JP2010060731A - Toner, image forming method, and development device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an image forming method including a toner replenishing configuration that does not cause an occurrence of fogging or overbrimming of toner associated with the toner replenishment even when a multiplicity of sheets are printed under a low-temperature and low humidity environment or under a high-temperature and high humidity environment over a long period of time. <P>SOLUTION: The method has a replenishing process for replenishing nonmagnetic monocomponent toner (Y) to a development container filled with nonmagnetic monocomponent toner (X) from an exchangeable replenishment toner container, wherein formula (1) of 30%≤α≤50% and formula (2) of 0.85≤α/β≤1.00 are satisfied where α represents the degree of aggregation of the toner (Y), and β represents the degree of aggregation of a mixture of the toner (Y) and the toner formed by sifting the toner (Y) by a vibration screen with a mesh of 53 μm opening size for six times. The toners (X) and (Y) contain toner particles and fatty acid metal salt with a median diameter (D50) on a volumetric basis being 0.15-1.00 μm. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a toner, an image forming method, and a developing device that make an electrostatic charge latent image visible.

  In recent years, with the development of computers and multimedia, there is a demand for means for outputting further high-definition full-color images in a wide range of fields from offices to homes. Heavy users demand high durability that does not deteriorate image quality even when a large number of copies or prints are made. In small offices and homes, high-quality images are obtained, and the size and fixing temperature of the device are reduced in terms of space and energy. We want to lower the temperature. Various studies have been carried out from various viewpoints to achieve these objects.

  Under such circumstances, when the toner in the image forming apparatus is consumed, the cartridge system replaces the toner replenishing container that is detachable to the image forming apparatus with a new toner replenishing container, and supplies the toner to the apparatus. Forming devices are known. As a result, copying or printing of a large number of sheets can be achieved with less frequent replacement of the cartridge, and further, it is not necessary to fill the apparatus or cartridge with a large amount of toner from the beginning of printing, thereby achieving downsizing of the apparatus. Therefore, it is preferable.

  However, all of the series of operations associated with the image forming operation involve contact between toner and toner or toner and member, and the toner repeatedly receives a load each time such contact occurs. Due to such a load, a part or all of the toner is damaged, and the fluidity and triboelectric chargeability required for the toner gradually decrease. This is due to the fact that, by using the toner replenishment type image forming method, the toner that has not deteriorated is successively replenished into the developing device as described above, so that the toner deterioration speed is in a easing direction. . However, according to the study by the present inventors, the toner that is present in the vicinity of the toner carrier and has not contributed to the development deteriorates in the developing unit, and as a result, the triboelectric chargeability and fluidity are reduced. . Then, the toner deteriorated due to the durability and the newly supplied replenishment toner are mixed, so that the toner aggregates and the fluidity is further deteriorated. The toner in such a state is more non-uniform in the cartridge in terms of charge amount, charge distribution, and toner physical properties represented by toner transportability. Further, it has been found that if the toner in such a state is continuously used, problems on the image such as density unevenness, fogging, and toner blur drop (toner lump falls on the spot on the image) occur. Such a phenomenon has partially occurred even in a conventional all-in-one cartridge having no replenishment configuration. That is, the toner staying in the dead space in the cartridge may be mixed with the durable toner for some reason, such as vibration is applied to the machine at the end of the durability. However, in the case of a developing device having a replenishment configuration, the mixing of old and new toner as described above is performed temporarily, not temporarily, and the cartridge life is generally long. In addition, since once deteriorated toner tends to be difficult to contribute to the development, a larger amount of such deteriorated toner is accumulated in the developing device having the replenishment configuration. As a result, the mixing frequency of the new and old toners is further increased, and the deterioration degree of some deteriorated toners is further advanced due to the accumulation. Further, in a developing device having a replenishment configuration, since toner is generally transported through a replenishment path and reaches the developing unit, toner deterioration tends to easily proceed due to the share in the transport process. For the above reasons, a developing device having a replenishment configuration is more severe in terms of toner deterioration and mixing of old and new toner as compared with a conventional all-in-one cartridge, and the above-mentioned image defects are more prominent. It was.

  In particular, such a phenomenon is appearing in a technical trend of lowering the melting point of the toner as a toner characteristic due to a demand for energy saving in addition to a high gloss on the image. As a result, the toner is more susceptible to stress due to contact and rubbing with the above-mentioned members and toners, and the fluidity and triboelectric chargeability of the toner itself tend to be lower than ever. This trend is expected to accelerate further in the future, and toners are required to have both softness and high durability capable of achieving high gloss and energy saving.

  On the other hand, there is a technology that takes an approach from toner to these problems.

  For example, it is disclosed that image quality and fog are improved by defining the relationship between the particle size of toner particles having a certain storage modulus or the particle size distribution of toner particles and the particle size and distribution of fatty acid metal salt ( For example, Patent Documents 1 and 2).

  Further, it is disclosed that fog, toner scattering and toner leakage are suppressed by containing an additive (alumina and titanium oxide) that defines the work function relationship with the base particles and a fatty acid metal salt (for example, Patent Document 3).

  Certainly, such measures have made it possible to reduce fog, toner scattering, and toner leakage, and to achieve high durability and high image quality stability. However, as a result of intensive studies by the present inventors, the toner described in Patent Document 1 is effective in reducing the initial fogging because the particle size of the fatty acid metal salt used is too large, but printing a large number of sheets. When it did, it turned out that the change of charging property becomes large and it tends to generate fog. It has been found that the toners described in Patent Documents 2 and 3 have the problem of fogging due to a decrease in chargeability when the number of printed sheets increases in a severe environment of low temperature and low humidity and high temperature and high humidity.

  Further, there is a technique that defines the degree of aggregation of toner. In this document, the ratio between the initial stage and the degree of aggregation after 20 hours of idling of the developing part is defined, and it is disclosed that a good image quality can always be provided without deterioration (Patent Document 4). However, it has been found that the present technology also has problems such as fogging due to a decrease in chargeability, density unevenness, or toner blurring in a severe environment of low temperature and low humidity and high temperature and high humidity.

  In addition to each of the above-mentioned problems, in any of the countermeasures, especially when a large number of sheets are printed for a long period of time with an apparatus having a replenishment configuration in a high temperature and high humidity environment, it is caused by agglomeration due to mixing of deteriorated durability toner and new supply toner It was found that the bad image occurred. Even in the printing of a large number of sheets, which is required in the market, it is actually necessary to improve various characteristics in order to obtain stable developability without depending on the use environment.

Japanese Patent Laid-Open No. 9-311499 JP 2002-296829 A JP 2007-148198 A JP 2001-147570 A

  The present invention is to provide a toner, an image forming method, and a developing device that solve the above-described background art. In other words, it has a toner replenishment configuration, and even when a large number of sheets are printed for a long time in a low temperature, low humidity, high temperature, high humidity environment, there is no occurrence of fogging or toner blurring due to toner replenishment, and toner with a uniform density. Another object is to provide an image forming method and further a developing device.

The present invention relates to a charging step of charging the electrostatic latent image carrier with a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and contact with the toner carrier. A step of regulating the toner on the toner carrier with the toner layer regulating member formed, a development step of developing the electrostatic latent image with the toner on the toner carrier, and the toner image via or via the intermediate transfer member In an image forming method having a transfer step of transferring to a transfer material without
The image forming method includes a replenishment step of replenishing a nonmagnetic monocomponent toner (Y) from a replaceable replenishment toner container to a developing container filled with the nonmagnetic monocomponent toner (X),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β , Satisfy the following formulas (1) and (2),
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula In addition, the toners (X) and (Y) are at least toner particles and a volume-based median diameter (D50). The present invention relates to an image forming method characterized by containing a fatty acid metal salt having a thickness of 0.15 μm to 1.00 μm.

The present invention also provides a toner carrier for carrying and developing toner, a toner layer regulating member for contacting the surface of the toner carrier to regulate the thickness of the toner layer, and a toner on the toner carrier. A toner supply member for supplying the toner, a toner conveying means provided above the rotation center axis of the toner supply member for conveying the toner in the longitudinal direction of the toner supply member, and a toner for supplying the toner carrier A storage container for storing the toner, a toner carrier, the toner layer regulating member, the toner supply member, the toner conveying means, and a stirring chamber for supplying toner to the developing chamber composed of the storage container, In the developing device in which the developing chamber has a toner inlet from the stirring chamber and a toner outlet to the stirring chamber,
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. The present invention relates to a developing device comprising a fatty acid metal salt having a size of 00 μm.

Furthermore, the present invention provides a toner carrier for carrying and developing toner, a toner layer regulating member for contacting the surface of the toner carrier to regulate the thickness of the toner layer, and supplying the toner to the toner carrier. A toner supply member for conveying the toner, a toner conveying means provided above the rotation center axis of the toner supply member for conveying the toner in the longitudinal direction of the toner supply member, and a toner for supplying the toner to the toner carrier A storage container for storing the toner carrier, a toner layer regulating member, a toner supply member, a toner transporting unit, and a stirring chamber for supplying toner to a development chamber composed of the storage container; A toner used in a developing device having a toner inlet from the stirring chamber and a toner outlet to the stirring chamber;
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. The present invention relates to a toner comprising a fatty acid metal salt of 00 μm.

  According to the present invention, a toner replenishment configuration is provided, and even when a large number of sheets are printed for a long time in a low temperature and low humidity and high temperature and high humidity environment, there is no occurrence of fogging and toner blurring due to toner replenishment, and the density is uniform. A toner, an image forming method, and a developing device can be obtained.

  Hereinafter, the present invention will be described in detail.

  As described above, the toner is rubbed against various members in the process of forming a series of images. The rubbing between the toner and the member is considered important from the viewpoint of uniformly triboelectrically charging the toner. In addition, when an image is formed by an image forming apparatus having a replenishment configuration, friction between toners becomes important, such as mixing of deteriorated durability toner and new replenishment toner. Since the toner is uniformly charged or deteriorated due to the rubbing, the present inventors have conducted intensive studies focusing on the contact surface on which they act, that is, the toner surface. Specifically, intensive investigations have been made by paying attention to so-called external additives such as a fluidity improver present on the surface of the toner. In addition, intensive studies were also conducted on the mixing of durability deteriorated toner, which is considered to be a cause of image damage when an image is formed with an image forming apparatus having a replenishment configuration, and a new replenishment toner. It has been found that a toner, an image forming method, and a developing device that can improve the above problems can be obtained by containing the toner and further exhibiting a specific aggregation degree.

Specifically, a charging step of charging the electrostatic latent image carrier with a charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and applying the toner onto the toner carrier. A step of regulating the toner on the toner carrier with the toner layer regulating member in contact, a development step of developing the electrostatic latent image with the toner on the toner carrier, the toner image via the intermediate transfer member, or In an image forming method having a transfer step of transferring to a transfer material without intervention,
The image forming method includes a replenishment step of replenishing a nonmagnetic monocomponent toner (Y) from a replaceable replenishment toner container to a developing container filled with the nonmagnetic monocomponent toner (X),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β , Satisfy the following formulas (1) and (2),
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula In addition, the toners (X) and (Y) have at least toner particles and a volume-based median diameter (D50). Is an image forming method characterized by containing a fatty acid metal salt of 0.15 μm to 1.00 μm.

A toner carrier for carrying the toner and developing the toner; a toner layer regulating member that is in contact with the surface of the toner carrier to regulate the thickness of the toner layer; and for supplying the toner to the toner carrier. A toner supply member; a toner conveying means provided above the rotation center axis of the toner supply member for conveying toner in a longitudinal direction of the toner supply member; and a storage for storing toner to be supplied to the toner carrier. A developing chamber composed of a container, the toner carrier, the toner layer regulating member, the toner supply member, the toner conveying means, and the storage container. In a developing device having a toner inlet from a stirring chamber and a toner outlet to the stirring chamber,
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. A developing apparatus comprising a fatty acid metal salt of 00 μm.

Further, a toner carrier for carrying and developing toner, a toner layer regulating member that is in contact with the surface of the toner carrier to regulate the thickness of the toner layer, and for supplying toner to the toner carrier A toner supply member; a toner conveying means provided above the rotation center axis of the toner supply member for conveying toner in a longitudinal direction of the toner supply member; and a storage for storing toner to be supplied to the toner carrier. A developing chamber composed of a container, the toner carrier, the toner layer regulating member, the toner supply member, the toner conveying means, and the storage container. A toner used in a developing device having a toner inlet from a stirring chamber and a toner outlet to the stirring chamber;
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. A toner characterized by containing a fatty acid metal salt of 00 μm.

Although the detailed reason why the effects of the present invention can be obtained by using the toner, the image forming method, and the developing device as described above is not clear, the present inventors consider as follows.
In other words, in a developing device having a replenishment configuration, mixing of durable toner and new replenishment toner is an essential requirement. Arise. Further, as described above, the durable toner is a residual toner that does not contribute to development in the cartridge and is subjected to physical stress by various members. Therefore, the toner sieved six times with a mesh having an opening diameter of 53 μm according to the present invention is a toner to which physical stress is intentionally applied, and is an image of a durable toner in the cartridge. In other words, the cohesion degree ratio α / β corresponds to the change in cohesion degree due to the mixing of the durable toner and the new replenishing toner, and setting this value to 0.85 to 1.00 suppresses the increase in the cohesion degree due to the mixing. Therefore, it is considered that various image problems do not occur.

  However, it is not sufficient to satisfy the above-described aggregation ratio (α / β) in order to exhibit the effects of the present invention, and the toner has a median diameter (D50) of at least 0.15 μm to 1 on the basis of toner particles and volume. It is essential to contain a fatty acid metal salt of 0.000 μm. Fatty acid metal salts are known as so-called metal soaps, and are known to have an effect of preventing filming on a cleaning aid or an electrostatic latent image carrier when contained in toner. In the present invention, since it is a finer fatty acid metal salt as compared with a conventional fatty acid metal salt, it can not be expressed in the prior art by allowing the toner to be present more uniformly on the toner surface by containing the particles. The effects of the present invention are exhibited. In other words, the mixing of the durable toner and the new replenishing toner proceeds physically more rapidly due to the lubricant effect of the fine fatty acid metal salt. Further, it is considered that the electrostatic aggregating action between the toners caused by excessive frictional charging is suppressed by suppressing excessive friction between the toners. And it thinks that the increase in the aggregation degree by mixing will decrease by this. Furthermore, it is thought that physical stress with various members can be alleviated by containing the fatty acid metal salt of the present invention. As a result, the synergistic effect that the deterioration of the durable toner is suppressed and the change in the aggregation degree is further suppressed is exhibited.

  Here, when α / β is less than 0.85, the increase in the degree of aggregation due to the mixing of the durable toner and the replenishing toner is large, and particularly when the replenishment process is performed remarkably in a high-temperature and high-humidity environment, density unevenness and fogging are caused. In addition, toner dropout becomes noticeable. In addition, when the fatty acid metal salt of the present invention is not contained, the effect is not exhibited and the occurrence of uneven density, fogging, and toner dropout is not suppressed, and fogging in a low-temperature and low-humidity environment also occurs remarkably. . Furthermore, even if a fatty acid metal salt is contained, if the median diameter (D50) on a volume basis is less than 0.15 μm, the action as a lubricant is reduced, resulting in density unevenness, fogging, and toner dropping in a high temperature and high humidity environment. However, the occurrence of fog in a low-temperature and low-humidity environment becomes significant. On the other hand, if it exceeds 1.00 μm, the fatty acid metal salt tends to be unevenly present on the surface of the toner particles, so that when the durable toner and the newly supplied toner are mixed, the degree of aggregation of the toner increases, resulting in density unevenness, fogging, The toner falls out. A more preferable range of the median diameter (D50) is 0.15 μm to 0.75 μm, and within this range, the effects of the present invention can be stably obtained. A more preferable range is 0.30 μm to 0.60 μm, and the effect of the present invention can be obtained more stably in this range.

