided on the surface of the brush 22a as necessary for the purpose of stabilizing the surface shape, environmental stability, and the like of the brush 22a. As a component constituting the coating layer, it is preferable to use a coating layer component that can be deformed according to the bending of the brush fiber, and these are not limited as long as the material can maintain flexibility. Polyolefin resins such as polyethylene, polypropylene, chlorinated polyethylene, chlorosulfonated polyethylene, etc .; polystyrene, acrylic (for example, polymethyl methacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, Polyvinyl and polyvinylidene resins such as polyvinyl carbazole, polyvinyl ether, and polybiliketones; vinyl chloride-vinyl acetate copolymers; silicone resins composed of organosiloxane bonds or modified products thereof (for example, alkyd resins, Modified products by reester resin, epoxy resin, polyurethane, etc.); Fluororesin such as perfluoroalkyl ether, polyfluorovinyl, polyfluorovinylidene, polychlorotrifluoroethylene; polyamide; polyester; polyurethane; polycarbonate; urea-formaldehyde resin, etc. Amino resins; epoxy resins, composite resins of these, and the like.

Next, FIG. 2 is a cross-sectional view for explaining an outline of a configuration example of a process cartridge using a protective agent coating apparatus as a reference means according to the present invention. The process cartridge 11 is detachably mounted as the image forming unit 10 of the image forming apparatus.
A process cartridge 11 shown in FIG. 2 includes a drum-shaped photosensitive member 1 as an image carrier, a charging device (charging roller in the illustrated example) 3 as a charging unit that charges the photosensitive member 1, and a charged photosensitive member. 1. A latent image forming means (not shown) for forming an electrostatic latent image by irradiating a laser beam L or the like on 1 and a developing means for developing the electrostatic latent image on the photoreceptor 1 with a toner into a visible image A developing device 5, a transfer unit 6 that transfers a toner image on the photoconductor 1 to a transfer medium (or an intermediate transfer medium) 7, and a cleaning unit that removes toner remaining on the surface of the photoconductor 1 after transfer. The cleaning device 4 includes a cleaning device 4 and a protective agent coating device 2 disposed in a portion from the cleaning device 4 to the charging device 3.

In FIG. 2, a charging device 3 is a charging roller to which a direct current (DC) voltage or a voltage obtained by superimposing an alternating current (AC) voltage is applied by a high voltage power source (not shown), for example. The developing device 5 includes a developing sleeve 51 which is a developer carrying member that carries and conveys toner particles or a mixture of toner particles and carrier particles, and a developer stirring and conveying member that conveys the developer while stirring. 52, 53 and the like.
As in FIG. 1, the protective agent coating device 2 disposed facing the photosensitive member 1 mainly includes a protective agent bar 21, a protective agent supply member 22, a pressing force applying mechanism 23, a protective layer forming mechanism 24, and the like. Composed.
The photosensitive member 1 has a surface on which partially deteriorated protective agent, toner component, and the like remain after the transfer process, but the surface residue is cleaned and cleaned by the cleaning member 41 of the cleaning device 4. In FIG. 2, the blade-shaped cleaning member 41 is in contact with an angle similar to a so-called counter type (or leading type).

  The protective agent of the protective agent bar 21 is supplied by the protective agent supply member 22 to the surface of the photosensitive member from which the residual toner and the deteriorated protective agent have been removed by the cleaning device 4, and the protective agent supplied to the photosensitive member surface. Is thinned by the protective layer forming mechanism 24 to form an amorphous film-like protective layer. At this time, the protective agent used in the present invention has a better adsorptivity to the portion of the photoreceptor surface that is highly hydrophilic due to electrical stress. Therefore, even if the surface of the photoconductor starts to deteriorate partially, the progress of deterioration of the photoconductor itself can be prevented by adsorption of the protective agent.

  The photosensitive member 1 on which the protective layer is formed is charged by the charging roller 3 and then an electrostatic latent image is formed by exposure with a laser beam L or the like, and is developed with the toner of the developing device 5 as a developing unit to be visualized. Then, the image is transferred to a transfer medium (or intermediate transfer medium) 7 by a transfer device (transfer roller or the like) 6 which is a transfer means outside the process cartridge.

Next, FIG. 3 is a schematic configuration diagram illustrating a configuration example of an image forming apparatus 100 including a protective agent coating apparatus as a reference unit according to the present invention.
The image forming apparatus 100 includes an image forming apparatus main body (printer unit) 110 that performs image formation, a document reading unit (scanner unit) 120 installed on the upper part of the main unit 110, and an automatic document supply unit installed thereon. A paper device (ADF) 130 and a paper feed unit 200 installed at the lower part of the image forming apparatus main body 110 are provided, and have a function of a copying machine. The image forming apparatus 100 has a communication function with an external device, and can be used as a printer or a scanner by connecting to a personal computer or the like outside the device. In addition, it can be used as a facsimile or a multifunction machine by connecting to a telephone line or an optical line.

  In the image forming apparatus main body 110, four image forming units (image forming stations) 10 having the same configuration and different toner colors of the developing device 5 are arranged side by side. The four image forming units 10 are arranged on the photosensitive member. Images with different toner colors (for example, yellow (Y), magenta (M), cyan (C), and black (K) images) are formed, and the toner images of the respective colors are transferred onto the transfer medium or intermediate transfer medium. Thus, a multicolor or full color image can be formed. In the example of FIG. 3, the four image forming units 10 are juxtaposed along the belt-like intermediate transfer medium 7 stretched around a plurality of rollers, and each color formed by each image forming unit is provided. The toner image is once superimposed on the intermediate transfer medium 7 and transferred, and then transferred to a sheet-like transfer medium such as paper by the secondary transfer device 12.

  The image forming unit 10 for each color has the same configuration as that in FIG. 2, and the protective agent coating device 2, the charging device 3, and the latent image forming device 8 are arranged around the drum-shaped photoconductor 1 (1Y, 1M, 1C, 1K). An exposure unit such as a laser beam from the laser beam, a developing device 5, a primary transfer device 6, and a cleaning device 4 are arranged. Similarly to FIG. 2, the image forming unit 10 of each color includes a process cartridge 11 in which a protective agent coating device 2, a charging device 3, a developing device 5, and a cleaning device 4 are provided in the cartridge together with the photoreceptor 1. Used. The process cartridge is detachably attached to the image forming apparatus main body 110.

Next, the operation of the image forming apparatus shown in FIG. 3 will be described. Here, a series of processes for image formation will be described using a negative-positive process. Since the operation of each image forming unit is the same, the operation of one image forming unit will be described here.
The drum-shaped photoreceptor 1, which is an image carrier represented by an organic photoreceptor (OPC) having an organic photoconductive layer, is neutralized by a neutralizing lamp (not shown) or the like, and a charging member (for example, a charging roller) is used. The charging device 3 is uniformly charged negatively.
When the charging device 3 charges the photoreceptor 1, a voltage of an appropriate magnitude suitable for charging the photoreceptor 1 to a desired potential from a voltage application mechanism (not shown) to the charging member or A charging voltage in which an AC voltage is superimposed on this is applied.

The charged photoreceptor 1 is a laser beam irradiated by a laser scanning type latent image forming apparatus 8 including, for example, a plurality of laser light sources, a coupling optical system, an optical deflector, a scanning imaging optical system, and the like. Then, a latent image is formed (the absolute value of the exposed portion potential is lower than the absolute value of the non-exposed portion potential).
That is, laser light emitted from a laser light source (for example, a semiconductor laser) is deflected and scanned by an optical deflector composed of a polygonal polygonal mirror (polygon) that rotates at high speed, thereby forming a scanning image formed of a scanning lens, a mirror, and the like. The surface of the photoconductor 1 is scanned in the rotation axis direction (main scanning direction) of the photoconductor 1 via the optical system.

The latent image formed in this manner is developed with a developer made of toner particles or a mixture of toner particles and carrier particles supplied onto the developing sleeve 51 which is a developer carrying member of the developing device 5, and toner A visual image is formed.
At the time of developing the latent image, a voltage applying mechanism (not shown) is applied to the developing sleeve 51 with a voltage of an appropriate magnitude between the exposed portion and the non-exposed portion of the photoreceptor 1 or an AC voltage superimposed thereon. A bias is applied.

The toner image formed on the photoreceptor 1 of the image forming unit 10 corresponding to each color by the above operation is sequentially superimposed on the intermediate transfer medium 7 by the primary transfer device 6 composed of a transfer roller or the like for primary transfer. Is done. On the other hand, in synchronization with the image forming operation and the primary transfer operation, the paper feed roller 202 and the separation roller are selected from the paper feed cassettes selected from the multi-stage paper feed cassettes 201a, 201b, 201c, and 201d of the paper feed unit 200. A sheet-like transfer medium such as paper is fed by a paper feed mechanism 203, and is conveyed to a secondary transfer unit via conveyance rollers 204, 205, 206 and registration rollers 207. In the secondary transfer unit, the toner image on the intermediate transfer medium 7 is secondarily transferred to the transferred transfer medium by a secondary transfer device (for example, a secondary transfer roller) 12. In the above transfer step, it is preferable that a potential having a polarity opposite to the charging polarity of the toner is applied to the primary transfer device 6 and the secondary transfer device 12 as a transfer bias.
After the secondary transfer, the transfer medium is separated from the intermediate transfer medium 7 to obtain a transfer image. Further, the toner particles remaining on the photoreceptor 1 after the primary transfer are collected into the toner collection chamber in the cleaning device 4 by the cleaning member 41 of the cleaning device 4. Further, the toner particles remaining on the intermediate transfer medium 7 after the secondary transfer are collected into the toner collection chamber in the cleaning device 9 by the cleaning member of the belt cleaning device 9.

  The image forming apparatus 100 shown in FIG. 3 is a so-called tandem type intermediate transfer type image forming apparatus in which a plurality of the above-described image forming units 10 are arranged along the intermediate transfer medium 7. A plurality of toner images having different colors sequentially formed on the respective photoreceptors 1 (1Y, 1M, 1C, and 1K) are once transferred onto the intermediate transfer medium 7 and then transferred like a paper at a time. Transfer to media. The transfer medium onto which the toner image has been transferred is sent to the fixing device 14 by the conveying device 13 and the toner is fixed by heat or the like. The fixed transfer medium is discharged to a paper discharge tray 17 by a transport device 15 and a paper discharge roller 16. The image forming apparatus 100 also has a double-sided printing function. During double-sided printing, the conveyance path downstream of the fixing device 9 is switched, and the transfer medium on which the image on one side is fixed is transferred to the front and back sides via the double-sided conveyance apparatus 210. The paper is reversed, and is fed again to the secondary transfer unit by the transport roller 206 and the registration roller 207, and the image is transferred to the back side. The transfer medium after transfer is conveyed to the fixing device 9 in the same manner as described above to fix the image, and the transfer medium after fixing is discharged to the discharge tray 17.

  In addition, in the above configuration, a tandem type direct transfer type image forming apparatus that directly transfers to a transfer medium such as paper without using an intermediate transfer medium can be provided. In place of the transfer medium, a transfer belt or the like that carries and transfers the transfer medium is used, and a plurality of toner images having different colors that are sequentially created on the respective photoreceptors 1 (1Y, 1M, 1C, and 1K) by the image forming units 10 The toner may be directly transferred onto a transfer medium such as paper conveyed by a transfer belt and then sent to a fixing device to fix the toner by heat or the like.

In the image forming apparatus as described above, the charging device 3 is preferably a charging device in which a charging member is disposed in contact with or in close proximity to the surface of the photoreceptor, so that a so-called corotron using a discharge wire is used. Compared with a corona discharger called “Scorotron”, the amount of ozone generated during charging can be greatly reduced.
However, in the charging device 3 that charges the charging member in contact with or close to the surface of the photosensitive member, since the discharge is performed in the region near the surface of the photosensitive member as described above, the electrical stress on the photosensitive member 1 increases. Tend to.
Therefore, by using the protective agent coating apparatus 2 as the reference means according to the present invention , the photoconductor 1 can be maintained for a long time without deteriorating, so that the fluctuation of the image over time and the fluctuation of the image due to the use environment are greatly increased. Therefore, stable image quality can be ensured.

Next, a photoconductor preferably used in the process cartridge and the image forming apparatus according to the reference means of the present invention will be described.
In the photoreceptor, which is an image carrier used in the image forming apparatus of the reference means according to the present invention , a photosensitive layer is provided on a conductive support. The photosensitive layer is composed of a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, or a charge generation layer provided on the charge transport layer. There is a reverse layer type. In addition, a protective layer can be provided on the photosensitive layer in order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, and the like of the photoreceptor. An undercoat layer may be provided between the photosensitive layer and the conductive support. In addition, an appropriate amount of a plasticizer, an antioxidant, a leveling agent and the like can be added to each layer as necessary.

  As the conductive support of the photosensitive member, one having a volume resistance of 10 ^ 10 Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation A metal oxide such as indium is deposited or sputtered on a film or cylindrical plastic or paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. After forming the tube into a drum shape, it is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like. A drum-shaped support having a diameter of 20 to 150 mm, preferably 24 to 100 mm, and more preferably 28 to 70 mm can be used. If the diameter of the drum-shaped support is 20 mm or less, it is physically difficult to arrange the charging, exposure, development, transfer, and cleaning steps around the drum. If the diameter of the drum-shaped support is 150 mm or more, image formation is performed. The apparatus becomes undesirably large. In particular, when the image forming apparatus is a tandem type, it is necessary to mount a plurality of photoconductors, and thus the diameter is preferably 70 mm or less, and preferably 60 mm or less. Further, endless nickel belts and endless stainless steel belts disclosed in JP-A-52-36016 can also be used as the conductive support.

As the undercoat layer of the photoreceptor used in the image forming apparatus of the reference means according to the present invention , a resin, or a material mainly composed of a white pigment and a resin, and the surface of the conductive substrate are chemically or electrochemically oxidized. Although a metal oxide film etc. can be illustrated, what has a white pigment and resin as a main component is preferable. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among them, it is most preferable to contain titanium oxide that is excellent in preventing charge injection from the conductive substrate. As the resin used for the undercoat layer, thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methylcellulose, thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy, one or various kinds of these Mixtures can be exemplified.

Examples of the charge generating material of the photoreceptor used in the image forming apparatus of the reference means according to the present invention include azo pigments such as monoazo pigments, bisazo pigments, trisazo pigments, tetrakisazo pigments, triarylmethane dyes, and thiazines. Dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone Inorganic materials such as pigments, organic pigments and dyes such as squarylium pigments, phthalocyanine pigments, selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, amorphous silicon can be used, Charge generation materials can be used alone or in combination. The undercoat layer may be a single layer or a plurality of layers.

Examples of the charge transport material of the photoreceptor used in the image forming apparatus of the reference means according to the present invention include, for example, anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, One or many kinds of styryl hydrazone compounds, enamine compounds, butadiene compounds, distyryl compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, triphenylmethane derivatives, etc. Can be used as a mixture.

  The binder resin used to form the photosensitive layer of the charge generation layer and the charge transport layer is electrically insulating and is a known thermoplastic resin, thermosetting resin, photocurable resin, and photoconductive material. Suitable binder resins include, for example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, Ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, polysulfone, polyethersulfone, ABS resin and other thermoplastic resins, phenolic resin, epoxy Resin, urethane resin, melamine resin, isocyanate resin, alkyd resin, Examples thereof include a thermosetting resin such as a ricone resin, a thermosetting acrylic resin, a type of binder resin such as a photoconductive resin such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene, or a mixture of various types of binder resins. In particular, it is not limited to these.

As antioxidant, the following are used, for example.
Monophenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di- t-butyl-4-hydroxyphenyl) propionate, 3-t-butyl-4-hydroxynisol and the like.

