JP5441386B2 - Black toner and toner kit for full color image formation - Google Patents

Description

  The present invention relates to a black toner and a full-color image forming toner kit used in a recording method using an electrophotographic method, an electrostatic recording method, a magnetic recording method, or the like. More specifically, the present invention relates to a black toner and a full-color image forming toner kit used in a copying machine, a printer, and a fax machine that form an image by forming a toner image on an electrostatic latent image carrier in advance and then transferring the image onto a transfer material.

Conventionally, in electrophotography, a photoconductive substance is generally used, and an electrostatic charge image is formed on a photoreceptor by various means, and then the electrostatic charge image is developed using toner, and if necessary After the toner image is transferred to a transfer material such as paper, it is fixed by heating, pressure, heating and pressing, or solvent vapor to obtain a toner image.

  In recent years, with the development of the information society, copiers, printers, and fax machines that use such electrophotographic processes have become widespread, and these devices are increasingly required to be smaller, lighter, faster, and more reliable. It is coming.

  In addition, the shift to colorization of these devices has advanced remarkably, and in order to meet the demands for photographic image quality, higher color development and glossiness are required than before, and the toner melting characteristics and toner are fixed smoothly. In particular, fixing technology is important.

  On the other hand, in a general electrophotographic image forming apparatus, the fixing process by heating and pressurizing is the process that consumes the most power in the apparatus. Technology research is ongoing.

  As a toner technique for achieving low-temperature fixing, a method for lowering the glass transition point (Tg) of a binder resin constituting the toner and a method for lowering the molecular weight are generally known. However, by simply lowering the Tg and molecular weight of the resin constituting the toner, the storage stability of the toner and the robustness against repeated image forming operations are impaired.

  In addition, even if fixing is possible at a low temperature, a slight temperature fluctuation during fixing causes an offset in which a part of the toner image is transferred to the fixing member, and the fixed image adheres to the fixing member together with the medium. The actual situation is that the problem of winding easily occurs, and the temperature range in which stable fixing is possible becomes extremely narrow.

  These adverse effects are known to be phenomena depending on the melt viscoelastic properties in the fixing nip of toner. In particular, when fixing at low temperatures or under conditions where the process speed is fast and sufficient heat is not given to the toner, the exfoliation of the release agent contained as a fixing aid is inferior and the release effect is not sufficiently exerted. The viscoelastic properties of the resin itself constituting the toner are particularly important.

  In order to solve the above problems, a method for controlling the molecular weight distribution at a high level and a toner having excellent low-temperature fixing properties by controlling dynamic viscoelastic behavior by containing a high molecular weight component and a low molecular weight component have been proposed. (For example, see Patent Documents 1, 2, and 3).

  Also proposed are low-temperature fixable toners that have improved dynamic viscoelastic behavior using a modified polyester resin having generally sharp melting characteristics or a so-called hybrid resin in which a polyester resin and a styrene-acrylic resin are crosslinked. (For example, see Patent Documents 4, 5 and 6).

  These toners both improve the resin composition that constitutes the toner, so that they have both rapid melting characteristics at low temperatures and elastic characteristics that do not easily adhere to the fixing member, so that they can exhibit a fixing effect in a wide fixing temperature range. It controls the balance of elasticity and exhibits excellent low-temperature fixability.

  However, only with these toners excellent in low-temperature fixability, when a solid black image is output on plain paper, density irregularities and lightness irregularities in which the fibers of the paper are visible in spots are newly noticeable. It turns out to cause problems.

  In particular, this phenomenon is conspicuous when a full-color image forming apparatus is used to output a monochromatic solid black image of black toner.

  The fixing temperature control of the full-color image forming apparatus is set to a temperature control capable of fixing a high applied amount image in which a plurality of colors are superimposed because it is necessary to melt and mix a plurality of color toners. When fixing a toner specialized for low-temperature fixability at such a high fixing temperature, when the temperature and pressure are applied in the fixing nip, the molten toner having a low melt viscosity penetrates deeply into the paper fiber, It is suggested that this is a phenomenon in which the transparency of the fiber is particularly noticeable in a black image having a remarkable contrast.

  In a full-color image forming apparatus, reproduction of black with single-color black toner that does not depend on process black is an important technique that leads to high image quality in order to improve shadow preparation and uniform gloss control in the paper surface. Also in a monochrome image forming apparatus, the uniformity of a solid black image is an important factor that determines image quality.

  However, a black toner that exhibits excellent low-temperature fixability and good solid black image quality has not yet been realized.

Japanese Patent Laid-Open No. 10-171156 JP-A-8-278662 JP 2008-26518 A Japanese Patent Laid-Open No. 11-194542 JP 2003-156880 A JP 2004-157342 A

  An object of the present invention is to provide a black toner and a toner kit for forming a full-color image, which have solved the problems of the prior art as described above.

  That is, an object of the present invention is to provide a black toner and a full-color image-forming toner kit that have good developability and excellent low-temperature fixability that suppresses paper fiber show-through, density unevenness, and brightness variation in solid black images. There is.

  Another object of the present invention is to provide a black toner capable of achieving high image glossiness and stable offset resistance, and a full color image formation capable of providing a high-quality image with little difference in image glossiness. To provide a toner kit.

  It is another object of the present invention to provide a black toner and a full-color image forming toner kit capable of maintaining stable image quality with less fogging over severe use conditions and the life of the cartridge.

  The above object is achieved by the present invention described below.

That is, the present invention is a black toner having a styrene-based binder resin, carbon black, a wax component, and toner particles containing a polar styrene-based resin, and an inorganic fine powder,
In the measurement by the dynamic viscoelasticity test of the black toner,
(I) the maximum value of the loss elastic modulus G ″ is 50 ° C. or more and 62 ° C. or less,
(Ii) When the temperature at which the loss tangent tan δ exhibits the minimum value is the temperature P1, the temperature P1 is 120 ° C. or higher and 155 ° C. or lower,
(Iii) The value tan δ (P1) of tan δ at the temperature P1 is 0.50 or more and 5.00 or less,
(Iv) The value G ′ (P1) of the storage elastic modulus at the temperature P1 is 7.0 × 10 ² Pa or more and 1.0 × 10 ⁴ Pa or less,
(V) When the storage elastic modulus at temperature (P1-20) ° C. is G ′ (P1-20) and the storage elastic modulus at temperature (P1 + 20) ° C. is G ′ (P1 + 20), {LogG ′ ( P1-20) -LogG meets the relationship '(P1)} <{LogG ' (P1) -LogG '(P1 + 20)}, and,
The absolute molecular weight Mw measured by high-temperature GPC-RALLS-viscosity analysis of the orthodichlorobenzene (ODCB) soluble component of the black toner is 4.0 × 10 ⁴ or more and 2.0 × 10 ⁵ or less,
The common logarithm (log [Iv (s)]) of the viscosity Iv (s) of the resin component (s) having an absolute molecular weight (Mw) logarithm (log [Mw]) of 5.00 or more in the analysis is expressed as the absolute molecular weight. When the slope when plotted against the common logarithm of Mw (s) (log [Mw (s)]) is a (s), a (s) is 0.30 or more and 0.70 or less,
The common logarithm (log [Iv (a)]) of the viscosity Iv (a) of all the resin components (a) in the chromatogram detected by the viscometer in the analysis is the common logarithm (log [Mw] of the absolute molecular weight Mw (a). A (s) / a (a) is 0.20 or more and 0.80 or less, where a (a) is the slope when plotted against (a)])
This is a black toner.
The present invention also provides yellow toner having yellow toner particles and inorganic fine powder containing a yellow colorant and a binder resin, and magenta toner particles and inorganic fine powder containing a magenta colorant and a binder resin. A cyan toner having cyan toner particles and inorganic fine powder containing a cyan colorant and a binder resin, and black toner particles and inorganic fine powder containing carbon black and a binder resin. A full color image forming toner kit having black toner,
The black toner is a black toner having the above configuration,
The maximum values of the loss modulus G ″ measured by the dynamic viscoelasticity test of the yellow toner, the magenta toner, and the cyan toner are all 50 ° C. or more and 62 ° C. or less, and are 10 ° C. lower than the (P1). Is (P1-10), and a temperature higher by 10 ° C. is (P1 + 10), the loss tangent tan δ in the temperature range of (P1-10) to (P1-10) is less than the tan δ of the black toner. A full-color image forming toner kit, which is large and has a value of 0.70 to 10.00.

  According to the present invention, it is possible to achieve stable solid development characteristics regardless of the number of printed sheets, regardless of the number of printed sheets, to achieve excellent solid black image quality with little variation in brightness, and to low temperature fixing characteristics with high image gloss. An excellent black toner and toner kit for forming a full color image can be provided.

  Hereinafter, the present invention will be described in detail.

  As a result of intensive studies on the mechanism of density unevenness and brightness unevenness in a solid black fixed image of a single color black toner that can be fixed at low temperature, the present inventors have found that the difference is derived from the uneven surface of the recording material surface fiber during fixing. It was found that there are two reasons for the occurrence.

  When a solid black single color image is output on ordinary plain paper, the unfixed image before the fixing process is sparse on the surface where the toner is relatively evenly placed on the convex surface of the paper fiber and the concave surface of the paper fiber. The presence of an intruded portion is observed with a microscope. The resin characteristics of a toner excellent in low-temperature fixability are generally designed to exhibit a sufficiently low melt viscosity even in a low-temperature region. Accordingly, when the fixing temperature fluctuates to a high level, the melt viscosity tends to decrease with higher sensitivity.

  In the fixing nip, the black toner placed on the convex surface of the paper fiber that is in reliable contact with the surface of the fixing member is easily melted because a sufficient amount of heat is applied, and penetrates deeply into the paper fiber because the melt viscosity is low. . As a result, the thickness of the toner layer covering the fiber convex surface after passing through the fixing nip is reduced.

  Since it becomes thin, the brightness unevenness which a white density sees through along a paper fiber will be produced.

  On the other hand, when sparse toner in the fiber recesses passes through the fixing nip, there is a surface that cannot partially contact the surface of the fixing member due to the steric hindrance of the protruding fiber. The toner present on this surface receives heat from the surface of the fixing member in a non-contact manner, but several toners aggregate together due to heat in a minute time passing through the nip, and the toner that has sparsely filled the recesses. A phenomenon that the covering area is reduced was confirmed. This phenomenon that toners that are close to each other are aggregated so as to shrink does not only reduce the covering area, but also fixes in an incomplete state leaving grains, so that a sufficiently smooth surface can be formed. This will further promote light and shade unevenness.

  That is, in order to improve the density unevenness of the solid black image in the conventional toner having the low temperature fixability, the excessive penetration of the molten toner in the paper fiber convex portion and the toner aggregation and the granular maintenance in the paper fiber concave portion are eliminated. It turns out that two issues need to be overcome.

  This problem is a phenomenon that is not seen at all in a fixed image using conventional toner at a conventional fixing temperature.

  The present inventors have studied in detail the relationship between the dynamic viscoelasticity of the toner and the above-described density unevenness generation mechanism, and thereby, the black having excellent solid black reproducibility with uniform density and brightness without impairing the low-temperature fixability. Invented the toner.

The black toner of the present invention is a black toner having at least a styrene-based binder resin, carbon black, a wax component, a toner particle containing a polar styrene-based resin, and an inorganic fine powder. The maximum value of the loss modulus G ″ measured by the viscoelasticity test is 50 ° C. or more and 62 ° C. or less, and the temperature (P1) at least showing the minimum value of the loss tangent tan δ is 120 ° C. or more and 155 ° C. or less. Tangent minimum value tan δ (P1) is 0.50 or more and 5.00 or less, and storage elastic modulus value G ′ (P1) at P1 is 7.0 × 10 ² Pa or more and 1.0 × 10 ⁴ Pa or less. Yes, when the storage elastic modulus at P1-20 ° C. is G ′ (P1-20) and the storage elastic modulus at P1 + 20 ° C. is G ′ (P1 + 20), {LogG ′ (P1-20) −Lo G and satisfies the relation of '(P1)} <{LogG' (P1) -LogG '(P1 + 20)}.

  The characteristics of the present invention will be described below using the dynamic viscoelastic profile of the toner of the present invention shown in FIG.

  FIG. 1 is an example of a black toner of the present invention, which is a dynamic viscoelastic profile measured from 30 ° C. to 200 ° C. at a temperature rising rate of 2 ° C./min while applying a sinusoidal vibration wave having a frequency of 1 Hz.