  Further, when the aggregation degree α of the toner of the present invention is less than 30%, it is difficult to triboelectrically charge the toner, and the decrease in density and the occurrence of fog cannot be suppressed.

  Further, when the aggregation degree α exceeds 60%, the toner transportability in the developing unit is lowered and the image density is lowered or the density followability when a solid image is output is deteriorated.

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

The toner of the present invention preferably has a span value B defined by the following formula (3) of the fatty acid metal salt contained in the toner of 1.75 or less.
Span value B = (D95s−D5s) / D50s (3) Formula D5s: 5% integrated diameter D50s of fatty acid metal salt based on volume D: Median diameter of fatty acid metal salt based on volume (D50)
D95s: 95% integrated diameter of fatty acid metal salt based on volume

  As described above, by making the fatty acid metal salt of the present invention have a certain degree of particle size distribution, it is possible to make the fatty acid metal salt more uniformly present in the toner, and the effects of the present invention can be expressed more stably. Here, when the span value B exceeds 1.75, the charging property becomes unstable due to the variation in the particle diameter of the fatty acid metal salt present in the toner, and density unevenness, fogging, and toner dropout also occur. there's a possibility that. The span value B is more preferably 1.50 or less, and if it is 1.50 or less, the effects of the present invention can be obtained stably.

  Further, it is preferable that the toner layer regulating member has an elastomer layer of either polyamide or polyester at a contact portion with the toner carrier.

  The elastic blade having a charge-imparting layer having an elastomer layer of either polyamide or polyester according to the present invention has a characteristic that an elastomer of polyamide or polyester gives an appropriate triboelectric charge to the toner. And high image density can be realized. Further, since the elastomer of polyamide or polyester has elasticity, the pressure contact force between the toner carrier and the toner layer regulating member does not vary locally, and the toner is uniformly distributed on the toner carrier. The thickness can be maintained with a uniform triboelectric charge amount. Furthermore, since the toner of the present invention contains a minute fatty acid metal salt, each particle is loosened without the toner aggregating, so that the uniform triboelectric charging property by this elastomer can be increased synergistically. As a result, it is easy to form a good image free from image defects such as density unevenness and supply fog.

Further, the Shore D hardness of the elastomer layer is γ °, and a load of 2.9 × 10 ⁻⁴ N at a load speed of 9.8 × 10 ⁻⁵ N / sec at 25 ° C. in the toner micro-compression test is applied to the toner. In the displacement curve from unloading to unloading, when the ratio (restoration rate) of the unloading return and the maximum displacement is Z (25),
25 ° ≦ γ ≦ 75 °
0.4 ≦ γ / Z (25) ≦ 2.0
It is preferable that

  The Shore D hardness of the elastomer layer is preferably from 25 degrees to 75 degrees from the viewpoint of toner fusing property. That is, if it is less than this range, it becomes difficult to sufficiently and uniformly triboelectrically charge the toner, and as a result, image defects such as density unevenness and supply fog may occur. In addition, if it exceeds this range, the hardness of the elastomer itself is high, so that the deterioration of the toner is promoted, particularly due to the toner fusing due to the crushing or broken pieces of the toner during long-term use in a high temperature and high humidity environment. This may cause toner charging failure. The Shore D hardness of the blade member can be adjusted by the blending ratio of the components in the elastomer, and the Shore D hardness of the elastomer layer corresponding to the development process can be achieved as required.

Further, the restoration rate at a load of 2.9 × 10 ⁻⁴ N at a load speed of 9.8 × 10 ⁻⁵ N / sec at 25 ° C. in the Shore D hardness γ ° of the elastomer layer and a micro-compression test of the toner. The relationship of (Z (25)) is 0.4 ≦ γ / Z (25) ≦ 2.0, which is a preferable form for expressing the effect of the toner of the present invention. That is, this relational expression expresses the relationship between the hardness of the toner of the present invention and the elastomer layer that frictionally charges the toner. Here, if γ / Z (25) is less than 0.4, it means that the toner tends to be excessively hard with respect to the elastomer layer, and it is difficult to sufficiently and uniformly frictionally charge the toner. Prone. On the other hand, if it exceeds 2.0, the elastomer layer tends to be excessively hard against the toner, and the pressure contact force of the toner layer regulating member to the toner may vary locally. In addition, the toner tends to deteriorate particularly during long-term use in a high-temperature and high-humidity environment.

  A detailed description of the toner layer regulating member used in the present invention will be described later.

  The fatty acid metal salt suitably used in the present invention is preferably a metal salt selected from zinc, calcium, magnesium, aluminum and lithium of higher fatty acids having 12 or more carbon atoms, more preferably a zinc or calcium salt. is there. When the metal species is zinc or calcium, the effects of the present invention are more easily obtained. Moreover, generation | occurrence | production of a free fatty acid is easy to be suppressed when a C12 or more fatty acid is used. The free fatty acid is preferably 0.20% or less, and if it is more than 0.20%, fog is likely to occur.

  Examples of the fatty acid metal salt include zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, lithium stearate, and zinc laurate.

  The addition amount of the fatty acid metal is preferably 0.02 parts by mass or more and 0.50 parts by mass or less with respect to 100 parts by mass of the toner particles. More preferably, they are 0.05 mass part or more and 0.30 mass part or less. When the amount is less than 0.02 parts by mass, it is difficult to obtain the effect of the present invention. When the amount is more than 0.05 parts by mass, it is difficult to obtain stability of image density.

  The toner of the present invention preferably contains silica and hydrotalcite.

  When the toner of the present invention contains silica, for example, not only the transportability of the toner from the replenishing port to the developing unit is improved, but also the mixing property of the durable toner and the new replenishing toner is improved. Further, since the hydrotalcite is appropriately contained, the toner is appropriately charged even during the conveyance of the toner. Thereby, moderate electrostatic repulsion between the toners is generated, and aggregation of the toner in the process is suppressed, so that the toner transportability is improved.

  Further, when the content of the silica in the toner is A and the content of the hydrotalcite is B, it is preferable that 5.0 ≦ A / B ≦ 30.0. In order to express the effects of the silica and hydrotalcite, the blending ratio of both becomes important. When A / B is less than 5.0, the content of silica with respect to hydrotalcite is small and sufficient toner transportability may not be obtained, and frictional charging by hydrotalcite becomes excessive and toner aggregation occurs. May occur. Further, when A / B exceeds 30.0, the content of hydrotalcite with respect to silica is small, and appropriate electrostatic repulsion due to appropriate charging by hydrotalcite may not be obtained. The transportability may deteriorate.

  The average circularity of the toner of the present invention is preferably 0.970 to 0.995. When the average circularity of the toner is less than 0.970, not only the chargeability of the toner is likely to be non-uniform, but also the fluidity of the toner tends to deteriorate, so that the mixability of the durable toner and the newly supplied toner also decreases. . Furthermore, the added fatty acid metal salt may be present unevenly on the toner surface, and uneven density, fogging, and toner dropping are likely to occur.

  The toner of the present invention preferably contains a compound having an ether bond represented by the following structural formula (1) or (2).

〔式中、Ｒ₁乃至Ｒ₁₁は、炭素数１乃至６までのアルキル基であり、互いに同じであっても、異なっていても良い。〕

[Wherein R _{1 to} R ₁₁ are alkyl groups having 1 to 6 carbon atoms and may be the same or different from each other. ]

  Since the ether compound is excellent in compatibility with the binder resin, it is considered that when the ether compound is contained in the toner, it is dispersed in a nearly uniform state. Further, since oxygen atoms are elements having high electronegativity, the negative charges generated in the toner are delocalized. Since the ether compound has these two characteristics, the presence of the ether compound stabilizes the negative charge of the toner. Therefore, the effect of containing the ether compound is particularly remarkable when the toner of the present invention is a negative triboelectrically chargeable toner. In addition, it has the effect of suppressing charge-up even in the case of positive frictional charging.

  The ether compound has tertiary carbon and has a bulky structure. Since the functional group centered on tertiary carbon functions as a steric hindrance, it is hardly affected by water and charge leakage is suppressed. However, since the carbon bonded to the oxygen atom rotates, the functional group that can become steric hindrance can move, and the water molecule involved in the leakage of triboelectric charge is a small molecule. Must not. As a result, the functional group centered on the tertiary carbon functions as an appropriate steric hindrance.

  Therefore, by combining the above-described ether compound with the toner of the present invention, the macroscopic behavior such as the fluidity of the toner due to the inclusion of the fatty acid metal salt of the present invention and the uniform charging within one toner particle due to the inclusion of the ether compound. Microscopic phenomena such as sex act synergistically. In the developing device having the replenishment configuration, the durable toner and the new replenishment toner are mixed well, and the occurrence of density unevenness and fogging during replenishment is easily suppressed.

When R _{1 to} R ₁₁ have 1 to 6 carbon atoms, an effect as an appropriate steric hindrance is obtained, an appropriate balance between hydrophobicity and hydrophilicity is obtained, and a binder resin is used. By obtaining the solubility, the charging uniformity of the toner is easily improved. When the number of carbon atoms is 1 to 4, the above effect is further improved.

  Further, the ether compound needs to be contained in the toner in the range of 5 to 1,000 ppm in order to sufficiently exhibit the above effects. More preferably, it is 10 to 800 ppm. More preferably, it is 10 to 500 ppm. The ether compound preferably contains at least one compound having the above structure, and may contain an ether compound having another structure. The content at that time is the total amount of the ether compounds contained.

  When the content of the ether compound in the toner is 5 to 1000 ppm, a good triboelectric charge amount is easily obtained, and uniform toner charge is easily obtained.

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

  Further, in order to achieve a better fluidity of the toner of the present invention, it is preferable to control the toner particle size within a certain range. Specifically, the toner of the present invention preferably has a weight average particle diameter (D4) of 5 to 8 μm. If the weight average particle diameter (D4) is less than 5 m, toner packing is likely to occur, and the fluidity is lowered. On the other hand, when the weight average particle diameter (D4) of the toner exceeds 8 μm, voids in the toner tend to increase, so that excessive fluidity tends to occur. And since these tend to cause deterioration of the uniform chargeability of the toner, such toner tends to cause density unevenness and fog during replenishment.

  Furthermore, if the number percentage of particles of 4.00 μm or less in the particle size distribution based on the number of toners is in the range of 3 to 30%, the fluidity of the toner of the present invention can be further improved. This is because, by reducing the ratio of the small particle size toner that is relatively highly charged and easy to pack, the difference in charge amount between the old and new toner is reduced, and the decrease in fluidity is suppressed. This is because matching with the fatty acid metal salt having a small particle size and a moderately sharp particle size distribution of the invention is promoted. In other words, the inventors consider that the mixing state in the external addition step of the toner particles and the fatty acid metal salt of the present invention tends to be uniform, and the homogenization process effectively proceeds. The weight average particle diameter (D4) of the toner and the number% of particles of 4.00 μm or less in the number-based particle size distribution can be adjusted by means such as control of the central particle diameter and classification.

  Below, the material used by this invention is demonstrated.

  Examples of the binder resin used in the present invention include polystyrene; a styrene-substituted homopolymer such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, Styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethacrylic acid methyl copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene copolymer such as copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Coalescence; acrylic resin; methacrylic tree ; Polyvinyl acetate; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  The comonomer for the styrene monomer of the styrene copolymer includes acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, doditer acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methacrylic acid. Monocarboxylic acid having a double bond such as methyl acid, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, maleate Dicarboxylic acids having a double bond such as dimethyl acid and its substitutes; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene; Sulfonyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p A styrene derivative such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl accelerator Acrylic polymerizable monomers such as N-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate Body; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n- Octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl meta Methacrylic polymerizable monomers such as relate and dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinylmethyl And vinyl ethers such as ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone.

  As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above-described monofunctional polymerizable monomers are used alone or in combination of two or more, or the above-mentioned monofunctional polymerizable monomers and polyfunctional polymerizable monomers are used in combination. . The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  Examples of the wax used in the present invention include the following. Petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax, petrolactam; montan wax and derivatives thereof; hydrocarbon waxes and derivatives thereof according to the Fischer-Tropsch method; polyolefin waxes and derivatives thereof such as polyethylene wax and polypropylene wax; carnauba wax Natural waxes such as candelilla wax and derivatives thereof. Examples of the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, the following are mentioned. Higher fatty alcohols; fatty acids such as stearic acid and palmitic acid; acid amide waxes; ester waxes; hardened castor oil and its derivatives; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability. More preferably, a compound containing 50 to 95% by mass of a compound having the same total number of carbon atoms has high wax purity and easily develops the effects of the present invention from the viewpoint of developability.

  The toner of the present invention is preferably obtained in an aqueous medium. Examples of the method for producing toner particles in an aqueous medium include the following methods. An emulsion aggregation method in which an emulsion composed of essential toner components is aggregated in an aqueous medium; a suspension granulation method in which the essential toner components are dissolved in an organic solvent and then the organic solvent is volatilized after granulation in the aqueous medium. A suspension polymerization method or an emulsion polymerization method in which a polymerizable monomer in which an essential toner component is dissolved is directly granulated in an aqueous medium and then polymerized; a method in which an outer layer is then formed on the toner by using seed polymerization; A microcapsule method represented by drying in liquid.

  Among these, the suspension polymerization method is particularly preferable as the one that easily exhibits the effects of the present invention. In this suspension polymerization method, a polymerizable monomer is uniformly dissolved or dispersed with a wax and a colorant (and a polymerization initiator, a crosslinking agent, a charge control agent, and other additives as necessary) to achieve polymerization. A monomer composition is used. Thereafter, the polymerizable monomer composition is dispersed in an aqueous medium containing a dispersion stabilizer using a suitable stirrer, and a polymerization reaction is performed to obtain toner particles having a desired particle size. is there. After the polymerization, the toner particles are filtered, washed and dried by a known method, and if necessary, a fluidity improver is mixed and adhered to the surface to obtain the toner of the present invention.

  In the case of producing toner by this suspension polymerization method, since the shape of individual toner particles is almost spherical, the charge amount distribution is relatively uniform. Further, it is easy to obtain a toner that maintains a high transferability with little dependence on external additives.

  Examples of the polymerizable monomer for producing the toner by the suspension polymerization method include the monofunctional polymerizable monomer and the polyfunctional polymerizable monomer.

  As the polymerization initiator used in the present invention, an oil-soluble initiator and / or a water-soluble initiator is used. Preferably, the half-life at the reaction temperature during the polymerization reaction is 0.5 to 30 hours. When the polymerization reaction is carried out at an addition amount of 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer, a polymer having a maximum between 10,000 and 100,000 is usually obtained. A toner having strength and melting characteristics can be obtained.

  As polymerization initiators, the following 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbohydrate) were used. Nitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2- Ethyl hexanoate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4- Peroxidation such as dichlorobenzoyl peroxide and lauroyl peroxide System polymerization initiators and the like.

  Particularly preferred is a polymerization initiator that produces the ether compound as described above upon decomposition during the polymerization reaction.

  In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  As the black colorant used in the present invention, carbon black, a magnetic material, and a toned color of each color using the following yellow / magenta / cyan colorant are used. In particular, since dyes and carbon black have many polymerization-inhibiting properties, care must be taken when using them.

  Examples of the yellow colorant used in the present invention include compounds typified by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds. Specifically, the following C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 62, 73, 74, 83, 93, 94, 95, 97, 109, 110, 111, 120, 128, 129, 138, 147, 150, 151, 154, Examples include 155, 168, 180, 185, 214 and the like.

  Examples of the magenta colorant used in the present invention include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, the following C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 48: 4, 57: 1, 81: 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like can be exemplified.

  Examples of the cyan colorant used in the present invention include copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like. Specifically, C.I. I. Pigment blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66, and the like.