Bisphenol compounds 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 ′ -Thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol) and the like.

-High molecular phenol compound 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocophenols, and the like.

Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- ( 2-octadecenyl) -5-methylhydroquinone and the like.

Organic sulfur compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

  As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Is appropriate.

  A leveling agent may be added to the charge transport layer. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the chain are used, and the amount used is 100 parts by weight of binder resin. 0 to 1 part by weight is suitable.

  As described above, the surface layer is provided to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor. Examples of the surface layer include a polymer having a mechanical strength higher than that of the photosensitive layer and a polymer in which an inorganic filler is dispersed. The polymer used for the surface layer may be either a thermoplastic polymer or a thermosetting polymer, but the thermosetting polymer has a high mechanical strength and does not wear due to friction with the cleaning blade. It is very preferable because of its extremely high ability to suppress. If the surface layer has a thin film thickness, there is no problem even if it does not have the charge transport capability. However, if the surface layer without the charge transport capability is formed thick, the sensitivity of the photoreceptor decreases, the potential increases after exposure, and the residual layer remains. Since the potential rise is likely to occur, it is preferable to use the above-mentioned charge transporting substance in the surface layer or to use a polymer having a charge transporting capability for the protective layer. When the surface layer is provided, the mechanical strength of the photosensitive layer and the surface layer is generally greatly different, and therefore the protective layer is worn away due to friction with the cleaning blade. It is important that the surface layer has a sufficient film thickness, and is 0.01 to 12 μm, preferably 1 to 10 μm, more preferably 2 to 8 μm. If the film thickness of the surface layer is 0.1 μm or less, it is not preferable because it is too thin and easily disappears due to friction with the cleaning blade, and wear of the photosensitive layer proceeds from the disappeared portion. When the film thickness of the surface layer is 12 μm or more, the sensitivity is lowered, the potential after exposure is increased, and the residual potential is easily increased. In particular, when a polymer having charge transport capability is used, the cost of the polymer having charge transport capability is high. This is not preferable.

  As the polymer used for the surface layer, polycarbonate that is transparent to the writing light at the time of image formation and excellent in insulation, mechanical strength, and adhesiveness is used. In addition, ABS resin, ACS resin, olefin- Vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin , Polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resin, etc. It may be. These polymers may be thermoplastic polymers, but in order to increase the mechanical strength of the polymers, they are crosslinked with a crosslinking agent having a polyfunctional acryloyl group, carboxyl group, hydroxyl group, amino group, etc. By using a curable polymer, the mechanical strength of the surface layer is increased, and wear due to friction with the cleaning blade can be greatly reduced.

  In the surface layer, fine particles of metal or metal oxide can be dispersed in order to increase the mechanical strength of the surface layer. Examples of the metal oxide include titanium oxide, tin oxide, potassium titanate, TiO, TiN, zinc oxide, indium oxide, and antimony oxide. In addition, for the purpose of improving wear resistance, fluorine resins such as polytetrafluoroethylene, silicone resins, and those obtained by dispersing inorganic materials such as these resins can be added.

In the above reference embodiment, the image carrier is described as a photoconductor. However, the image carrier of the reference means according to the present invention performs primary transfer of a toner image formed on the photoconductor to perform color superposition, and further transfer media. It may be an intermediate transfer medium used for image formation by so-called intermediate transfer method.
As the intermediate transfer medium, a medium having a volume resistance of 10 ^ 5 to 10 ^ 11 Ω · cm 2 is preferable. When the surface resistance is less than 10 ^ 5Ω / □, when transferring the toner image from the photoconductor onto the intermediate transfer medium, so-called transfer dust may be generated in which the toner image is disturbed due to discharge. If it exceeds 11Ω / □, after the toner image is transferred from the intermediate transfer medium to a transfer medium such as paper, the counter charge of the toner image remains on the intermediate transfer medium and appears as a residual image on the next image. is there.

As an intermediate transfer medium, for example, a metal oxide such as tin oxide or indium oxide, or conductive particles such as carbon black or a conductive polymer, alone or in combination, kneaded with a thermoplastic resin, and then extruded into a belt shape Alternatively, a cylindrical plastic can be used. In addition to this, the above-mentioned conductive particles and conductive polymer are added to a resin solution containing a thermal crosslinking reactive monomer or oligomer, if necessary, and subjected to centrifugal molding while heating to obtain an intermediate transfer medium on an endless belt. You can also.
When providing a surface layer on the intermediate transfer medium, among the surface layer materials used for the above-mentioned photoreceptor surface layer, the composition excluding the charge transport material is appropriately adjusted in combination with a conductive substance, Can be used.

Next, a toner suitably used in the process cartridge and the image forming apparatus according to the reference means of the present invention will be described.
First, the toner of the reference means according to the present invention preferably has an average circularity of 0.93 to 1.00. In the reference means according to the present invention , the value obtained from Equation 2 below is defined as the circularity. This circularity is an index of the degree of unevenness of the toner particles, and indicates 1.00 when the toner is a perfect sphere, and the circularity becomes smaller as the surface shape becomes more complicated.
Circularity SR = perimeter of a circle having the same area as the particle projection area / perimeter of the particle projection image (Formula 2)

When the average circularity is in the range of 0.93 to 1.00, the surface of the toner particles is smooth, and the contact area between the toner particles and between the toner particles and the photosensitive member is small, so that the transferability is excellent.
Since the toner particles have no corners, the developer agitation torque in the developing device is small, and the agitation drive is stabilized so that no abnormal image is generated.
Since there are no angular toner particles in the toner that forms the dots, when the pressure is brought into contact with the transfer medium during the transfer, the pressure is uniformly applied to the entire toner that forms the dots, and the transfer is not easily lost.
Since the toner particles are not angular, the abrasive power of the toner particles themselves is small, and the surface of the image carrier is not damaged or worn.

Next, a method for measuring the circularity will be described.
The circularity can be measured using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics.
As a specific measuring method, 0.1 to 0.5 ml of a surfactant, preferably alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water from which impure solids have been removed in advance, and further measurement is performed. Add about 0.1-0.5g of sample. The suspension in which the sample is dispersed is subjected to dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the shape and particle size of the toner are measured by the above apparatus with the dispersion concentration being 3000 to 10000 / μl.

In the reference means according to the present invention , it is preferable that the weight average diameter D4 of the toner is 3 to 10 μm.
In this range, since the toner particles have a sufficiently small particle size with respect to the minute latent image dots, the dot reproducibility is excellent.
When the weight average diameter D4 is less than 3 μm, phenomena such as a decrease in transfer efficiency and a decrease in blade cleaning properties tend to occur.
When the weight average diameter D4 exceeds 10 μm, it is difficult to suppress scattering of characters and lines.

Further, the toner according to the reference means of the present invention preferably has a ratio (D4 / D1) of the weight average diameter D4 and the number average diameter D1 of 1.00 to 1.40. The closer the value of (D4 / D1) is to 1, the sharper the particle size distribution of the toner.
Therefore, when (D4 / D1) is in the range of 1.00 to 1.40, the selective development due to the toner particle size does not occur, and the stability of the image quality is excellent.
Since the toner particle size distribution is sharp, the triboelectric charge amount distribution is also sharp, and fogging is suppressed.
When the toner particle size is uniform, the latent image dots are developed so as to be arranged in a precise and orderly manner, so that the dot reproducibility is excellent.

Next, a method for measuring the particle size distribution of toner particles will be described.
Examples of the measuring device for the particle size distribution of toner particles by the Coulter counter method include Coulter Counter TA-II and Coulter Multisizer II (both manufactured by Coulter). The measurement method is described below.

  First, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant to 100 to 150 ml of an aqueous electrolytic solution. Here, the electrolytic solution is a solution prepared by preparing a 1% NaCl aqueous solution using primary sodium chloride. For example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the measurement device is used to measure the volume and number of toner particles or toner using a 100 μm aperture as an aperture. Volume distribution and number distribution are calculated. From the obtained distribution, the weight average diameter D4 and the number average diameter D1 of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

  In addition, as such a substantially spherical toner, a toner composition containing a polyester prepolymer having a functional group containing a nitrogen atom, a polyester, a colorant, and a release agent in an aqueous medium in the presence of fine resin particles. A toner that undergoes crosslinking and / or elongation reaction is preferred. The toner produced by this reaction can reduce the hot offset by curing the toner surface, and can prevent the fixing device from becoming dirty and appearing on the image.

  Examples of the prepolymer comprising a modified polyester resin that can be used for toner preparation include a polyester prepolymer (A) having an isocyanate group, and examples of a compound that extends or crosslinks with the prepolymer include amines (B). Can be mentioned.

  Examples of the polyester prepolymer (A) having an isocyanate group include a product obtained by further reacting a polyester having an active hydrogen group with a polyisocyanate (3), which is a polycondensate of polyol (1) and polycarboxylic acid (2). Can be mentioned. Examples of the active hydrogen group possessed by the polyester include hydroxyl groups (alcoholic hydroxyl groups and phenolic hydroxyl groups), amino groups, carboxyl groups, mercapto groups, and the like. Among these, alcoholic hydroxyl groups are preferred.

  Examples of the polyol (1) include a diol (1-1) and a tri- or higher valent polyol (1-2). (1-1) alone or (1-1) and a small amount of (1-2) Mixtures are preferred. Diol (1-1) includes alkylene glycol (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, etc.); alkylene ether glycol (diethylene glycol) , Triethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, etc.); alicyclic diols (1,4-cyclohexanedimethanol, hydrogenated bisphenol A, etc.); bisphenols (bisphenol A, bisphenol) F, bisphenol S, etc.); alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, etc.) adduct of the above alicyclic diol; Alkylene oxide phenol compound (ethylene oxide, propylene oxide, butylene oxide, etc.), etc. adducts. Among them, preferred are alkylene glycols having 2 to 12 carbon atoms and alkylene oxide adducts of bisphenols, and particularly preferred are alkylene oxide adducts of bisphenols and alkylene glycols having 2 to 12 carbon atoms. It is a combined use. The trihydric or higher polyol (1-2) includes 3 to 8 or higher polyhydric aliphatic alcohols (glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, etc.); trihydric or higher phenols (Trisphenol PA, phenol novolak, cresol novolak, etc.); and alkylene oxide adducts of the above trivalent or higher polyphenols.

  Examples of the polycarboxylic acid (2) include dicarboxylic acid (2-1) and trivalent or higher polycarboxylic acid (2-2). (2-1) alone and (2-1) with a small amount of ( The mixture of 2-2) is preferred. Dicarboxylic acid (2-1) includes alkylene dicarboxylic acid (succinic acid, adipic acid, sebacic acid, etc.); alkenylene dicarboxylic acid (maleic acid, fumaric acid, etc.); aromatic dicarboxylic acid (phthalic acid, isophthalic acid, terephthalic acid) And naphthalenedicarboxylic acid). Of these, preferred are alkenylene dicarboxylic acids having 4 to 20 carbon atoms and aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the trivalent or higher polycarboxylic acid (2-2) include aromatic polycarboxylic acids having 9 to 20 carbon atoms (trimellitic acid, pyromellitic acid, and the like). In addition, as polycarboxylic acid (2), you may make it react with polyol (1) using the acid anhydride or lower alkyl ester (methyl ester, ethyl ester, isopropyl ester, etc.) of the above-mentioned thing.

  The ratio of the polyol (1) to the polycarboxylic acid (2) is usually 2/1 to 1/1, preferably 1. as the equivalent ratio [OH] / [COOH] of the hydroxyl group [OH] and the carboxyl group [COOH]. 5/1 to 1/1, more preferably 1.3 / 1 to 1.02 / 1.

  Examples of the polyisocyanate (3) include aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); Diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.); aromatic aliphatic diisocyanates (α, α, α ′, α′-tetramethylxylylene diisocyanate, etc.); isocyanurates; the polyisocyanates as phenol derivatives, oximes, caprolactam And a combination of two or more of these.

  The ratio of the polyisocyanate (3) is usually 5/1 to 1/1, preferably 4 /, as an equivalent ratio [NCO] / [OH] of the isocyanate group [NCO] and the hydroxyl group [OH] of the polyester having a hydroxyl group. 1 to 1.2 / 1, more preferably 2.5 / 1 to 1.5 / 1. When [NCO] / [OH] exceeds 5, low-temperature fixability deteriorates. If the molar ratio of [NCO] is less than 1, the urea content in the modified polyester will be low, and the hot offset resistance will deteriorate. The content of the polyisocyanate (3) component in the prepolymer (A) having an isocyanate group at the terminal is usually 0.5 to 40% by weight, preferably 1 to 30% by weight, more preferably 2 to 20% by weight. It is. If it is less than 0.5% by weight, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. On the other hand, if it exceeds 40% by weight, the low-temperature fixability deteriorates.

  The number of isocyanate groups contained per molecule in the prepolymer (A) having an isocyanate group is usually 1 or more, preferably 1.5 to 3 on average, more preferably 1.8 to 2.5 on average. It is. If it is less than 1 per molecule, the molecular weight of the urea-modified polyester will be low, and the hot offset resistance will deteriorate.

  As amines (B), diamine (B1), trivalent or higher polyamine (B2), aminoalcohol (B3), aminomercaptan (B4), amino acid (B5), and amino acids B1-B5 blocked (B6) etc. are mentioned. Examples of the diamine (B1) include aromatic diamines (phenylenediamine, diethyltoluenediamine, 4,4′diaminodiphenylmethane, etc.); alicyclic diamines (4,4′-diamino-3,3′dimethyldicyclohexylmethane, diaminecyclohexane, Isophorone diamine etc.); and aliphatic diamines (ethylene diamine, tetramethylene diamine, hexamethylene diamine etc.) and the like. Examples of the trivalent or higher polyamine (B2) include diethylenetriamine and triethylenetetramine. Examples of amino alcohol (B3) include ethanolamine and hydroxyethylaniline. Examples of amino mercaptan (B4) include aminoethyl mercaptan and aminopropyl mercaptan. Examples of the amino acid (B5) include aminopropionic acid and aminocaproic acid. Examples of the B1 to B5 amino group blocked (B6) include ketimine compounds and oxazoline compounds obtained from the B1 to B5 amines and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.). Among these amines (B), preferred are B1 and a mixture of B1 and a small amount of B2.

  Furthermore, if necessary, the molecular weight of the urea-modified polyester can be adjusted using an elongation terminator. Examples of the elongation terminator include monoamines (diethylamine, dibutylamine, butylamine, laurylamine, etc.), and those obtained by blocking them (ketimine compounds).

  The ratio of amines (B) is the equivalent ratio [NCO] / [NHx] of isocyanate groups [NCO] in the prepolymer (A) having isocyanate groups and amino groups [NHx] in amines (B). The ratio is usually 1/2 to 2/1, preferably 1.5 / 1 to 1 / 1.5, more preferably 1.2 / 1 to 1 / 1.2. When [NCO] / [NHx] exceeds 2 or less than 1/2, the molecular weight of the urea-modified polyester (i) becomes low, and the hot offset resistance deteriorates. In the present invention, the polyester (i) modified with a urea bond may contain a urethane bond together with a urea bond. The molar ratio of the urea bond content to the urethane bond content is usually 100/0 to 10/90, preferably 80/20 to 20/80, and more preferably 60/40 to 30/70. When the molar ratio of the urea bond is less than 10%, the hot offset resistance is deteriorated.