  The greatest feature of the toner of the present invention is that the maximum value of the loss elastic modulus G ″ is 50 ° C. to 62 ° C. and the loss tangent tan δ is 120 ° C. to 155 ° C. The temperature indicated by the maximum value of the loss elastic modulus G ″ is a value generally treated as the glass transition temperature (Tg) in the dynamic viscoelasticity test of the resin, and the resin (Tg) obtained by a differential scanning calorimeter (DSC) Are strictly different. In the present invention, the temperature indicated by the maximum value of G ″ in the dynamic viscoelasticity test having a correlation between low-temperature fixability and development characteristics is treated as an essential physical property value.

  The temperature indicated by the maximum value of the loss elastic modulus G ″ in the present invention is a resin characteristic that does not impair development quality, is excellent in low-temperature fixability, and serves as a basis for stable fixing performance in a wide temperature range.

  When the maximum value of the loss elastic modulus G ″ is less than 50 ° C., the development characteristics of the toner may be inferior when left in a severe environment or stress accompanying repeated development operations.

  On the other hand, when the maximum value of the loss elastic modulus G ″ exceeds 62 ° C., the low-temperature fixability is impaired.

  The more preferable value of the loss elastic modulus G ″ in the present invention is 52 ° C. or more and 60 ° C. or less, and more stable offset resistance and solid black image reproducibility can be obtained. I can show.

  The toner of the present invention must have a minimum value in a temperature range of 120 ° C. or more and 155 ° C. or less in the temperature profile of loss tangent tan δ. The appearance of the minimum value of the loss tangent tan δ originates from the relaxation phenomenon of the storage elastic modulus G ′. For example, a micro-crosslinked structure is introduced into the resin component constituting the toner, or a substance having a filler effect is added. Is achieved.

  In the present invention, both the excellent low-temperature fixability and solid black density uniformity can be satisfied by controlling the maximum appearance temperature of the loss elastic modulus G ″ and the relaxation characteristics of the storage elastic modulus G ′ to a specific state. I found.

  The storage elastic modulus G 'of the toner of the present invention is characterized in that a sudden change in elastic modulus characteristics occurs at the relaxation point (P1). In the temperature range until the relaxation point (P1) is reached, it has a so-called rubber-like characteristic that maintains the storage elastic modulus G ′ at a constant elastic modulus, and prevents the phenomenon of fixing soaking that occurs at the convex portion of the paper fiber. Thus, the effect of maintaining the elastic modulus and suppressing the decrease in the melt viscosity can work and be suppressed. It has also been found that this storage elastic modulus G 'maintaining characteristic has an effect of preventing the agglomeration due to abrupt melting even against the sparse aggregation phenomenon of the toner in the paper fiber recesses.

  On the other hand, the rapid reduction characteristic of the storage modulus G ′ after the relaxation point (P1) is an essential characteristic that enables low-temperature fixability. In addition, it has the effect of transferring isolated toner that has escaped aggregation to a molten state quickly and without variation even with respect to the phenomenon of paper fiber recesses, so that a smooth fixed image without graininess can be obtained, and a low-temperature fixable toner Density unevenness that was a peculiar problem can be solved.

  The relaxation point (P1) in the present invention is a value defined as the minimum value of tan δ in the dynamic viscoelasticity profile of the toner, and it is essential that the relaxation point (P1) is 120 ° C. or higher and 155 ° C. or lower.

  Even a toner having a relaxation characteristic in the storage elastic modulus G ′, when the relaxation point (P1) is less than 120 ° C., the effect of eliminating the fixing density unevenness of the solid black image does not appear, whereas it exceeds 155 ° C. In this case, low temperature fixing cannot be achieved.

  In the present invention, a more preferable appearance temperature of the relaxation point (P1) is 125 ° C. or more and 150 ° C. or less, and a low-temperature fixable toner that has a wide fixable temperature range and gives a clean solid image can be obtained.

The magnitude of the relaxation characteristic for effectively exhibiting the low temperature fixability and the solid black density uniformity, which is the effect of the present invention, is the value of the storage elastic modulus on the low temperature side at 20 ° C. with respect to the relaxation point P1 as G ′ ( P1-20), where the value of the storage elastic modulus at 20 ° C. on the high temperature side with respect to the relaxation point P1 is G ′ (P1 + 20), {LogG ′ (P1-20) −LogG ′ (P1)} <{LogG ′ When the relationship of (P1) −LogG ′ (P1 + 20)} is satisfied and the loss tangent tan δ is the minimum value indicated by the relaxation point (P1) is tan δ (P1), tan δ (P1) is 0.50 or more and 5 0.000 or less, and G ′ (P1) is 7.0 × 10 ² Pa or more and 1.0 × 10 ⁴ Pa or less when the value of the storage elastic modulus at the relaxation point (P1) is G ′ (P1). It is essential.

  This is because the change amount of G ′ at the temperature of 20 ° C. before and after the relaxation point (P1) indicated by the minimum value of the loss tangent tan δ shows a change in physical properties having a change in slope in the exponential function. Is expressed.

  Furthermore, the amount of change in the storage elastic modulus G ′ preferred in the present invention is 0.05 <{LogG ′ (P1) −LogG ′ (P1 + 20)} − {LogG ′ (P1-20) −LogG ′ (P1)} <0. .40 relationship.

  By controlling the value of {LogG ′ (P1) −LogG ′ (P1 + 20)} − {LogG ′ (P1-20) −LogG ′ (P1)} within the above range, more stable low temperature fixing property and excellent It is possible to achieve both solid black quality.

  The loss tangent tan δ in dynamic viscoelasticity is a parameter representing the ratio of the loss elastic modulus and storage elastic modulus defined as tan δ = G ″ / G ′.

  In the fixing nip, an unfixed image on the paper as a fixing substrate is subjected to heat under different conditions of pressure distribution in a minute time due to the influence of the unevenness of the paper fiber.

  In order to achieve good fixing quality under such circumstances, it is important to control the balance between the elastic property and the viscous property while maintaining a constant storage elastic modulus G ′.

If G ′ (P1) at the relaxation point (P1) is less than 7.0 × 10 ² Pa, the elastic modulus is small and viscosity reduction cannot be suppressed, and therefore the frequency of occurrence of lightness unevenness and density unevenness of a solid black image increases. .

On the other hand, when G ′ (P1) exceeds 1.0 × 10 ⁴ Pa, the melt viscosity cannot be sufficiently lowered due to the high modulus of elasticity, making it difficult to reproduce low-temperature fixability and high gloss.

A more preferable range of G ′ (P1) is 8.0 × 10 ² Pa or more and 8.0 × 10 ³ Pa or less, and it has low temperature fixing characteristics, dark black image reproducibility and high image gloss. It is particularly excellent in improving the image quality.

  When the minimum value tan δ (P1) at the relaxation point (P1) is less than 0.50, the viscous behavior is small relative to the elastic behavior and is governed by the behavior of the elastic behavior, so that low temperature fixability and high glossiness are reproduced. Sexuality is impaired.

  On the other hand, when the minimum value tan δ (P1) exceeds 5.00, the property of viscosity behavior is large with respect to the elastic behavior, and therefore, the lightness unevenness occurs without suppressing the melt penetration into the paper fiber at the time of fixing.

  In the present invention, the method of controlling the dynamic viscoelasticity having the above-described characteristics is to suppress the glass transition temperature and molecular weight of the styrene main binder to a low level, and to adjust the polarities of the styrene resin and carbon black. This is achieved by adjusting the physical properties and blending ratio.

  That is, by adding a polar styrene-based resin and carbon black to a resin composition that originally has a low melt viscosity, the structural strength is supplemented and the elastic modulus is relaxed.

  Specifically, the melt viscosity can be adjusted by adjusting the type and amount of carbon black, and the loss elastic modulus G ″ can be maintained at a high level. Also, the acid value of the polar styrene resin Further, by controlling the hydroxyl value and Tg, the appearance temperature of the relaxation point and the value of the storage elastic modulus G ′ can be controlled.

  By satisfying the dynamic viscoelasticity exhibited by the toner of the present invention, a significant decrease in the melt viscosity with respect to temperature change, which has been a drawback of conventional low-temperature fixable toners, is suppressed, and soaking into paper fibers and toners are instantly absorbed. Aggregation is suppressed and both low-temperature fixability and solid black quality are achieved.

  Hereinafter, preferable physical property values capable of exhibiting the effects of the present invention more stably will be described.

In the toner of the present invention, the storage elastic modulus G ′ (P1) indicated by the relaxation point (P1) in the dynamic viscoelasticity profile of the toner described above, and the storage elastic modulus G at a temperature lower by 20 ° C. than the relaxation point (P1). The relationship with “G” (P1-20) indicated by “
0.10 ≦ {LogG ′ (P1-20) −LogG ′ (P1)} ≦ 0.65
A more preferred range is
0.15 ≦ {LogG ′ (P1-20) −LogG ′ (P1)} ≦ 0.60
It is preferable to satisfy the relationship.

  The relationship of {LogG ′ (P1-20) −LogG ′ (P1)} is a value representing the characteristics of the storage elastic modulus G ′ in the temperature range immediately before reaching the relaxation point (P1) as a change amount of G ′. Yes, it exhibits different characteristics depending on the cross-linked state and structural control of the resin constituting the toner.

  When the value of {LogG ′ (P1-20) −LogG ′ (P1)} is less than 0.1, especially when the fixing nip passage time is shortened under high-speed process conditions, the influence of the elastic component in the molten state of the toner. May appear and glossiness may be reduced.

  On the other hand, if the value of {LogG ′ (P1-20) −LogG ′ (P1)} exceeds 0.65, the elasticity of the toner in the molten state is insufficient, and the uniformity of the solid black image may be impaired. .

In the toner of the present invention, the value of the storage elastic modulus G ′ (P1 + 20), which is 20 ° C. higher than the relaxation point (P1) in the dynamic viscoelasticity profile of the toner described above, is 1.0 × 10 ² Pa or more. It is preferably 5.0 × 10 ³ Pa or less, more preferably 1.0 × 10 ² Pa or more and 1.0 × 10 ³ Pa or less.

  By maintaining the storage elastic modulus G ′ characteristic at a temperature 20 ° C. higher than the relaxation point (P1) within a certain range, both low-temperature fixability and solid black image quality can be further stabilized.

When the value of the storage elastic modulus G ′ (P1 + 20) is less than 1.0 × 10 ² Pa, the offset property may be inferior when the fixing temperature is shifted to the high temperature side.

On the other hand, when the value of the storage elastic modulus G ′ (P1 + 20) exceeds 5.0 × 10 ³ Pa, the minimum fixable temperature may be high or the glossiness may be low.

  In the toner of the present invention, the loss tangent tan δ (P1) indicated by the relaxation point (P1) in the dynamic viscoelasticity profile of the toner described above, and the loss tangent tan δ (P1 + 20) indicated at a temperature 20 ° C. higher than the relaxation point (P1). It is preferable that {tanδ (P1 + 20) −tanδ (P1)} is 0.10 or more and 3.00 or less, more preferably 0.20 or more and 2.00 or less.

  The relationship of {tan δ (P1 + 20) −tan δ (P1)} is that the balance between the elastic component and the viscous component in the rubber state before passing through the relaxation point, and the balance between the elastic component and the viscous component in the molten state at a temperature 20 ° C. higher than the relaxation point. It shows the amount of change.

  When the relationship of {tan δ (P1 + 20) −tan δ (P1)} is less than 0.10, there is a case where a fixed image in which a part of the granularity is left is obtained, particularly when the amount of applied toner of the unfixed image is large. This is not preferable because it leads to lowering of the degree and deterioration of fixing property.

  On the other hand, if the relationship of {tan δ (P1 + 20) −tan δ (P1)} exceeds 3.00, it is not preferable because of a significant decrease in melt viscosity, which may lead to a decrease in offset or solid black fixed image quality.

In the toner of the present invention, in the dynamic viscoelasticity profile of the toner described above, the relaxation point (P1) and the storage elastic modulus G ′ at 20 ° C. before and after the relaxation point (P1) and G ′ (P1) −20), G ′ (P1 + 20)
{G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)}> 1.0
More preferably,
{G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)} <6.0
It is preferable to satisfy the relationship.

  The relationship {G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)} is based on the rate of change in storage elastic modulus immediately after the relaxation point (P1). The value obtained by subtracting the rate of change in the storage elastic modulus immediately before P1) is defined, and the change characteristic indicated by the elastic component before and after the relaxation point is defined.

  By controlling the value of {G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)} to a value greater than 1.0, the minimum fixable temperature is further lowered. And a high glossiness tends to be obtained.

  On the other hand, the brightness of the solid black image is controlled by controlling the value of {G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)} not to exceed 6.0. Unevenness, density unevenness and offset resistance can be further improved, which is preferable.