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

  The toner of the present invention may contain a charge control agent in order to stabilize the charging characteristics. As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high charging speed and can stably maintain a constant charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibition property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, alkylsalicylic acid, dialkylsalicylic acid, naphthoic acid, dicarboxylic acid, metal salts or metal complexes of azo dyes or azo pigments, sulfonic acids Alternatively, a polymer compound having a carboxylic acid group in the side chain, a boron compound, a silicon compound, and a calixarene can be used. Examples of the positive charge control agent include a quaternary ammonium salt, a polymer compound having the quaternary ammonium salt in the side chain, a guanidine compound, a nigrosine compound, and an imidazole compound.

  The amount of these charge control agents to be used is determined by the toner production method including the type of binder resin, the presence or absence of other additives, and the dispersion method, and is not uniquely limited. When added internally, it is preferably used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. Further, when added externally, the amount is preferably 0.005 to 1.0 part by mass, more preferably 0.01 to 0.3 part by mass with respect to 100 parts by mass of the toner.

  A dispersion stabilizer is added to the aqueous medium. The following inorganic compounds used as dispersion stabilizers are calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, sulfuric acid. Examples include calcium, barium sulfate, bentonite, silica, alumina and the like.

  Examples of the organic compound include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose, polyacrylic acid and its salt, starch and the like. These dispersion stabilizers are preferably used in an amount of 0.2 to 20 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

  When an inorganic compound is used as the dispersion stabilizer, a commercially available one may be used as it is, but in order to obtain finer particles, the inorganic compound may be generated and used in an aqueous medium.

  For example, in the case of calcium phosphate, a sodium phosphate aqueous solution and a calcium chloride aqueous solution may be mixed under high stirring.

  Furthermore, in the toner of the present invention, a fluidity improver may be added to the toner particles for the purpose of improving the fluidity of the toner particles. As the fluidity improver, the following fluororesin powders such as fine vinylidene fluoride powder and polytetrafluoroethylene fine powder; fatty acid metal salts such as zinc stearate, calcium stearate and lead stearate; titanium oxide powder, oxidation Metal powder such as aluminum powder and zinc oxide powder, or powder obtained by hydrophobizing the above metal oxide; and silica fine powder such as wet process silica and dry process silica, or silica with silane coupling agent and titanium coupling Examples thereof include surface-treated silica fine powder that has been surface-treated with a treating agent such as an agent and silicone oil.

  The fluidity improver is preferably used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass of the toner particles.

  The physical property value measuring method of the present invention will be described below.

<Measurement of toner aggregation degree α and β>
The toner aggregation degree α was measured as follows.

    As the measuring apparatus, a “powder tester” (manufactured by Hosokawa Micron Co., Ltd.) having a vibration table side surface portion connected with a digital display vibrometer “Digivibro MODEL 1332A” (manufactured by Showa Keiki Co., Ltd.) was used. Then, a sieve with a mesh size of 25 μm (635 mesh), a sieve with a mesh size of 38 μm (390 mesh), and a sieve with a mesh size of 75 μm (200 mesh) were stacked in this order on the vibrating table of the powder tester. The measurement was performed as follows in an environment of 23 ° C. and 60% RH.

  (1) The vibration width of the vibration table was adjusted in advance so that the displacement value of the digital display vibrometer was 0.60 mm (peak-to-peak).

  (2) 5 g of toner that had been allowed to stand for 24 hours in an environment of 15 ° C. and 10% RH was precisely weighed and gently placed on a sieve having an opening of 75 μm (200 mesh).

(3) After vibrating the sieve for 15 seconds, the mass of the toner remaining on each sieve was measured, and the degree of aggregation was calculated based on the following equation.
Aggregation degree (%) = {(sample mass (g) on a sieve having an opening of 150 μm) / 5 (g)} × 100
+ {(Sample mass on a sieve having an opening of 75 μm (g)) / 5 (g)} × 100 × 0.6
+ {(Sample mass (g) on a sieve having an opening of 38 μm) / 5 (g)} × 100 × 0.2

  Further, the aggregation degree β was measured by the same method except that the following samples were used as measurement samples.

  (A) In a 23 ° C., 60% RH environment, a sieve having a mesh size of 53 μm (300 mesh) is set on the shaking table of the same apparatus as that used for the measurement of the cohesion degree α. Then, 15 g of the toner left for 24 hours is placed on the sieve.

  (B) Adjust the vibration width of the shaking table so that the displacement value of the digital display vibrometer is 1.0 mm (peak-to-peak), then vibrate the sieve for 1 minute, and collect the toner that passed through the sieve The toner remaining on the screen is removed by air blowing.

  (C) (A) and (B) are again performed on the collected toner passing through the sieve, and the toner sample obtained by passing through the sieve six times in total is left in a 15 ° C., 10% RH environment for 24 hours.

  (D) 4.0 g of the above 6-screen sieve toner and 1.0 g of unsieved toner previously left for 24 hours in a 15 ° C., 10% RH environment at 15 ° C., 10% RH, 50 ml of poly A sample mixed in a bottle (shaker: model YS-LD (manufactured by Yayoi Co., Ltd.), 150 rpm × 3 minutes) is used as a measurement sample.

<Measurement of median diameter (D50) and span value B of fatty acid metal salt>
The volume-based median diameter (D50) of the fatty acid metal salt used in the present invention is measured according to JIS Z8825-2 (2001), and is specifically as follows.

  As a measuring device, a laser diffraction / scattering particle size distribution measuring device “LA-920” (manufactured by Horiba, Ltd.) is used. The dedicated software “HORIBA LA-920 for Windows (registered trademark) WET (LA-920) Ver. 2.02” attached to LA-920 is used for setting measurement conditions and analyzing measurement data. As the measurement solvent, ion-exchanged water from which impure solids are removed in advance is used.

  The measurement procedure is as follows.

  (1) A batch type cell holder is attached to LA-920.

  (2) A predetermined amount of ion-exchanged water is put into a batch type cell, and the batch type cell is set in a batch type cell holder.

  (3) The inside of the batch cell is stirred using a dedicated stirrer chip.

  (4) Press the “refractive index” button on the “display condition setting” screen and select the file “110A000I” (relative refractive index 1.10).

  (5) In the “display condition setting” screen, the particle diameter reference is set as the volume reference.

  (6) After performing warm-up operation for 1 hour or more, the optical axis is adjusted, the optical axis is finely adjusted, and blank measurement is performed.

  (7) Put about 60 ml of ion-exchanged water in a glass 100 ml flat bottom beaker. Among them, as a dispersant, “Contaminone N” (a nonionic surfactant, an anionic surfactant, a 10% by weight aqueous solution of a neutral detergent for washing a pH 7 precision measuring instrument comprising an organic builder, Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting the product (manufactured) with ion exchange water about 3 times by mass is added.

  (8) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (9) The beaker of (7) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the aqueous solution in a beaker may become the maximum.

  (10) In a state where the aqueous solution in the beaker of (9) is irradiated with ultrasonic waves, about 1 mg of a fatty acid metal salt is added to the aqueous solution in the beaker little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In this case, the fatty acid metal salt may solidify and float on the liquid surface. In this case, ultrasonic dispersion is performed for 60 seconds after the mass is submerged by shaking the beaker. Moreover, in ultrasonic dispersion, it adjusts suitably so that the water temperature of a water tank may become 10 to 40 degreeC.

  (11) The aqueous solution in which the fatty acid metal salt prepared in the above (10) is dispersed is immediately added little by little to a batch type cell, taking care not to enter bubbles, and the transmittance of the tungsten lamp is 90% to 95%. Adjust so that Then, the particle size distribution is measured. Based on the obtained volume-based particle size distribution data, a median diameter (D50), a 5% integrated diameter, and a 95% integrated diameter are calculated to obtain a span value B.

<Measurement of Shore D hardness of elastomer layer>
The hardness of the elastomer layer was measured based on JIS K 6253 (1993).

<Measurement of restoration rate (Z (25))>
Next, a measurement method of the micro compression test will be described with reference to FIG.

  FIG. 1 is a profile (displacement curve) when toner is measured in the micro-compression test of the present invention. The horizontal axis represents the amount of displacement of the toner and the vertical axis represents the amount of load applied to the toner.

For the micro compression test in the present invention, an ultra micro hardness tester ENT1100 manufactured by Elionix Co., Ltd. was used. The working indenter was measured using a 20 μm × 20 μm square flat indenter. 1-1 is an initial state before starting the test, and a load is applied at a speed of 9.8 × 10 ⁻⁵ N / sec with respect to the maximum load of 2.94 × 10 ⁻⁴ N. Immediately after reaching the maximum load, the state is 1-2, and the displacement amount at this time is X ₂ (μm). In the state of 1-2, leave with the load for 0.1 sec. The state immediately after the end of standing is 1-3, and the maximum displacement at this time is X ₃ (μm), and further unloads at a speed of 9.8 × 10 ⁻⁵ N / sec through the maximum load, When the load becomes 0, the state is 1-4. The amount of displacement at this time is X ₄ (μm).

The restoration rate Z (25) was determined as 100 × (X ₃ −X ₄ ) / X ₃ .

  In actual measurement, a toner is applied on a ceramic cell, and minute air is blown so that the toner is dispersed on the cell. The cell is set in the apparatus and measured.

  In the measurement, the cell was brought into a temperature-controllable state, and the temperature of this cell was taken as the measurement temperature. That is, Z (25) was measured at a cell temperature of 25 ° C. In the micro compression test according to the present invention, the toner is dispersed on the cell, and then the cell is placed on the main body. Thereafter, after the cell reaches the measurement temperature, it is left for 10 minutes or more, and then the measurement is started.

  For the measurement, while looking through the microscope attached to the apparatus, select the measurement screen (horizontal width: 160 μm, vertical width: 120 μm) in which one toner exists. In order to eliminate the displacement error as much as possible, a toner having a number average particle diameter (D1) of ± 0.2 μm is selected and measured. An arbitrary toner is selected from the measurement screen, and the toner particle diameter measuring means on the measurement screen measures the major and minor diameters of the toner particles using the software attached to the microhardness meter ENT1100. From this, a toner having an aspect ratio [(major axis + minor axis) / 2] value of D1 of ± 0.2 μm was selected and measured.

With respect to the measurement data, 100 arbitrary particles were selected and measured, and with respect to Z (25) obtained as a measurement result, the remaining 80 values obtained by removing 10 from the maximum value and the minimum value were used as data. And Z (25) was calculated | required as the arithmetic mean value of the 80 pieces.
A method for measuring the number average diameter (D1) of the toner will be described later.

<Measuring method of weight average particle diameter (D4) and number average particle diameter (D1)>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. For setting the measurement conditions and analyzing the measurement data, the attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) is used. Note that the measurement is performed with 25,000 effective measurement channels.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, the dedicated software was set as follows.

  On the “Change Standard Measurement Method (SOM)” screen of the dedicated software, set the total count in the control mode to 50,000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter Set the value obtained using By pressing the “Threshold / Noise Level Measurement Button”, the threshold and noise level are automatically set. In addition, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the “aperture tube flush after measurement” is checked.

  In the “Pulse to particle size conversion setting” screen of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

  The specific measurement method is as follows.

  (1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, the dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the dedicated software.

  (2) About 30 ml of the electrolytic aqueous solution is put into a glass 100 ml flat bottom beaker. In this, "Contaminone N" (nonionic surfactant, anionic surfactant, 10% by weight aqueous solution of neutral detergent for pH7 precision measuring instrument cleaning, made by organic builder, manufactured by Wako Pure Chemical Industries, Ltd. About 0.3 ml of a diluted solution obtained by diluting 3) with ion-exchanged water is added.

  (3) Two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, and an ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikki Bios Co., Ltd.) having an electrical output of 120 W is prepared. About 3.3 l of ion-exchanged water is placed in the water tank of the ultrasonic disperser, and about 2 ml of Contaminone N is added to the water tank.

  (4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the liquid level of the electrolyte solution in a beaker may become the maximum.

  (5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.

  (6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.

  (7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set in the dedicated software is the weight average particle size (D4). When the number% is set, the “average diameter” on the “analysis / number statistics (arithmetic average)” screen is the number average particle diameter (D1).

<Calculation method of particle number% of 4.00 μm or less in particle size distribution based on number>
The number% of particles having a particle size of 4.00 μm or less in the number-based particle size distribution in the toner is calculated by analyzing the data after measuring the Multisizer 3 described above.

  The number% of particles of 4.00 μm or less in the toner is calculated by the following procedure. First, graph / number% is set with the dedicated software, and the measurement result chart is displayed in number%. Then, check “<” in the particle size setting portion on the “format / particle size / particle size statistics” screen, and enter “4” in the particle size input section below. The numerical value of the “<4 μm” display portion when the “analysis / number statistical value (arithmetic mean)” screen is displayed is the number% of particles of 4.00 μm or less in the toner.

<Measurement of average circularity of toner>
The average circularity of the toner of the present invention is calculated under the following conditions using a flow type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) according to the operation manual of the apparatus.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000 type” (manufactured by Sysmex Corporation) is to take a flowing particle as a still image and perform image analysis. The sample added to the sample chamber is fed into the flat sheath flow cell by a sample suction syringe. The sample fed into the flat sheath flow is sandwiched between sheath liquids to form a flat flow. The sample passing through the flat sheath flow cell is irradiated with strobe light at 1/60 second intervals, and the flowing particles can be photographed as a still image. Further, since the flow is flat, the image is taken in a focused state. The particle image is captured by a CCD camera, and the captured image is subjected to image processing at an image processing resolution of 512 × 512 (0.37 × 0.37 μm per pixel), and the contour of each particle image is extracted, Projected area, perimeter, etc. are measured.

  The image signal is A / D converted by the image processing unit, captured as image data, and image processing for determining the presence or absence of particles is performed on the stored image data.

  Next, contour enhancement processing is performed as preprocessing for accurately extracting the contour of the particle image.

  Next, the image data is binarized at an appropriate threshold level.

  When the image data is binarized at a certain appropriate threshold level, each particle image becomes a binarized image as shown in FIG. Next, it is determined whether each of the binarized particle images is an edge point (contour pixel representing a contour), and in which direction there is an edge point adjacent to the target edge point. Information, that is, chain code is generated.

Next, the projected area S and the perimeter L of each particle image are obtained. Using the area S and the perimeter L, the equivalent circle diameter and the circularity are obtained. The circular equivalent diameter is a diameter of a circle having the same area as the projected area of the particle image. The circularity (C) is obtained by dividing the circumference of the circle obtained from the circular diameter by the circumference of the projected particle image. And is calculated by the following formula.
C = 2 × (πS) ^1/2 / L

  When the particle image is circular, the degree of circularity is 1, and the degree of unevenness on the outer periphery of the particle image increases, and the degree of circularity decreases.

  After calculating the circularity of each particle, the range of the circularity of 0.2 to 1.0 is divided into 800, and the average circularity is calculated using the center value of the dividing points and the number of measured particles.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and after adding alkylbenzene sulfonate as a dispersant, 0.02 g of a measurement sample is further added. , Uniformly disperse. As a dispersing means, an ultrasonic disperser UH-50 type (manufactured by SMT Co., Ltd.) having a φ5 mm titanium alloy chip as a vibrator is used and subjected to a dispersion treatment for 5 minutes to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of this dispersion may not become 40 degree | times or more.

  The average circularity C, which means the average value of the circularity frequency distribution, is calculated from the following equation, where ci is the circularity (center value) at the dividing point i of the particle size distribution and m is the number of measured particles.

  To measure the circularity of the toner, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner concentration at the time of measurement is 3000 to 10,000 / μl, and 1000 or more toners are measured. To do. After measurement, this data was used to determine the average circularity.

  Next, the toner layer regulating member used in the present invention will be described.