By these reactions, a modified polyester used in the toner of the reference means according to the present invention, particularly urea-modified polyester (i) can be prepared. These urea-modified polyesters (i) are produced by a one-shot method or a prepolymer method. The weight average molecular weight of the urea-modified polyester (i) is usually 10,000 or more, preferably 20,000 to 10,000,000, more preferably 30,000 to 1,000,000. If it is less than 10,000, the hot offset resistance deteriorates. The number average molecular weight of the urea-modified polyester is not particularly limited when the unmodified polyester (ii) described later is used, and may be a number average molecular weight that can be easily obtained to obtain the weight average molecular weight. (I) When used alone, the number average molecular weight is usually 20000 or less, preferably 1000 to 10000, and more preferably 2000 to 8000. When it exceeds 20000, the low-temperature fixability and the glossiness when used in a full-color apparatus are deteriorated.

Further, in the reference means according to the present invention, not only the polyester (i) modified with the urea bond is used alone, but also the polyester (ii) not modified with this (i) is contained as a binder resin component. You can also By using (ii) in combination, the low-temperature fixability and glossiness when used in a full-color apparatus are improved, which is preferable to single use. Examples of (ii) include the same polycondensates of polyol (1) and polycarboxylic acid (2) as in the polyester component (i) above, and preferred ones are also the same as (i). (Ii) is not limited to unmodified polyester, but may be modified with a chemical bond other than a urea bond, and may be modified with a urethane bond, for example. It is preferable that (i) and (ii) are at least partially compatible with each other in terms of low-temperature fixability and hot offset resistance. Accordingly, the polyester component (i) and (ii) preferably have similar compositions. When (ii) is contained, the weight ratio of (i) and (ii) is usually 5/95 to 80/20, preferably 5/95 to 30/70, more preferably 5/95 to 25/75, Particularly preferred is 7/93 to 20/80. If the weight ratio of (i) is less than 5%, the hot offset resistance deteriorates, and it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability.

  The peak molecular weight of (ii) is usually 1000-30000, preferably 1500-10000, more preferably 2000-8000. If it is less than 1000, heat-resistant storage stability will deteriorate, and if it exceeds 10,000, low-temperature fixability will deteriorate. The hydroxyl value of (ii) is preferably 5 or more, more preferably 10 to 120, and particularly preferably 20 to 80. If it is less than 5, it is disadvantageous in terms of both heat-resistant storage stability and low-temperature fixability. The acid value of (ii) is usually 1-30, preferably 5-20. By having an acid value, it tends to be negatively charged.

In the reference means according to the present invention , the glass transition point (Tg) of the binder resin is usually 50 to 70 ° C., preferably 55 to 65 ° C. If it is less than 50 ° C., the blocking of the toner during high temperature storage deteriorates, and if it exceeds 70 ° C., the low-temperature fixability becomes insufficient. Due to the coexistence of the urea-modified polyester resin, the dry toner as a reference means according to the present invention tends to have good heat-resistant storage stability even when the glass transition point is low, as compared with a known polyester-based toner. As the storage elastic modulus of the binder resin, the temperature (TG ′) at which 10000 dyne / cm 2 is obtained at a measurement frequency of 20 Hz is usually 100 ° C. or higher, preferably 110 to 200 ° C. If it is less than 100 ° C., the resistance to hot offset deteriorates. As the viscosity of the binder resin, the temperature (Tη) at 1000 poise at a measurement frequency of 20 Hz is usually 180 ° C. or less, preferably 90 to 160 ° C. If it exceeds 180 ° C., the low-temperature fixability deteriorates. That is, TG ′ is preferably higher than Tη from the viewpoint of achieving both low temperature fixability and hot offset resistance. In other words, the difference between TG ′ and Tη (TG′−Tη) is preferably 0 ° C. or higher. More preferably, it is 10 degreeC or more, Most preferably, it is 20 degreeC or more. The upper limit of the difference is not particularly limited. Further, from the viewpoint of achieving both heat-resistant storage stability and low-temperature fixability, the difference between Tη and Tg is preferably 0 to 100 ° C. More preferably, it is 10-90 degreeC, Most preferably, it is 20-80 degreeC.

  The binder resin can be produced by the following method. The polyol (1) and the polycarboxylic acid (2) are heated to 150 to 280 ° C. in the presence of a known esterification catalyst such as tetrabutoxytitanate or dibutyltin oxide, and the generated water is distilled off as necessary. Thus, a polyester having a hydroxyl group is obtained. Next, this is reacted with polyisocyanate (3) at 40 to 140 ° C. to obtain a prepolymer (A) having an isocyanate group. Further, (A) is reacted with amines (B) at 0 to 140 ° C. to obtain a polyester modified with a urea bond. When (3) is reacted and (A) and (B) are reacted, a solvent can be used as necessary. Usable solvents include aromatic solvents (toluene, xylene, etc.); ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.); esters (ethyl acetate, etc.); amides (dimethylformamide, dimethylacetamide, etc.) and ethers And those inert to the isocyanate (3), such as tetrahydrofuran (such as tetrahydrofuran). When polyester (ii) not modified with urea bond is used in combination, (ii) is produced by the same method as polyester having a hydroxyl group, and this is dissolved in the solution after completion of the reaction of (i) and mixed. To do.

In addition, the toner used for the reference means according to the present invention can be manufactured generally by the following method, but is not limited thereto.
The aqueous medium used for the reference means according to the present invention may be water alone, or a solvent miscible with water may be used in combination. Examples of the miscible solvent include alcohol (methanol, isopropanol, ethylene glycol, etc.), dimethylformamide, tetrahydrofuran, cellosolves (methylcellosolve, etc.), lower ketones (acetone, methyl ethyl ketone, etc.) and the like.

  The toner particles may be formed by reacting a dispersion composed of a prepolymer (A) having an isocyanate group in an aqueous medium with (B), or using a urea-modified polyester (i) produced in advance. good. As a method for stably forming a dispersion comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium, a toner raw material comprising urea-modified polyester (i) or prepolymer (A) in an aqueous medium is used. And a method of dispersing by shearing force. The prepolymer (A) and other toner compositions (hereinafter referred to as toner raw materials), a colorant masterbatch, a release agent, a charge control agent, an unmodified polyester resin, etc. are dispersed in an aqueous medium. It may be mixed at the time of formation, but it is more preferable to mix the toner raw materials in advance and then add and disperse the mixture in the aqueous medium. In the present invention, other toner materials such as a colorant, a release agent, and a charge control agent do not necessarily have to be mixed when forming particles in an aqueous medium, but after the particles are formed. , May be added. For example, after forming particles containing no colorant, the colorant can be added by a known dyeing method.

  The dispersion method is not particularly limited, and known equipment such as a low-speed shear method, a high-speed shear method, a friction method, a high-pressure jet method, and an ultrasonic wave can be applied. In order to make the particle size of the dispersion 2 to 20 μm, a high-speed shearing type is preferable. When a high-speed shearing disperser is used, the rotational speed is not particularly limited, but is usually 1000 to 30000 rpm, preferably 5000 to 20000 rpm. The dispersion time is not particularly limited, but in the case of a batch method, it is usually 0.1 to 5 minutes. The temperature during dispersion is usually 0 to 150 ° C. (under pressure), preferably 40 to 98 ° C. Higher temperatures are preferred in that the dispersion made of urea-modified polyester (i) or prepolymer (A) has a low viscosity and is easy to disperse.

  The amount of the aqueous medium used relative to 100 parts of the toner composition containing the urea-modified polyester (i) and the prepolymer (A) is usually 50 to 2000 parts by weight, preferably 100 to 1000 parts by weight. If the amount is less than 50 parts by weight, the dispersion state of the toner composition is poor and toner particles having a predetermined particle diameter cannot be obtained. If it exceeds 20000 parts by weight, it is not economical. Moreover, a dispersing agent can also be used as needed. It is preferable to use a dispersant because the particle size distribution becomes sharp and the dispersion is stable.

  In the step of synthesizing the urea-modified polyester (i) from the prepolymer (A), the amine (B) may be added and reacted before the toner composition is dispersed in the aqueous medium, or may be dispersed in the aqueous medium. An amine (B) may be added later to cause a reaction from the particle interface. In this case, urea-modified polyester is preferentially produced on the surface of the manufactured toner, and a concentration gradient can be provided inside the particles.

  Anionic surfactants such as alkylbenzene sulfonates, α-olefin sulfonates and phosphates, alkylamines as dispersants for emulsifying and dispersing the oily phase in which the toner composition is dispersed in a liquid containing water Amine salts such as salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridinium salts, alkylisoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, polyhydric alcohol derivatives, such as alanine, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine and N-alkyl N, amphoteric surfactants such as N- dimethyl ammonium betaine and the like.

  Further, by using a surfactant having a fluoroalkyl group, the effect can be obtained in a very small amount. Preferred anionic surfactants having a fluoroalkyl group include fluoroalkyl carboxylic acids having 2 to 10 carbon atoms and metal salts thereof, disodium perfluorooctanesulfonyl glutamate, 3- [omega-fluoroalkyl (C6-C11). ) Oxy] -1-alkyl (C3-C4) sodium sulfonate, 3- [omega-fluoroalkanoyl (C6-C8) -N-ethylamino] -1-propanesulfonic acid sodium, fluoroalkyl (C11-C20) carboxylic acid And metal salts, perfluoroalkylcarboxylic acids (C7 to C13) and metal salts thereof, perfluoroalkyl (C4 to C12) sulfonic acids and metal salts thereof, perfluorooctanesulfonic acid diethanolamide, N-propyl-N- (2-hydroxyethyl) -Fluorooctanesulfonamide, perfluoroalkyl (C6-C10) sulfonamidopropyltrimethylammonium salt, perfluoroalkyl (C6-C10) -N-ethylsulfonylglycine salt, monoperfluoroalkyl (C6-C16) ethyl phosphate, etc. Is mentioned.

  Product names include Surflon S-111, S-112, S-113 (Asahi Glass Co., Ltd.), Florard FC-93, FC-95, FC-98, FC-129 (Sumitomo 3M Co., Ltd.), Unidyne DS-101. DS-102 (manufactured by Taikin Kogyo Co., Ltd.), Mega-Fac F-ll0, F-120, F-113, F-191, F-812, F-833 (Dainippon Ink Co., Ltd.), Xtop EF- 102, 103, 104, 105, 112, 123A, 123B, 306A, 501, 201, 204 (manufactured by Tochem Products), and Fgentent F-100, F-150 (manufactured by Neos).

  Cationic surfactants include aliphatic primary, secondary or secondary amine acids that are right on the fluoroalkyl group, aliphatic quaternary ammonium salts such as perfluoroalkyl (C6 1 C10) sulfonamidopropyltrimethylammonium salts, benzalkco Nickel salts, benzethonium chloride, pyridinium salts, imidazolinium salts, trade names include Surflon S-21 (Asahi Glass Co., Ltd.), Florard FC-135 (Sumitomo 3M Co., Ltd.), Unidyne DS-202 (Daikin Industries Co., Ltd.) Megafac F-150, F-824 (manufactured by Dainippon Ink, Inc.), Xtop EF-132 (manufactured by Tochem Products Co., Ltd.), Footgent F-1300 (manufactured by Neos), and the like.

Tricalcium phosphate, calcium carbonate, titanium oxide, colloidal silica, hydroxyapatite and the like can also be used as inorganic compound dispersants that are hardly soluble in water.
Further, the dispersed droplets may be stabilized by a polymer protective colloid. For example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride and other (meth) acrylic monomers containing hydroxyl groups Bodies such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-acrylate Chloro-2-hydroxypropyl, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, glycerol monoacrylate, glycerol monomethacrylate, N -Methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of compounds containing vinyl alcohol and carboxyl groups, such as Pinyl acetate, pinyl propionate, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, pinylviridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, etc. Homopolymers or copolymers such as those having nitrogen atoms or heterocyclic rings thereof, polyoxyethylene, polyoxypropylene, polymers Oxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonylphenyl Polyoxyethylenes such as esters, celluloses such as methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose can be used.

If an acid such as calcium phosphate salt or an alkali-soluble substance is used as the dispersion stabilizer, the calcium phosphate salt is removed from the fine particles by dissolving the calcium phosphate salt with an acid such as hydrochloric acid and then washing with water. To do. It can also be removed by operations such as enzymatic degradation.
When a dispersant is used, the dispersant may remain on the surface of the toner particles, but it is preferable from the charged surface of the toner that the dispersant is washed and removed after the elongation and / or crosslinking reaction.

  Furthermore, in order to lower the viscosity of the toner composition, a solvent in which the urea-modified polyester (i) or the prepolymer (A) is soluble can be used. The use of a solvent is preferable in that the particle size distribution becomes sharp. The solvent is preferably volatile from the viewpoint of easy removal. Examples of the solvent include toluene, xylene, benzene, carbon tetrachloride, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, trichloroethylene, chloroform, monochlorobenzene, dichloroethylidene, methyl acetate, ethyl acetate, Methyl ethyl ketone, methyl isobutyl ketone and the like can be used alone or in combination of two or more. In particular, aromatic solvents such as toluene and xylene and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane, chloroform and carbon tetrachloride are preferred, and aromatic solvents such as toluene and xylene are more preferred. The usage-amount of the solvent with respect to 100 parts of prepolymers (A) is 0-300 parts normally, Preferably it is 0-100 parts, More preferably, it is 25-70 parts. When a solvent is used, it is removed by heating under normal pressure or reduced pressure after elongation and / or crosslinking reaction.

  The elongation and / or cross-linking reaction time is selected depending on the reactivity of the isocyanate group structure of the prepolymer (A) and the amines (B), but is usually 10 minutes to 40 hours, preferably 2 to 24 hours. is there. The reaction temperature is generally 0 to 150 ° C, preferably 40 to 98 ° C. Moreover, a well-known catalyst can be used as needed. Specific examples include dibutyltin laurate and dioctyltin laurate.

  In order to remove the organic solvent from the obtained emulsified dispersion, a method in which the temperature of the entire system is gradually raised to completely evaporate and remove the organic solvent in the droplets can be employed. Alternatively, the emulsified dispersion can be sprayed into a dry atmosphere to completely remove the water-insoluble organic solvent in the droplets to form toner fine particles, and the aqueous dispersant can be removed by evaporation together. . As a dry atmosphere in which the emulsified dispersion is sprayed, a gas obtained by heating air, nitrogen, carbon dioxide gas, combustion gas, or the like, in particular, various air currents heated to a temperature equal to or higher than the boiling point of the highest boiling solvent used is generally used. Sufficient quality can be obtained with a short treatment such as spray dryer, belt dryer or rotary kiln.

When the particle size distribution at the time of emulsification dispersion is wide and washing and drying processes are performed while maintaining the particle size distribution, the particle size distribution can be adjusted by classification into a desired particle size distribution.
In the classification operation, the fine particle portion can be removed in the liquid by a cyclone, a decanter, centrifugation, or the like. Of course, the classification operation may be performed after obtaining the powder as a powder after drying. The unnecessary fine particles or coarse particles obtained can be returned to the kneading step and used for the formation of particles. At that time, fine particles or coarse particles may be wet.
Moreover, it is preferable to remove the used dispersant from the obtained dispersion as much as possible, but it is preferable to carry out it simultaneously with the classification operation described above.

The obtained toner powder after drying is mixed with different kinds of particles such as release agent fine particles, charge control fine particles, fluidizing agent fine particles, and colorant fine particles, or gives mechanical impact force to the mixed powder. Thus, it is possible to prevent detachment of foreign particles from the surface of the composite particle obtained by immobilizing and fusing on the surface.
Specific means include a method of applying an impact force to the mixture by blades rotating at high speed, a method of injecting and accelerating the mixture in a high-speed air stream, and causing particles or composite particles to collide with an appropriate collision plate, etc. is there. As equipment, Ong mill (manufactured by Hosokawa Micron Co., Ltd.), I-type mill (manufactured by Nippon Pneumatic Co., Ltd.) has been modified to lower the pulverization air pressure, hybridization system (manufactured by Nara Machinery Co., Ltd.), kryptron System (manufactured by Kawasaki Heavy Industries, Ltd.), automatic mortar, etc.