  As a means for controlling the more preferable dynamic viscoelastic properties exhibited by the toner of the present invention described above, a method for devising the cross-linked structure and molecular weight distribution of the resin component constituting the toner, and different dynamic viscoelastic properties. A method of blending several types of resins, a method of changing viscoelastic properties by adding an additive that exhibits a filler effect in the resin component, a method of structurally changing viscoelastic properties by using toner particles as a core-shell structure, or the like It is possible to control by a composite method.

  Among these, the method of controlling the cross-linked structure and branch density of the resin component constituting the toner is preferable because it has excellent viscoelasticity control and can exhibit the most stable low-temperature fixing characteristics and durable development characteristics.

The toner of the present invention has an absolute molecular weight Mw measured by high-temperature GPC-RALLS-viscosity analysis of orthodichlorobenzene (ODCB) soluble component is 4.0 × 10 ⁴ or more and 2.0 × 10 ⁵ or less,
The common logarithm (log [Iv (s)]) of the viscosity Iv (s) of the resin component (s) having an absolute molecular weight (Mw) logarithm (log [Mw]) of 5.00 or more in the analysis is expressed as the absolute molecular weight. The gradient a (s) when plotted against the common logarithm of Mw (s) (log [Mw (s)]) is 0.30 or more and 0.70 or less, and the chromatograph detected by the viscometer in the analysis Plot of common logarithm (log [Iv (a)]) of viscosity Iv (a) of all resin components (a) in grams against common logarithm (log [Mw (a)]) of absolute molecular weight Mw (a) When a (a) is the inclination at the time, the a (s) / a (a) is preferably 0.20 or more and 0.80 or less.

  In the high temperature GPC-RALLS-viscosity analysis, distribution information of the linear polymer and the branched polymer is obtained. In general, as the molecular weight of a polymer increases, the viscosity increases due to the bulky structure. Further, when comparing the viscosities of polymers having the same molecular weight and different degrees of branching, the higher the degree of branching, the smaller the molecular spread and the smaller the radius of rotation. Accordingly, when a common logarithm (log [Iv]) of viscosity Iv is plotted against a common logarithm (log [Mw]) of absolute molecular weight Mw in a polymer composed of a single monomer repeating structure, a linear linear relationship is obtained. Is obtained. Since the gradient of the branched polymer is smaller than the gradient of the straight line indicated by the linear polymer, the distribution state of the branched polymer in the molecular weight distribution can be roughly grasped by utilizing this relationship.

  In general, the thermal properties of polymers with a small absolute molecular weight are loosely entangled between the molecular chains of the polymers, so that free motion is relatively active when heat is applied even if a branched structure is introduced, It is considered difficult to maintain the elastic modulus.

  However, in the present invention, by introducing a branched structure into the resin component, carbon black having a highly developed structure structure and a branched structure of the polar resin and the main binder that exist together in an interaction cause local entanglement. It is considered a thing.

  The entangled structure via carbon black, which is present in large numbers in the toner particles, is considered to act as a flexible cross-linking point of the main binder, and shifts the rubbery elastic state to a high temperature range against a decrease in viscosity accompanying a temperature increase. It becomes possible.

Therefore, as a resin composition that suitably achieves the dynamic viscoelasticity of the present invention, the weight average molecular weight (Mw) of the absolute molecular weight is 4.0 × 10 ⁴ or more and 2.0 × 10 ⁵ or less, and this size is high. Those containing a polymer having a branched molecule are preferred.

  By using a resin composition having a branched structure, the resin viscosity and elastic modulus at the time of fixing can be controlled to good values, and good fixing performance and high image glossiness can be obtained.

  Further, a resin composition that is more preferable for achieving the dynamic viscoelasticity of the present invention is preferably a resin composition in which a polymer having a branched structure is distributed on the high molecular weight side.

  When the degree of branching of the high molecular weight component is large, the structural strength can be further increased, and because they have a composition with a small absolute molecular weight, the viscosity decrease is remarkably quick with increasing temperature, A clearer solid black image can be achieved.

  In addition, the effect | action which acts on the dynamic viscoelasticity of the resin composition which has distribution in a branching degree is a maintenance characteristic until it reaches the relaxation point (P1) of storage elastic modulus G ', and the change degree of the melt viscosity after a relaxation point, ie, The change of the loss tangent tan δ can be controlled.

The resin component (s) having a common logarithm (log [Mw]) of 5.00 or more of the absolute molecular weight (Mw) in the present invention is preferably 4.0 × 10 ⁴ or more of Mw, which is a preferred absolute molecular weight of the present invention. In the Mw distribution of 0 × 10 ⁵ or less, it means an extraction component on the high molecular weight side.

  In this high molecular weight extracted component, the common logarithm (log [Iv (s)]) of viscosity Iv (s) was plotted against the common logarithm (log [Mw (s)]) of absolute molecular weight Mw (s). The slope a (s) is defined as an index of the degree of branching indicated by the high molecular weight component.

  By setting the degree of branching a (s) of the resin component of the toner of the present invention to 0.30 or more and 0.70 or less, the crosslinking component works effectively, and both high image glossiness and low temperature fixing characteristics are stable. It is planned.

  Further, the distribution of the degree of branching in the present invention is a value obtained as a ratio of the degree of branching shown by the component (s) on the high molecular weight side described above to the degree of branching shown by the total molecular weight component (a) soluble in ODCB. It is defined as

  That is, the common logarithm (log [Iv (a)]) of the viscosity Iv (a) of all resin components (a) in the chromatogram detected by the viscometer is used as the common logarithm (log [Mw (a) of the absolute molecular weight Mw (a). a)]), the value obtained as a (s) / a (a) is shown, where a (a) is the slope when plotted.

  The value of a (s) / a (a) is 0.20 or more and 0.80 or less, more preferably 0.35 or more and 0.70 or less, and still more preferably 0.30 or more and 0.60 or less. In fixing, the distribution of the crosslinking component of the resin works effectively, and the temperature range where fixing can be performed can be further expanded.

  Further, the inclination a (a) indicated by the total resin component (a) of the toner of the present invention is preferably 0.50 or more and 1.40 or less.

  By controlling the branching degree a (a) indicated by all the resin components to the state indicated by the above range, it is possible to further widen the fixable temperature range and improve the stability of the fixing quality.

  In the present invention, the method of obtaining the slope a when plotting the common logarithm (log [Iv]) of the viscosity Iv against the common logarithm (log [Mw]) of the absolute molecular weight (Mw) is the analysis software attached to the main body. It is obtained by performing Mark-Houwink-Sakurada Plots and specifying an arbitrary analysis range (see FIG. 2).

  In order to control the molecular weight and branching degree distribution of the resin component constituting the toner of the present invention, a plurality of types of resin components whose molecular weight and branching degree are controlled in advance are blended using a compatibilizing agent as necessary. In the case of directly producing toner particles by polymerizing monomers by the polymerization method or polymerization method, an initiator with a high hydrogen abstraction effect is selected, and the crosslinking method and graft polymerization are controlled by adjusting the addition method and activity conditions. Thus, a method of controlling branching can be mentioned. It can also be controlled by selecting the monomer species and adding a crosslinking agent.

  In the toner of the present invention, the THF-insoluble content of the toner is preferably 10.0% by mass or less.

  The resin that constitutes the THF-insoluble component is a so-called ultra-polymer component that has been highly crosslinked, and such a component has an effect of increasing the offset property at the time of fixing, but is suppressed to 10.0% by mass or less. Therefore, more stable low-temperature fixing characteristics and high glossiness can be exhibited.

  The toner of the present invention preferably has a maximum peak molecular weight of from 10,000 to 3,000 by GPC measurement of the THF soluble component of the toner.

  The maximum peak molecular weight exhibited by the THF-soluble component is one of important factors that serve as a basis for the melt viscosity at the time of fixing. By setting the maximum peak molecular weight within the above range, excellent offset property and smoother solid black image fixing quality can be reproduced.

  The toner of the present invention contains a styrene resin having polarity as an essential component in addition to the styrene binder resin.

  The characteristic dynamic viscoelastic behavior of the present invention is that a resin having a relatively high glass transition point having a polar group and carbon black are uniformly dispersed in a main binder having a low glass transition point constituting toner particles. We believe that this will be achieved.

  The characteristic dynamic viscoelastic behavior of the toner of the present invention includes a characteristic that suppresses a significant decrease in viscosity during melting and maintains the elastic modulus up to a certain temperature, and a rapid relaxation of elastic modulus at temperatures after the certain temperature. It is what has. Although the reason is not necessarily clarified, the present inventors consider the causal relationship between the addition of the polar resin and the above expression of the characteristics as follows.

  In general, it is known that many functional units exist on the surface of carbon black, but it is considered that these functional groups and a resin having a polar group are present at a closer distance due to an interaction such as a hydrogen bond.

  In the state where the high-order structure structure of carbon black and the polar resin are entangled and are uniformly dispersed in the main binder constituting the toner particles, the present inventors express the following characteristics: Expects.

  In other words, in the molten state of the main binder, the function as a structure is strengthened by partially functioning the thermal characteristics of the polar resin and strengthening the original filler effect of carbon black by entanglement with the resin. I believe that.

  Therefore, it is presumed that the function of maintaining the melt viscosity and the storage elastic modulus works until reaching a certain temperature due to the structural factors described above, and that the transition to the melted state is promptly performed at temperatures after that.

  In order to effectively express the above functions, it is necessary that there is some compatibility between the main binder component and the polar resin to be added.

  It is essential to use a styrene main binder resin and a resin having a styrenic polar group as the constituents of the toner particles of the present invention, and the viscosity is extremely sensitive to temperature changes due to excellent compatibility. Elastic change can be expressed.

  In the present invention, the inclusion of a resin having a polar group is presumed to have another effect described below.

  In general, conventional toners with excellent low-temperature fixing properties have to set the glass transition point of the binder resin low. Therefore, when stored or transported or subjected to heat or stress in the developing machine, a release agent is added. The agent tended to bleed out to the particle surface.

  When bleed-out of a release agent or the like occurs, the surface properties of the toner particles also change, which causes a reduction in charge amount and a reduction in development quality. Therefore, the toner having low temperature fixability is required to improve the durability that can maintain the development quality as well as the fixing quality.

  In response to this problem, when a styrenic binder resin, carbon black, and a styrenic resin having a polar group are used as essential components of the toner particles, the effect of suppressing the bleeding out of the release agent contained in the toner particles is reduced. It was confirmed that there was.

  The reason for this is not necessarily clear, but the present inventors believe that the reason is as follows.

  The polar group, which is said to be present on the surface of the carbon black particles, and the polar group of the polar resin exhibit an affinity due to the interaction, and as a result, the polarity of the carbon black is weakened.

  It is speculated that carbon black, whose polarity has been weakened, has a relatively strong affinity with the added release agent, so that the supplement effect of the release agent-derived bleed-out component with carbon black is increased. .

  As the styrene-based binder resin constituting the toner of the present invention, a copolymer with an acrylic resin or an acrylic acid resin based on a styrene resin is suitable. By using a copolymer, the degree of freedom in resin design for achieving the dynamic viscoelastic behavior of the present invention is increased, and an excellent effect on development stability is exhibited.

  The polar styrene resin contained in the toner of the present invention has an Mw of 8000 to 50000, an acid value or a hydroxyl value of 3 mgKOH / g to 30 mgKOH / g, and is based on the binder resin component constituting the toner particles. The content is preferably 3.0 parts by mass or more and 30.0 parts by mass or less.

  By setting the Mw of the styrenic resin having a polar group within the above range, the compatibility with the styrenic binder resin is excellent, so that the effects of fixing characteristics and developing characteristics can be more effectively exhibited.

  By setting the acid value or hydroxyl value of the styrenic resin having a polar group in the above range, the affinity with carbon black functions suitably, so that the fixing quality and the durable developability are further improved.

  In addition, by setting the content of the styrenic resin having a polar group in the above range, more stable fixing quality can be obtained in a wide fixing temperature range.

  The glass transition temperature of the styrenic resin having a polar group is preferably 80 ° C. or higher and 120 ° C. or lower. By making the glass transition temperature of the styrenic resin having a polar group contained in the toner particles of the present invention within the above temperature, the compatibility effect with the styrenic binder resin of the present invention and the structural elastic modulus can be improved. The reinforcing effect can be enhanced and excellent low-temperature fixing performance can be exhibited.

  Specific examples of the styrenic resin having a polar group of the present invention include a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, and a styrene-maleic acid copolymer.