  The toner layer regulating blade according to the present invention has a configuration in which at least a blade member and a supporting member for the blade member are laminated in the same peripheral shape. The blade member is formed using a blade member composition containing a polyester-based polymer. Specifically, the surface transfer sheet is fed into a mold for injection molding, arranged so as to be in contact with the inner surface of the cavity, the mold is closed, and then the composition for blade member is injected into the mold cavity, and the surface transfer sheet The blade member can be formed by solidifying and solidifying with. In this blade member, the surface from which the surface transfer sheet is peeled is used as a charge control surface, and the surface of the blade member facing the charge control surface is bonded to the support member. This is a toner layer regulating blade.

  The composition for the toner layer regulating blade member is laminated on the surface transfer sheet, and the property of the surface transfer sheet surface is replicated on the blade member to form the charge control surface. For this reason, the blade member according to the present invention differs from the conventional blade member formed by a mold or the like in the way of the transfer surface. The charge control surface serving as a replica surface of the resin film that is a surface transfer sheet is a relatively easily required surface state (10-point average surface roughness Rz is preferably 3.5 μm or less, more preferably 1.0 μm or less, More preferably, it is 0.3 μm or less). In addition, the quality of the product obtained is stable with less variation compared to the case of using a mold.

  In the fine structure of the charge control surface, it is important to be smooth, and even if it is measured as a relatively coarse numerical value for the macro, it may be smooth to the micro. That is, even if the roughness is 2 to 4 μm, if the microstructure is preferably 0.5 μm or less, more preferably 0.4 μm or less, and even more preferably 0.3 μm or less, the roughness having a relatively large amplitude. The profile is expected to have a sufficient effect.

  In addition, the toner layer regulating blade according to the present invention can be operated without peeling off the surface transfer sheet until just before the developing device is mounted at a predetermined position, and can be used as it is as a component (product) of the toner layer regulating blade. That is, the surface transfer sheet also serves as a protective sheet for the blade member of the toner layer regulating blade, and is effective against scratches and chipping on the blade surface during transportation and handling. Hereinafter, the present invention will be described in more detail.

  The toner layer regulating blade provided by the present invention is applicable to, for example, the conventional developing device shown in FIG. 10, and its shape is substantially the same as the toner layer regulating blade in FIG. Further, a blade member may be laminated on the entire surface of the support member. In particular, when the support member is also fed into the mold, the blade member is usually laminated on the entire support member.

  Hereinafter, the manufacturing method of the toner layer regulating blade of the present invention will be described in accordance with each step with reference to FIG. First, a surface transfer sheet (501) for forming the charge control surface of the blade member is inserted into the mold for injection molding so as to be in contact with the inner surface of the gap (507) (cavity) for molding the blade member. To place. The position where the surface transfer sheet is disposed may be on the fixed mold (505) side or the movable mold (504) side. Moreover, it is preferable that the surface of the surface transfer sheet (501) to be transferred to the charge control surface is protected by the protective film (502) until just before being placed on the mold. Further, in the present invention, as shown in FIG. 12, the support member (503) is also fed into the mold in advance so as to be in contact with the surface facing the surface transfer sheet in the gap (507) for forming the blade member. It may be placed and closed. The support member (503) is a metal thin plate sheet provided with an adhesive layer in advance, and the adhesive layer is preferably protected by the protective film (502a) until just before being placed in the mold.

  FIG. 13 shows a state of a clamped mold, in which a surface transfer sheet (501) and a support member (503) are arranged on the inner surface of a gap (507) in which a blade member is formed. In this state, the blade member composition is injection-molded from the front side of the paper through the gate (506). And as shown in FIG. 14, the molded article on which the surface transfer sheet (501), the blade member (508), and the support member (503) were laminated | stacked can be obtained. An adhesive layer is formed between the blade member (508) and the support member (503).

  The composition for a blade member is usually injected from an injection port (gate) that communicates with the cavity, but the injection port may be provided in an opening that communicates with the longitudinal end of the cavity, which is the longitudinal direction of the blade shape. Further, it is preferable to provide the injection port on the fixed side of the mold in order to stabilize the production.

  The blade member formed in this way is formed into a desired blade shape or a precursor shape that can be additionally processed to the blade shape. The precursor shape is formed a little larger after that in order to cut out to the designed dimensions.

  The surface transfer sheet and the support member may be continuously sent into a mold for injection molding using a long one, and the surface transfer sheet and the support member which are individually cut into a desired blade shape are molded into the mold. It may be set in the cavity.

  The surface transfer sheet and support member combined with the mold shape can be cut long by cutting the surface transfer sheet and support member covering the cavity forming surface at a predetermined position when the mold for injection molding is closed. It may be cut off from the film sheet. Alternatively, it may be cut by punching. For cutting and cutting, a cutting means provided separately in the mold, such as a cutter blade or a heat cutter, can be used. Or you may cut | disconnect by the clamping force at the time of mold closing of the male type | mold of a metal mold | die, and a female type | mold.

  Usually, the case that is cut from the movable side is the main body, but the end of cutting may be the movable mold side (surface transfer sheet side) or the fixed mold side (support member sheet side). In addition, if both the insert member sheets (surface transfer sheet and support member) are made by a production process covered with a protective film until just before the insertion, the blade component member surface can be protected, which contributes to an improvement in the yield rate. .

  Next, the surface transfer sheet used in the present invention will be described. A resin film is used as the surface transfer sheet. Since the surface transfer sheet is used as an insert member, a sheet having a high melting point or a high thermal deformation temperature is preferable. Specifically, it is preferably a thermosetting resin film or a thermoplastic resin film having a melting point equal to or higher than the injection molding temperature of the blade member. However, even a resin film having a melting point lower than the injection molding temperature can be used as a surface transfer sheet if the surface of the mold in contact with the resin can be lowered so that the resin film is not easily deformed. In addition, the time from injection to molding and removal from the mold can be shortened, and if the surface transfer sheet used in the meantime does not deform so as to cause a problem, the plastic resin film having a melting point lower than the molding temperature of the blade member can also be used. It can be used as a transfer sheet. For example, when the surface transfer sheet is used with a large thickness, the deformation of the surface transfer sheet within the blade member molding and manufacturing time may not be a problem.

  Examples of the thermosetting resin include unsaturated polyester resin, phenol resin, epoxy resin, urea resin, melamine resin, diallyl phthalate resin, alkyd resin, silicone resin, polyimide resin, etc. , Epoxy / amino resins, epoxy / phenol resins, epoxy esters / amino resins, acrylic / amino resins, polyester / amino resins, alkyd / amino resins, self-curing acrylic resins, etc., and crosslinking agents Any type of thermosetting resin can be used.

  In addition, when divided by reaction type, the condensation type thermosetting resin prepolymer includes novolac type phenol resin prepolymer, resol type phenol resin prepolymer, novolac type alkylphenol resin prepolymer, resol type alkylphenol resin prepolymer, Modified resin prepolymers of xylene / formaldehyde condensate or toluene / formaldehyde condensate.

  Also, polyaddition type thermosetting resin prepolymers include bisphenol A diglycidyl ether, alicyclic dialcohol diglycidyl ether, bisphenol A bis (α-methylglycidyl ether), alicyclic dialcohol bis ( There are solid or liquid epoxy resin prepolymers such as α-methylglycidyl ether).

  The thermoplastic resin film used varies depending on the composition of the blade member and the injection molding temperature. For example, there are the following ones.

  Thermoplastic resins include liquid crystalline polyester resin, polyimide resin, syndiotactic polystyrene resin, polycyclohexanedimethylene terephthalate resin, syndiotactic polystyrene resin, polyvinyl acetate, polyacrylonitrile, polybutadiene, polyvinyl alcohol, polystyrene, and high impact. Rubber-reinforced styrene resin such as polystyrene, medium impact polystyrene, styrene-acrylonitrile copolymer (SAN resin), acrylonitrile-butyl acrylate rubber-styrene copolymer (AAS resin), acrylonitrile-ethylenepropyl rubber-styrene copolymer (AES), acrylonitrile-chlorinated polyethylene-styrene copolymer (ACS), ABS resin (for example, acrylonitrile- Styrene resins such as diene-styrene copolymer, acrylonitrile-butadiene-styrene-alphamethylstyrene copolymer, acrylonitrile-methyl methacrylate-butadiene-styrene copolymer), modified polyphenylene ether (m-PPE) resin, polymethyl Acrylic resins such as methacrylate (PMMA), olefin resins such as low density polyethylene (LDPE), high density polyethylene (HDPE), and polypropylene (PP), vinyl chloride resins such as polyvinyl chloride and polyvinylidene chloride, ethylene chloride Polyvinyl chloride resins such as vinyl vinyl acetate copolymer, ethylene vinyl chloride copolymer, polyester resins such as polybutylene terephthalate (PBTP, PBT), polycarbonate (PC), modified polycarbonate, etc. -Bonate resins, polyamide resins such as polyamide 66, polyamide 6 and polyamide 46, polyacetal (POM) resins such as polyoxymethylene copolymers and polyoxymethylene homopolymers, other engineering resins, super engineering resins such as polyethersulfone (PES), polyetherimide (PEI), thermoplastic polyimide (TPI), polyetherketone (PEK), polyetheretherketone (PEEK), polyphenylene sulfide (PSU) and the like.

  Cellulose derivatives such as cellulose acetate (CA), cellulose acetate butyrate (CAB), ethyl cellulose (EC), liquid crystal polymers such as liquid crystal polymers and liquid crystal aromatic polyesters, thermoplastic polyurethane elastomers (TPU), thermoplastic styrene butadienes Examples include thermoplastic elastomers such as elastomers (SBC), thermoplastic polyolefin elastomers (TPO), thermoplastic polyester elastomers (TPEE), thermoplastic vinyl chloride elastomers (TPVC), and thermoplastic polyamide elastomers (TPAE). In addition, those having high temperature resistance as insert members or those modified to have high temperature resistance are preferable.

  As the surface transfer sheet, these thermosetting resins and thermoplastic resins can be used as appropriate, and among them, polyester resins, polyamide resins, polyolefin resins, copolymers thereof, or polymer alloys thereof. It is preferable to use a film containing any one or more of these, and a film containing any one or more of polyethylene terephthalate, polyethylene-2,6-naphthalate, a copolymer thereof, or a polymer alloy thereof. .

  The resin film used as the surface transfer sheet preferably has a smooth surface because the charge control surface of the blade member becomes its replica surface. Specifically, the 10-point average roughness Rz is preferably 0.3 μm or less. Furthermore, since the surface transfer sheet is used as an insert sheet in the mold, it is preferable that the surface transfer sheet can withstand a predetermined high temperature (injection molding temperature of the blade member) and maintain a smooth surface property. The thickness of the surface transfer sheet to be used may be determined as appropriate, but is usually 50 to 200 μm.

  The surface transfer sheet used in the present invention is preferably made into a laminated film with a protective film (502) covering the surface, specifically, the surface used to form the charge control surface of the blade member. A method of peeling the laminated thin film as a protective film and setting it in the mold cavity immediately before feeding the surface transfer sheet into the mold is preferable.

  The surface side of the surface transfer sheet (the surface on which the blade member composition is deposited) uses a replica of the surface of the resin film to form the charge control surface, and is preferably smoother. It is preferable that protection is provided until just before feeding into the cavity.

  The protective film (502) is not particularly limited. For example, the protective film (502) is a polyethylene film having a thickness of 50 to 200 μm, an acrylic film having a thickness of 30 to 80 μm, a fluorine film having a thickness of 12 to 25 μm, and an ethylene vinyl having a thickness of 10 to 50 μm. Alcohol film, polycarbonate film having a thickness of 10 to 50 μm, unstretched polyester film having a thickness of 50 to 100 μm, unstretched polypropylene film having a thickness of 12 to 100 μm, unstretched polybutylene terephthalate film having a thickness of 20 to 100 μm, thickness 10 Examples thereof include a cellulose acetate film having a thickness of 100 μm, a polystyrene film having a thickness of 10 to 100 μm, and a polyvinyl chloride film having a thickness of 10 to 100 μm.

  Lamination of the protective film (502) and the surface transfer sheet may be performed by either an inflation method or a T-die extrusion method as long as a desired laminated film can be obtained. Further, the surface covering protective film (502) and the surface transfer sheet (501) may be bonded together. For example, as a low-adhesive adhesive layer, natural rubber-based, synthetic rubber-based, silicone-based, acrylic-based, etc. A pressure-sensitive adhesive made of hot melt resin is formed on the stretched film by a method such as reverse coating, roll coating or gravure printing, and the two are bonded together. Although the protective film for surface coating and the film for surface transfer sheet are adhered to each other by this low-adhesive adhesive, the adhesive force thereof is relatively weak and both can be easily peeled off.

  In order to reduce the adhesive force, a small amount of non-adhesive fine particles such as fluorine-based fine particles may be dispersed and applied to the surface of the adhesive.

  As described above, in the present invention, the support member is also sent to the mold in advance, placed so as to be in contact with the surface facing the surface transfer sheet in the cavity and closed, and then the blade member composition is placed in the mold cavity. The blade member may be formed by injection. In this case, an adhesive is applied between the metal thin plate, which is a support member before being mounted on the mold, and the protective film, and when the protective film is peeled off, an adhesive layer is applied to the metal thin plate. It is preferable to have such a configuration. When a high-temperature composition for a blade member is injected, the adhesive on the metal thin plate is melt-bonded to the formed blade member by the heat. In this case, there is no need to separately bond the thin metal plate and the blade member, and the bonding is performed in a certain process. Therefore, uniform bonding is applied to each formed blade, and more stable quality is obtained. It is done.

  Even if the adhesive is not applied in advance, a necessary adhesive force may be obtained depending on the relationship between the metal and the blade member. For example, when the sulfur component in the resin of the blade member and the copper or zinc in the metal of the support member are bonded, an adhesive force is generated ("Adhesion between rubber and metal", Journal of Rubber Association, No. 1). 73, No. 4, 2000).

As the support member 4a of the toner layer regulating blade, a metal or resin flat plate, a stainless steel plate, a phosphor bronze plate, an aluminum plate, or the like can be used, but a metal thin plate sheet is preferably used. The size and shape of the support member may be determined as appropriate. The adhesive layer that bonds the support member and the blade member is not particularly limited, but for example, rubber-based, acrylic-based, silicone-based, polyvinyl ether-based, etc., if classified by the type of fluid state, Examples include emulsion adhesives, solvent-soluble adhesives, hot melt adhesives, and the like. The adhesive application amount may be determined as appropriate, but is usually 50 to 150 g / m ^2, and the thickness of the adhesive layer may be determined as appropriate, but is usually 20 to 100 μm. In order to protect the adhesive layer, the support member used in the present invention is preferably formed as a laminated film with a protective film that covers the adhesive layer, and is protected immediately before the support member is fed into the mold. A method of peeling a laminated thin film film, which is a film, and setting it in a mold cavity is preferable. It does not specifically limit as a protective film, The same thing as the protective film of the above-mentioned surface transfer sheet is mentioned.

  Next, the blade member will be described. The blade member is preferably a polyamide or polyester elastomer.

  A suitable elastomer as the polyamide elastomer is a polyether block amide which is a block copolymer of polyamide and polyether. The block copolymer of polyether and polyamide shows friction charging ability by the polyamide component and shows elasticity by the polyether component. Therefore, when used as a developer amount regulating elastic blade, a coating or additive for improving the friction charging property Therefore, it is possible to obtain a developer amount regulating blade with excellent productivity. Furthermore, if it is configured with a support layer, it is possible to prevent image defects due to a decrease in contact pressure between the developer carrying member and the developer amount regulating blade due to permanent deformation (sagging).

  Polyamides obtained by polycondensation between polyamides 6,6,6,6,10,6,12,11,12,12,12 and different monomers of those polyamides as polyamides of polyamide and polyether block copolymers Preferably, those obtained by carboxylating the terminal amino group of polyamide with a dibasic acid or the like are used.