  As the colorant used in the toner, pigments and dyes conventionally used as toner colorants can be used. Specifically, carbon black, lamp black, iron black, ultramarine, nigrosine dye, Aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6C lake, calco oil blue, chrome yellow, quinacridone red, benzidine yellow, rose bengal and the like can be used alone or in combination.

  Furthermore, if necessary, in order to give the toner particles magnetic properties, magnetic components such as iron oxides such as ferrite, magnetite and maghemite, metals such as iron, cobalt and nickel, or alloys of these with other metals. May be contained alone or in combination in the toner particles. Moreover, these components can also be used / used together as a colorant component.

The number average diameter of the colorant in the toner used in the reference means according to the present invention is desirably 0.5 μm or less, preferably 0.4 μm or less, more preferably 0.3 μm or less.
When the number average diameter of the colorant in the toner is larger than 0.5 μm, the dispersibility of the pigment does not reach a sufficient level, and preferable transparency may not be obtained.
A colorant having a fine particle diameter of less than 0.1 μm is sufficiently smaller than a half wavelength of visible light, and thus is considered not to adversely affect light reflection and absorption characteristics. Therefore, the colorant particles of less than 0.1 μm contribute to good color reproducibility and transparency of the OHP sheet having a fixed image. On the other hand, if there are many colorants having a particle size larger than 0.5 μm, the transmission of incident light is hindered or scattered, and the brightness and color of the projected image of the OHP sheet tend to decrease. There is.
Further, if there are many colorants having a particle size larger than 0.5 μm, the colorant is detached from the surface of the toner particles, and various problems such as fogging, drum contamination, and poor cleaning are liable to occur. In particular, the colorant having a particle size larger than 0.7 μm is preferably 10% by number or less of the total colorant, and more preferably 5% by number or less.

In addition, by adding a wetting liquid in advance with a part or all of the binder resin and kneading the colorant, the binder resin and the colorant are initially sufficiently adhered, In the toner production process, the colorant is dispersed more effectively in the toner particles, the dispersed particle diameter of the colorant is reduced, and better transparency can be obtained.
As the binder resin used for kneading in advance, the resins exemplified as the binder resin for toner can be used as they are, but are not limited thereto.

As a specific method for kneading the mixture of the binder resin and the colorant with the wetting liquid in advance, for example, the binder resin, the colorant and the wetting liquid are obtained after mixing with a blender such as a Henschel mixer. The obtained mixture is kneaded at a temperature lower than the melting temperature of the binder resin by a kneader such as a two-roll or three-roll to obtain a sample.
In addition, as the wetting liquid, a general one can be used in consideration of the solubility of the binder resin and the paintability with the colorant, but in particular, an organic solvent such as acetone, toluene, butanone, or water, It is preferable from the viewpoint of dispersibility of the colorant.
Among these, the use of water is more preferable from the viewpoint of environmental considerations and maintaining the dispersion stability of the colorant in the subsequent toner production process.
According to this manufacturing method, not only the particle diameter of the colorant particles contained in the obtained toner is reduced, but also the uniformity of the dispersion state of the particles is increased, so that the color reproducibility of the projected image by OHP is further improved. Get better.

In addition, as long as the configuration of the reference means according to the present invention is adopted, a release agent represented by wax can be contained in the toner together with the binder resin and the colorant.
Known release agents can be used, such as polyolefin wax (polyethylene wax, polypropylene wax, etc.); long chain hydrocarbons (paraffin wax, sasol wax, etc.); carbonyl group-containing wax, etc. .

  Of these, carbonyl group-containing waxes are preferred. Carbonyl group-containing waxes include polyalkanoic acid esters (carnauba wax, montan wax, trimethylolpropane tribehenate, pentaerythritol tetrabehenate, pentaerythritol diacetate dibehenate, glycerin tribehenate, 1,18. -Octadecandiol diol distearate, etc.); polyalkanol esters (tristearyl trimellitic acid, distearyl maleate, etc.); polyalkanoic acid amides (ethylene diamine dibehenyl amide, etc.); polyalkylamides (trimellitic acid tristearyl amide, etc.) And dialkyl ketones (such as distearyl ketone).

  Among these carbonyl group-containing waxes, polyalkanoic acid esters are preferred. The melting point of these release agents is usually 40 to 160 ° C, preferably 50 to 120 ° C, more preferably 60 to 90 ° C. A wax having a melting point of less than 40 ° C. has an adverse effect on heat resistant storage stability, and a wax having a melting point of more than 160 ° C. tends to cause a cold offset when fixing at a low temperature. Further, the melt viscosity of the wax is preferably 5 to 1000 cps, more preferably 10 to 100 cps as a measured value at a temperature 20 ° C. higher than the melting point. Waxes exceeding 1000 cps have poor effects for improving hot offset resistance and low-temperature fixability. The content of the wax in the toner is usually 0 to 40% by weight, preferably 3 to 30% by weight.

In addition, a charge control agent may be contained in the toner as necessary in order to accelerate the toner charge amount and its rise. Here, since a color change occurs when a colored material is used as the charge control agent, a material that is colorless and close to white is preferable.
Any known charge control agent can be used. Examples include triphenylmethane dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkyls. Amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based activator, salicylic acid metal salt, metal salt of salicylic acid derivative, and the like. Specifically, Bontron P-51 of a quaternary ammonium salt, E-82 of an oxynaphthoic acid metal complex, E-84 of a salicylic acid metal complex, E-89 of a phenol condensate (above, Orient Chemical Co., Ltd.) Manufactured), TP-302, TP-415 of quaternary ammonium salt molybdenum complex (above, manufactured by Hodogaya Chemical Co., Ltd.), copy charge PSY VP2038 of quaternary ammonium salt, copy blue PR of triphenylmethane derivative, Quaternary ammonium salt copy charge NEG VP2036, copy charge NX VP434 (above, manufactured by Hoechst), LRA-901, boron complex LR-147 (manufactured by Nippon Carlit), quinacridone, azo pigment, other sulfonic acid groups Of polymers with functional groups such as carboxylic groups and quaternary ammonium salts Thing, and the like.

In the reference means according to the present invention , the amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method. Although not limited, Preferably it is used in 0.1-10 weight part with respect to 100 weight part of binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline. These charge control agents can be dissolved and dispersed after being melt-kneaded with a masterbatch and resin, or may be added when directly dissolving and dispersing in an organic solvent, or may be fixed on the toner surface after preparation of toner particles. Also good.
Further, when the toner composition is dispersed in the aqueous medium during the toner production process, resin fine particles mainly for stabilizing the dispersion may be added.

  The resin fine particles used may be any resin that can form an aqueous dispersion, and may be a thermoplastic resin or a thermosetting resin. For example, vinyl resins, polyurethane resins, epoxy resins, polyester resins, Examples thereof include polyamide resin, polyimide resin, silicon resin, phenol resin, melamine resin, urea resin, aniline resin, ionomer resin, and polycarbonate resin. As the resin fine particles, two or more of the above resins may be used in combination. Of these, vinyl resins, polyurethane resins, epoxy resins, polyester resins, and combinations thereof are preferred because an aqueous dispersion of fine spherical resin particles is easily obtained.

  The vinyl resin is a polymer obtained by homopolymerization or copolymerization of a vinyl monomer, such as a styrene- (meth) acrylate resin, a styrene-butadiene copolymer, a (meth) acrylic acid-acrylate polymer, Examples include, but are not limited to, styrene-acrylonitrile copolymers, styrene-maleic anhydride copolymers, styrene- (meth) acrylic acid copolymers, and the like.

Further, inorganic fine particles can be preferably used as an external additive for assisting the fluidity, developability and chargeability of the toner particles.
The primary particle diameter of the inorganic fine particles is preferably 5 mμ to 2 μm, and particularly preferably 5 mμ to 500 mμ. Moreover, it is preferable that the specific surface area by BET method is 20-500 m < ² > / g. The proportion of the inorganic fine particles used is preferably 0.01 to 5% by weight of the toner, and particularly preferably 0.01 to 2.0% by weight. Specific examples of the inorganic fine particles include, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate, zinc oxide, tin oxide, quartz sand, clay, mica, wollastonite, diatomaceous earth. Examples include soil, chromium oxide, cerium oxide, pengala, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, and silicon nitride.

  Other polymer fine particles, for example, polystyrene obtained by soap-free emulsion polymerization, suspension polymerization, dispersion polymerization, methacrylate ester, acrylate copolymer, polycondensation system such as silicone, benzoguanamine, nylon, thermosetting resin And polymer particles.

  Such a fluidizing agent can be surface-treated to increase hydrophobicity and prevent deterioration of flow characteristics and charging characteristics even under high humidity. For example, silane coupling agents, silylating agents, silane coupling agents having an alkyl fluoride group, organic titanate coupling agents, aluminum coupling agents, silicone oils, modified silicone oils and the like are preferable surface treatment agents. .

  Examples of the cleaning property improver for removing the developer after transfer remaining on the photoreceptor or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate and stearic acid, such as polymethyl methacrylate fine particles, polystyrene. Examples thereof include fine polymer particles produced by soap-free emulsion polymerization of fine particles and the like. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

By using these toners, a high-quality toner image having excellent development stability can be formed as described above. However, the toner that is not transferred to the transfer medium or intermediate transfer medium by the transfer device and remains on the image carrier is difficult to remove by the cleaning device due to its fineness and good rolling properties. May end up. In order to completely remove the toner from the image carrier, it is necessary to strongly press a toner removing member such as a cleaning blade against the image carrier. Such a load not only shortens the life of the image carrier and the cleaning device, but also uses extra energy.
When the load on the image carrier is reduced, the toner and the small-diameter carrier on the image carrier are not sufficiently removed, and these damage the surface of the image carrier when passing through the cleaning device. It becomes a factor which fluctuates performance.

As described above, the image forming apparatus of the reference example according to the present invention is excellent in the tolerance for the variation of the surface state of the image carrier, particularly the presence of the low resistance portion, and the charging performance fluctuation of the image carrier, etc. Since the configuration is highly suppressed, an image with extremely high image quality can be stably obtained over a long period of time when used in combination with the toner having the above configuration.
The image forming apparatus of the reference means according to the present invention is applied not only to the above-described toner having a configuration suitable for obtaining a high-quality image, but also to an irregularly shaped toner by a pulverization method. Needless to say, the life of the apparatus can be greatly extended.

As a material constituting such a pulverized toner, those usually used as an electrophotographic toner can be applied without particular limitation.
Examples of general binder resins used in the toner include homopolymers of styrene such as polystyrene, poly p-chlorostyrene, polyvinyltoluene, and the like; styrene / p-chlorostyrene copolymers; Styrene / propylene copolymer, styrene / vinyl toluene copolymer, styrene / vinyl naphthalene copolymer, styrene / methyl acrylate copolymer, styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, Styrene / octyl acrylate copolymer, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / Acrylonitrile copolymer, styrene / vinyl methyl ketone copolymer, Styrene copolymers such as tylene / butadiene copolymers, styrene / isoprene copolymers, styrene / maleic acid copolymers; polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, polybutyl methacrylate, etc. Acrylic ester-based homopolymers and copolymers thereof; polyvinyl derivatives such as polyvinyl chloride and polyvinyl acetate; polyester-based polymers, polyurethane-based polymers, polyamide-based polymers, polyimide-based polymers, polyol-based polymers, Examples thereof include an epoxy polymer, a terpene polymer, an aliphatic or alicyclic hydrocarbon resin, an aromatic petroleum resin, and the like. These can be used alone or in combination, but are not particularly limited thereto. Among these, at least one selected from styrene-acrylic copolymer resins, polyester resins, and polyol resins is more preferable from the viewpoint of electrical characteristics, cost, and the like. Furthermore, it is more preferable to use a polyester-based resin and / or a polyol-based resin as having good fixing characteristics.

  For the reasons described above, the same resin component as the binder resin of the toner contained in the coating layer of the charging member includes a linear polyester resin composition, a linear polyol resin composition, and a linear styrene acrylic resin. At least one of the compositions or these cross-linked products can be preferably used.

  In the pulverized toner, together with these resin components, the colorant component, wax component, charge control component, and the like as described above are premixed as necessary, and then kneaded at a temperature close to the melting temperature of the resin component, and then cooled. Thereafter, a toner may be prepared through a pulverization and classification step, and the above-mentioned external additive components may be appropriately added and mixed as necessary.

[Embodiment 1 ]
Next, embodiments according to the first to seventh means of the present invention will be described. This embodiment is a generalized evaluation method used for the evaluation of the protective agent coating apparatus of Reference Embodiment 1 described above. The solid is not limited to a photoconductor, but the amount of deposits on various solid surfaces. Can be evaluated.

  In order to investigate whether the amount of deposits when a thin film-like deposit is present on the solid surface can be grasped, the present inventors use the ATR (Attenuated Total Reflection) method to analyze the deposit on the solid surface. Was done. In the ATR method, the penetration depth of infrared light changes depending on the crystal used and the incident angle condition, so the spectrum obtained even if the same sample is measured is different, and it is derived from the solid surface depending on the crystal used and the incident angle condition. Only the peak that is detected is detected, only the peak only of the deposit is detected, and both the peak derived from the solid surface and the peak derived from the deposit are detected. Among various conditions, the presence of deposits on the solid surface is determined from the obtained spectrum under conditions in which both the crystal used and the incident angle are finely changed to detect both peaks derived from the solid surface and peaks derived from the deposit. We eagerly investigated whether the amount could be evaluated.

  Here, in the ATR method, the intensity ratio changes depending on the pressure with which the sample is pressed, so the intensity of the spectrum cannot be followed directly. Therefore, when setting the sample during measurement, if the gap between the jig for fixing the sample and the crystal can be kept constant, or if the pressing pressure is constant, an IR spectrum can be obtained under certain conditions. When the sample is set, the gap between the jig that holds the sample and the crystal can be kept constant, and the amount of deposit on the solid surface is changed. No sample was measured. Thus, for each spectrum obtained, the peaks in the spectrum were assigned, and the area of the peak derived from the solid surface was calculated. As a result, the peak area derived from the solid surface was smaller in the sample with more deposits. In addition, paying attention to the IR spectrum of the sample with more adhering matter, the reduction ratio of the peak area derived from the solid surface was calculated, and as the peak area with a larger wave number, the reduction ratio of the peak area tended to be larger It was in. Next, the peak intensity of any one of the peaks derived from the solid surface (reference peak) is zero for the IR spectrum of the sample to which the deposit is attached and the IR spectrum of the sample to which the deposit is not attached. When the IR spectrum of the sample with no deposit is reduced and subtracted from the IR spectrum of the sample with the deposit, the difference spectrum is obtained. In the region having a smaller wave number, a peak derived from the solid surface remained in the difference spectrum. Further, the peak area of the peak derived from the remaining solid surface increased as the amount of the adhering sample increased.

  Further, the ratio of the area of the peak derived from the solid surface in the region having a wave number smaller than that of the reference peak in the difference spectrum to the area of the reference peak in the IR spectrum of the sample to which the deposit before taking the difference spectrum is attached (in the difference spectrum The ratio of the area gradually increases as the amount of adhering material increases. It was.