  Moreover, when the styrenic resin having a polar group of the present invention has a hydroxyl value, it is preferably, for example, a vinyl polymer having at least a repeating unit (I) represented by the following structural formula.

（式中、Ｒ₁は（ＣＨ₂）ｎ，ｎ＝１〜４、或いは炭素数が１〜６のアルキル基であり、繰り返し単位（Ｉ）は複数種類であっても良い。）

(In the formula, R ₁ is (CH ₂ ) n, n = 1 to 4 or an alkyl group having 1 to 6 carbon atoms, and the repeating unit (I) may be of plural types.)

In the present invention, when a polymer composition having at least the repeating unit (I) represented by the above structural formula is used, a plurality of types of repeating units (I) may exist. In the above structural formula, R ₁ represents (CH ₂ ) n, n = 1 to 4, or an alkyl group having 1 to 6 carbon atoms.

  Examples of the repeating unit (I) include polymers such as hydroxymethyl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, and hydroxyisobutyl methacrylate. .

  Examples of the polymer composition having the repeating unit (I) include a styrene-hydroxymethyl methacrylate copolymer, an α-methylstyrene-2-hydroxyethyl methacrylate copolymer, and a styrene-α-methylstyrene-2-hydroxyethyl. Methacrylate copolymer, styrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer, styrene-n-butyl acrylate-2-hydroxyethyl methacrylate-methyl methacrylate copolymer, styrene-α-methylstyrene Examples thereof include 2-hydroxyethyl methacrylate-methyl methacrylate copolymer and styrene-α-methylstyrene-2-hydroxyethyl methacrylate-methacrylic acid-methyl methacrylate copolymer.

  The toner particles of the present invention preferably contain a polymer or copolymer having a sulfonic acid group, a sulfonic acid group or a sulfonic acid ester group.

  The resin component has a function of enhancing the dispersibility of the styrenic polar resin and other internal additives having a polarity in the styrenic binder resin. Quality and charging stability can be further improved.

  In particular, when the resin having a polar group, which is an essential component of the present invention, has a poor dispersibility, the charging environment characteristics are adversely affected. Therefore, the presence of the above resin excellent in charge control ability and also acting as a dispersion aid. Is very effective in improving developability.

  Examples of the monomer for producing the polymer having a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group of the present invention include styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and 2-methacrylamide. -2-methylpropane sulfonic acid, vinyl sulfonic acid, methacryl sulfonic acid and their alkyl esters.

  The polymer containing a sulfonic acid group, a sulfonic acid group salt or a sulfonic acid ester group used in the present invention may be a homopolymer of the monomer, but the monomer and other monomer It may be a copolymer with a body. As a monomer that forms a copolymer with the above monomer, there is a vinyl polymerizable monomer, and the monofunctional polymerizable monomer or the multifunctional polymerization exemplified in the description of the binder resin component above. Sex monomers can be used.

  The polymer having a sulfonic acid group or the like preferably contains 0.01 to 5.0% by mass with respect to 100 parts by mass of the polymerizable monomer or binder resin. More preferably, it is 0.1 to 3.0% by mass.

  When the polymer having the sulfonic acid group or the like is 0.01 to 5.00% by mass, the effect of dispersing the toner component can be more stably exhibited, and the fixing quality and the charging stability effect are excellent.

  The toner particles of the present invention are preferably produced in an aqueous medium.

  When manufactured in an aqueous medium, the composition uniformity between toner particles of the material constituting the toner particles is increased, and thus more excellent fixing performance and development characteristics can be expressed.

  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.

  In particular, when the toner of the present invention is produced using the suspension polymerization method, the styrenic resin having a polar group, which is an essential component, forms a re-shell of toner particles due to the difference in SP value of the constituent components. The toner having the so-called core-shell structure can further improve both the low-temperature fixing quality and the charging performance because the function of blocking the core particles having a low glass transition point is activated by the resin forming the outer shell.

  The black toner of the present invention contains carbon black as an essential component as a colorant. In addition to the function as a colorant, the function of the carbon black in the present invention has the function of increasing the structural strength by the interaction with the polar resin described above, thereby achieving the dynamic viscoelastic behavior of the present invention. This is an essential component.

  According to the study by the present inventors, the whole picture is not necessarily elucidated, but in the resin composition in which carbon black is uniformly dispersed in the binder resin, the viscosity is maintained and the elastic property is slightly changed in the low-temperature fixing process. It was confirmed that the filler effect was improved.

  This effect is difficult to detect in a toner corresponding to the conventional fixing process because the influence of the viscoelastic behavior of the resin characteristics is large.

  However, it was confirmed that a toner having a low molecular weight component as a main component and having a low melting property functions as a slight elastic component in a molten state.

  This property does not exhibit an effective elastic modulus simply by dispersing carbon black in a resin showing a low molecular weight component, and is complicated such as the crosslinking density of the binder resin component and the presence of a polar resin or a release agent. It is known that the effect is reproduced by the interaction.

  The carbon black contained in the toner of the present invention has an average primary particle size of 10 nm to 100 nm, a DBP oil absorption of 35 ml / 100 g to 170 ml / 100 g, a pH of 5.0 to 10.0, and toner particles It is preferable that content with respect to is 5.0 mass% or more and 12.0 mass% or less.

  By making carbon black the above physical properties and addition amount, the function of increasing the structural strength due to the filler effect and the effect of capturing the bleed-out component of the release agent function more stably. Further expansion and durability development characteristics can be enhanced.

  In addition, when the toner of the present invention is produced by suspension polymerization, it is possible to control the amount of the low molecular weight component and the amount of the crosslinking component to a desired distribution by making good use of the polymerization inhibitory property of the carbon black. This is possible, and the low-temperature fixing quality can be further improved.

  When the primary particle size of carbon black is less than 10 nm, such carbon black has high cohesiveness and also tends to be incorporated into a release agent, so that the dispersibility in toner particles is poor and the coloring power is low. May be.

  On the other hand, when it exceeds 100 nm, the function as a structure in the toner particles is weak, and the coloring power itself tends to be low, which is not preferable.

  When the DBP oil absorption of carbon black is less than 35 ml / 100 g, the higher order structure of carbon black tends to be relatively small, so that the filler effect is small and the effect of maintaining the loss elastic modulus G ″ is weakened.

  On the other hand, when the amount exceeds 170 ml / 100 g, the affinity with the wax component increases, and the wax tends to be taken in. Therefore, the wax cannot be exuded quickly at the time of fixing, and the releasing effect may be impaired.

  When the pH of the carbon black is less than 5.0, since such carbon black has many surface functional groups, it becomes a polymerization inhibiting factor for the main binder when used in the polymerized toner, and the molecular weight control becomes difficult.

  On the other hand, when the pH of the carbon black exceeds 10.0, the filler effect is reduced because the functional group is small and the affinity with the polar resin is poor.

  When the black toner of the present invention is applied to a full color image forming method comprising at least a yellow toner, a magenta toner, and a cyan toner, the maximum value of the loss elastic modulus G ″ measured by the dynamic viscoelasticity test of each color toner Are present at 50 ° C. or more and 62 ° C. or less, and the values of the loss tangent tan δ in the temperature range of 10 ° C. before and after the temperature (P1) indicating the minimum value of the loss tangent (tan δ) of the black toner are all tan δ of the black toner. And greater than or equal to 0.70 and less than or equal to 10.00.

  By setting the dynamic viscoelasticity of the black toner and the color toner within the above range, it is possible to bring the secondary and tertiary colors constituting the full-color image closer to the gloss value indicated by the single color black toner. A full-color fixed image excellent in balance and color developability can be obtained.

  Also, depending on the output image, a case of using so-called process black that reproduces black by the tertiary color of the color toner can be considered.

  Even in such a case, it is possible to control the difference between the textures of single color black and process black as much as possible, thereby further enhancing the expressive power of a full color image.

  By setting the maximum value of the loss elastic modulus G ″ of the color toner to 50 ° C. or more and 62 ° C. or less, high color development and high glossiness in a full color image can be sufficiently exhibited, and the black toner of the present invention can be fixed at low temperature. And a full color fixing image quality excellent in solid black image quality.

  In the temperature range of 10 ° C. before and after the temperature (P1) indicating the minimum value of the loss tangent (tan δ) of the black toner, the value of the loss tangent tan δ of the color toner is larger than the value of tan δ of the black toner and 0.70 or more and 10 By setting it to 0.000 or less, the solid black quality of black toner and the color mixing property of multiple colors of color toner can be exhibited in a balanced manner in the low-temperature fixing process, and a full color image excellent in color space reproducibility can be obtained. It is done.

  Next, a preferable configuration for exhibiting the effects of the present invention more stably will be described.

  The glass transition temperature (Tg) obtained by a differential scanning calorimeter (DSC) of the toner of the present invention is more preferably 40 ° C. or higher and 60 ° C. or lower.

  By setting the temperature within the above range, it becomes easy to control the dynamic viscoelastic property of the toner of the present invention to a preferable profile, and stable low-temperature fixing performance can be exhibited.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 4.5 μm or more and 8.0 μm or less. By setting the weight average particle diameter (D4) of the toner within the above range, the stability of the charge distribution is further increased. Therefore, the development characteristics having excellent dot reproducibility with less fog even when the use environment conditions are changed. Can be satisfied.

  The average circularity of the toner of the present invention is the circularity measured by a flow type particle image measuring apparatus having an image processing resolution of 512 × 512 pixels (0.37 μm × 0.37 μm per pixel). It is analyzed by dividing into 800 circularity ranges of 000, and preferably 0.960 or more and 0.995 or less.

  The measurement principle of the flow-type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) is to capture flowing particles 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, The projected area S, the peripheral length L, and the like are measured.

  Next, the equivalent circle diameter and the circularity are obtained using the area S and the peripheral length L. The equivalent circle diameter is the diameter of a circle having the same area as the projected area of the particle image, and the circularity C is a value obtained by dividing the circumference of the circle obtained from the equivalent circle diameter by the circumference of the projected particle image. And is calculated by the following formula.

Circularity C = 2 × (π × S) ^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 0.200 to 1.000 is divided into 800, the arithmetic average value of the obtained circularity is calculated, and the value is defined as the average circularity.

  When the average circularity of the toner is 0.960 or more, particularly in a high-speed one-component development system, an effect of suppressing development blade fusion caused by distorted particles is effective, so that the durability characteristics are excellent. On the other hand, when the average circularity is 0.995 or less, the blade cleaning property of so-called transfer residual toner remaining on the latent image carrier is improved, which is preferable.

  Below, the material used by this invention is demonstrated.

  Examples of the binder resin for the toner particles of the present invention include styrene such as polystyrene and polyvinyltoluene, and homopolymers of substitution products thereof; styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer. Styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylaminoethyl acrylate copolymer, styrene- Methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether Copolymer, styrene-vinyl Styrene copolymers such as methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer; polymethyl methacrylate, polybutyl methacrylate , Polyvinyl acetate, polyethylene, polypropylene, polyvinyl butyral, silicone resin, polyester resin, polyamide resin, epoxy resin, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, Aromatic petroleum resins and the like can be used singly or in combination, but the styrene copolymer is always contained so as to be the main component of the toner particles (the resin most contained in the constituent resin components).

  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. be able to. Since the polyfunctional polymerizable monomer also acts as a crosslinking agent, it is effective as a method for reproducing desired dynamic viscoelasticity by adjusting the degree of branching of the resin component.

  The toner of the present invention preferably uses a crosslinking agent during the synthesis of the binder resin as a means for controlling the molecular weight and branching degree of the binder resin component.

  Examples of the crosslinking agent used in the present invention include the following as the bifunctional crosslinking agent. Divinylbenzene, bis (4-acryloxypolyethoxyphenyl) propane, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200, # 400, # 600 diacrylate, dipropylene glycol diacrylate, polypropylene Glycol diacrylate, polyester-type diacrylate (MANDA Nippon Kayaku), and diacrylate above instead of diacrylate Thing.

  The following are mentioned as a polyfunctional crosslinking agent. Pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane, diallyl phthalate, tri Allyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.02 to 2.00 parts by mass, more preferably 0.05 to 1.00 parts by mass with respect to 100 parts by mass of the monomer.

  An oil-soluble initiator and / or a water-soluble initiator is used as a polymerization initiator that can be used by the toner of the present invention to control the molecular weight and the degree of branching of the binder resin. 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 with 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 can be obtained.

  As polymerization initiators, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), Azo or diazo polymerization initiators such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobisisobutyronitrile; benzoyl peroxide, t-butylperoxy 2-ethylhexano Ate, t-butyl peroxypivalate, t-butyl peroxyisobutyrate, t-butyl peroxyneodecanoate, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoylper Peroxide polymerization such as oxide and lauroyl peroxide Initiator and the like.