  Examples of dibasic acids include aliphatic saturated dicarboxylic acids such as succinic acid, succinic acid, adipic acid, suberic acid, sebacic acid, and dodecanedioic acid; aliphatic unsaturated dicarboxylic acids such as maleic acid; phthalic acid, terephthalic acid, etc. Aromatic dicarboxylic acids; and polydicarboxylic acids synthesized from diols such as these dibasic acids and ethylene glycol, butanediol, hexanediol, octanediol, decanediol, and the like are used.

  The polyether component includes homopolymerized or copolymerized polyether diols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polyether diamines with both ends aminated. These polyethers and carboxylated polyamides Thus, a block copolymer of polyether and polyamide having an ester bond (polyether polyester polyamide) or an amide bond (polyether polyamide) is formed.

  The polyamide component is preferably 20% by mass to 80% by mass from the viewpoint of realizing sufficient elasticity with the toner having sufficient triboelectric chargeability and Shore D hardness as desired values.

  Further, an elastomer suitable as a polyester elastomer is a polyester elastomer of a block copolymer of an aromatic, for example, a hard segment component having an ester group adjacent to a benzene ring and the like, and a soft segment component made of polyether, particularly thermoplastic. A polyester elastomer is more preferable.

  As the hard segment component of the polyester elastomer, for example, phthalic acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, p-phenylenedicarboxylic acid and the like are preferable. As the soft segment component, ethylene glycol, propylene glycol, 1 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, triethylene glycol, polytetraethylene glycol, polytetramethylene glycol and the like are preferable. The Shore D hardness of the polyester elastomer can be adjusted by the blending ratio of the hard segment component and the soft segment component, and the Shore D hardness of the polyester elastomer corresponding to the development process as required can be achieved.

  The material for forming the blade member (resin composition) may be any material that can form a blade member having physical properties as a predetermined blade member, and contains various additives other than the resin component as necessary. be able to.

  The blade member also has many elements that are regulated by process conditions, but it is preferable to adjust the performance by adding an appropriate amount of a conductive material in addition to the main material so as to have a predetermined charging performance. As the conductive material, known materials can be used, such as carbon fine particles such as carbon black and graphite; metal fine particles such as nickel, silver, aluminum and copper; tin oxide, zinc oxide, titanium oxide, aluminum oxide, silica and the like. Conductive metal oxide fine particles doped with impurity ions having different valences as main components; conductive fibers such as carbon fibers; metal fibers such as stainless steel fibers; the surface of carbon whiskers and potassium titanate whiskers as metal oxides And conductive whisker such as conductive potassium titanate whisker conductively treated with carbon and the like; and conductive polymer fine particles such as polyaniline and polypyrrole. What is necessary is just to determine the compounding quantity suitably as needed. However, a fine conductive material and a conductive material having a shape having little influence on the surface roughness are preferable so that the surface of the blade member becomes smoother.

  In order to realize a sufficient function as a blade, the thickness of the blade member used is preferably 1 μm or more, preferably 10 μm or more, and may be 50 μm or more, or may be 100 μm or more. On the other hand, in order to achieve appropriate contact, uniformly charge the developer particles, and suppress wear, the thickness is preferably 300 μm or less, preferably 100 μm or less, and sometimes 50 μm or less. Further, from the same viewpoint, the thickness of the support member is preferably 50 μm or more, more preferably 80 μm or more, further preferably 90 μm or more, most preferably 100 μm or more, and preferably 150 μm or less. Further, from the same viewpoint, the thickness of the toner layer regulating blade (total thickness in the laminated structure) is preferably the sum of the thickness of the blade member as described above and the thickness of the support member as described above. For example, it is preferably 51 μm or more and 450 μm or less. The toner layer regulating blade according to the present invention preferably originally has a thinner thickness in order to effectively prevent leakage of developer particles at the end thereof.

  The blade member obtained by injection molding in this way has a surface transfer sheet on one side, and also has a support member on the surface facing the surface transfer sheet when the support member is disposed in the mold cavity. The blade member having only the surface transfer sheet without the support member is then bonded to the support member of the blade member. Specifically, the surface of the blade member facing the surface transfer sheet and the support member of the blade member are bonded together via an adhesive layer.

  As the support member 4a of the toner layer regulating blade, as described above, a metal or resin flat plate, a stainless steel plate, a phosphor bronze plate, an aluminum plate, or the like can be used.

  The size and shape of the support member may be determined as appropriate. FIG. 15 shows an example of the toner layer regulating blade according to the present invention in FIG. 15A as a plan view and FIG. 15B as a cross-sectional view. The blade member 30 and the supporting member 31 are laminated and bonded on the entire surface of the toner layer regulating blade, and the planar shape of the blade member 30 and the supporting member 31 is the same as the planar shape of the toner layer regulating blade. In other words, the peripheral shape of both the support member and the blade member is the peripheral shape of the blade, that is, the peripheral shape is the same as the blade, and the peripheral edge (side surface) of the supporting member and the peripheral edge (side surface) of the blade member. The peripheral end surfaces of the entire blade are formed by both of these end surfaces. In addition, as long as the objective effect of the present invention can be achieved, it is not necessary that the side surfaces of the support member and the blade member exactly coincide with each other to form the blade side surface. It only has to be affixed.

  The support member and the blade member may be bonded together by an adhesive such as a hot-melt adhesive, or may be joined using an adhesive tape. What is necessary is just to determine a joining method suitably by the process conditions etc. to be used. Examples of the adhesive used here include rubber-based, acrylic-based, silicone-based, polyvinyl ether-based, and the like. If classified by the type having fluidity, an emulsion adhesive, a solvent-soluble adhesive, There are hot melt adhesives.

  Then, the laminated body of the support member, the blade member, and the surface transfer sheet is cut into a predetermined blade shape by a press or the like. The size and shape of the cavity at the time of injection molding, and the size and shape of both when the blade member and the support member are bonded can be set to a predetermined size as a blade. In view of damage to the end portion, scratching, etc., it is preferable to form a large piece and cut it into a predetermined shape. However, in the case where there is no problem such as scratching in the molding process, it may be molded into a predetermined size using a cavity having a blade shape and bonded without being molded in such a large size. Finally, the surface transfer sheet is peeled off from the blade member, and the surface of the blade member that appears is used as the charge control surface.

  Since the occurrence of image defects such as image unevenness and streaks can be sufficiently suppressed, the 10-point average roughness Rz of the charge control surface is preferably 0.3 μm or less, and a surface transfer sheet is placed in advance in the mold. According to the method of the present invention, the charge control surface having such a surface roughness can be formed stably and effectively.

  Next, the image forming method of the present invention will be described with reference to FIG.

  The present invention is an image forming method which is contact one-component development having a mechanism for replenishing toner sequentially while confirming a printing rate and a toner seat surface from a replaceable toner cartridge to a developing cartridge.

  FIG. 2 shows a schematic configuration of an embodiment of an image forming apparatus in which the image forming method of the present invention is performed. In the present invention, the present invention is embodied in an image forming apparatus that performs monochromatic image formation, but the present invention is not limited to this.

  In an image forming apparatus in which the image forming method of the present invention is performed, a drum-shaped electrophotographic photosensitive member as an image bearing member, that is, a photosensitive drum 110 is supported at a substantially central portion so as to be rotatable in the arrow direction. . When the image forming operation starts, the charging unit 210 uniformly charges the surface of the photosensitive drum 110. Thereafter, a laser irradiation unit 310 as an exposure unit performs exposure corresponding to image information on the surface of the photosensitive drum 110, and an electrostatic latent image is formed on the photosensitive drum 110. According to the present invention, the triboelectric charge of the photosensitive drum 110 has a negative polarity, and the portion where the negative triboelectric charge is attenuated by exposure from the laser irradiation unit 310 forms an image portion.

  Thereafter, the electrostatic latent image is visualized by toner as a developer supplied from the developing device 410 as the photosensitive drum 110 rotates, and a so-called toner image is formed on the photosensitive drum 110. In this embodiment, the development is performed by reversal development, and the toner having the same polarity (negative polarity) as the triboelectric charge adheres to the image portion on the photosensitive drum 110 where the negative charge is attenuated. Further, toner is sequentially replenished to the developing device 410 from a toner hopper 510 as a developer containing unit.

  On the other hand, the recording material P stored in a cassette (not shown) is transferred from the toner image on the photosensitive drum 110 to the transfer region where the photosensitive drum 1 and the transfer roller 610 as a transfer unit abut by the paper feed roller 910. It is conveyed synchronously to reach.

  Thus, when the toner image on the photosensitive drum 110 and the recording material P reach the transfer area, the toner image is transferred onto the recording material P by the action of the transfer electric field formed in the transfer area by the transfer roller 610. Thereafter, the recording material P carrying the unfixed toner image is heated by the fixing means (heat roller) 810a provided in the fixing device 810 and pressurized by the pressure means 810b, and the unfixed toner image is formed on the recording material P. It is fixed and an image is formed.

  The photosensitive drum 110 that has finished transferring the toner image is subjected to removal of residual toner remaining on the surface of the photosensitive drum 110 by a cleaning device 710 having a blade-like cleaning unit, and is ready for a subsequent image forming operation.

  Next, the developing device 410 and the toner hopper 510 provided in the image forming apparatus of the present invention will be further described. FIG. 3 shows a schematic configuration of the developing device 410 and the toner hopper 510 according to the present invention and the vicinity thereof.

  According to the present invention, the developing device 410 employs a contact development method in which development is performed in a state in which a developing roller 411 as a toner carrier is brought into contact with the photosensitive drum 110 and toner is “contacted” with the photosensitive drum 110. Yes.

  In the developing device 410, the developing container 416 is partially open on the side facing the photosensitive drum 110, and the developing roller 411 as a toner carrier can rotate in the direction of the arrow so as to be partially exposed from the opening. Is supported by the developing container 416. The developing roller 411 includes an elastic body and is in contact with the photosensitive drum 110 with a predetermined contact pressure. In addition, a blowing prevention sheet 417 is provided at the opening of the developing container 416 in order to prevent toner from scattering from the lower portion of the developing roller 411.

  The developing roller 411 is a semiconductive elastic roller composed of silicone in which a conductive agent such as carbon is dispersed, a low-hardness rubber material such as urethane or foam, or a combination thereof.

  An agitating member 414 serving as a developer agitating means is rotatably provided in the upper portion of the developing container 416 opposite to the opening, and agitates the toner in the developing container 416 and the toner replenished from the toner hopper 510. Region R is formed.

  A developing container 416 sandwiching the stirring region R and a toner surface using an optical system including a light emitting unit 415a, a transmission window 415b, and a light receiving unit 415c for detecting the height of the toner surface of the stirring region R on the outside. Detection means 415 is arranged. The ratio of the light transmission time when the toner surface changes with the rotation of the stirring member 414 is measured to obtain the height information of the toner surface in the stirring region R.

  Below the stirring region R, a supply roller 413 as a developer supply / collection means is disposed in contact with the development roller 411. The supply roller 413 is an elastic roller made of an elastic foam, and rotates in the reverse direction at the contact point with respect to the developing roller 411.

  The toner that is sufficiently stirred by the stirring member 414 in the stirring region R and then supplied to the vicinity of the supply roller 413 mainly due to the movement due to gravity is conveyed by the supply roller 413 and supplied to the developing roller 411.

  The developing container 416 is provided with a blade 412 as a toner layer thickness regulating member so as to pressurize the developing roller 411. The blade 412 is an elastic regulating member in which an insulating layer 412a is provided on the surface of the contact surface of the developing roller 411 on a thin plate-like metal plate 412b. The layer thickness of the toner supplied onto the developing roller 411 is regulated by the blade 412 and is applied to form a thin layer of toner on the developing roller 411. Further, the friction with the surfaces of the developing roller 411 and the blade 412 at this time gives the toner a sufficient triboelectric charge for use in development.

  Thereafter, the toner thin layer on the developing roller 411 is conveyed to a developing area (developing nip) where the photosensitive drum 110 and the developing roller 411 are in contact with the rotation of the developing roller 411, and the toner is transferred to the photosensitive drum 110. Provided for development in contact. That is, a power source (not shown) is connected so that a developing electric field is formed between the photosensitive drum 110 and the developing roller 411. The toner on the developing roller 411 is transferred to the electrostatic latent image on the photosensitive drum 110 by the action of the developing electric field, and a toner image is formed on the photosensitive drum 110 to visualize the electrostatic latent image.

  Further, the toner applied on the developing roller 411 and carried and transported to the developing nip does not contribute to the development, and the toner further carried on the developing roller 411 is rubbed by the supply roller 413 due to the rubbing by the supply roller 413. 411 is peeled off from above. A part of the toner is supplied again to the developing roller 411 by the supplying roller 413 together with the toner newly supplied to the supplying roller 413, and the rest is returned to the developing container 416. In the present invention, the supply roller 403 has two functions as toner supply and recovery means. However, the present invention is not limited to this, and the toner supply means and the toner recovery means are provided separately. Is also possible.

  Further, the developing device 410 is configured to be detachable from the image forming apparatus, and is replaced with a predetermined life (in this embodiment, set to 60,000 sheets in terms of A4 size). .

  In the arrangement of each component, the stirring member 414 has a vertical lower end γ of its movable range, a vertical upper end α of the supply roller 413, or a contact β with a developing roller 411 of a blade 412 as a regulating means described later. The higher one (in this embodiment, the contact point β between the blade 412 and the developing roller 411) is disposed above. Further, the image forming apparatus obtains the toner surface height information from the toner surface detecting means 415, so that the container on the upper surface of the developing container 416 from the vertical lower end γ of the movable range of the stirring member 414 by the control procedure described later. The replenishment from the toner hopper 510 is controlled so that the toner surface is maintained within a certain range from γ ′ to δ ′ in the drawing within the wall height δ.

  In the toner hopper 510, a stirring member 514 for releasing the toner in the toner hopper 510 and a supply roller 513 for supplying toner from the toner hopper 510 to the developing device 410 are disposed. A certain amount of toner per predetermined driving time can be supplied to the developing device 410 according to the command.

  Next, toner amount detection and toner replenishment operations will be described.

  As described above, in this embodiment, the stirring member 414 is provided in the developing container 416 of the developing device 410 so as to be rotatable in the direction of the arrow, and stirs the toner in the developing container 416 and the toner replenished from the toner hopper 510. The stirring region R to be formed is formed.

  Further, an optical toner surface detecting means 415 for detecting the height of the toner surface of the stirring region R is disposed outside the developing container 416 sandwiching the stirring region R, and rotation of the stirring member 414 is performed. Accordingly, the ratio of the light transmission time when the agent surface of the toner changes is measured, and the height information of the toner surface in the stirring region R is obtained.

  The image forming apparatus receives the toner surface height information from the toner surface detecting means 415, and issues a toner replenishment command when the toner surface level decreases to γ ′ in the figure, and the replenishment roller 513 of the toner hopper 510 Start driving. By this toner replenishment command, the replenishment roller 513 replenishes the developing device 410 with a certain amount of toner per predetermined driving time. Further, when this replenishment operation is continued and the toner surface detecting means 415 detects that the level of the toner surface has increased to δ ′ in the figure, the image forming apparatus stops the toner replenishment command, and the replenishment roller 513 replenishes the toner. To stop.

  As a result, the height of the toner surface in the developing device is within the range from the vertical lower end γ of the movable range of the stirring member 414 to the height δ of the container wall on the upper surface of the developing container 416. It is controlled to be kept within a certain range.

  In this embodiment, γ ′ is set to a position higher than the center of the movable range of the stirring member 414, and δ ′ is set to be lower than the upper end in the vertical direction of the movable range of the stirring member 414.

  The replenishing roller 513 is disposed vertically above the stirring region R formed by the stirring member 414, and is configured so that the replenished toner passes through the stirring region R with certainty.