  That is, according to the present invention, in the evaluation method for evaluating the amount of deposits on the solid surface, the IR spectrum A of the solid surface without deposits and the deposits measured by the ATR method of the infrared absorption spectrum method adhered. When the IR spectrum B of the solid surface is compared, it is a peak derived from the solid that exists in both the IR spectrum A and the IR spectrum B, and of the solid-derived peak, it is derived from the deposit in the IR spectrum B. There are at least two peaks that do not overlap with the peak. Of the two peaks, the peak with the highest wave number in IR spectrum A is peak a1, the peak with the lower wave number is peak a2, and peaks a1, a2 The peaks in the IR spectrum B corresponding to the wave numbers detected at the same wave numbers are defined as peaks b1 and b2, and the peak a1 in the IR spectrum A is high. The spectrum obtained by multiplying IR spectrum A by [h (b1) / h (a1)] (IR spectrum A ′ and h (a1)) and the height of peak b1 in IR spectrum B being h (b1) The spectrum obtained by subtracting from IR spectrum B is IR spectrum C, and peaks corresponding to wave numbers detected at the same wave numbers as peaks a 1 and a 2 in IR spectrum C are peaks c 1 and c 2. When the area of the peak b1 in the IR spectrum B is S (b1) and the area of the peak c2 in the IR spectrum C is S (c2), the area S (b1) of the peak b1 in the IR spectrum B and the IR spectrum The amount of deposits on the solid surface is evaluated from the ratio (S (c2) / S (b1)) of the peak c2 in C to the area S (c2).

  Here, the deposit is a substance different from the solid to be deposited, and the deposit may not be a single substance, but may be various kinds of substances. Moreover, when there are many kinds of deposits, they may be uniformly mixed or have a multilayer structure. When there is unevenness in the adhered matter, it can be evaluated without problems if the unevenness interval is 0.3 mm or less.

  Further, here, a peak derived from a solid that exists in both IR spectrum A and IR spectrum B, and of the solid-derived peaks, a peak that does not overlap with a peak derived from a deposit in IR spectrum B 7, in the state shown in the schematic diagram 1-1 of FIG. 7, the peak b (solid peak) in the IR spectrum B has the same wave number as the peak a (solid peak) in the IR spectrum A is detected. And the bottom of the peak M of the deposit does not overlap with the bottom of the peak of the peak b.

Here, IR spectrum, the intensity of the light having the infrared light source with respect to the wave number (wavelength) distribution, which is viewed how changes by the sample specimen is usually the reciprocal of a wavelength wavenumber (in cm ^-1 ) On the horizontal axis, and the vertical axis represents transmittance (T) and absorbance (A) and is drawn as a curve. The transmittance is the ratio of the energy transmitted through the sample to the energy incident on the sample, and the absorbance is a common logarithm of the reciprocal of the transmittance. It is well known that absorbance and sample concentration are in a proportional relationship (Lambert-Beer's law), and an absorbance spectrum must be used for quantitative calculations. The IR spectrum used in the present invention is an absorbance spectrum.

  Devices for measuring IR spectra are broadly divided into dispersive infrared spectrophotometers and Fourier transform infrared spectrophotometers, and because of their high time efficiency, light usage rate, wave number resolution, and wave number accuracy, Fourier transform red Outer spectrophotometers (FT-IR) are the current mainstream. As a measurement method, there are various measurement accessories in addition to the normal transmission method, and the measurement method can be selected according to the form of the sample and information to be known. Among various measurement accessories, the ATR method can measure an IR spectrum with almost no sample processing, and has recently become quite popular as a measurement accessory for FT-IR.

  In this ATR method, the sample is brought into contact with the ATR crystal and measurement is performed. Therefore, even if the same sample is measured depending on the contact state between the ATR crystal and the sample, the peak intensity varies, making quantitative analysis difficult. Therefore, in recent years, various accessories have been widely used to control the contact state, and the accessory can keep the gap between the jig for fixing (pressing) the sample and the ATR crystal constant. There are accessories that keep the pressure applied to the accessories and the sample constant, accessories that have a pressure gauge for the pressure applied to the sample, and variable pressure.

When these accessories are used, the variation in peak intensity is reduced, but when the same sample is measured several times while keeping the gap between the jig for fixing the sample and the crystal constant, it is about 20%. I had a variation. Therefore, in order to estimate the amount of deposits on the solid surface, it is necessary to perform normalization using a reference peak.
The peak to be normalized is preferably a peak derived from a functional group that does not overlap with other peaks, has a strong peak intensity, and hardly changes due to deterioration.

  In addition, infrared light is not reflected at the sample interface, but is totally reflected after entering the sample side by a certain depth. The penetration depth of infrared light is defined as the distance at which the intensity of infrared light becomes 1 / e of the intensity on the sample surface when the sample is irradiated with infrared light, and is expressed by the following formula 1. From Equation 1, the depth at which infrared light enters the sample varies depending on the incident angle, the refractive index and wave number (wavelength) of the ATR crystal, and the measurement wavelength increases as the incident angle θ increases and the refractive index of the ATR crystal increases. The shorter the is, the smaller the depth of penetration, and information closer to the surface is reflected in the spectrum.

dp = λ / 2πn ₁ [sin ² θ− (n ₂ / n ₁ ) ² ] ^1/2 (Formula 1)
However,
dp: penetration depth n ₂ and n ₁ : refractive index of crystal and sample θ: incidence angle λ: wavelength.

  The wave number (wavelength) of the peak selected as the ATR crystal, the incident angle of infrared light, and the index is appropriately selected according to the film thickness of the deposit. The wave number of the peak selected as the ATR crystal, the incident angle of the infrared light and the index is less than 100%, preferably 1 to 70%, more preferably 2 to 60% of the penetration depth of the infrared light. It is selected appropriately.

  When the film thickness of the deposit is 100% or more with respect to the penetration depth of the infrared light, the peak derived from the solid surface is not detected. Therefore, the deposit is not suitable for evaluating the abundance of the deposit using the evaluation method of the present invention. In addition, it is not preferable that the film thickness of the deposit is too thin with respect to the penetration depth of the infrared light at the selected peak wave number, because the sensitivity is reduced.

ATR measurement is performed on a sample with a deposit on the solid surface under the condition of a specific ATR crystal and an incident angle of infrared light, and the penetration depth at the wave number of a specific peak in the obtained spectrum is measured. Compared to the film thickness, if the penetration depth is too deep or too shallow relative to the thickness of the deposit, that is, only the deposit is detected because the penetration depth is too shallow, and the peak derived from the solid surface is detected. If the penetration depth is too deep and the peak intensity of the peak from the deposit is too small, the penetration depth is determined by the refractive index of the ATR crystal, the incident angle of the infrared light and the detected wavelength of the peak ( It is possible to adjust the ratio between the thickness of the deposit and the penetration depth to an optimum value by changing the penetration depth.
That is, it is necessary to adjust the penetration depth appropriately by changing the refractive index of the ATR crystal, the incident angle of infrared light, and the wave number of the peak selected as an index for calculating the amount of deposit according to the thickness of the deposit.

Commonly used ATR crystals include KRS-5 (refractive index 2.4), germanium (refractive index 4.0), AMTIR (refractive index 2.5), silicon (refractive index 3.4), Examples include zinc selenide (refractive index 2.4) and diamond (refractive index 2.4).
Moreover, the incident angle of infrared light generally used for ATR measurement is 30 to 85 °.

  As described above, a phenomenon in which a peak derived from the solid surface remains in a region where the wave number is smaller than the reference peak in the difference spectrum is caused by the fact that the penetration depth of infrared light depends on the wave number. . When deposits adhere to the solid surface, the peak intensity of the peak derived from the solid surface decreases accordingly, but the degree of decrease varies depending on the penetration depth, and decreases as the penetration depth increases on the low wavenumber side. The degree is small.

  Originally, there is a deposit on the solid surface, and when the IR spectrum of the sample with and without the deposit is taken, only the peaks derived from the deposit (different materials) are different. Although it appears to appear in the spectrum, solids in a region where the wave number is smaller than the reference peak in the difference spectrum due to the degree to which the peak derived from the solid surface changes depending on the penetration depth (wave number). A peak derived from the surface is seen. In addition, the peak intensity of the peak derived from the solid surface seen in the difference spectrum becomes stronger as the thickness of the deposit increases.

  First, with reference to the schematic diagram of [Example 1] shown in FIG. 8, a phenomenon in which a peak derived from the solid surface remains in a region where the wave number is smaller than the reference peak in the difference spectrum will be described. Here, the following four assumptions are assumed and the following STEP 1 to STEP 3 are performed.

<Premise 1> Peaks A and B exist in the spectrum of the photoreceptor.
<Premise 2> The penetration depth of peak B is twice the penetration depth of peak A.
<Prerequisite 3> The peak intensity when no deposit is attached is the same for both peaks A and B.
<Premise 4> Peak A and peak B decrease in peak intensity when adhering matter adheres, but in [Example 1] shown in FIG. 8, peak A has peak intensity when there is adhering matter. It is assumed that it becomes 3/4 (decrease by 1/4) of the peak intensity when there is not. The rate of decrease in the peak intensity varies depending on the thickness of the deposit, and the thickness of the deposit in [Example 1] is set to be thinner than the thickness of the deposit in [Example 2] of FIG. 9 described later. .

<STEP1>
Compare the state when there is no deposit and when there is no deposit.
<STEP2>
The peak A1 is reduced so that the peak intensity of the peak A1 when there is no deposit is the same as the peak intensity A2 when there is an deposit.
Also, the peak B1 is multiplied by the same value as the coefficient when the peak A1 is reduced.
<STEP3>
The peak A3 and the peak B3 reduced as in STEP2 are subtracted from the peak A2 and the peak B2 when there is an adhering substance, respectively.

Here, peaks A1 to A4 and B1 to B4 in [Example 1] shown in FIG. 8 represent the following.
Peak A1, peak B1: Peak A and peak B when there is no deposit.
Peak A2 and Peak B2: Peak A and Peak B when there are deposits.
Peak A3, Peak B3: Peak A and Peak B after STEP2 operation.
Peak A4, Peak B4: Peak A and Peak B after STEP3 operation.

Based on the above preconditions, peaks A and B at each stage in the schematic diagram of [Example 1] shown in FIG. 8 will be described in detail below.
(1) When no deposit is present Peak A1 and peak B1 have the same peak intensity.
(2) When there is a deposit The intensity of peak A2 is reduced by ¼ with respect to the intensity of peak A1 (peak A2). Since the penetration depth of peak B is twice the penetration depth of peak A, the rate of decrease in peak intensity due to the adhering matter is smaller than that of peak A, and is 1/8 of the intensity of peak B1. Decreasing (peak B2) (To be exact, when the penetration depth is twice different, the effect is not halved, but here it is halved for simplicity).
(3) After reduction by the operation of STEP2 When comparing peak A1 and peak A2, peak A2 is 3/4 of peak A1, so both peak A1 and peak B1 are normalized by multiplying by 3/4 (peaks A3, B3). ).
(4) After subtraction by STEP3 When peak A3 is subtracted from peak A2, peak A4 becomes zero (disappears), and when peak B3 is subtracted from peak B2, peak B4 is 1/8 of peak B1 Remains in strength.

  The peak B4 in [Example 1] shown in FIG. 8 corresponds to a peak derived from the solid surface that is seen remaining in a region having a smaller wave number than the reference peak in the difference spectrum. From this, it can be seen that due to the difference in penetration depth, in the region where the wave number is smaller than the reference peak in the difference spectrum, the peak derived from the solid surface remains without being subtracted. On the other hand, in a region having a larger wave number than the reference peak in the difference spectrum, a peak derived from the solid surface appears as a convex peak. In the present invention, for the sake of easy understanding, the peak S (c2) remaining in the difference spectrum is set to have a positive value, that is, the condition that b1 is smaller in wave number than a1, but c2 is lower. (S (c2) / S (b1)) is on the surface of the solid even under conditions where S (c2) is negative and has a negative value, that is, b1 has a larger wave number than a1. It functions as an index for evaluating the amount of deposits. Under such a condition that S (c2) is a negative value, the amount of deposit on the solid surface can be evaluated using the absolute value of (S (c2) / S (b1)) as an index. Is possible.

Next, using [Example 1] shown in FIG. 8 and [Example 2] shown in FIG. 9, the peak intensity of the peak derived from the solid surface remaining in the difference spectrum increases as the thickness of the deposit increases. Is schematically described.
Here, the operations of assumptions 1 to 3 and STEP 1 to STEP 3 are the same as those in [Example 1], and assumption 4 is the following conditions.

<Premise 4> Peaks A and B decrease in peak intensity when adhering material adheres, but in [Example 2] shown in FIG. 9, peak A has peak intensity when there is adhering material and no adhering material. It is assumed that it becomes 2/4 of the peak intensity (decreases by 2/4). As mentioned earlier, the thickness of the deposit in [Example 1] is smaller than the thickness of the deposit in [Example 2].

Based on the above preconditions, peaks A and B at each stage in the schematic diagram of [Example 2] shown in FIG. 9 will be described in detail below.
(1) When no deposit is present Peak A1 and peak B1 have the same peak intensity.
(2) When there is a deposit The intensity of peak A2 is reduced by 2/4 with respect to the intensity of peak A1 (peak A2). Since the penetration depth of peak B is twice the penetration depth of peak A, the rate of decrease in peak intensity due to the adhering matter is smaller than that of peak A, and is ¼ of the intensity of peak B1. Decreasing (peak B2) (To be exact, when the penetration depth is twice different, the effect is not halved, but here it is halved for simplicity).
(3) After reduction by STEP 2 When comparing peak A1 and peak A2, peak A2 is 2/4 of peak A1, so both peak A1 and peak B1 are normalized by multiplying by 2/4 (peaks A3, B3). ).
(4) After subtraction by STEP3 When peak A3 is subtracted from peak A2, peak A4 becomes zero (disappears), and when peak B3 is subtracted from peak B2, peak B4 is a peak that is 1/4 of peak B1. Remains in strength.

The peak B4 in [Example 1] in FIG. 8 and [Example 2] in FIG. 9 corresponds to a peak derived from the solid surface, which is observed in a region having a smaller wave number than the reference peak in the difference spectrum. When [Example 1] and [Example 2] are compared, the peak intensity of peak B4 is stronger in [Example 2] where the thickness of the deposit is thicker, and in the region where the wave number is shorter than the reference peak. It can be seen that the peak intensity of the peak derived from the solid surface remaining in the difference spectrum increases as the thickness of the film increases.
From these examples, the intensity of peak B4 increases as the difference in penetration depth between peak A and peak B increases (the difference in wave number increases). For example, assuming that the penetration depth of peak B is three times the penetration depth of peak A, the peak intensity of peak B4 is further increased.

In the present invention, the penetration depth at the wave number of infrared light from which the peak a2 is detected is 130% or more, preferably 170% or more of the penetration depth at the wave number of infrared light from which the peak a1 is detected. Preferably, it is 200% to 300%.
When the penetration depth at the wave number of infrared light at which the peak a2 is detected is 130% or less of the penetration depth at the wave number of infrared light at which the peak a1 is detected, the index (S (c2) / S ( This is not preferable because the sensitivity of b1)) is reduced. Further, when the penetration depth at the wave number of the infrared light from which the peak a2 is detected is 300% or more of the penetration depth at the wave number of the infrared light from which the peak a1 is detected, the index (S (c2) / This is not preferable because the sensitivity of S (b1)) becomes small.

In the present invention, the solid surface may be a mixture as long as it has a uniform composition. Further, a surface layer laminated on the substrate may be used as long as it is sufficiently thicker than the penetration depth of the IR spectrum.
Further, when the solid to be evaluated is an organic photoreceptor, it is particularly effective. Since the organic photoreceptor is greatly affected by the formed image even if the deposit is very small, the amount of the deposit on the organophotoreceptor is evaluated using the evaluation method of the present invention. It is very useful to evaluate and estimate the adhesion amount in order to maintain a high-quality image.