  In the present invention, a method of controlling the degree of branching of the binder resin is effective as one means for controlling the desired viscoelastic properties.

  The most preferable initiator selection and conditions for controlling the branching degree of the binder resin include a method in which an initiator having a high hydrogen abstraction effect is used in an active state at the initial stage of the polymerization reaction. As the initiator having a high hydrogen abstraction ability, an organic peroxide-based initiator is preferable, and a perbutyl-based organic peroxide that generates a t-butoxy radical is most preferable. Moreover, the preferable atmosphere of the active state of the initiator in the present invention includes, for example, a polymerization state at a temperature higher by 10 ° C. or more than the 10-hour half-life temperature of the initiator.

  Further, as the resin component constituting the toner of the present invention, it is preferable to use a resin component in which the average molecular weight is controlled to a low molecular weight and the degree of branching of only the polymer side component is increased in the molecular weight distribution. Such a resin component easily exhibits elasticity maintenance due to entanglement of molecular chains at the time of fixing and melting and rapid elastic relaxation due to short chain length, and is most excellent in low-temperature fixability and fixing quality. The method for obtaining such a resin component can be achieved, for example, by using the above-described initiator having a high hydrogen abstraction ability in an active state and additionally adding it during the polymerization reaction.

  In the present invention, as a means for controlling the degree of polymerization of the polymerizable monomer constituting the binder resin, a known chain transfer agent, polymerization inhibitor or the like can be further added and used.

  In the present invention, it is essential to contain a wax component in order to reproduce the releasing effect and high glossiness in the fixing process at a low temperature.

  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 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; hydrogenated castor oil and derivatives thereof; plant waxes; Among these, ester wax and hydrocarbon wax are preferable from the viewpoint of excellent releasability at low-temperature fixing. Furthermore, in the toner of the present invention, since the dispersion state of the wax component in the binder resin is effective in controlling the dynamic viscoelasticity, it is most preferable to contain a hydrocarbon wax having excellent monodispersibility.

  The wax is preferably contained in an amount of 4 to 25 parts by mass with respect to 100 parts by mass of the binder resin. When the amount of the wax is 4 to 25 parts by mass, an excellent release effect is exhibited by having an appropriate wax bleeding property when the toner is heated and pressurized. Further, it is possible to prevent the wax from seeping out on the toner surface due to various stresses applied to the toner in the developing device, and uniform triboelectric chargeability of each toner can be obtained.

  When the black toner of the present invention is applied to a full-color image forming process, the other color toners each contain a colorant as an essential component in order to impart coloring power.

  Examples of the colorant preferably used in the present invention include the following organic pigments or dyes and inorganic pigments.

  As the organic pigment or organic dye as the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, or a basic dye lake compound can be used. Specific examples include the following. C. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. Pigment Blue 66.

  Examples of the organic pigment or organic dye as the magenta colorant include the following. Condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds. Specific examples include the following. C. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment Red 254.

  As the organic pigment or organic dye as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specific examples include the following. C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. Pigment Yellow 194.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant used in the toner of the present invention is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is preferably used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  When a toner is obtained using a polymerization method in the present invention, it is necessary to pay attention to the polymerization inhibition property and water phase migration property of the colorant. Preferably, surface modification, for example, by a substance that does not inhibit polymerization is used. It is better to apply a hydrophobic treatment to the colorant. In particular, since many dyes have polymerization inhibition properties, care must be taken when using them. A preferable method for surface-treating the dye system includes a method in which a polymerizable monomer is polymerized in the presence of these dyes in advance, and the obtained colored polymer is added to the monomer system.

  In the toner of the present invention, in addition to the polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group having excellent charge control properties as described above, a charge control agent may be added as necessary. It can also be used as a mixture with particles.

  In particular, the charge characteristics of the above-mentioned polymer or copolymer having a sulfonic acid group, a sulfonic acid group, or a sulfonic acid ester group are excellent in the function of maintaining the charge amount. When used in combination, more stable development characteristics can be obtained.

  As the charge control agent, known ones can be used, and in particular, a charge control agent that has a high frictional charging speed and can stably maintain a constant triboelectric charge amount is preferable. Further, when the toner is produced by a direct polymerization method, a charge control agent having a low polymerization inhibitory property and substantially free from a solubilized product in an aqueous dispersion medium is particularly preferable.

  Examples of charge control agents include those that control the toner to be negatively charged, such as organometallic compounds and chelate compounds. Examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Others include aromatic oxycarboxylic acids, aromatic mono and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenols. Further examples include urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, and resin charge control agents.

  Examples of charge control agents include those that control the toner to be positively charged. Nigrosine modified products with nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Onium salts such as certain phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid , Ferricyanides, ferrocyanides); metal salts of higher fatty acids; resin-based charge control agents.

  The toner of the present invention can contain these charge control agents alone or in combination of two or more.

  Among these charge control agents, a metal-containing salicylic acid-based compound is preferable in order to sufficiently exhibit the effects of the present invention, and the metal is particularly preferably aluminum or zirconium. The most preferred charge control agent is an aluminum 3,5-di-tert-butylsalicylate compound.

  A preferable blending amount of the charge control agent is 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, it is not essential to add a charge control agent to the toner of the present invention, and the toner does not necessarily contain a charge control agent by actively utilizing frictional charging with the toner layer thickness regulating member or the toner carrier. There is no need to let it.

  When the toner of the present invention is produced by the suspension polymerization method, a wax, a polar resin and a colorant (in addition, a polymerization initiator, a crosslinking agent, a charge control agent and other additives as necessary) are added to the polymerizable monomer. A polymerizable monomer composition is obtained by uniformly dissolving or dispersing. 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 addition, it is preferable to manage the dissolved oxygen in the reaction vessel as a method for efficiently proceeding the polymerization reaction. If there is little dissolved oxygen, the polymerization reaction will be more efficient. As a result, the generation of low molecular weight components that adversely affect development durability and fixability can be suppressed, and stable performance can be exhibited.

  As the dispersant used for preparing the aqueous dispersion medium, known inorganic and organic dispersants can be used.

  Specifically, examples of the inorganic dispersant include the following. Tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, alumina Is mentioned. Examples of the organic dispersant include polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, carboxymethyl cellulose sodium salt, and starch.

  Commercially available nonionic, anionic and cationic surfactants can also be used. Examples of such surfactants include the following. Sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, calcium oleate.

  As the dispersant used in preparing the aqueous dispersion medium used in the toner of the present invention, an inorganic, poorly water-soluble dispersant is preferable, and a poorly water-soluble inorganic dispersant that is soluble in an acid is preferably used.

  In the present invention, when preparing an aqueous dispersion medium using a poorly water-soluble inorganic dispersant, the amount of these dispersants used is 0.2 with respect to 100 parts by mass of the polymerizable vinyl monomer. It is preferable that it is thru | or 2.0 mass parts. In the present invention, it is preferable to prepare an aqueous dispersion medium using 300 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

  In the present invention, when preparing an aqueous dispersion medium in which the poorly water-soluble inorganic dispersant as described above is dispersed, a commercially available dispersant may be used as it is. Further, in order to obtain dispersant particles having a fine uniform particle size, a water-based dispersion medium can be prepared by generating a poorly water-soluble inorganic dispersant as described above in a liquid medium such as water under high-speed stirring. Good. For example, when tricalcium phosphate is used as a dispersant, a preferred dispersant can be obtained by mixing aqueous sodium phosphate solution and aqueous calcium chloride solution at high speed to form fine particles of tricalcium phosphate. .

  The toner particles of the present invention are externally added with inorganic fine powder as a fluidizing agent.

  As the inorganic fine powder added to the toner particles of the present invention, silica is preferable, and silica fine powder having a number average primary particle size of 4 to 80 nm is preferable. In the present invention, when the number average primary particle size is in the above range, the fluidity of the toner is improved and the storage stability of the toner is also improved.

  The number average primary particle size of the inorganic fine powder is measured as follows.

  The number average primary particle size is obtained by observing with a scanning electron microscope and measuring the particle size of 100 inorganic fine powders in the field of view to determine the average particle size.

  Silica and fine powders such as titanium oxide, alumina, or double oxides thereof can be used in combination. Among the inorganic fine powders used in combination with silica, titanium oxide is preferable.

Examples of the silica of the inorganic fine powder include both dry silica produced by vapor phase oxidation of silicon halide or dry silica called fumed silica, and wet silica produced from water glass. As the inorganic fine powder, dry silica having less silanol groups on the surface and inside the silica fine powder and less production residue of Na ₂ O and SO ₃ ²⁻ is preferable. In addition, dry silica can also be used to produce composite fine powders of silica and other metal oxides by using other metal halogen compounds such as aluminum chloride and titanium chloride together with silicon halogen compounds in the production process. Silica also includes them.

  The inorganic fine powder is added to improve the fluidity of the toner and to make the triboelectric charge of the toner base particles uniform. Hydrophobic treatment of inorganic fine powder can provide functions such as adjustment of triboelectric charge amount of toner, improvement of environmental stability, improvement of characteristics under high humidity environment, etc. It is preferable to use inorganic fine powder. When the inorganic fine powder added to the toner absorbs moisture, the triboelectric charge amount as the toner decreases, and the developability and transferability tend to decrease.

  Examples of the treatment agent for the hydrophobic treatment of the inorganic fine powder include the following. Unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, and organotitanium compounds. These treatment agents may be used alone or in combination.

  Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, when the inorganic fine powder is hydrophobized with a coupling agent, or at the same time or after the treatment, the hydrophobized inorganic fine powder treated with silicone oil is treated with silicone oil even in a high humidity environment. Is kept high and the selective developability is reduced.

  Next, an example of an image forming method and an image forming apparatus that can use the toner of the present invention will be described with reference to FIGS.

  3 and 4 are cross-sectional views of a tandem type color LBP (color laser printer) and process cartridge adopting a non-magnetic one-component contact developing system, which are suitable for image formation using the toner of the present invention. However, the toner of the present invention is not limited to use in these apparatuses.

<Process cartridge>
FIG. 3 is a schematic cross-sectional view of a process cartridge 7 (hereinafter also referred to as “cartridge”) that can be suitably used in the image forming method using the toner of the present invention.

  The cartridge 7 includes a photosensitive drum 1, a cleaner unit 50 having a charging unit 2 and a cleaning unit 6, and a developing unit 4 </ b> A having a developing unit 4 that develops an electrostatic latent image formed on the photosensitive drum 1. Have. The photosensitive drum 1 is rotatably attached to the cleaning frame 31 constituting the cleaner unit 50 via a bearing member (not shown).

    The photosensitive drum 1 has a charging roller 2 for uniformly charging the photosensitive layer provided on the outer peripheral surface of the photosensitive drum 1, and a developer (residual toner) remaining on the photosensitive drum 1 after transfer is removed. The cleaning blade 60 for making contact is in contact. The toner (removed toner) removed from the surface of the photosensitive drum 1 by the cleaning blade 60 is stored in a removed toner storage chamber 35 provided in the cleaning frame 31.

    The developing unit 4A has a developing frame body 45 (45a, 45b, 45e) that accommodates toner, and the developing roller 40 (rotated in the direction of arrow Y) is rotatably attached to the developing frame body 45 via a bearing member. It is supported. Further, a toner supply roller 43 (rotated in the arrow Z direction) and a toner regulating member 44 are provided in contact with the developing roller 40. Further, the developing device frame 45 is provided with a toner transport mechanism 42 for stirring the toner contained therein and transporting the toner to the toner supply roller 43.

  The developing unit 4A is supported so as to be swingable with respect to the cleaner unit 50. That is, the coupling holes 47 and 48 provided at both ends of the developing device frame 45 are aligned with the support holes (not shown) provided at both ends of the cleaning frame 31 of the cleaner unit 50, and pins (not shown) are inserted from both ends of the cleaner unit 50. It is out.

  Further, the developing unit 4A is always urged by a pressure spring (not shown) so that the developing roller 40 contacts the photosensitive drum 1 with the support hole as the rotation axis.