  With such a configuration, as described above, the toner surface in the stirring region R in the developing device is controlled so that the mixing and stirring of the toner in the developing device and the replenishment toner is sufficiently performed by the stirring member 414. After the mixing and stirring are sufficiently performed, the toner is slowly supplied to the vicinity of the supply roller 413 due to toner consumption due to image formation and movement mainly due to gravity based on the positional relationship between the stirring region R, the supply roller 413, and the blade 412. This prevents the supplied toner from being supplied to the developing roller in a state where it is not sufficiently mixed with the toner in the developing device, thereby preventing the occurrence of density unevenness, fogging, and toner dropout that have occurred. Is possible. Further, since the height of the toner surface is controlled so as not to hit the container wall on the upper surface of the developing container 416, the toner does not fill up in the developing container 416 due to excessive replenishment, and the toner pressure does not increase. Problems such as promotion of toner deterioration, toner leakage, density unevenness due to toner coat unevenness, and drive torque increase can also be prevented.

Regarding the positional relationship of each component having the effect of the present invention, the relational expression “vertical upper end α of the supply roller 413 <contact β with the developing roller 411 of the blade 412 <vertical lower end γ of the movable range of the stirring member 414”
In addition, as shown in FIG. 4, when the vertical positional relationship between the vertical upper end α of the supply roller 413 and the contact β of the blade 412 with the developing roller 411 is reversed, the movable range of the stirring member 404 is changed. The lower end γ in the vertical direction may be set further above the upper end α in the vertical direction of the supply roller 413, which is the higher one.

In this case, the relational expression is
“Contact point β of blade 412 with developing roller 411 <vertical upper end α of supply roller 413 <vertical lower end γ of movable range of stirring member 414”
It becomes.

  Further, as shown in FIG. 4, when the stirring region R in which the stirring member 414 is disposed and the developing chamber including the developing roller 411 and the supply roller 413 are separated by the developing chamber-stirring region opening 418, the developing is performed. One of them is to arrange the stirring region R above the chamber-stirring region opening 418 and to satisfy the above condition.

  Further, as shown in FIG. 5, the stirring region R where the stirring member 414 is disposed and the developing chamber including the developing roller 411 and the supply roller 413 are separated by a developing chamber-stirring region opening 418. The stirring region R is disposed above the developing chamber-stirring region opening 418, the vertical upper end κ of the developing chamber-stirring region opening 418, the vertical upper end α of the supply roller 413, or the developing roller of the blade 412. The lower end γ in the movable range of the stirring member 414 is disposed above the upper end κ in the vertical direction of the developing chamber-stirring region opening 418. As a result, the replenished toner is sufficiently mixed with the toner in the developing device and then slowly supplied to the developing chamber due to toner consumption and movement due to gravity to be used for development. Therefore, the effect of the present invention is further obtained. I can do it.

In this case, the relational expression is
“Vertical upper end κ of developing chamber-stirring region opening 418 <contact β of blade 412 with developing roller 411 <upper vertical end α of supply roller 413 and vertical upper end κ of developing chamber-stirring region opening 418 <stirring member 414. Vertical lower end γ of movable range 414 "
Or
“Vertical upper end κ of developing chamber-stirring region opening 418 <Upper vertical direction α of supply roller 413 <Contact β with developing roller 411 of blade 412 and vertical upper end κ of developing chamber-stirring region opening 418 <stirring” Vertical lower end γ of movable range of member 414 "
It becomes.

  In the present invention, the predetermined range γ ′ to δ ′ in which the toner surface height of the toner is controlled is set above the movable center of the stirring member and below the upper end in the vertical direction of the movable range of the stirring member. "The toner always exists within the movable range of the toner and the toner does not contact the upper surface of the developing device container" is a range "below the height of the container wall on the upper surface of the developing device and above the lower end in the vertical direction of the movable range of the stirring means" If it is within the range, it may be set as appropriate depending on the range in which the stirring effect is sufficiently large depending on the shape, rotation speed, and outer diameter of the stirring member and the detection accuracy of the toner surface of the detection means. In the case of using a rotating stirring means, for example, “below the lower one third of the vertical height in the movable range of the stirring means and below the upper end in the vertical direction of the movable range of the stirring means”, more preferably as in the present invention. The effect of the stirring of the stirring means can be effectively utilized by “being above the movable center of the stirring means and below the upper end in the vertical direction of the movable range of the stirring means”.

  In the present invention, an optical system is used as the developer amount detecting means 415. However, for example, the piezoelectric vibrator sensor 415d shown in FIG. 5 may be used, and a toner surface having a certain height exists within the scope of the present invention. It can be replaced by a detection means capable of identifying whether or not, for example, a strain gauge, an arbitrary detection element using a pressurized conductive sheet, or an electrostatic antenna type detection means.

  The position of the replenishing roller with respect to the agitation region R is not only vertically above the agitation region as in the present invention, but the toner replenished by the developing container wall or the like is guided to the agitation region R and reliably passes through the agitation region. If there is, it is also possible to dispose it obliquely upward.

  However, even when the sequential toner replenishing method is used so as to keep the toner amount of the present invention to the minimum, there is a case where an adverse effect on the image occurs due to the mixing of the replenishing toner at the end of the endurance and the toner not related to the development. This mainly occurs after the nominal life has been exceeded, but it is necessary to approach from the toner side in order to eliminate the negative effects of this image.

  The present invention will be specifically described with reference to the following examples. However, this does not limit the present invention in any way. A method for producing toner particles will be described below. Unless otherwise specified, all parts and% in the examples and comparative examples are based on mass.

<Production of fatty acid metal salt 1>
A receiving container with a stirrer was prepared, and the stirrer was rotated at 350 rpm. 500 mass parts of 0.5 mass% sodium stearate aqueous solution was thrown into this receiving container, and liquid temperature was adjusted to 85 degreeC. Next, 525 mass parts of 0.2 mass% zinc sulfate aqueous solution was dripped at this receptacle over 15 minutes. After the completion of charging the whole amount, the reaction was terminated by aging for 10 minutes at the temperature during the reaction.

Next, the fatty acid metal salt slurry thus obtained was washed by filtration. The obtained washed fatty acid metal salt cake was roughly crushed and then dried at 105 ° C. using a continuous instantaneous air dryer. Then, after pulverizing with a nano grinding mill [NJ-300] (manufactured by Sanrex) under conditions of an air volume of 6.0 m ³ / min and a processing speed of 80 kg / h, reslurry and fine particles using a wet centrifugal classifier After removal of the coarse particles, the fatty acid metal salt 1 was obtained by drying at 80 ° C. using a continuous instantaneous air flow dryer. The obtained fatty acid metal salt 1 had a volume-based median diameter (D50) of 0.45 μm and a span value B of 0.92. The physical properties of the fatty acid metal salt 1 are shown in Table 1, and the particle size distribution is shown in FIG.

<Production of fatty acid metal salt 2>
In fatty acid metal salt 1, except that 0.5% by mass sodium stearate aqueous solution is changed to 0.25% by mass sodium stearate aqueous solution, and 0.2% by mass zinc sulfate aqueous solution is changed to 0.15% by mass zinc sulfate aqueous solution. Fatty acid metal salt 2 was obtained in the same manner as fatty acid metal salt 1. The obtained fatty acid metal salt 2 had a volume-based median diameter (D50) of 0.33 μm and a span value B of 0.81. The physical properties of the fatty acid metal salt 2 are shown in Table 1, and the particle size distribution is shown in FIG.

<Production of fatty acid metal salt 3>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.7 calcium chloride aqueous solution. The reaction was terminated by aging for 5 minutes. The pulverization conditions were changed to an air volume of 5.0 m ³ / min, and after pulverization, fine coarse powder was removed with an air classifier to obtain fatty acid metal salt 3. The resulting fatty acid metal salt 3 had a volume-based median diameter (D50) of 0.58 μm and a span value B of 1.69. The physical properties of the fatty acid metal salt 3 are shown in Table 1.

<Production of fatty acid metal salt 4>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 2.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 1.0% by mass calcium chloride aqueous solution. The reaction was terminated by aging for 5 minutes. Other steps were carried out in the same manner as in fatty acid metal salt 1 to obtain fatty acid metal salt 4. The obtained fatty acid metal salt 4 had a volume-based median diameter (D50) of 0.60 μm and a span value B of 1.51. The physical properties of the fatty acid metal salt 4 are shown in Table 1.

<Production of fatty acid metal salt 5>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was added to 0.25% by mass sodium stearate aqueous solution, 0.2% by mass zinc sulfate aqueous solution to 0.15% by mass zinc sulfate aqueous solution, and The condition was changed to an air volume of 10.0 m ³ / min, and the pulverization process was performed three times. The resulting fatty acid metal salt 5 had a volume-based median diameter (D50) of 0.18 μm and a span value B of 1.34. The physical properties of the fatty acid metal salt 5 are shown in Table 1.

<Production of fatty acid metal salt 6>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.7% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.3% by mass zinc sulfate aqueous solution. The pulverization conditions were an air volume of 4.0 m ³ / min and a processing speed of 50 kg / h. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 6. The obtained fatty acid metal salt 6 had a volume-based median diameter (D50) of 0.64 μm and a span value B of 0.98. The physical properties of the fatty acid metal salt 6 are shown in Table 1.

<Production of fatty acid metal salt 7>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Further, the reaction was terminated by aging for 15 minutes. The pulverization condition was an air volume of 4.0 m ³ / min. Other steps were carried out in the same manner as fatty acid metal salt 1 to obtain fatty acid metal salt 7. The obtained fatty acid metal salt 7 had a volume-based median diameter (D50) of 0.72 μm and a span value B of 1.26. The physical properties of the fatty acid metal salt 7 are shown in Table 1.

<Production of fatty acid metal salt 8>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 1.0% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.4% by mass zinc sulfate aqueous solution. Moreover, the classification process after performing a grinding | pulverization process was not performed but the fatty-acid metal salt 8 was obtained. The obtained fatty acid metal salt 8 had a volume-based median diameter (D50) of 0.63 μm and a span value B of 1.79. The physical properties of the fatty acid metal salt 8 are shown in Table 1.

<Production of fatty acid metal salt 9>
In fatty acid metal salt 1, the 0.2% by mass zinc sulfate aqueous solution was changed to a 0.3% by mass lithium chloride aqueous solution. Otherwise, the fatty acid metal salt 9 was obtained in the same manner as the fatty acid metal salt 1. The obtained fatty acid metal salt 9 had a volume-based median diameter (D50) of 0.33 μm and a span value B of 0.85. The physical properties of the fatty acid metal salt 9 are shown in Table 1.

<Production of fatty acid metal salt 10>
In fatty acid metal salt 1, 0.5% by mass sodium stearate aqueous solution was changed to 0.05% by mass sodium stearate, and 0.2% by mass zinc sulfate aqueous solution was changed to 0.02% by mass zinc sulfate aqueous solution. Further, the pulverization condition was set to an air volume of 10.0 m ³ / min, and the pulverization step was performed three times. Thereafter, the classification step was not performed, and coarse particles were removed by passing through a mesh to obtain a fatty acid metal salt 10. The resulting fatty acid metal salt 10 had a volume-based median diameter (D50) of 0.12 μm and a span value B of 1.70. The physical properties of the fatty acid metal salt 10 are shown in Table 1.

<Fatty acid metal salt 11>
Commercially available zinc stearate (trade name; MZ2 manufactured by NOF Corporation) is used as fatty acid metal salt 11. The median diameter (D50) on a volume basis was 1.29 μm, and the span value B was 1.61. The physical properties of the fatty acid metal salt 11 are shown in Table 1. The particle size distribution is shown in FIG.

(Production example of polymer having sulfonic acid group, sulfonic acid group or sulfonic acid ester group)
In a pressurizable reaction vessel equipped with a reflux tube, a stirrer, a thermometer, a nitrogen introduction tube, a dropping device and a decompression device, 250 parts of methanol as a solvent, 150 parts of 2-butanone and 100 parts of 2-propanol, styrene as a monomer 92.5 parts, 5 parts of 2-ethylhexyl acrylate, and 2.5 parts of 2-acrylamido-2-methylpropanesulfonic acid were added and heated to reflux temperature with stirring. A solution obtained by diluting 0.30 part of t-butylperoxy-2-ethylhexanoate as a polymerization initiator with 20 parts of 2-butanone was added dropwise over 50 minutes, and stirring was continued for 5 hours. Further, t-butylperoxy was further added. A solution prepared by diluting 0.15 part of 2-ethylhexanoate with 20 parts of 2-butanone was added dropwise over 30 minutes, and the mixture was further stirred for 5 hours to complete the polymerization.

  The polymer obtained after the polymerization solvent was distilled off under reduced pressure was coarsely pulverized to 100 μm or less using a cutter mill equipped with a 150 mesh screen. Let the obtained polymer be a sulfonic acid group containing polymer. The weight average molecular weight (Mw) of the polymer was 35,000.

(Toner Production Example 1)
Add 3.3 parts of tricalcium phosphate to 900 parts of ion-exchanged water heated to 60 ° C., and stir at 10,000 rpm using a TK homomixer (made by Tokushu Kika Kogyo Co., Ltd.) to obtain an aqueous medium. It was.

on the other hand,
Styrene 65 parts n-butyl acrylate 35 parts saturated polyester resin 7.0 parts (polycondensate of propylene oxide modified bisphenol A and terephthalic acid, Tg = 65 ° C., Mn = 5000, Mw / Mn = 2.4)
Sulfonic acid group-containing polymer 2 parts Aluminum salicylate compound 1 part (Bontron E-88, manufactured by Orient Chemical Co., Ltd.)
C. I. Pigment Blue 15: 3 7 parts di-t-butyl ether 0.02 part The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.). This monomer composition was heated to 60 ° C., and 14 parts of an ester wax mainly composed of stearyl stearate (maximum endothermic peak 67 ° C. in DSC measurement, Mw = 1200) was added and dissolved therein. In this, 10 parts of a polymerization initiator 2,2′-azobis-2,4-dimethylvaleronitrile (10 hour half-life temperature 51 ° C.) was dissolved.

The aqueous medium in the polymerizable monomer system was added to, and stirred 65 ° C., 10 min at 10,000rpm at TK homomixer under N ₂ atmosphere and granulated. Thereafter, the mixture was reacted at 60 ° C. for 6 hours while stirring with a paddle stirring blade. Thereafter, the liquid temperature was raised to 80 ° C., and stirring was further continued for 4 hours. After completion of the reaction, the suspension was cooled at a cooling rate of −5 ° C./min.

  Hydrochloric acid was added to the suspension cooled to room temperature (25 ° C.) to dissolve the calcium phosphate salt, followed by filtration and washing with water to obtain wet colored particles 1.

  Next, after drying the particles at 40 ° C. for 12 hours, air classification was performed to adjust the particle size and particle size distribution to obtain toner particles (1).

100 parts of the toner particles, 1.5 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil as an external additive and a primary particle size of 12 nm, and hydrotalcite (Kyowa Chemical Co., Ltd.) Manufactured, DHT-4A) 0.1 part, and fatty acid metal salt 1 was further mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 1. The results are shown in Table 2.

(Toner Production Example 2)
Toner 2 was obtained in the same manner except that the amount of fatty acid metal salt 1 in Toner Production Example 1 was changed to 0.05 part. The results are shown in Table 2.

(Toner Production Example 3)
Toner 3 was obtained in the same manner except that the fatty acid metal salt 1 in Toner Production Example 1 was changed to the fatty acid metal salt 2. The results are shown in Table 2.

(Toner Production Example 4)
Toner 4 was obtained in the same manner except that fatty acid metal salt 1 in Toner Production Example 1 was changed to fatty acid metal salt 3. The results are shown in Table 2.

(Toner Production Example 5)
Toner 5 was obtained in the same manner except that fatty acid metal salt 1 in Toner Production Example 1 was changed to fatty acid metal salt 4. The results are shown in Table 2.