  In the present invention, the organophotoreceptor preferably contains an organic compound having a carbonate bond, and the peak a1 is preferably a peak derived from a carbonate bond. When an organic compound having a carbonate bond is contained, it is preferable because the strength of the photoreceptor is increased, and since the carbonate bond is a stable bond, there is almost no change in peak intensity due to deterioration. Highly preferred.

  In the present invention, the deposit on the surface of the photoreceptor is a protective agent having a function of protecting the photoreceptor. The protective agent is very thin, and in order to maintain high-quality image output over a long period of time, it may not be too much or too little, and it is preferable that it is placed on the photoreceptor by an appropriate amount. Assessing the amount of protective agent present on the body is very important for maintaining high quality images.

In the present invention, the protective agent preferably contains 50% by weight or more of paraffin. Paraffin is excellent in protecting the photoconductor, and normal paraffin, isoparaffin, and cycloparaffin are chemically stable because they do not easily react with paraffin. It is preferably used in terms of
In the present invention, the protective agent contains paraffin in an amount of 50% by weight or more, preferably 60% by weight or more, and more preferably 70% by weight or more. When the ratio of paraffin in the protective agent is 50% by weight or less, a sufficient effect of protecting the photoreceptor cannot be expected, which is not preferable. When components other than paraffin have a photoreceptor protecting effect, the proportion of paraffin in the protective agent may be 50% by weight or less.

In addition to paraffin, the protective agent may contain a cyclic olefin copolymer (COC) and / or an amphiphilic organic compound.
Amphiphilic organic compounds are classified into anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, and composites thereof.

The nonionic surfactant is preferably an esterified product of an alkyl carboxylic acid of the following chemical formula 1 and a polyhydric alcohol.
C _n H _{2n + 1} COOH (Chemical Formula 1)
However, n in a formula shows the integer of 15-35.

  By using a linear alkyl carboxylic acid as the alkyl carboxylic acid of Formula 1, the hydrophobic surface of the amphiphilic organic compound can be easily arranged on the surface of the photoreceptor on which the amphiphilic organic compound is adsorbed. This is a preferred mode because the adsorption density on the surface becomes particularly high.

The alkyl carboxylic acid ester in one molecule is hydrophobic, and the larger the number, the more the dissociable substances generated by air discharge are prevented from adsorbing on the surface of the image carrier, and the surface of the image carrier in the charged region. It is effective to reduce the electrical stress on. However, if the proportion of the alkyl carboxylic acid ester is too large, the portion of the polyhydric alcohol that exhibits hydrophilicity is obscured and sufficient adsorption performance may not be exhibited depending on the surface state of the image carrier. .
Therefore, the average number of ester bonds per molecule of the amphiphilic organic compound is preferably 1 to 3.
The average number of ester bonds per molecule of these amphiphilic organic compounds can be adjusted by selecting one or more from a plurality of amphiphilic organic compounds having different numbers of ester bonds.

Examples of the amphiphilic organic compound include an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant as described above.
Examples of anionic surfactants include alkylbenzene sulfonate, α-olefin sulfonate, alkane sulfonate, alkyl sulfate, alkyl polyoxyethylene sulfate, alkyl phosphate, long chain fatty acid salt, α -Anion (anion) at the end of the hydrophobic site, such as sulfo fatty acid ester salt and alkyl ether sulfate, and alkali metal ions such as sodium and potassium, and alkaline earth metal ions such as magnesium and calcium , Compounds in which metal ions such as aluminum and zinc, ammonium ions, and the like are bonded.

Examples of cationic surfactants include a cation (cation) at the end of a hydrophobic site, such as alkyltrimethylammonium salt, dialkylmethylammonium salt, alkyldimethylbenzylammonium salt, etc., and chlorine, fluorine , Bromine and the like, and compounds in which phosphate ions, nitrate ions, sulfate ions, thiosulfate ions, carbonate ions, hydroxide ions, and the like are bonded.
Examples of amphoteric surfactants include dimethylalkylamine oxide, N-alkylbetaines, imidazoline derivatives, alkyl amino acids and the like.

  Examples of nonionic surfactants include alcohol compounds such as long-chain alkyl alcohols, alkyl polyoxyethylene ethers, polyoxyethylene alkyl phenyl ethers, fatty acid diethanolamides, alkyl polyglucooxides, polyoxyethylene sorbitan alkyl esters, Examples include ether compounds and amide compounds. In addition, long-chain alkyl carboxylic acids such as lauric acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, and melicic acid, and polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, erythritol, and hexitol And ester compounds with these partial anhydrides are also preferred.

More specific examples of the ester compound include glyceryl monostearate, glyceryl distearate, glyceryl monopaltimate, glyceryl dilaurate, glyceryl trilaurate, glyceryl dipaltimate, glyceryl tripartinate, glyceryl dimyristate, and glyceryl trimistate. Glyceryl stearate, glyceryl monopartate, glyceryl monoarachidate, glyceryl diarachidate, glyceryl monobehenate, glyceryl behenate stearate, glyceryl stearate stearate, glyceryl monomontanate, glyceryl monomelinate, and its substitutes, Sorbitan monostearate, sorbitan tristearate, sorbitan monopartitic acid, sorbitan dipartitic acid, Sorbitan palmitate, sorbitan dimyristate, sorbitan trimistate, sorbitan palmitate, sorbitan monoarachidate, sorbitan diarachidate, sorbitan dibehenate, sorbitan monobehenate, sorbitan stearate, sorbitan monostearate, sorbitan monomontanate, monomelicic acid Examples include, but are not limited to, sorbitans of alkylcarboxylic acids such as sorbitan, and their substitutes.
Moreover, these amphiphilic organic compounds may use a single kind, and may use multiple types together.

  In the case of evaluating a protective agent coating apparatus for applying a protective agent to the surface of an image carrier (photoreceptor) using the evaluation method for evaluating the amount of deposits on the solid surface in the present invention, the protective agent coating apparatus (S (c2) / S (b1)), which is an indicator of the amount of deposits in the evaluation method within a certain coating time, Then, the protective agent coating device is accepted.

Next, a photoconductor used as an image carrier of an image forming apparatus will be described as a solid that can be suitably evaluated in the present invention.
In the photoreceptor used in the image forming apparatus of the reference technique according to the present invention , a photosensitive layer is provided on a conductive support. The photosensitive layer is composed of a single layer type in which a charge generation material and a charge transport material are mixed, a forward layer type in which a charge transport layer is provided on the charge generation layer, or a charge generation layer provided on the charge transport layer. There is a reverse layer type. In addition, a protective layer can be provided on the photosensitive layer in order to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, and the like of the photoreceptor. An undercoat layer may be provided between the photosensitive layer and the conductive support. In addition, an appropriate amount of a plasticizer, an antioxidant, a leveling agent and the like can be added to each layer as necessary.

  As the conductive support of the photosensitive member, one having a volume resistance of 10 ^ 10 Ω · cm or less, for example, metals such as aluminum, nickel, chromium, nichrome, copper, gold, silver, platinum, tin oxide, oxidation A metal oxide such as indium is deposited or sputtered on a film or cylindrical plastic or paper, or a plate of aluminum, aluminum alloy, nickel, stainless steel, etc. After forming the tube into a drum shape, it is possible to use a tube that has been surface-treated by cutting, superfinishing, polishing, or the like. A drum-shaped support having a diameter of 20 to 150 mm, preferably 24 to 100 mm, and more preferably 28 to 70 mm can be used. If the diameter of the drum-shaped support is 20 mm or less, it is physically difficult to arrange the charging, exposure, development, transfer, and cleaning steps around the drum. If the diameter of the drum-shaped support is 150 mm or more, image formation is performed. The apparatus becomes undesirably large. In particular, when the image forming apparatus is of a tandem type as shown in FIG. 3, it is necessary to mount a plurality of photoreceptors 1, and therefore the diameter is preferably 70 mm or less, and preferably 60 mm or less. Further, an endless nickel belt and an endless stainless steel belt disclosed in Patent Document 8 (Japanese Patent Laid-Open No. 52-36016) can also be used as the conductive support.

As the undercoat layer of the photosensitive member used in the image forming apparatus of the reference means according to the present invention, the resin or the white pigment and the resin as the main component, and the surface of the conductive substrate are chemically or electrochemically oxidized. Although a metal oxide film etc. can be illustrated, what has a white pigment and resin as a main component is preferable. Examples of the white pigment include metal oxides such as titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide. Among them, it is most preferable to contain titanium oxide that is excellent in preventing charge injection from the conductive substrate. As the resin used for the undercoat layer, thermoplastic resins such as polyamide, polyvinyl alcohol, casein, and methylcellulose, thermosetting resins such as acrylic, phenol, melamine, alkyd, unsaturated polyester, and epoxy, one or various kinds of these Mixtures can be exemplified.

Examples of the charge generating material of the photoreceptor used in the image forming apparatus of the reference means according to the present invention include azo pigments such as monoazo pigments, bisazo pigments, trisazo pigments, tetrakisazo pigments, triarylmethane dyes, and thiazines. Dyes, oxazine dyes, xanthene dyes, cyanine dyes, styryl dyes, pyrylium dyes, quinacridone pigments, indigo pigments, perylene pigments, polycyclic quinone pigments, bisbenzimidazole pigments, indanthrone Inorganic materials such as pigments, organic pigments and dyes such as squarylium pigments, phthalocyanine pigments, selenium, selenium-arsenic, selenium-tellurium, cadmium sulfide, zinc oxide, titanium oxide, amorphous silicon can be used, Charge generation materials can be used alone or in combination. The undercoat layer may be a single layer or a plurality of layers.

Examples of the charge transport material of the photoreceptor used in the image forming apparatus of the reference means according to the present invention include, for example, anthracene derivatives, pyrene derivatives, carbazole derivatives, tetrazole derivatives, metallocene derivatives, phenothiazine derivatives, pyrazoline compounds, hydrazone compounds, styryl compounds, One or many kinds of styryl hydrazone compounds, enamine compounds, butadiene compounds, distyryl compounds, oxazole compounds, oxadiazole compounds, thiazole compounds, imidazole compounds, triphenylamine derivatives, phenylenediamine derivatives, aminostilbene derivatives, triphenylmethane derivatives, etc. Can be used as a mixture.

  The binder resin used to form the photosensitive layer of the charge generation layer and the charge transport layer is electrically insulating and is a known thermoplastic resin, thermosetting resin, photocurable resin, and photoconductive material. Suitable binder resins include, for example, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, Ethylene-vinyl acetate copolymer, polyvinyl butyral, polyvinyl acetal, polyester, phenoxy resin, (meth) acrylic resin, polystyrene, polycarbonate, polyarylate, thermoplastic resin such as polysulfone, polyethersulfone, ABS resin, phenol resin , Epoxy resin, urethane resin, melamine resin, isocyanate resin, alkyd resin, Examples thereof include a thermosetting resin such as a ricone resin, a thermosetting acrylic resin, a type of binder resin such as a photoconductive resin such as polyvinyl carbazole, polyvinyl anthracene, and polyvinyl pyrene, or a mixture of various types of binder resins. In particular, it is not limited to these.

As antioxidant, the following are used, for example.
Monophenol compounds 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylphenol, stearyl-β- (3,5-di- t-butyl-4-hydroxyphenyl) propionate, 3-t-butyl-4-hydroxynisol and the like.

Bisphenol compounds 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4 ′ -Thiobis- (3-methyl-6-t-butylphenol), 4,4'-butylidenebis- (3-methyl-6-t-butylphenol) and the like.

-High molecular phenol compound 1,1,3-tris- (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3 '-Bis (4'-hydroxy-3'-t-butylphenyl) butyric acid] glycol ester, tocophenols, and the like.

Paraphenylenediamines N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, N-phenyl-N-sec-butyl-p-phenylenediamine, N, N′-di-isopropyl-p-phenylenediamine, N, N′-dimethyl-N, N′-di-t-butyl-p-phenylenediamine and the like.

Hydroquinones 2,5-di-t-octylhydroquinone, 2,6-didodecylhydroquinone, 2-dodecylhydroquinone, 2-dodecyl-5-chlorohydroquinone, 2-t-octyl-5-methylhydroquinone, 2- ( 2-octadecenyl) -5-methylhydroquinone and the like.

Organic sulfur compounds Dilauryl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, ditetradecyl-3,3′-thiodipropionate, and the like.

Organic phosphorus compounds Triphenylphosphine, tri (nonylphenyl) phosphine, tri (dinonylphenyl) phosphine, tricresylphosphine, tri (2,4-dibutylphenoxy) phosphine and the like.

  As the plasticizer, those used as plasticizers for general resins such as dibutyl phthalate and dioctyl phthalate can be used as they are, and the amount used is about 0 to 30 parts by weight with respect to 100 parts by weight of the binder resin. Is appropriate.

  A leveling agent may be added to the charge transport layer. As the leveling agent, silicone oils such as dimethyl silicone oil and methylphenyl silicone oil, polymers or oligomers having a perfluoroalkyl group in the chain are used, and the amount used is 100 parts by weight of binder resin. 0 to 1 part by weight is suitable.

  As described above, the surface layer is provided to improve the mechanical strength, abrasion resistance, gas resistance, cleaning property, etc. of the photoreceptor. Examples of the surface layer include a polymer having a mechanical strength higher than that of the photosensitive layer and a polymer in which an inorganic filler is dispersed. The polymer used for the surface layer may be either a thermoplastic polymer or a thermosetting polymer, but the thermosetting polymer has a high mechanical strength and does not wear due to friction with the cleaning blade. It is very preferable because of its extremely high ability to suppress. If the surface layer has a thin film thickness, there is no problem even if it does not have the charge transport capability. However, if the surface layer without the charge transport capability is formed thick, the sensitivity of the photoreceptor decreases, the potential increases after exposure, and the residual layer remains. Since the potential rise is likely to occur, it is preferable to use the above-mentioned charge transporting substance in the surface layer or to use a polymer having a charge transporting capability for the protective layer. When the surface layer is provided, the mechanical strength of the photosensitive layer and the surface layer is generally greatly different, and therefore the protective layer is worn away due to friction with the cleaning blade. It is important that the surface layer has a sufficient film thickness, and is 0.01 to 12 μm, preferably 1 to 10 μm, more preferably 2 to 8 μm. If the film thickness of the surface layer is 0.1 μm or less, it is not preferable because it is too thin and easily disappears due to friction with the cleaning blade, and wear of the photosensitive layer proceeds from the disappeared portion. When the film thickness of the surface layer is 12 μm or more, the sensitivity is lowered, the potential after exposure is increased, and the residual potential is easily increased. In particular, when a polymer having charge transport capability is used, the cost of the polymer having charge transport capability is high This is not preferable.

  As the polymer used for the surface layer, polycarbonate that is transparent to the writing light at the time of image formation and excellent in insulation, mechanical strength, and adhesiveness is used. In addition, ABS resin, ACS resin, olefin- Vinyl monomer copolymer, chlorinated polyether, allyl resin, phenol resin, polyacetal, polyamide, polyamideimide, polyacrylate, polyallylsulfone, polybutylene, polybutylene terephthalate, polyethersulfone, polyethylene, polyethylene terephthalate, polyimide, acrylic resin , Polymethylbenten, polypropylene, polyphenylene oxide, polysulfone, polystyrene, AS resin, butadiene-styrene copolymer, polyurethane, polyvinyl chloride, polyvinylidene chloride, epoxy resin, etc. It may be. These polymers may be thermoplastic polymers, but in order to increase the mechanical strength of the polymers, they are crosslinked with a crosslinking agent having a polyfunctional acryloyl group, carboxyl group, hydroxyl group, amino group, etc. By using a curable polymer, the mechanical strength of the surface layer is increased, and wear due to friction with the cleaning blade can be greatly reduced.