  At the time of development, the toner stored in the toner container 41 is conveyed to the toner supply roller 43 by the toner stirring mechanism 42. The toner supply roller 43 supplies toner to the developing roller 40 by rubbing with the developing roller 40, and causes the toner to adhere on the developing roller 40. The toner adhered on the developing roller 40 reaches the toner regulating member 44 as the developing roller 40 rotates. Then, the toner regulating member 44 regulates the toner to form a predetermined toner thin layer, and gives a desired charge amount. The toner thinned on the developing roller 40 is conveyed to the developing unit in which the photosensitive drum 1 and the developing roller 40 come close as the developing roller 40 rotates. Then, in the developing unit, the latent image is developed by attaching to the electrostatic latent image formed on the surface of the photosensitive drum 1 by a developing bias applied to the developing roller 40 from a power source (not shown). The toner remaining on the surface of the developing roller 40 without contributing to the development of the electrostatic latent image is returned into the developing frame 45 as the developing roller 40 rotates. Then, it is peeled off and collected from the developing roller 40 at the rubbing portion with the toner supply roller 43. The collected toner is stirred and mixed with the remaining toner by the toner stirring mechanism 42.

  Here, an elastic roller is used as the developing roller 40, and a method of bringing the roller into contact with the surface of the photosensitive drum 1 can be used. In general, in a developing method in which a toner carrier and a photoreceptor are in contact with each other, toner is easily damaged or deformed. However, when the toner described in the present invention is used, such a change can be effectively suppressed. preferable.

In the developing method in which the toner carrying member and the photosensitive member are in contact with each other, development is performed by an electric field acting between the photosensitive member and the elastic roller facing the surface of the photosensitive member through the toner. Therefore, the surface of the elastic roller or the vicinity of the surface has a potential, and it is necessary to have an electric field in a narrow gap between the surface of the photosensitive member and the surface of the toner carrying member. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region to keep the electric field while preventing conduction with the surface of the photoreceptor, or a method of providing a thin insulating layer on the surface layer of the conductive roller. . Further, a conductive resin sleeve in which the side facing the surface of the photoconductor is coated with an insulating material on the conductive roller, or a conductive layer is provided on the side not facing the photoconductor with an insulating sleeve is also possible. . Further, it is possible to employ a configuration in which a rigid roller is used as the toner carrier and the photosensitive member is a flexible material such as a belt. The resistance value of the roller as the toner carrier is preferably in the range of 10 ^{2 to} 10 ⁹ Ω · cm.

  As the surface shape of the toner carrier, when the surface roughness Ra (μm) is set to 0.1 to 3.0, both high image quality and high durability can be achieved. The surface roughness Ra correlates with the toner conveying ability and the toner charging ability. When the surface roughness Ra of the toner carrier exceeds 3.0, it is difficult not only to make the toner layer on the toner carrier thin, but also the chargeability of the toner is not improved, so that improvement in image quality cannot be expected. . Since the toner carrying ability on the surface of the toner carrier is suppressed by setting it to 3.0 or less, the toner layer on the toner carrier is thinned, and the number of contact between the toner carrier and the toner increases. Since the chargeability of the toner is also improved, the image quality is synergistically improved. On the other hand, when the surface roughness Ra is smaller than 0.1, it becomes difficult to control the toner coat amount.

  In the present invention, the surface roughness Ra of the toner carrier is an arithmetic average roughness defined in Japanese Industrial Standard (JIS) B06014.2.1. In the present invention, a surface roughness measuring device (Surfcoder SE3500 manufactured by Kosaka Laboratory Co., Ltd.) was used to measure from an arbitrary point on the surface of the toner carrier in a direction parallel to the rotation axis of the toner carrier. The cut-off value was 0.8 mm, the measurement length was 2.5 mm, and the measurement speed was 0.1 mm / second.

  In the image forming method using the process cartridge of FIG. 3, the toner carrier rotates in the same direction as the peripheral speed of the photoconductor, but may rotate in the opposite direction. When the rotation is in the same direction, it is preferable to set the peripheral speed of the toner carrying member to be 1.05 to 3.0 times the peripheral speed of the photosensitive member.

  When the peripheral speed of the toner carrier is less than 1.05 times the peripheral speed of the photoreceptor, the stirring effect received by the toner on the photoreceptor is insufficient, and good image quality cannot be expected. On the other hand, when the peripheral speed ratio exceeds 3.0, toner deterioration due to mechanical stress and toner adhesion to the toner carrier are generated and promoted, which is not preferable.

  When the toner carrier is an elastic roller, a structure having an elastic layer on the surface is preferably used. The hardness of the material of the elastic layer used for the elastic roller is preferably 30 to 60 degrees (ASKER-C / load 1 kg).

  Further, the toner coating amount is controlled by the toner regulating member 44, and the toner regulating member 44 is in contact with the developing roller 40 through the toner layer. At this time, the contact pressure between the toner regulating member 44 and the developing roller 40 is preferably in a range of 0.05 N / cm to 0.5 N / cm as a linear pressure.

  The linear pressure is a load applied per length of the toner regulating member. For example, when a 1.2 N load is applied to the toner regulating member having a contact length of 1 m and brought into contact with the developing roller. The linear pressure is 1.2 N / m. If the linear pressure is less than 0.05 N / cm, it is difficult to control the toner coating amount and uniform triboelectric charging, resulting in fogging. On the other hand, if the linear pressure is higher than 0.5 N / cm, the toner particles are subjected to an excessive load, and therefore, deformation of the particles and adhesion of the toner to the toner regulating member or the developing roller are likely to occur.

  The free end portion of the toner regulating member 44 may have any shape. For example, in addition to a linear cross-sectional shape, an L-shape that is bent near the tip, or a shape that bulges in the vicinity of the tip. Etc. are preferably used.

  As the toner regulating member, a material in which a metal elastic body such as stainless steel, steel, phosphor bronze or the like is used as a base material and a resin is adhered or coated on a portion that contacts the sleeve contact portion is preferably used.

  Furthermore, by applying a DC electric field and / or an AC electric field to the toner regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the loosening action on the toner, and sufficient image density is achieved. A good quality image can be obtained.

<Image forming apparatus>
FIG. 4 is a schematic cross-sectional view showing an example of an image forming apparatus to which the toner of the present invention can be applied. The image forming apparatus 100 has four image forming stations Pa, Pb, Pc, and Pd arranged in parallel in the vertical direction. The process cartridges 7 (7a, 7b, 7c, 7d) are detachably attached to the image forming stations Pa, Pb, Pc, Pd by attachment means (not shown). For full-color image formation, yellow toner particles containing at least a yellow colorant and a binder resin and yellow toner having an inorganic fine powder, magenta toner particles containing at least a magenta colorant and a binder resin, and inorganic toner Magenta toner having fine powder, cyan toner particles containing at least a cyan colorant and a binder resin, cyan toner having inorganic fine powder, black toner particles containing at least carbon black and a binder resin, and inorganic toner A full-color image forming toner kit having black toner having fine powder is used. The magenta, cyan, yellow, and black cartridges 7a, 7b, 7c, and 7d have the same configuration.

    In this schematic diagram, the image forming stations Pa, Pb, Pc, and Pd are arranged side by side with a slight inclination in the vertical direction, but they may be arranged in the vertical direction without being inclined. Further, the process cartridge 7 may be the same as that illustrated in FIG. 3 or may be different.

  Each cartridge 7 (7a, 7b, 7c, 7d) includes a photosensitive drum 1 (1a, 1b, 1c, 1d). The photosensitive drum 1 is driven to rotate counterclockwise in the drawing by a driving means (not shown). The following means are provided around the photosensitive drum 1 in order according to the rotation direction. (A) Charging means 2 (2a, 2b, 2c, 2d) for uniformly charging the surface of the photosensitive drum 1. (B) A scanner unit 3 (3a, 3b, 3c, 3d) that irradiates a laser beam based on image information to form an electrostatic latent image on the photosensitive drum 1. (C) Developing means 4 (4a, 4b, 4c, 4d) for developing a toner image by attaching a developer (hereinafter referred to as “toner”) to the electrostatic latent image. (D) A transfer device 5 that transfers the toner image on the photosensitive drum 1 to the recording medium S. (E) Cleaning means 6 (6a, 6b, 6c, 6d) for removing toner remaining on the surface of the photosensitive drum 1 after transfer.

  Here, the photosensitive drum 1 and the charging means 2, the developing means 4, and the cleaning means 6, which are process means, are integrally constituted by a cartridge frame to form a cartridge to constitute a cartridge 7.

  The photosensitive drum 1 (1a, 1b, 1c, 1d) is configured by providing a photosensitive layer on the outer peripheral surface of a cylinder. Both ends of the photosensitive drum 1 are rotatably supported by support members. Then, when a driving force from a driving motor (not shown) is transmitted to one end portion, it is rotationally driven counterclockwise.

As the photoconductor, a photoconductor drum having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used. Further, the binder resin of the organic photosensitive layer in the OPC photoreceptor is not particularly limited. Of these, polycarbonate resins, polyester resins, and acrylic resins are particularly preferable because they are excellent in transferability and hardly cause toner fusion to the photoreceptor and filming of external additives.

  As the charging means 2 (2a, 2b, 2c, 2d), a contact charging type is used. The charging means 2 is a conductive roller formed in a roller shape. The roller is brought into contact with the surface of the photosensitive drum 1 and a charging bias voltage is applied to the roller. As a result, the surface of the photosensitive drum 1 is uniformly charged.

  As a preferable process condition when the charging roller is used, the contact pressure of the roller is 0.05 to 5 N / cm as a linear pressure. As the applied voltage, a DC voltage or a DC voltage superimposed with an AC voltage is preferably used. When a DC voltage superimposed with an AC voltage is used, it is preferable that AC voltage = 0.5 to 5 dVpp, AC frequency = 50 Hz to 5 kHz, and DC voltage = ± 0.2 to ± 1.5 kV. When a DC voltage is used, the DC voltage is preferably ± 0.2 to ± 5 kV.

  As charging means other than the charging roller, there are a method using a charging blade and a method using a conductive brush. These contact charging means have an effect that a high voltage is unnecessary and generation of ozone is reduced as compared with non-contact corona charging. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

  In the scanner unit 3 (3a, 3b, 3c, 3d), a laser diode (not shown) passes image light corresponding to an image signal through a polygon mirror (not shown) and an imaging lens (not shown) rotated at high speed. Then, the surface of the charged photosensitive drum 1 is exposed according to image information. As a result, an electrostatic latent image is formed on the photosensitive drum.

  The developing means 4 (4a, 4b, 4c, 4d) is composed of a toner container 41 that stores magenta, cyan, yellow, and black toners, respectively, and feeds toner in the toner container 41. To the toner supply roller 43.

  The toner supply roller 43 rotates in the clockwise direction in the figure, and supplies toner to the developing roller 40 as a toner carrying member and does not contribute to the development of the electrostatic latent image. Perform stripping.

  The toner supplied to the developing roller 40 is applied to the outer periphery of the developing roller 40 (rotated clockwise) by the toner regulating member 44 pressed against the outer periphery of the developing roller 40, and is given an electric charge. Then, a developing bias is applied to the developing roller 40 facing the photosensitive drum 1 on which the latent image is formed. Then, toner development is performed on the photosensitive drum 1 in accordance with the latent image.

  The transfer device 5 is provided with an electrostatic transfer belt 11 that circulates and moves so as to face and contact all the photosensitive drums 1 (1a, 1b, 1c, 1d). The transfer belt 11 is stretched around a driving roller 13, driven rollers 14a and 14b, and a tension roller 15, and electrostatically attracts the recording medium S to the outer peripheral surface on the left side in the drawing. The transfer belt 11 circulates so that the recording medium S is brought into contact with the photosensitive drum 1. As a result, the recording medium S is conveyed to the transfer position by the transfer belt 11 and the toner image on the photosensitive drum 1 is transferred.

  The transfer roller 12 (12a, 12b, 12c, 12d) is arranged in parallel at a position in contact with the inside of the transfer belt 11 and facing the four photosensitive drums 1 (1a, 1b, 1c, 1d). A bias is applied to the transfer rollers 12 at the time of transfer, and an electric charge is applied to the recording medium S via the electrostatic transfer belt 11. The toner image on the photosensitive drum 1 is transferred to the recording medium S in contact with the photosensitive drum 1 by the electric field generated at this time.

  The feeding unit 16 feeds and transports the recording medium S to the image forming stations Pa, Pb, Pc, and Pd. A plurality of recording media S are stored in the cassette 17 in the feeding unit 16. At the time of image formation, the feeding roller 18 (half-moon roller) and the registration roller 19 are driven and rotated according to the image forming operation. The feeding roller 18 separates and feeds the recording medium S in the cassette 17 one by one, and then stops the recording medium S by abutting against the registration roller 19. Thereafter, the registration roller 19 feeds the recording medium S to the electrostatic transfer belt 11 in synchronization with the rotation of the transfer belt 11 and the image writing position.