(Toner Production Example 6)
Toner 6 was obtained in the same manner as in Toner Production Example 1 except that the amount of polymerization initiator 2,2′-azobis-2,4-dimethylvaleronitrile (10 hour half-life temperature 51 ° C.) was changed to 15 parts. . The results are shown in Table 2.

(Toner Production Example 7)
Toner 7 was obtained in the same manner as in Toner Production Example 1 except that the amount of polymerization initiator 2,2′-azobis-2,4-dimethylvaleronitrile (10 hour half-life temperature 51 ° C.) was changed to 8 parts. . The results are shown in Table 2.

(Toner Production Example 8)
Toner 8 was prepared in the same manner as in Toner Production Example 1 except that the amount of polymerization initiator 2,2′-azobis-2,4-dimethylvaleronitrile (10 hour half-life temperature 51 ° C.) was changed to 16.5 parts. Obtained. The results are shown in Table 2.

(Toner Production Example 9)
A toner 9 was obtained in the same manner except that the fatty acid metal salt 1 of Toner Production Example 1 was changed to the fatty acid metal salt 5. The results are shown in Table 2.

(Toner Production Example 10)
Toner 10 was obtained in the same manner except that fatty acid metal salt 1 of toner production example 1 was changed to fatty acid metal salt 6. The results are shown in Table 2.

(Toner Production Example 11)
Toner 11 was obtained in the same manner except that fatty acid metal salt 1 in Toner Production Example 1 was changed to fatty acid metal salt 7. The results are shown in Table 2.

(Toner Production Example 12)
Toner 12 was obtained in the same manner except that fatty acid metal salt 1 of toner production example 1 was changed to fatty acid metal salt 8. The results are shown in Table 2.

(Toner Production Example 13)
A toner 13 was obtained in the same manner except that the fatty acid metal salt 1 of Toner Production Example 1 was changed to the fatty acid metal salt 9. The results are shown in Table 2.

(Toner Production Example 14)
Toner 14 was obtained in the same manner except that the hydrotalcite of Toner Production Example 1 was not added. The results are shown in Table 2.

(Toner Production Example 15)
Toner 15 was obtained in the same manner except that the amount of hydrophobic silica fine powder added in Toner Production Example 1 was changed to 1.6 parts and the amount of hydrotalcite added was 0.2 parts. The results are shown in Table 2.

(Toner Production Example 16)
Toner 16 was obtained in the same manner except that the amount of hydrophobic silica fine powder added in Toner Production Example 1 was changed to 1.96 parts and the amount of hydrotalcite added was 0.07 parts. The results are shown in Table 2.

(Toner Production Example 17)
Toner 17 was obtained in the same manner except that the amount of hydrophobic silica fine powder added in Toner Production Example 1 was changed to 1.2 parts and the amount of hydrotalcite added was 0.4 parts. The results are shown in Table 2.

(Toner Production Example 18)
Toner 18 was obtained in the same manner except that the amount of hydrophobic silica fine powder added in Toner Production Example 1 was changed to 1.6 parts and the amount of hydrotalcite added was 0.5 parts. The results are shown in Table 2.

(Toner Production Example 19)
1.0 part of tricalcium phosphate is added to 900 parts of ion-exchanged water heated to 65 ° C., and stirred at 10,000 rpm using a TK homomixer (manufactured by Special Machine Industries) to obtain an aqueous medium. It was.

on the other hand,
Styrene 80 parts n-Butyl acrylate 20 parts Saturated polyester resin 7.0 parts (Polycondensate of propylene oxide modified bisphenol A and terephthalic acid, Tg = 65 ° C., Mn = 5000, Mw / Mn = 2.4)
Sulfonic acid group-containing polymer 2 parts Aluminum salicylate compound 1 part (Bontron E-88, manufactured by Orient Chemical Co., Ltd.)
C. I. Pigment Blue 15: 3 7 parts di-t-butyl ether 0.02 part The above formulation was uniformly dispersed and mixed using an attritor (Mitsui Miike Chemical Co., Ltd.). This monomer composition was heated to 65 ° C., and 9 parts of an ester wax mainly composed of stearyl stearate (maximum endothermic peak 67 ° C. in DSC measurement, Mw = 1200) was added and dissolved therein. In this, 4 parts of a polymerization initiator 2,2′-azobis-2,4-dimethylvaleronitrile (10 hour half-life temperature 51 ° C.) was dissolved.

The aqueous medium in the polymerizable monomer system was added to, and stirred 65 ° C., 10 min at 10,000rpm at TK homomixer under N ₂ atmosphere and granulated. Thereafter, the mixture was reacted at 65 ° C. for 6 hours while stirring with a paddle stirring blade. Thereafter, the liquid temperature was raised to 80 ° C., and stirring was further continued for 4 hours. After completion of the reaction, the suspension was cooled at a cooling rate of −5 ° C./min.

  Hydrochloric acid was added to the suspension cooled to room temperature (25 ° C.) to dissolve the calcium phosphate salt, followed by filtration and washing with water to obtain wet colored particles 19.

  Next, after drying the particles at 40 ° C. for 12 hours, the dried product is finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), and the resulting finely pulverized product is classified by wind to adjust the particle size and particle size distribution. Toner particles 19 were obtained.

100 parts of the toner particles, 1.5 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil as an external additive and a primary particle size of 12 nm, and hydrotalcite (Kyowa Chemical Co., Ltd.) Manufactured, DHT-4A) 0.1 part, and fatty acid metal salt 1 was further mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 19. The results are shown in Table 2.

(Toner Production Example 20)
Toner 20 was obtained in the same manner except that the di-t-butyl ether of Toner Production Example 1 was not added. The results are shown in Table 2.

(Toner Production Example 21)
In Toner Production Example 1, the amount of tricalcium phosphate added is 4.0 parts, and hydrophobic silica fine powder (BET value treated with silicone oil is 200 m ² / g, primary particle size is 12 nm) is added. Toner 21 was obtained in the same manner except that the amount was changed to 1.8 parts and the addition amount of fatty acid metal salt 1 was changed to 0.12 parts. The results are shown in Table 2.

(Toner Production Example 22)
In Toner Production Example 1, the amount of tricalcium phosphate added is 2.5 parts, and hydrophobic silica fine powder (BET value treated with silicone oil is 200 m ² / g, primary particle size is 12 nm) is added. Toner 22 was obtained in the same manner except that the amount was changed to 1.3 parts and the addition amount of fatty acid metal salt 1 was changed to 0.8 parts. The results are shown in Table 2.

(Toner Production Example 23)
In Toner Production Example 1, the amount of tricalcium phosphate added was 4.2 parts, and hydrophobic silica fine powder (BET value treated with silicone oil was 200 m ² / g, primary particle size was 12 nm) was added. Toner 23 was obtained in the same manner except that the amount was changed to 1.9 parts. The results are shown in Table 2.

(Toner Production Example 24)
In Toner Production Example 1, the addition amount of tricalcium phosphate was 2.4 parts, and hydrophobic silica fine powder (BET value treated with silicone oil was 200 m ² / g and primary particle size was 12 nm) was added. Toner 24 was obtained in the same manner except that the amount was changed to 1.2 parts. The results are shown in Table 2.

(Toner production 25)
Styrene / butyl acrylate copolymer produced by solution polymerization method (glass transition temperature: 65 ° C., weight average molecular weight: 12500, Mw / Mn: 2.4) 100 parts Styrene produced by suspension polymerization method Acrylic acid copolymer (glass transition temperature: 59 ° C., weight average molecular weight: 573,000, Mw / Mn: 2.0) 100 parts Aluminum salicylate compound (Bontron E-88; manufactured by Orient Chemical Co., Ltd.) 4 parts Sulfonic acid group-containing polymer 3 parts C.I. I. Pigment Blue 15: 3 8 parts, di-t-butyl ether 0.06 part, styrene-methacrylic acid-methyl methacrylate 5 parts (styrene / methacrylic acid / methyl methacrylate = 95.85 / 1.65 / 2.50, Mp = 15000, Mw = 7900, Tg = 89 ° C., acid value = 10.9 mgKOH / g, Mw / Mn = 2.17)
・ Ester wax mainly composed of stearyl stearate (Maximum endothermic peak in DSC measurement: 67 ° C., Mw = 1200) 4 parts The above materials are mixed in a blender, melt kneaded in a biaxial extruder heated to 110 ° C., and cooled. The kneaded product was coarsely pulverized with a hammer mill, and the coarsely pulverized product was finely pulverized with a turbo mill (manufactured by Turbo Kogyo Co., Ltd.), followed by air classification to adjust the particle size and particle size distribution to obtain colored particles. Next, the colored particles were heated and spheronized at 70 ° C. for 1 hour under a nitrogen atmosphere using a spray dryer, and then cooled to obtain toner particles 25.

100 parts of the toner particles, 1.5 parts of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil as an external additive and a primary particle size of 12 nm, and hydrotalcite (Kyowa Chemical Co., Ltd.) Manufactured, DHT-4A) 0.1 part, and fatty acid metal salt 1 was further mixed with a Henschel mixer (Mitsui Miike Chemical Co., Ltd.) to obtain toner 25. The results are shown in Table 2.

(Toner Production Example 26)
C. of Toner Production Example 1 I. Pigment Blue 15: 3 to C.I. I. A toner 26 was obtained in the same manner except that the pigment yellow 17 was used. The results are shown in Table 2.

(Toner Production Example 27)
C. of Toner Production Example 1 I. Pigment Blue 15: 3 to C.I. I. A toner 27 was obtained in the same manner except that the pigment red 122 was used. The results are shown in Table 2.

(Toner Production Example 28)
C. of Toner Production Example 1 I. Pigment Blue 15: 3 carbon black (DBP oil absorption: 42cm ^3/100 g, a specific surface area: 60 m ² / g) except for changing the obtain toner 28 in the same manner. The results are shown in Table 2.

(Comparative toner production example 1)
In Toner Production Example 1, the amount of tricalcium phosphate added was 2.5 parts. In addition, a comparison was made in the same manner except that the amount of hydrophobic silica fine powder treated with silicone oil as an external additive was 200 m ² / g and the primary particle size was 12 nm was changed to 2.0 parts. Toner 1 was obtained. The results are shown in Table 2.

(Comparative toner production example 2)
In Toner Production Example 1, the amount of tricalcium phosphate added was 4.0 parts. In addition, the addition amount of hydrophobic silica fine powder having a BET value of 200 m ² / g treated with silicone oil as an external additive and a primary particle size of 12 nm was changed to 1.1 parts, and the primary particle size was further 250 nm. Comparative toner 2 was obtained in the same manner except that 0.05 part of rutile type titanium oxide fine powder was added. The results are shown in Table 2.

(Comparative toner production example 3)
In Toner Production Example 1, the addition amount of tricalcium phosphate was changed to 4.0 parts, the addition amount of fatty acid metal salt 1 was changed to 0.01 parts, and an aluminum salicylate compound (Bontron E- 88; manufactured by Orient Chemical Co.) Comparative toner 3 was obtained in the same manner except that 0.1 part was added. The results are shown in Table 2.

(Comparative toner production example 4)
Comparative toner 4 was obtained in the same manner except that fatty acid metal salt 1 of toner production example 1 was changed to fatty acid metal salt 10. The results are shown in Table 2.

(Comparative toner production example 5)
A comparative toner 5 was obtained in the same manner except that the fatty acid metal salt 1 of Toner Production Example 1 was changed to the fatty acid metal salt 11. The results are shown in Table 2.

(Comparative Toner Production Example 6)
A comparative toner 6 was obtained in the same manner except that the fatty acid metal salt 1 of Toner Production Example 1 was not added. The results are shown in Table 2.

<Example 1 of production of toner layer regulating member>
As a surface transfer sheet, a polyethylene terephthalate film (trade name: E5000, thickness: 100 μm, ten-point average surface roughness Rz = 0.2 μm, manufactured by Toyobo Co., Ltd.) produced by extrusion molding, and a protective film for its surface coating A laminate of a polypropylene film (manufactured by Ube Industries, Ltd., trade name: UBE Polypro J309GL, thickness 80 μm) with a light adhesive was used. First, this surface transfer sheet was fed into an injection molding mold while peeling off the surface covering protective film, and placed so as to be in contact with the inner surface of the cavity, and the mold was closed. A polyester elastomer (Toray DuPont) is used as a blade member composition at a mold temperature of 40 ° C. in a gap (mold cavity) provided between the surface transfer sheet and the mold after the mold is clamped. Made by company, product name: Hytrel 3046, Shore D hardness is 25 degrees) After solidifying, it is melt-injected at about 250 ° C. so that the thickness becomes 200 μm, and solidified by being in close contact with the surface transfer sheet and solidified to be a blade member Formed.

  Next, a phosphor bronze plate having a spring elasticity as a supporting member (plate thickness 0.12 mm, width 22 mm, length 200 mm) is attached to the surface of the obtained blade member facing the surface transfer sheet as an adhesive (manufactured by Toyo Morton, A product name: Adcoat AD-76P1) was used for bonding and cutting into a desired blade shape. The blade member was a plate-like molded product having a width of 5 mm, a length of 200 mm, and a thickness of 0.2 mm. Finally, the surface transfer sheet was peeled off from the blade member, and the toner layer regulating member 1 was produced using the surface of the blade member that appeared as the charge control surface.

<Manufacture example 2 of toner layer regulating member>
Toner layer regulating member 2 was prepared in the same manner as in Production Example 1 of toner layer regulating member, except that the polyester elastomer was changed to Toray DuPont's trade name: Hytrel 5557 (Shore D hardness 55 °).

<Example 3 of production of toner layer regulating member>
Toner layer regulating member 3 was produced in the same manner as in Production Example 1 of toner layer regulating member, except that the polyester elastomer was changed to Toray DuPont's trade name: Hytrel 2751 (Shore D hardness 75 degrees).

<Example 4 of production of toner layer regulating member>
Toner layer regulating member 4 was produced in the same manner as in Production Example 1 of toner layer regulating member, except that the polyester elastomer was changed to Toyobo Co., Ltd., trade name: Perprene E-450B (Shore D hardness 78 degrees).

<Manufacture example 5 of toner layer regulating member>
In Production Example 1 of the toner layer regulating member, the polyester elastomer was changed to a polyamide elastomer having a Shore D hardness of 50 degrees (12-nylon carboxylated with dodecanedioic acid and polytetramethylene glycol polycondensation), A toner layer regulating member 5 was produced in the same manner except that the melting temperature and the mold temperature were changed to 200 ° C. and 30 ° C., respectively.

<Manufacture example 6 of toner layer regulating member>
In Production Example 1 of the toner layer regulating member, the polyester elastomer is changed to a polyamide elastomer having a Shore D hardness of 20 degrees (12-nylon carboxylated with dodecanedioic acid and polytetramethylene glycol polycondensation), A toner layer regulating member 6 was produced in the same manner except that the melting temperature and the mold temperature were changed to 200 ° C. and 30 ° C., respectively.

<Example 7 of production of toner layer regulating member>
In the same manner as in Production Example 1 of the toner layer regulating member, except that the polyester elastomer is changed to a polyurethane-polyether block copolymer elastomer (DIC Bayer Polymer Co., Ltd., trade name: T-8195N, Shore D hardness is 55 degrees). A toner layer regulating member 7 was produced.

<Example 1>
The toner 1 is a non-magnetic one-component developer, and the developer is used in a high temperature and high humidity condition (temperature 30 ° C., humidity 80% RH) and in a normal temperature and humidity environment (temperature 23 ° C., humidity 50% RH) and low temperature. Image evaluation was performed under low humidity conditions (temperature 15 ° C., humidity 10% RH). An image forming apparatus that has performed image evaluation will be described below.

  As the image forming apparatus, HP Color LaserJet CP6015dn (manufactured by Hewlett Packard) was used, and the following conditions (a) to (e) were changed or modified.