  In the surface layer, fine particles of metal or metal oxide can be dispersed in order to increase the mechanical strength of the surface layer. Examples of the metal oxide include titanium oxide, tin oxide, potassium titanate, TiO, TiN, zinc oxide, indium oxide, and antimony oxide. In addition, for the purpose of improving wear resistance, fluorine resins such as polytetrafluoroethylene, silicone resins, and those obtained by dispersing inorganic materials such as these resins can be added.

  Here, as the protective agent coating apparatus for applying the protective agent to the photosensitive member as described above, for example, as shown in FIG. 4, a blade, a brush, and a protective agent bar are mounted on the coating device. Is rotated at a predetermined speed by a gear (not shown), and the brush contacts the protective agent bar to scrape off the protective material. Subsequently, the protective agent scraped off by the rotation of the brush is supplied to the surface of the photosensitive member. The photosensitive member supplied with the protective agent passes through the blade by the rotation of the photosensitive member, and there is an apparatus having a mechanism in which the supplied protective agent is stretched by the blade and the protective agent is applied. The specific configuration and operation of the protective agent coating device, the process cartridge including the protective agent coating device, and the image forming apparatus are as described in the first embodiment.

Next, although the specific Example of evaluation of the protective agent coating device of the reference means based on this invention demonstrated by the above-mentioned reference form 1 is described, this invention is not limited to a following example.
FIG. 4 is a diagram showing an outline of the configuration of the protective agent coating apparatus used for the evaluation of this embodiment, and shows a simplified configuration similar to that of the protective agent coating apparatus 2 of FIG. In the example of FIG. 4, the blade of the protective agent coating apparatus is in contact with the surface of the photoconductor in a counter manner, but the present invention is not limited to this.
In the column “Example 1”, “Example 1” is read as “Reference Example 1”.

[Photoconductor]
The production of the photoreceptor to which the protective agent was applied was performed as follows.
An undercoat layer, a charge generation layer, a charge transport layer, and a protective layer were applied in that order on an aluminum drum (conductive support) having a diameter of 30 mm, and then dried, and a 3.6 μm undercoat layer, about 0.0. Twenty photoconductors comprising a 14 μm charge generation layer, a 23 μm charge transport layer, and a protective layer of about 3.5 μm were prepared. At this time, coating of the protective layer was performed by a spray method, and other than that was performed by a dip coating method. For evaluation, 11 photoconductors were used, and the remaining photoconductors were stored as spares. Details of the protective layer were as follows.

(Protective layer)
Z-type polycarbonate: 10 parts Triphenylamine compound (the following structural formula 1): 7 parts Alumina fine particles (particle size 0.3 μm): 5 parts Tetrahydrofuran: 400 parts Cyclohexanone: 150 parts

[Production method of protective agent bar (1)]
Production of the protective agent bar used was carried out as follows.
94 parts by weight of FT115 (manufactured by Nippon Seiwa Wax), 6 parts by weight of TOPAS-TM (manufactured by Chicona), placed in a glass container with a lid, and stirred by a hot stirrer whose temperature is controlled at 160 to 250 ° C. While melting.

The protective agent, which has been stirred and melted, is poured so as to fill an aluminum mold having an internal size of 12 mm × 8 mm × 350 mm heated to 115 ° C. in advance, allowed to cool to 88 ° C. on a wooden table, and then an aluminum table The solid was removed from the mold and cooled to room temperature with a weight on it to prevent warping.
After cooling, both ends in the longitudinal direction were cut and the bottom surface was cut to prepare a protective agent bar (1) of 7 mm × 8 mm × 310 mm. Double-sided tape was affixed to the bottom surface of the protective agent bar (1) and fixed to a metal support.

The photoconductor and protective agent bar (1) were subjected to IR analysis using FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)). The graph of FIG. 6 shows the absorbance spectrum, and spectrum A and spectrum M in the figure respectively show the spectrum of the photoconductor and the spectrum of the protective agent of the protective agent bar (1). In spectrum A obtained by the photoreceptor, a peak derived from the carbonate linkage 1770 cm ^-1 (peak a1 (1770cm ^-1)), was observed.
Here, when the ATR measurement was performed on the photosensitive member, the photosensitive layer of the photosensitive member was peeled off from the aluminum substrate with a size of 1 cm × 1 cm using a cutter to obtain a measurement sample.

[ Reference Example 1-1]
Brush (3) (thickness: 20 denier, density: 50,000 per square inch) for applying a protective agent to each photoconductor using photoconductor (1-1) and photoconductor (1-2) As shown in FIG. 4, the protective agent coating device is mounted on the brush, and the protective agent bar (1) is pressed against the brush with a spring pressure of 5 N, and the brush is brought into contact with the photosensitive member. ) And the photoreceptor (1-2) were each coated with a protective agent (referred to as a protective agent coating apparatus (1)). The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively.

With respect to the photosensitive member (1-1) and the photosensitive member (1-2) after application of the protective agent with different application times (20 minutes or 100 minutes), sampling was performed for each photosensitive member at each application time, and each sample was subjected to FT- IR analysis using IR Avatar370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)), and the spectrum of the photoconductor after applying the protective agent as shown in the graph of FIG. 6B. B (coating time 100 minutes) (absorbance spectrum) was obtained.
Then, spectrum A was subtracted from spectrum B obtained to obtain spectrum C (C in FIG. 6: difference spectrum). Here, when the difference spectrum is taken, the peak intensity (h (a1)) of the peak (peak a1) at 1770 cm ^{−1 in} the spectrum A is changed to the peak intensity (h of the peak (peak b1) at 1770 cm ^{−1 in} the spectrum B. In order to be the same as (b1)), the spectrum A was multiplied by a coefficient [h (b1) / h (a1)] and subtracted so that the peak at 1770 cm ⁻¹ disappeared in the difference spectrum. Further, the peak area S (b1) of the peak b1 was obtained.
Furthermore, the peak area S (c2) of the peak observed at 815 cm ⁻¹ in the difference spectrum C was calculated to obtain (S (c2) / S (b1)).
The coating amount index (S (c2) / S (b1)) thus determined was 0.072. Similarly, when the index of coating amount (S (c2) / S (b1)) at a coating time of 20 minutes was determined, it was 0.020.

  Here, Table 1 shows the integration range of the wave number and area of the background start point and end point when obtaining the area of each peak.

[ Reference Example 1-2]
Brush (2) (thickness: 10 denier, density: 50,000 per square inch) for applying a protective agent to each photoconductor using photoconductor (2-1) and photoconductor (2-2) As shown in FIG. 4, the urethane blade is attached to the protective agent coating apparatus, the protective agent bar (1) is pressed against the brush with a spring pressure of 5 N, and the brush is brought into contact with the photosensitive member for 20 minutes or 100 minutes. A protective agent was applied to each of the photoreceptor (2-1) and the photoreceptor (2-2). The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as a protective agent coating device (2)).

  FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) is applied to the photoreceptor (2-1) and the photoreceptor (2-2) after applying the protective agent. And (S (c2) / S (b1)) was calculated as in Example 1-1. After application for 20 minutes, (S (c2) / S (b1)) = 0. 022 After application for 100 minutes, (S (c2) / S (b1)) = 0.028.

[Production method of protective agent bar (2)]
The production of the second protective agent bar was carried out as follows.
60 parts by weight of FT115 (manufactured by Nippon Seiwa), 18 parts by weight of sorbitan tristearate (HLB: 1.5), 22 parts by weight of normal paraffin (average molecular weight 640), put in a glass container with a lid The mixture was melted with stirring by a hot stirrer whose temperature was controlled at 180 ° C.
The protective agent, which has been stirred and melted, is poured into an aluminum mold having an inner dimension of 12 mm × 8 mm × 350 mm that has been heated to 115 ° C. in advance, and is allowed to cool to 90 ° C. on a wooden table. The solid was removed from the mold and cooled to room temperature with a weight on it to prevent warping.
After cooling, both ends in the longitudinal direction were cut, and the bottom surface was cut to prepare a protective agent bar (2) of 7 mm × 8 mm × 310 mm. Double-sided tape was affixed to the bottom surface of the protective agent bar (2) and fixed to a metal support.

[Comparative Example 1-1]
Brush (3) (thickness: 20 denier, density: 50,000 per square inch) to apply a protective agent to each photoconductor using photoconductor (3-1) and photoconductor (3-2) 4 and the urethane blade as shown in FIG. 4, the protective agent bar (2) is pressed against the brush with a spring pressure of 6N, and the brush is brought into contact with the photosensitive member for 20 minutes or 100 minutes. A protective agent was applied to each of the photoreceptor (3-1) and the photoreceptor (3-2). The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as protective agent coating device (3)).

FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) is applied to the photoreceptor (3-1) and the photoreceptor (3-2) after applying the protective agent. And (S (c2) / S (b1)) was calculated as in Reference Example 1-1. After application for 20 minutes, (S (c2) / S (b1)) = 0. 064, after coating for 100 minutes, (S (c2) / S (b1)) = 0.12.

[Comparative Example 1-2]
Brush (1) (thickness: 10 denier, density: 30,000 per square inch) to apply a protective agent to each photoconductor using photoconductor (4-1) and photoconductor (4-2) As shown in FIG. 4, the urethane blade is mounted on a protective agent coating apparatus, the protective agent bar (1) is pressed against the brush with a spring pressure of 1.2 N, and the brush is brought into contact with the photosensitive member for 20 minutes or 100 The protective agent was applied to the photoreceptor (4-1) and the photoreceptor (4-2) for 5 minutes. The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as a protective agent coating device (4)).

  FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) for the photoreceptor (4-1) and the photoreceptor (4-2) after applying the protective agent And (S (c2) / S (b1)) was calculated as in Example 1-1. After application for 20 minutes, (S (c2) / S (b1)) = 0. After application for 010 and 100 minutes, (S (c2) / S (b1)) = 0.018.

[ Reference Example 1-3]
In the black and cyan photoreceptor units of Ricoh's tandem color image forming apparatus (IPSIO CX400) configured as shown in FIG. 3, the photoreceptors used in Reference Example 1-2 and Comparative Example 1-2 (2 -2) and photoconductor (4-2), a charging roller is placed directly above the photoconductor, and each charging roller is exposed to the same spring as the protective agent application device (2) and protective agent application device (4). Evaluation was carried out by pressing the photosensitive member at a linear velocity of 125 mm / sec and applying an alternating voltage of 1450 Hz and an amplitude of 1100 V to a direct current voltage of −600 V between the photosensitive member and the charging roller. Set the brush (2) and urethane blade so that the black photoconductor unit has the same conditions as the protective agent applicator (2), and set the cyan photoconductor unit to the same condition as the protective agent applicator (4). A brush (4) and a urethane blade were set so as to be.

As for the black and cyan units, five 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output and evaluated. The images output from the black and cyan units were high-quality images.
Next, using black and cyan units, a total of 30000 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output, and the images output from the black unit were high-quality images. In the image output from the cyan unit, light white streaks were observed.

Here, when the peak is used as an index calculated as 1250 cm ^-1, Reference Examples 1-1 and Comparative Examples 1-1 obtained photosensitive member (1-1), (1-2) and a photoreceptor (3 A difference spectrum is obtained from each spectrum B obtained from 1) and (3-2) in the same manner as in Reference Example 1-1, and in the difference spectrum C, a peak derived from the photoreceptor (peak c3) seen at 1250 cm ^-1 is obtained. ) The peak area S (c3) was replaced with S (c2) in Reference Example 1-1 and Comparative Example 1-1, and an index (S (c3) / S (b1)) was calculated.

[ Reference Example 1-4]
For the IR spectra obtained with the photoreceptor (1-1) and the photoreceptor (1-2) of Reference Example 1-1, the peak c2 (815 cm ⁻¹ ) used for index calculation is shown as c3 in Reference Example 1-4. change in (1250 cm ^-1), and calculates an area S (c3) of the peak of c3 in the difference spectrum C, indicator (S (c3) / S ( b1)) was determined, and after 20 minutes the coating Photosensitive member (1-1) has (S (c3) / S (b1)) = 0.13, and photosensitive member (1-2) after 100 minutes application has (S (c3) / S (b1)) = 0 .28.

Table 2 below shows the integration range of the wave number and area at the start and end points of the background when the area of the peak at 1250 cm ⁻¹ is obtained.

[Comparative Example 1-3]
Using the IR spectrum obtained in Comparative Example 1-1, the peak c2 (815 cm ⁻¹ ) used for index calculation was changed to the peak c3 (1250 cm ⁻¹ ) as in Example 1-4, and (S ( c3) / S (b1)) was calculated, and after application for 20 minutes (S (c3) / S (b1)) = 0.27, after application for 100 minutes (S (c3) / S (b1)) = 0.43.

[ Reference Example 1-5]
In the black and cyan photoconductor units of Ricoh's tandem color image forming apparatus (IPSIO CX400) configured as shown in FIG. 3, the photoconductors used in Reference Example 1-1 and Comparative Example 1-1 (1 -2) and a photoconductor (3-2) are applied under the same conditions, a charging roller is placed directly above the photoconductor, and the same as the protective agent application device (1) and protective agent application device (3) Each of the charging rollers is pressed against the photosensitive member by a spring, the linear velocity of the photosensitive member is set to 125 mm / second, and an AC voltage having a frequency of 1450 Hz and an amplitude of 1100 V is superimposed on the DC voltage of −600 V between the photosensitive member and the charging roller. Evaluation was performed. Set the brush (3) and urethane blade so that the black photoconductor unit has the same conditions as the protective agent coating device (1), and the cyan photoconductor unit has the same conditions as the protective agent coating device (3). A brush (3) and a urethane blade were set.

As for the black and cyan units, five 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output and evaluated. The images output from the black and cyan units were high-quality images.
Next, using black and cyan units, a total of 30000 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output, and the images output from the black unit were high-quality images. In the image output from the cyan unit, a light blackish (cyan color) was observed in the non-image area.

Next, specific examples of the method for evaluating the amount of solid surface deposits according to the present invention described in Embodiment 1 and the method for evaluating a protective agent coating apparatus using the evaluation method will be described. Is not limited to the following examples. In the column “Example 2”, “Example 2” is read as “Example 1”.

(Photoconductor)
The photosensitive member used was manufactured as follows.
An undercoat layer, a charge generation layer, a charge transport layer, and a protective layer were applied in that order on an aluminum drum (conductive support) having a diameter of 30 mm, and then dried, and a 3.6 μm undercoat layer, about 0.0. Twenty photoconductors comprising a 14 μm charge generation layer, a 23 μm charge transport layer, and a protective layer of about 3.5 μm were prepared. At this time, coating of the protective layer was performed by a spray method, and other than that was performed by a dip coating method. For the protective layer, a charge transporting layer having a formulation in which 23.8% by mass of alumina having an average particle size of 0.18 μm was added was used. For evaluation, 11 photoconductors were used, and the remaining photoconductors were stored as spares.

(Method for producing protective agent bar)
Production of the protective agent bar used was carried out as follows.
84 parts by weight of FT115 (manufactured by Nippon Seiwa Wax), 16 parts by weight of TOPAS-TM (manufactured by Chicona), put in a glass container with a lid, and stirred by a hot stirrer whose temperature is controlled at 160 to 250 ° C. While melting.
The protective agent, which has been stirred and melted, is poured so as to fill an aluminum mold having an internal size of 12 mm × 8 mm × 350 mm heated to 115 ° C. in advance, allowed to cool to 88 ° C. on a wooden table, and then an aluminum table The solid was removed from the mold and cooled to room temperature with a weight on it to prevent warping.
After cooling, both ends in the longitudinal direction were cut and the bottom surface was cut to prepare a protective agent bar of 7 mm × 8 mm × 310 mm. A double-sided tape was affixed to the bottom surface of the protective agent bar and fixed to a metal support.