  The fixing unit 20 fixes the toner images of a plurality of colors transferred to the recording medium S. The fixing unit 20 includes a heating roller 21a and a pressure roller 21b that presses against the heating roller 21a and applies heat and pressure to the recording medium S. That is, the recording medium S to which the toner image formed on the photosensitive drum 1 has been transferred is conveyed by the pressure roller 21b and applied with heat and pressure by the heating roller 21a when passing through the fixing unit 20. As a result, a plurality of color toner images are fixed on the surface of the recording medium S.

  As an image forming operation, the cartridges 7 (7a, 7b, 7c, 7d) are sequentially driven in accordance with the image forming timing. In response to the driving, the photosensitive drums 1a, 1b, 1c, and 1d are rotationally driven in the counterclockwise direction. Then, the scanner units 3 corresponding to the respective cartridges 7 are sequentially driven. By this driving, the charging roller 2 applies a uniform charge to the peripheral surface of the photosensitive drum 1. The scanner unit 3 exposes the circumferential surface of the photosensitive drum in accordance with the image signal to form an electrostatic latent image on the circumferential surface of the photosensitive drum. The developing roller 40 in the developing unit 4 forms (develops) a toner image on the circumferential surface of the photosensitive drum 1 by transferring the toner to the low potential portion of the electrostatic latent image.

  At the timing when the leading edge of the toner image formed on the circumferential surface of the most upstream photosensitive drum 1 is rotated and conveyed to the point facing the transfer belt 11, the print start position of the recording medium S coincides with the point facing the transfer belt 11. Thus, the registration roller 19 rotates to feed the recording medium S to the transfer belt 11.

  The recording medium S is pressed against the outer periphery of the transfer belt 11 so as to be sandwiched between the suction roller 22 and the transfer belt 11. A voltage is applied between the transfer belt 11 and the suction roller 22. Electric charges are induced in the recording medium S that is a dielectric and the dielectric layer of the transfer belt 11, and the recording medium S is electrostatically adsorbed on the outer periphery of the transfer belt 11. Thereby, the recording medium S is stably adsorbed to the electrostatic transfer belt 11 and conveyed to the most downstream transfer unit.

  While being conveyed in this manner, the toner image on each photosensitive drum 1 is sequentially transferred to the recording medium S by an electric field formed between each photosensitive drum 1 and the transfer roller 12.

  The recording medium S to which the four color toner images are transferred is separated from the electrostatic transfer belt 11 by the curvature of the belt driving roller 13 and is carried into the fixing unit 20. After the toner image is heat-fixed by the fixing unit 20, the recording medium S is discharged out of the main body by the paper discharge roller 23 with the image surface facing down from the paper discharge unit 24.

  In FIG. 4, a method using a heating roller for the fixing unit 20 is illustrated, but the toner of the present invention can also be suitably used for other fixing methods. 5 and 6 show an apparatus for fixing a toner image by heating a heat-resistant polymer film using a heating element.

  FIG. 5 shows a fixing device having a structure in which tension is always applied to the film.

  In the present invention, the heating element has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.

  The film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether) having high heat resistance are used. Copolymer), PTFE (polytetrafluoroethylene), polyimide, polyamide, and other polymer sheets, metal sheets such as aluminum, and laminate sheets composed of metal sheets and polymer sheets are used.

  A more preferable film structure is that these heat-resistant sheets have a release layer and / or a low resistance layer.

  Reference numeral 51 denotes a heating element fixedly supported by the apparatus, and includes a heater substrate 52, an energization heating resistor (heating element) 53, a temperature detecting element 54, and the like.

  The heater substrate 52 is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.

The heating element 53 is formed by screen printing or the like in an approximately 10 μm thickness and 1 to 3 mm wide linear or narrow strip of an electric resistance material along the longitudinal direction at a substantially central portion of the lower surface of the heater substrate 52 (on the side facing the film 55). It has been applied. As the electrical resistance material, for example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used.

  As an example, the temperature measuring element 54 is a temperature measuring resistor having a low heat capacity, such as a Pt film, which is provided by applying screen printing or the like on the substantially central portion of the upper surface of the heater substrate 52 (the side opposite to the surface on which the heating element 53 is provided). Is the body. A thermistor with a low heat capacity can also be used.

  In the case of the heating element 51 of this example, the heating element 53 having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 53 to generate heat over substantially the entire length. The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac according to the temperature detected by the temperature sensing element 54.

  When the heating element 51 is energized, the heat capacity of the heater substrate 52 and the heating element 53 is small, so that the surface of the heating element rapidly rises to a required fixing temperature (for example, 140 to 200 ° C.).

  The heat resistant film 55 is in contact with the heating body 51.

  To reduce the heat capacity and improve the quick start performance, the film 55 is a single layer or composite layer film with a total thickness of 100 μm or less and heat resistance / release properties, strength / durability of 20 μm or more. it can.

  For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coat layer to which conductive whiskers and the like are added is applied to a thickness of 10 μm.

  The support roller 58 which is a rotating body is made of a rubber elastic body having good releasability such as silicon rubber, and is pressed against the heating body 51 via the film 55 to form a nip portion, and the film 55 is moved and driven at a predetermined speed. To do. When a recording material sheet as a material to be heated is introduced between the film 55 and the film 55, the recording material sheet is brought into close contact with the surface of the film 55, pressed against the heating body 51, and moved and driven together with the film 55.

  Another embodiment of an apparatus for fixing a toner image by heating a heat-resistant polymer film using a heating element will be described.

  FIG. 6 shows a fixing device having a structure in which no tension is applied to the film (tension-free type).

  In the present invention, the heating element has a small heat capacity and has a linear or planar heating section, and the maximum temperature of the heating section is preferably 100 to 300 ° C.

  The film is preferably a heat-resistant sheet having a thickness of 1 to 100 μm. As these heat-resistant sheets, polyester, PET (polyethylene terephthalate), PFA (tetrafluoroethylene-perfluoroalkyl vinyl ether) having high heat resistance are used. Copolymer), PTFE (polytetrafluoroethylene), polyimide, polyamide, and other polymer sheets, metal sheets such as aluminum, and laminate sheets composed of metal sheets and polymer sheets are used.

  A more preferable film structure is that these heat-resistant sheets have a release layer and / or a low resistance layer.

  Reference numeral 64 denotes a low heat capacity linear heater fixedly supported by the apparatus, which includes a heater substrate 64a, an energizing heating resistor (heating element) 64b, a surface protective layer 64c, a temperature detecting element 64d, and the like.

  The heater substrate 64a is a member having heat resistance, insulation, low heat capacity, and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm, and a length of 240 mm.

The heating element 64b is coated with an electric resistance material in a linear or narrow strip shape having a thickness of about 10 μm and a width of 1 to 3 mm along the longitudinal direction at a substantially central portion of the lower surface (the side facing the film 65) of the heater substrate 64a. The surface protective layer 64c is coated thereon with a heat resistant glass of about 10 μm. As the electrical resistance material, for example, Ag / Pd (silver palladium), Ta ₂ N, RuO ₂ or the like is used. Moreover, as a coating method of the electrical resistance material, a screen printing method or the like is used.

  The temperature measuring element 64d is, for example, a low-temperature-capacitance measuring resistor, such as a Pt film, that is provided by applying screen printing or the like to the substantially central portion of the upper surface of the heater substrate 64a (the side opposite to the surface on which the heating element 64b is provided). Is the body. A thermistor with a low heat capacity can also be used.

In the case of the heating element 64 of this example, the heating element 64b having a linear or planar shape is energized at a predetermined timing by an image formation start signal to cause the heating element 64b to generate heat over substantially the entire length.
The energization is AC 100 V, and the supplied power is controlled by controlling the phase angle of energization by an energization control circuit (not shown) including a triac according to the temperature detected by the temperature sensing element 64d.
Since the heat capacity of the heater substrate 64a, the heat generating element 64b, and the surface protective layer 64c is small when the heating element 64 is energized, the surface of the heating element rapidly rises to the required fixing temperature (for example, 140 to 200 ° C.). To do.

  The heat resistant film 65 is in contact with the heating body 64.

  To reduce the heat capacity and improve the quick start performance, the film 65 is a single layer or composite layer with a total thickness of 100 μm or less and heat resistance / release properties, strength / durability of 20 μm or more. it can.

  For example, polyimide, polyetherimide (PEI), polyethersulfone (PES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyetheretherketone (PEEK), polyparabanic acid (PPA), Alternatively, a composite layer film such as a polyimide film having a thickness of 20 μm, on at least the image contact surface side, PTFE (tetrafluoroethylene resin), fluororesin such as PAF / FEP, silicon resin, etc., and further, a conductive material (carbon black, graphite, And a releasable coat layer to which conductive whiskers and the like are added is applied to a thickness of 10 μm.

  The support roller 62, which is a rotating body, is made of a rubber elastic body having good releasability such as silicon rubber, and is pressed against the heating body 64 via the film 65 to form a nip portion, and the film 65 is driven to move at a predetermined speed. To do. When a recording material sheet as a material to be heated is introduced between the film 65 and the recording material sheet, the recording material sheet is brought into close contact with the surface of the film 65, pressed against the heating body 64, and moved and driven together with the film 65.

  Below, the measuring method of the physical-property value concerning this invention is demonstrated.

<Measuring method of dynamic viscoelasticity of toner>
As a measuring apparatus, a rotating plate type rheometer “ARES” (manufactured by TA INSTRUMENTS) is used.

  As a measurement sample, a sample obtained by press molding a toner into a disk shape having a diameter of 8.0 mm and a thickness of 2.0 ± 0.3 mm using a tablet molding machine in an environment of 25 ° C. is used.

  The sample is mounted on a parallel plate, heated from room temperature (25 ° C.) to 100 ° C. over 10 minutes to adjust the shape of the sample, then cooled to the measurement start temperature of viscoelasticity, and measurement is started. At this time, it is important to set the sample so that the initial normal force becomes zero. Further, as described below, in the subsequent measurement, the effect of normal force can be canceled by performing automatic tension adjustment (Auto Tension Adjustment ON).

The measurement is performed under the following conditions.
(1) Use a parallel plate with a diameter of 8.0 mm.
(2) The frequency (Frequency) is 1.0 Hz.
(3) The applied strain initial value (Strain) is set to 0.02%.
(4) Measure between 30 and 200 ° C. at a ramp rate of 2.0 ° C./min. In the measurement, the following automatic adjustment mode setting conditions are used. Measurement is performed in an automatic strain adjustment mode (Auto Strain).
(5) The maximum applied strain (Max Applied Strain) is set to 40.0%.
(6) The maximum torque (Max Allowed Torque) is set to 150.0 g · cm, and the minimum torque (Min Allowed Torque) is set to 1.0 g · cm.
(7) Set distortion adjustment (Strain Adjustment) as 20.0% of Current Strain. In the measurement, an automatic tension adjustment mode (Auto Tension) is adopted.
(8) The automatic tension direction (Auto Tension Direction) is set as the compression (Compression).
(9) The initial static force (Initial Static Force) is set to 10.0 g, and the automatic tension sensitivity (Auto Tension Sensitivity) is set to 40.0 g.
(10) As for the operating condition of the automatic tension (Auto Tension), the sample modulus is 1.0 × 10 ⁶ (Pa) or more.

<Analyzing Method of Toner High Temperature GPC-RALLS-Viscometer>
(I) Pretreatment 0.1 g of toner is put into a dedicated filtration container (for example, Tosoh dissolution filter, pore size: 10 μm), and put into a 15 ml test tube together with 10 ml of ODCB. This is dissolved at 135 ° C. for 24 hours using a solution filtration device (for example, DF-8020 manufactured by Tosoh Corporation).
After 12 hours, analysis was performed using the following apparatus.

(Ii) [Analysis conditions]
Apparatus: HLC-8121GPC / HT (manufactured by Tosoh Corporation)
DAWN EOS (manufactured by Wyatt Technology)
High temperature differential pressure viscosity detector (Viscotek)
Column: TSKgel GMHHR-H (30) HT 7.8 cm (ID) x 30.0 cm (L)
TSKgel GMHHR-H (20) HT 7.8 cm (ID) x 30.0 cm (L)
TSKgel GMHHR-H HT 7.8cm (ID) x 30.0cm (L)
Triple (made by Tosoh Corporation)
Detector 1: Multi-angle light scattering detector Wyatt DAWN EOS
Detector 2: High temperature differential pressure viscosity detector Detector 3: Bryce type dual flow differential refractometer temperature: 135 ° C
Solvent: o-dichlorobenzene (0.05% by weight of dibutylhydroxytoluene added)
Flow rate: 1.0 ml / min
Injection volume: 400 μl

  In this measurement, the molecular weight distribution and intrinsic viscosity based on the absolute molecular weight are directly output, and the measurement theory is as follows.