  (A) The process speed of the image forming apparatus was changed to 200 mm / sec, and the peripheral speed of the developing roller was changed to 280 mm / sec.

  (B) The process cartridge was modified so as not to detect the service life.

  (C) Modification was made so that the presence / absence of the cartridge was not detected, and durability evaluation and image evaluation could be performed even with a single color.

  (D) In the developing chamber 3 of this embodiment, as shown in FIG. 7I, the cross section of the developing chamber on the upstream side in the transport direction and the cross section of the developing chamber on the downstream side in the transport direction are the same shape, and the toner in the developing chamber is filled. The volume to be made was the same.

  As shown by the black portion in FIG. 7I, the cross-sectional area surrounded by the developing container 12 excluding the screw conveyance area in the area vertically above the rotation center axis of the supply roller (supply member) is defined as S. The conveyance area | region by a screw is an area | region enclosed by the highest point and lowest point of a screw shape. As shown in FIGS. 7A to 7C, the closest distance between the start point on the upstream side in the transport direction, the central portion in the transport direction, and the final point on the downstream side in the transport direction was adjusted to 7 mm. The cross-sectional area S1 on the upstream side in the conveyance direction indicated by the oblique line a in FIG. 7-I is equal to the cross-sectional area S3 on the downstream side in the conveyance direction indicated by the oblique line c in FIG.

  (E) The toner layer regulating member 2 was used as the toner layer regulating member.

  Under the above conditions, the temperature is 1 in an environment of high temperature and high humidity (30 ° C., 80% RH), normal temperature and humidity (23 ° C., 50% RH), and low temperature and low humidity (15 ° C., 10% RH). When printing out an image with a printing ratio of% up to 60,000 sheets, the following image evaluation was performed after the initial period, after 40,000 endurance, and after 60,000 endurance.

(1) Image Density Using a normal copying machine plain paper (75 g / m ² ) transfer material, output a solid image and measure its density (average of five points: upper right, lower right, center, upper left, lower left) ). The image density was measured using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
S: Image density is 1.50 or more A: Image density is 1.45 or more and less than 1.50 B: Image density is 1.30 or more and less than 1.45 C: Image density is 1.15 or more and less than 1.30 D: Image density is less than 1.15 (S is the best for evaluation, and then deteriorates in the order of A, B, C, D)

(2) Density uniformity In the above image density, the difference between the maximum value and the minimum value of the five measurement points was evaluated according to the following criteria.
S: Less than 0.02 A: 0.02 or more and less than 0.05 B: 0.05 or more and less than 0.10 C: 0.10 or more and less than 0.20 D: 0.20 or more (S is the best for evaluation) , A, B, C, D in order.

(3) Density uniformity at the time of replenishment Except for measuring the density uniformity after outputting 70 high-printed images (printing rate 50%), the same method as the density uniformity of (2) above was used.

(4) Fog For the measurement of the fog, the reflectance of the non-image part of the standard paper and the printout image was measured using a reflection densitometer manufactured by Tokyo Denshoku Co., Ltd., REFECTECTOMER MODEL TC-6DS. As a filter used in the measurement, an amber filter was used for printing with cyan toner, a blue filter was used for printing with yellow toner, and a green filter was used for printing with magenta toner and black toner. The fog was calculated from the measurement results by the following formula and evaluated according to the following criteria.
Fog (reflectance:%) = reflectance on standard paper (%) − reflectance of sample non-image area (%)
S: fog (reflectance) less than 0.5% A: fog (reflectance) of 0.5% or more and less than 1.0% B: fog (reflectance) of 1.0% or more, 1.5% Less than C: fog (reflectance) is 1.5% or more, less than 2.0% D: fog (reflectance) is 2.0 or more (in the evaluation, S is the best, and the order of A, B, C, D) And it gets worse.)

(5) Fog during replenishment The fog was measured in the same manner as the fog measurement in (3) above, except that 70 high-printed images (printing rate 50%) were output.

(6) Blur drop At each sampling, one solid image and one halftone image were output, and the blur level was determined on the basis of the following criteria from the number of toner drop drops in the halftone image. In the following criteria, A is good and C is bad.
A: No dropout at all B: Slight dropout (one on halftone image)
C: Dropping out (2-3 on the halftone image)
D: Severe dripping (4 or more on the halftone image)

  When the toner 1 was evaluated under the above conditions, it was found that the density was high and the uniformity thereof was satisfactory, and there was no fogging, replenishment fogging, or toner dropout. Detailed results are shown in Tables 3 to 5.

<Examples 2 to 5, 10, 11>
Under the same conditions as in Example 1, toner 2 to toner 5, 7, and 8 were evaluated. Detailed results are shown in Tables 3-5.

<Example 6>
In Example 1, the evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 7. Detailed results are shown in Tables 3-5.

<Example 7>
In Example 1, evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 1 and the toner to be evaluated was changed to toner 6. Detailed results are shown in Tables 3-5.

<Example 8>
In Example 1, the evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 3 and the toner to be evaluated was changed to the toner 6. Detailed results are shown in Tables 3-5.

<Example 9>
In Example 1, evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 5 and the toner to be evaluated was changed to toner 6. Detailed results are shown in Tables 3-5.

<Example 12>
In Example 1, the evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 6 and the toner to be evaluated was changed to the toner 9. Detailed results are shown in Tables 3-5.

<Example 13>
In Example 1, the evaluation was performed in the same manner except that the toner layer regulating member was changed to the toner layer regulating member 4 and the toner to be evaluated was changed to the toner 10. Detailed results are shown in Tables 3-5.

<Examples 14 to 29>
Toner 11 to toner 28 were evaluated under the same conditions as in Example 1. Detailed results are shown in Tables 3-5.

<Comparative Examples 1 to 6>
When the comparative toners 1 to 6 were evaluated under the same conditions as in Example 1, the density was lowered, and the density uniformity, fogging, replenishing fogging, and toner dropout levels were also poor. Detailed results are shown in Tables 3 to 5.

<Examples 30 to 32>
Examples 30 to 32 were performed in the same manner except that the configuration of the image forming apparatus used in Example 1 was as follows.

  FIG. 7 shows a schematic configuration of Examples 30 to 32 and the vicinity thereof.

  In the developing chamber 3 of this embodiment, as shown in FIG. 7-II, the cross section of the developing chamber on the upstream side in the transport direction is different from the cross section of the developing chamber on the downstream side in the transport direction. The filled volume is different.

  As shown by the black portion in FIG. 7-II, S is defined as a cross-sectional area surrounded by the developing container 12 excluding the screw conveyance region in the region vertically above the rotation center axis of the supply roller (supply member). The conveyance area | region by a screw is an area | region enclosed by the highest point and lowest point of a screw shape. This example was examined by newly installing a developing chamber filling block having the shape shown in FIG. 8 in the developing chambers of Examples 1 to 29. As shown in FIG. 7-IIa, the closest distance between the supply roller 2 and the newly-filled block in the developing container 12 is 3 mm at the upstream start point in the transport direction, and the closest distance is continuous as it goes downstream in the transport direction. As shown in FIG. 7-II b, the closest distance is 5 mm at the center in the transport direction, and as shown in FIG. 7-II c, the closest distance is 7 mm at the final point downstream in the transport direction. It is changing continuously to become. In FIG. 7-II, the cross-sectional area S1 on the upstream side in the conveying direction indicated by the oblique line a is smaller than the cross-sectional area S3 on the downstream side in the conveying direction indicated by the oblique line c in FIG. 7-II, and is continuous from S1 to S3. Is changing.

  Detailed results are shown in Tables 3-5.

<Examples 33 to 35>
Under the same conditions as in Example 32, the toners 26 to 28 were evaluated. Detailed results are shown in Tables 3 to 5.

It is a load-displacement curve in the micro compression test of toner. 1 is a schematic sectional view of an image forming apparatus of the present invention. FIG. 2 is a schematic cross-sectional view of the developing device and toner hopper of the present invention. FIG. 2 is a schematic cross-sectional view of the developing device and toner hopper of the present invention. FIG. 2 is a schematic cross-sectional view of the developing device and toner hopper of the present invention. It is an example of an image obtained by binarizing particle image data at an appropriate threshold level. It is a schematic block diagram of the apparatus of Examples 30-33. It is a schematic block diagram of the apparatus of Examples 30-33. It is explanatory drawing of a developing chamber filling block. FIG. 6 is a schematic view of a part where a developer amount regulating blade is mounted. It is the schematic which shows an example of a developing device. It is a figure which shows the manufacturing process of the sheet | seat for developer amount regulation blade members of this invention, and is the figure which has arrange | positioned the surface transfer sheet in the metal mold | die. It is a figure which shows the manufacturing process of the sheet | seat for developer amount regulation blade members of this invention, and is the figure which has arrange | positioned the surface transfer sheet and the supporting member in the metal mold | die. It is a figure which shows the manufacturing process of the sheet | seat for developer amount regulation blade members of this invention, and is a figure which shows the metal mold | die clamped. FIG. 3 is a schematic view of a developer amount regulating blade member sheet according to the present invention. (A) is a schematic plan view for explaining the developer amount regulating blade of the present invention, and (b) is a central sectional view in the longitudinal direction. It is a figure which shows the particle size distribution of the fatty-acid metal salt 1. It is a figure which shows the particle size distribution of the fatty-acid metal salt 2. It is a figure which shows the particle size distribution of the fatty-acid metal salt 11.

Explanation of symbols

110, 120, 100 Photosensitive drums 210, 220, 200 Charging means 310, 300 Exposure means 410, 420, 400 Development means 414, 424 Agitation means 415, 425 Toner surface detection means 510, 520, 500 Toner hopper 610, 620, 600 Transfer means 710, 720, 700 Cleaning means 1 Electrophotographic photoreceptor 2 Developer container 3 Developer image carrying member 4 Developer amount regulating blade 4a Support member 4b Blade member 5 Elastic roller 6 Developer 11 Photoconductor 12 Charging member 13 Electrostatic Latent image 14 Developing device 15 Transfer means 16 Cleaning means 18 Heat fixing roll 30 Blade member 31 Support member L Exposure means P Transfer material 501 Surface transfer sheet 502 Protective film 502a Protective film 503 Support member 504 Movable mold 505 Fixed mold 506 Injection gate section 50 Blade member forming the void (cavity)
508 Blade member

Claims (15)

A charging step of charging the electrostatic latent image carrier with charging means, an exposure step of exposing the charged electrostatic latent image carrier to form an electrostatic latent image, and a toner layer in contact with the toner carrier A step of regulating the toner on the toner carrier with a regulating member, a developing step of developing the electrostatic latent image with the toner on the toner carrier, and a transfer material with or without the toner image being passed through the intermediate transfer member In an image forming method having a transfer step of transferring to
The image forming method includes a replenishment step of replenishing a nonmagnetic monocomponent toner (Y) from a replaceable replenishment toner container to a developing container filled with the nonmagnetic monocomponent toner (X),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β , Satisfy the following formulas (1) and (2),
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula In addition, the toners (X) and (Y) are at least toner particles and a volume-based median diameter (D50). An image forming method comprising a fatty acid metal salt having a thickness of 0.15 μm to 1.00 μm. 2. The image forming method according to claim 1, wherein the fatty acid metal salt has a span value B defined by the following formula (3) of 1.75 or less.
Span value B = (D95s−D5s) / D50s (3) Formula D5s: 5% integrated diameter D50s of fatty acid metal salt based on volume D: Median diameter of fatty acid metal salt based on volume (D50)
D95s: 95% integrated diameter of fatty acid metal salt based on volume   3. The image forming method according to claim 1, wherein the toner layer regulating member has an elastomer layer of either polyamide or polyester at a contact portion with the toner carrier. The elastomer layer has a Shore D hardness of γ °, and a load of 2.9 × 10 ⁻⁴ N at a load speed of 9.8 × 10 ⁻⁵ N / sec at 25 ° C. in the toner micro-compression test was applied to the toner. In the displacement curve until unloading, when the ratio (restoration rate) between the unloading return displacement and the maximum displacement is Z (25),
25 ° ≦ γ ° ≦ 75 °
0.4 ≦ γ / Z (25) ≦ 2.0
The image forming method according to claim 3, wherein:   5. The image forming method according to claim 1, wherein a median diameter (D50) of the fatty acid metal salt on a volume basis is 0.15 μm to 0.75 μm.   6. The median diameter (D50) on a volume basis of the fatty acid metal salt is 0.30 μm to 0.60 μm, and the span value B is 1.50 or less, according to any one of claims 1 to 5. Image forming method.   7. The image forming method according to claim 1, wherein the fatty acid metal salt is fatty acid zinc or fatty acid calcium.   The image forming method according to claim 1, wherein the toner contains silica and hydrotalcite.   9. The toner according to claim 1, wherein 5.0 ≦ A / B ≦ 30.0 when the content of the silica in the toner is A and the content of the hydrotalcite is B. The image forming method described in 1.   10. The image forming method according to claim 1, wherein an average circularity of the toner is 0.970 to 0.995.   11. The image forming method according to claim 1, wherein the toner contains a compound having the following ether bond.     The weight average particle diameter (D4) of the toner is 5 μm or more and 8 μm or less, and the number% of particles of 4.00 μm or less in the particle size distribution based on the number of the toner is 3 or more and 30% or less. Item 12. The image forming method according to any one of Items 1 to 11.   13. The image forming method according to claim 1, wherein the toner particles are obtained in an aqueous medium. A toner carrier for carrying toner and developing, a toner layer regulating member that is in contact with the surface of the toner carrier to regulate the thickness of the toner layer, and a toner supply for supplying toner to the toner carrier A member, a toner conveying means that is provided above the rotation center axis of the toner supply member and conveys the toner in the longitudinal direction of the toner supply member, and a storage container that stores the toner to be supplied to the toner carrier. And a stirring chamber for supplying toner to a developing chamber composed of the toner carrier, the toner layer regulating member, the toner supply member, the toner conveying means, and the storage container, and the developing chamber is the stirring chamber. A developing device having a toner inlet from the toner and a toner outlet to the stirring chamber;
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. A developing device comprising a fatty acid metal salt of 00 μm. A toner carrier for carrying toner and developing, a toner layer regulating member that is in contact with the surface of the toner carrier to regulate the thickness of the toner layer, and a toner supply for supplying toner to the toner carrier A member, a toner conveying means that is provided above the rotation center axis of the toner supply member and conveys the toner in the longitudinal direction of the toner supply member, and a storage container that stores the toner to be supplied to the toner carrier. And a stirring chamber for supplying toner to a developing chamber composed of the toner carrier, the toner layer regulating member, the toner supply member, the toner conveying means, and the storage container, and the developing chamber is the stirring chamber. A toner used in a developing device having a toner inlet from the toner and a toner outlet to the stirring chamber,
In the cross section perpendicular to the longitudinal direction of the developing chamber, the cross section of the area surrounded by the storage container excluding the toner transport area is defined by the toner transporting unit and is vertically above the rotation axis of the toner supply member. The relationship between the cross-sectional area S1 on the upstream side in the toner transport direction and the cross-sectional area S2 on the downstream side in the transport direction satisfies S1 <S2.
The developing device has a developing container filled with non-magnetic one-component toner (X) and a replaceable replenishing toner container for replenishing the developing container with non-magnetic one-component toner (Y),
When the cohesion degree of the toner (Y) is α, and the cohesion degree of a mixture of the toner (Y) and the toner (Y) obtained by sieving the toner (Y) six times with a mesh having an opening diameter of 53 μm is β, the following ( 1) and (2) are satisfied,
30% ≦ α ≦ 50% (1) Formula 0.85 ≦ α / β ≦ 1.00 (2) Formula The toner has a median diameter (D50) based on at least toner particles and volume of 0.15 μm to 1. A toner comprising a fatty acid metal salt having a size of 00 μm.

Images