The protective agent bar and the photoreceptor were subjected to IR analysis using FT-IR Avatar370 (Thermo Electron Co., Ltd., ThunderDome (single reflection ATR, Ge, incident angle 45 °)). FIG. 10 shows an absorbance spectrum, and spectrum A and spectrum B in the figure respectively show the spectrum of the protective agent in the protective agent bar and the spectrum of the photoreceptor. In spectrum B obtained with the photoreceptor, a peak derived from a polycarbonate bond was observed at 1770 cm ⁻¹ . In spectrum A obtained with the protective agent bar, peaks derived from methylene groups were observed at 2850 cm ⁻¹ and 2920 cm ⁻¹ .
Here, when the ATR measurement was performed on the photosensitive member, the photosensitive layer of the photosensitive member was peeled off from the aluminum substrate with a size of 1 cm × 1 cm using a cutter to obtain a measurement sample.

Example 1 -1] (Evaluation of the protective agent application device (1))
In order to apply the protective agent of the protective agent bar to the photoconductor, the brush (2) (thickness: 10 denier, density: 50,000 per square inch) and urethane blade are mounted on the protective agent application device as shown in FIG. The brush was pressed against the photosensitive member with a spring pressure of 4.8 N, and the protective agent was applied to the photosensitive member (1-1) to the photosensitive member (1-5) while changing the application time (protective agent application device (1 )). The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively.
The photoconductor (1-4) coated with the protective agent for 120 minutes using the protective agent coating device (1) was sliced thinly using an ultramicrotome and subjected to TEM observation. The film thickness of the agent was 20-50 nm.

  For each of the photoconductors (1-1) to (1-5) after application of the protective agent, sampling is performed for each photoconductor with different application times (2, 10, 20, 40, 120 minutes). Each sample was subjected to IR analysis using FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)). The IR spectrum at a coating time of 120 minutes was as shown in spectrum C (absorbance spectrum of the photoreceptor after coating with the protective agent) shown in FIG.

In the obtained spectrum B and spectrum C, the height of the peak of the polycarbonate seen at 1770 cm ⁻¹ is defined as h (b) and h (c), respectively, and from spectrum C, spectrum B is expressed as [h (c) / h (b ]] Is subtracted, and spectrum D (difference spectrum) shown in FIG. 12 is obtained. The area S (815 cm ⁻¹ ) of the peak derived from the photoreceptor seen at 815 cm ⁻¹ in the obtained spectrum D was determined. Further, the area S (1770 cm ⁻¹ ) of the peak at 1770 cm ^{−1 in} the spectrum C was determined.
When the ratio S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) of these areas is determined for application times 2, 10, 20, 40, and 120 minutes, the value of the ratio increases as the application time increases. A trend was seen, 0.017 at 20 minutes and 0.028 at 120 minutes. Further, for the photoreceptor (1-5) coated with the protective agent for 40 minutes, the same analysis was performed using five samples in the circumferential direction, and S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) was calculated. As a result, the error of the ratio S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) was 19%.

[Example 1-2 ] (When other peaks are used)
Obtained in Example 1 -1, using spectral C and spectra D, it was analyzed as in Example 1 -1. In Example 1-1, was calculating the area of a peak of 815 cm ^-1 in the spectrum D, in the embodiment 1 -2 were calculated area of the peak of 1250 cm ^-1 in the spectrum D. Further, the area S (1770 cm ⁻¹ ) of the peak at 1770 cm ^{−1 in} the spectrum C was determined.
As in Example 1 -1, a ratio of the area ^{S (1250cm -1) / S (} 1770cm -1), the obtained for the coating time 2,10,20,40,120 min, ratio values are application time A tendency to increase with increase was seen, 0.23 at 20 minutes and 0.25 at 120 minutes. Further, for the photoreceptor (1-5) coated with the protective agent for 40 minutes, the same analysis was performed using five samples in the circumferential direction, and S (1250 cm ⁻¹ ) / S (1770 cm ⁻¹ ) was calculated. As a result, the error of the ratio S (1250 cm ⁻¹ ) / S (1770 cm ⁻¹ ) was 26%.

From Examples 1-1 and Example 1 -2, chosen in the area (the difference between the spectrum of the peak derived from the photosensitive member in the spectrum before taking the area and the difference spectrum of the peak derived from the photosensitive member in the difference spectrum It was found that the ratio of the peak (which is different from the peak) is a good indicator of the amount of the protective agent attached.

  Table 3 below shows the integration range of the wave number and area of the background start point and end point when obtaining the area of each peak.

(Acceptance judgment by using the evaluation method of Example 1 -1)
Example As 1 -1, estimate the protective agent coating amount ratio of the area of the peak of the peak area and 1770 cm ^-1 of the ^{815cm -1 S (815cm -1) /} S (1770cm -1) as an index protection In the method for evaluating the agent coating apparatus, when Sb / Sa when the protective agent is applied for 30 minutes is a threshold value of 0.015 or more and the threshold value when applied for 120 minutes is 0.10 or less, the protective agent is applied. The apparatus was accepted and evaluated as follows.

[Example 1-3 ]
Brush (2) (thickness: 10 denier, density: 50,000 per square inch) to apply a protective agent to each photoconductor using photoconductor (3-1) and photoconductor (3-2) As shown in FIG. 4, the protective blade is attached to the protective agent coating apparatus, the protective agent bar is pressed against the brush with a spring pressure of 5 N, and the brush is brought into contact with the photosensitive member. A protective agent was applied to (3-1) and the photoreceptor (3-2), respectively. The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as protective agent coating device (2)).

FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) is applied to the photoreceptor (3-1) and the photoreceptor (3-2) after applying the protective agent. perform IR analysis by using, S (815cm ^-1) as in example 2-1 / S was calculated ^{(1770cm -1), S (815cm} -1) after 30 minutes coating / S (1770 cm ^-1 ) = 0.023, 120 minutes after coating, S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) = 0.032, and the protective agent coating apparatus (2) was evaluated as acceptable.

Example 1 -4]
Brush (3) (thickness: 20 denier, density: 50,000 per square inch) to apply a protective agent to each photoconductor using photoconductor (4-1) and photoconductor (4-2) As shown in FIG. 4, the protective blade is attached to the protective agent coating apparatus, the protective agent bar is pressed against the brush with a spring pressure of 5 N, and the brush is brought into contact with the photosensitive member. A protective agent was applied to each of (4-1) and photoconductor (4-2). The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as protective agent coating device (3)).

FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) for the photoreceptor (4-1) and the photoreceptor (4-2) after applying the protective agent perform IR analysis by using, S (815cm ^-1) as in example 2-1 / S was calculated ^{(1770cm -1), S (815cm} -1) after 30 minutes coating / S (1770 cm ^-1 ) = 0.025, 120 minutes after coating, S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) = 0.070, and the protective agent coating device (3) was evaluated as acceptable.

Example 1 -5]
Brush (1) (thickness: 10 denier, density: 30,000 per square inch) to apply a protective agent to each photoconductor using photoconductor (5-1) and photoconductor (5-2) 4 and the urethane blade as shown in FIG. 4, the protective agent bar is pressed against the brush with a 2N spring pressure, and the brush is brought into contact with the photosensitive member for 30 minutes and 120 minutes. A protective agent was applied to (5-1) and photoreceptor (5-2), respectively. The linear speeds of the photosensitive member and the brush were 125 mm / s and 146 mm / s, respectively (referred to as a protective agent coating device (4)).

FT-IR Avatar 370 (Thermo Electron Co., Ltd., Thunder Dome (single reflection ATR, Ge, incident angle 45 °)) is applied to the photoreceptor (5-1) and the photoreceptor (5-2) after applying the protective agent. perform IR analysis by using, S (815cm ^-1) as in example 2-1 / S was calculated ^{(1770cm -1), S (815cm} -1) after 30 minutes coating / S (1770 cm ^-1 ) = 0.010 After 120 minutes of application, S (815 cm ⁻¹ ) / S (1770 cm ⁻¹ ) = 0.021, and the protective agent coating apparatus (4) was evaluated as rejected.

[Example 1-6]
In the black and cyan photoreceptor units of Ricoh's tandem color image forming apparatus (IPSIO CX400) configured as shown in FIG. 3, the photoreceptors used in Examples 2-3 and 2-5, respectively (3 -2) and photoconductor (5-2) are installed, a charging roller is placed directly above the photoconductor, and the charging roller is pressed against the photoconductor with the same spring as the protective agent coating device (2) and (4). The evaluation was performed by setting the linear velocity of the photoconductor to 125 mm / sec and applying an AC voltage having a frequency of 1450 Hz and an amplitude of 1100 V superimposed on a DC voltage of −600 V between the photoconductor and the charging roller. Set the brush (2) and urethane blade so that the black photosensitive unit is the same as the condition of the protective agent coating device (2), and the cyan photosensitive unit is the same condition as the protective agent coating device (4). A brush (1) and a urethane blade were set.

As for the black and cyan units, five 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output and evaluated. The images output from the black and cyan units were high-quality images.
Subsequently, when a total of 20000 1-by-1 halftone images of A4 size paper as shown in FIG. 5 were output using black and cyan units, the image output from the black unit was a high-quality image. White streaks were seen in the image output from the cyan unit.

From Example 1 -6, by setting the threshold as in Example 1 -3 and Example 1 -5, it was confirmed that it is determined the acceptance of the protective agent application device.

In addition to the analysis by FT-IR (ATR) method shown in Example 1 -1 1 -6, using ICP emission spectrometry and XPS analysis, we attempt to estimate the amount of the protective agent on the photoconductor However, the amount of the protective agent could not be evaluated from the results of ICP emission analysis and XPS analysis.

It is a schematic block diagram illustrating the principal components of an exemplary main configuration of an image forming apparatus provided with a protective layer forming device according to an reference embodiment reference means according to the present invention. It is a schematic sectional drawing of the process cartridge provided with the protective layer forming apparatus which shows one reference form of the reference means which concerns on this invention. It is a schematic block diagram of the image forming apparatus which comprises the protective layer forming apparatus which shows one reference form of the reference means which concerns on this invention. It is a schematic block diagram which shows the structural example of the protective layer forming apparatus used at the time of evaluation. It is a figure which shows the example of the output image for evaluation. It is a figure which shows an absorbance spectrum, Comprising: The spectrum A of the photoreceptor surface before application of the protective agent, the spectrum M of the protective agent alone, and the spectrum B of the photoreceptor after the protective agent is applied by the protective agent application apparatus, It is a figure which shows the spectrum C. FIG. It is a schematic diagram which shows the example of the peak which exists in IR spectrum A of the solid surface without a deposit | attachment, and IR spectrum B of the solid surface to which the deposit | attachment adhered. It is a schematic diagram which shows the example for demonstrating the evaluation method of this invention. It is a schematic diagram which shows another example for demonstrating the evaluation method of this invention. It is a figure which shows an absorbance spectrum, Comprising: It is a figure which shows the spectrum B of a protection agent independent, and the spectrum A of a photoreceptor. It is a figure which shows an absorbance spectrum, Comprising: It is a figure which shows the spectrum C of the photoreceptor after application | coating of a protective agent. It is a figure which shows the difference spectrum D of the spectrum C of FIG. 11, and the spectrum B of FIG.

Explanation of symbols

1 (1Y, 1M, 1C, 1K): photoconductor (image carrier)
2: Protective agent coating device 3: Charging device (charging means)
4: Cleaning device (cleaning means)
5: Developing device (developing means)
6: Primary transfer device (transfer means)
7: Intermediate transfer medium (or transfer medium)
8: Latent image forming device 9: Belt cleaning device 10: Image forming unit (image forming station)
11: process cartridge 12: secondary transfer device 13: transport device 14: fixing device 15: transport device 16: paper discharge roller 17: paper discharge tray 21: protective agent bar 22: protective agent supply member 22a: brush-like member (brush) )
22b: support 23: pressing force applying mechanism 24: protective layer forming mechanism 24a: blade-like member 24b: pressing member 41: cleaning member 42: cleaning pressing mechanism 51: developing sleeve 52, 53: developer stirring and conveying member 100: image Forming apparatus 110: Image forming apparatus main body (printer unit)
120: Document reading unit (scanner unit)
130: Automatic document feeder (ADF)
200: paper feed unit 201a-201d: paper feed cassette 202: paper feed roller 203: separation roller 204, 205, 206: transport roller 207: registration roller 210: transport device for both sides

Claims (7)

In the evaluation method for evaluating the abundance of deposits on the solid surface,
Is measured with a infrared absorption spectroscopy of ATR (Attenuated Total Reflection) method, when the deposit and IR spectra A without the solid surface of deposits compared the IR spectrum B of the solid surface attached,
A peak derived from the solid present in both the IR spectrum A and IR spectra B, of the solid from the peak, the peak does not overlap with a peak derived from deposits in the IR spectrum B is at least two Among the two peaks, the peak with the larger wave number in the IR spectrum A is the peak a1, the peak with the smaller wave number is the peak a2, and the wave number is detected at the same position as the peaks a1 and a2. The peaks in the IR spectrum B corresponding to the wave number are peaks b1 and b2,
When the height of the peak a1 in the IR spectrum A is h (a1) and the height of the peak b1 in the IR spectrum B is h (b1), the IR spectrum A is [h (b1) / h ( a1)] The spectrum obtained by subtracting the multiplied spectrum (referred to as IR spectrum A ′) from the IR spectrum B is referred to as IR spectrum C, and in this IR spectrum C, peaks a1 and a2 are detected at the same wave number. The peaks corresponding to wave numbers are peaks c1 and c2,
When the area of the peak b1 in the IR spectrum B is S (b1) and the area of the peak c2 in the IR spectrum C is S (c2),
Wherein the area of the peak b1 in the IR spectrum B S (b1), wherein from the ratio between the area S (c2) of the peak c2 in the IR spectrum C (S (c2) / S (b1)), on the solid surface abundance evaluation method of the solid surface deposit and evaluating the presence of the deposit. In the method for evaluating the abundance of solid surface deposits according to claim 1,
The penetration depth at the wave number of infrared light from which the peak a2 is detected is 130% or more of the penetration depth at the wave number of infrared light from which the peak a1 is detected . Kimono abundance evaluation method. The method for evaluating the abundance of solid surface deposits according to claim 1 or 2,
A method for evaluating the amount of solid surface deposits, characterized in that the solid for evaluating the amount of deposits on the solid surface is a photoconductor . In the solid surface deposit abundance evaluation method according to claim 3,
The photoconductor is an organic photoconductor containing an organic compound having a carbonate bond, and the peak a1 is a peak derived from the carbonate bond . In the method for evaluating the abundance of solid surface deposits according to claim 3 or 4 ,
The method for evaluating the abundance of solid surface deposits, wherein the deposits on the surface of the photoreceptor are protective agents having a function of protecting the photoreceptor . In abundance evaluation method according to claim 5 Symbol mounting the solid surface deposits,
The said protective agent contains 50 weight% or more of paraffin, The abundance evaluation method of the solid surface deposit | attachment characterized by the above-mentioned . In a method for evaluating a protective agent coating apparatus that applies a protective agent to the surface of an image carrier ,
Using the method for evaluating the amount of solid surface deposits according to any one of claims 1 to 6, when the protective agent is applied to the image carrier by the protective agent application device, a certain amount of application is performed. Within time, the area S (b1) of the peak b1 in the IR spectrum B and the area S (c2) of the peak c2 in the IR spectrum C, which are indicators of the amount of deposits in the abundance evaluation method The protective agent coating device evaluation method , wherein the protective agent coating device is passed when the ratio (S (c2) / S (b1)) is a value within a predetermined standard .

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