[Measurement theory]
M ₉₀ = R (θ ₉₀ ) / KC... Rayleigh equation M ₉₀ : molecular weight R (θ ₉₀ ) at 90 °: Rayleigh ratio at a scattering angle of 90 ° K: optical constant (= 2π ² n ² / λ ₀ ⁴ N _A · (dn / dc) ² )
C: Solution concentration Rg = (1/6) ^1/2 ([η] M ₉₀ / φ) ^1/3 ... Froly Fox formula Rg: radius of inertia η: intrinsic viscosity φ: shape element absolute molecular weight: M = R (Θ ₀ ) / KC
R (θ ₀ ) = R (θ ₉₀ ) / P (θ ₉₀ )
P (θ ₉₀ ) = 2 / X ² · (e ^−X − (1−X)) (X = 4πn / λ · Rg)
λ: wavelength (dn / dc): 0.068 ml / g in this patent.

  In the present invention, the slope of the weight average molecular weight of the absolute molecular weight and the common logarithm (log [Iv]) of the viscosity Iv representing the degree of branching plotted against the common logarithm (log [Mw]) of the absolute molecular weight (Mw) Was obtained using the dedicated software “TriSEC GPC Software GPC-LS-Viscometry Module Version 3.0 Rev. B. 05.15” (manufactured by Viscotek).

  In calculating the absolute molecular weight, a standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-10”, manufactured by Tosoh Corporation) is used, and a known molecular weight and intrinsic viscosity (for example, when F-10 is used, the weight is used). The average molecular weight (Mw) was 96400 and the intrinsic viscosity was 0.411 dl / g).

  The slope a was calculated by performing Mark-Houwink-Sakurada Plots with the dedicated software attached to the apparatus and specifying the analysis range.

  The definition of the total resin component (a) of the toner in the present invention is the total resin component of the chromatogram detected by the viscometer in the three-way simultaneous output profile of high temperature (at 135 ° C.) GPC-RALLS-viscosimeter analysis. Based on the analysis value of the area corresponding to.

  Further, the definition of the component (s) on the polymer side in the total resin component of the toner that holds the key of the present invention is a resin having a common logarithm (log [Mw]) of absolute molecular weight (Mw) in the analysis of 5.00 or more. Ingredient (s) is shown.

  In the present invention, the branching ratio of the resin component (s) having a common logarithm (log [Mw]) of the absolute molecular weight (Mw) to the branching degree of all the resin components (a) is 5.00 or more is defined as above. It is expressed by the component inclination ratio a (a) / a (s).

<Method for measuring molecular weight of toner>
The molecular weight distribution of the THF soluble part of the toner is measured by gel permeation chromatography (GPC) as follows.

First, the toner is dissolved in tetrahydrofuran (THF) at room temperature over 24 hours. The obtained solution is filtered through a solvent-resistant membrane filter “Maescho Disc” (manufactured by Tosoh Corporation) having a pore diameter of 0.2 μm to obtain a sample solution. The sample solution is adjusted so that the concentration of the component soluble in THF is about 0.8% by mass. Using this sample solution, measurement is performed under the following conditions.
Apparatus: HLC8120 GPC (detector: RI) (manufactured by Tosoh Corporation)
Column: Seven series of Shodex KF-801, 802, 803, 804, 805, 806, 807 (manufactured by Showa Denko KK)
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min
Oven temperature: 40.0 ° C
Sample injection volume: 0.10 ml

  In calculating the molecular weight of the sample, standard polystyrene resin (for example, trade name “TSK Standard Polystyrene F-850, F-450, F-288, F-128, F-80, F-40, F-20, F— 10, F-4, F-2, F-1, A-5000, A-2500, A-1000, A-500 ", manufactured by Tosoh Corporation) are used.

<Measuring method of glass transition temperature of toner>
The glass transition temperature of the toner in the present invention is measured according to ASTM D3418-82 using a differential scanning calorimeter “Q1000” (manufactured by TA Instruments).

  The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium.

  Specifically, about 10 mg of toner is precisely weighed, put in an aluminum pan, an empty aluminum pan is used as a reference, and the temperature rising rate is 10 ° C./min between a measurement range of 30 to 200 ° C. Measure with. In this temperature raising process, a specific heat change is obtained in the temperature range of 40 ° C to 100 ° C. At this time, the intersection of the intermediate point line of the base line before and after the change in specific heat and the differential heat curve is defined as the glass transition temperature Tg of the binder resin.

<Method for measuring the amount of THF insoluble in toner>
The THF-insoluble content of the resin component in the toner is measured as follows.

  About 1.0 g of toner is weighed (W1 g), put in a pre-weighed cylindrical filter paper (for example, trade name No. 86R (size 28 × 100 mm), manufactured by Advantech Toyo Co., Ltd.), and set in a Soxhlet extractor. Then, extraction is performed for 16 hours using 200 ml of tetrahydrofuran (THF) as a solvent. At this time, extraction is performed at a reflux rate such that the solvent extraction cycle is about once every 5 minutes.

  After the extraction is completed, the cylindrical filter paper is taken out and air-dried, and then vacuum-dried at 40 ° C. for 8 hours. The mass of the cylindrical filter paper including the extraction residue is weighed, and the mass of the extraction residue is subtracted from the mass of the cylindrical filter paper ( W2g) is calculated.

  And a THF insoluble content can be calculated | required by subtracting content (W3g) of components other than a resin component like following formula (1).

  THF insoluble matter (mass%) = {(W2-W3) / (W1-W3)} × 100 (1)

  Content of components other than a resin component can be measured by a well-known analysis means. When the analysis is difficult, the content of components other than the resin component (incineration residual ash content (W3′g)) in the toner is estimated as follows, and the THF-insoluble content is obtained by subtracting the content. be able to.

  The incineration residual ash content in the toner is obtained by the following procedure. About 2 g of toner is weighed (Wag) into a 30 ml magnetic crucible weighed in advance. Put the crucible in an electric furnace, heat at about 900 ° C for about 3 hours, let cool in the electric furnace, let it cool in a desiccator at room temperature for more than 1 hour, weigh the mass of the crucible containing the incineration residual ash, and crucible The incineration residual ash content (Wbg) is calculated by subtracting the mass of. Then, the mass (W3′g) of the incineration residual ash in the sample W1g is calculated by the following formula (2).

  W3 ′ = W1 × (Wb / Wa) (2)

In this case, the THF-insoluble matter is obtained by the following formula (3).
THF-insoluble matter (mass%) = {(W2-W3 ′) / (W1-W3 ′)} × 100 (3)

<Method for Measuring Toner Weight Average Particle Size (D4)>
The weight average particle diameter (D4) of the toner is calculated as follows. As a measuring device, a precise particle size distribution measuring device “Coulter Counter Multisizer 3” (registered trademark, manufactured by Beckman Coulter, Inc.) using a pore electrical resistance method equipped with a 100 μm aperture tube is used. 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) is calculated. The “average diameter” on the “analysis / volume statistics (arithmetic average)” screen when the graph / volume% is set by the dedicated software is the weight average particle diameter (D4).

<Measuring method of average circularity of toner>
The average circularity of the toner particles is measured by a flow type particle image analyzer “FPIA-3000” (manufactured by Sysmex Corporation) under the measurement and analysis conditions during the calibration operation.

  A specific measurement method is as follows. First, about 20 ml of ion-exchanged water from which impure solids are removed in advance is put in a glass container. 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 0.2 ml of a diluted solution obtained by diluting the solution with ion exchange water about 3 times by mass. Further, about 0.02 g of a measurement sample is added, and dispersion treatment is performed for 2 minutes using an ultrasonic disperser to obtain a dispersion for measurement. In that case, it cools suitably so that the temperature of a dispersion liquid may become 10 to 40 degreeC. As the ultrasonic disperser, a desktop type ultrasonic cleaner disperser (for example, “VS-150” (manufactured by VervoCrea)) having an oscillation frequency of 50 kHz and an electric output of 150 W is used. Ion exchange water is added, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.

  The flow type particle image analyzer equipped with a standard objective lens (10 ×) was used for the measurement, and a particle sheath “PSE-900A” (manufactured by Sysmex Corporation) was used as the sheath liquid. The dispersion prepared in accordance with the above procedure is introduced into the flow type particle image analyzer, and 3000 toner particles are measured in the HPF measurement mode and in the total count mode. Then, the binarization threshold at the time of particle analysis is set to 85%, the analysis particle diameter is limited to the circle equivalent diameter of 1.985 μm or more and less than 39.69 μm, and the average circularity of the toner particles is obtained.

  In the measurement, automatic focus adjustment is performed using standard latex particles (eg, “RESEARCH AND TEST PARTICLES Latex Microsphere Suspensions 5200A” manufactured by Duke Scientific) diluted with ion-exchanged water before starting the measurement. Thereafter, it is preferable to perform focus adjustment every two hours from the start of measurement.

  In the examples of the present application, a flow-type particle image analyzer that has been issued a calibration certificate issued by Sysmex Corporation, which has been calibrated by Sysmex Corporation, was used. Measurement was performed under the measurement and analysis conditions when the calibration certificate was received, except that the analysis particle size was limited to a circle equivalent diameter of 1.985 μm or more and less than 39.69 μm.

  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.

  First, a production example of the polar resin used in the production example of the toner of the present invention will be shown.

<Production Example 1 of Polar Resin>
-Styrene 93.35 parts-n-butyl acrylate 2.50 parts-Methyl methacrylate 2.50 parts-Methacrylic acid 1.65 parts-Perbutyl D (10-hour half-life temperature 54.6 ° C (manufactured by NOF Corporation)) 80 parts The above components were added dropwise over 2 hours after the inside of the container was sufficiently substituted with nitrogen and heated to 140 ° C. while stirring 200 parts of xylene in a four-necked flask. Furthermore, it was kept for 10 hours under reflux of xylene to complete the polymerization, and the solvent was distilled off under reduced pressure. The resin thus obtained was designated as polar resin no. Set to 1. Table 1 shows the physical properties of the obtained resin.

<Production Examples 2 to 14 of polar resin>
In the polar resin production example 1, the polar resin was changed in the same manner as in the polar resin production 1 except that the monomer composition to be added was changed to the copolymer composition shown in Table 1 and the addition amount of perbutyl D was changed. No. 2 to 14 were produced. The obtained polar resin No. The physical properties of 2 to 14 are shown in Table 1.

Ｓｔ：スチレン
ＢＡ：ｎ−ブチルアクリレート
ＭＭＡ：メチルメタクリレート
ＭＡＡ：メタクリル酸
α−ＭＳｔ：α−メチルスチレン
２ＨＥＭＡ：２−ヒドロキシエチルメタクリレート

St: styrene BA: n-butyl acrylate MMA: methyl methacrylate MAA: methacrylic acid α-MSt: α-methylstyrene 2HEMA: 2-hydroxyethyl methacrylate

  Table 2 shows a list of carbon blacks used in the following black toner production examples.

(Black toner production example 1)
A polymerized toner was produced according to the following procedure.

  To 1300 parts of ion-exchanged water heated to 60 ° C., 9 parts of tricalcium phosphate and 11 parts of 10% hydrochloric acid are added, and TK type homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) is used to make 10,000 r / min. The mixture was stirred and an aqueous medium having a pH of 5.2 was prepared.

Moreover, the following material was melt | dissolved at 100 r / min with the propeller-type stirring apparatus, and the solution was prepared.
・ Styrene ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 70.0 parts ・ n-Butyl acrylate ・ ・ ・ ・ ・ ・30.0 parts FCA1001NS (Fujikura Kasei Co., Ltd.) 1.0 parts polar resin 1 (described in Table 1) ) ... 20.0 parts

Next, in the above solution,
・ Carbon black No. 1 (listed in Table 2) ···································································· 6.5 Parts / wax HNP-10 (melting point 75 ° C .: made by Nippon Seiki Co., Ltd.) 10.0 parts divinylbenzene・ ・ ・ ・ ・ ・ 0.35 parts was added, and then the mixture was heated to a temperature of 65 ° C. and then stirred at 10,000 r / min with a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) Dissolved and dispersed.

Subsequently, the polymerizable monomer composition is charged into the aqueous medium, and as a polymerization initiator, perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF Corporation)) 8.0 parts The mixture was stirred at 70O 0 C using a TK homomixer at 10,000 r / min for 40 minutes and granulated.

In addition, when 30 minutes passed in the granulation process, 2.0 parts of perbutyl PV (10-hour half-life temperature 54.6 ° C. (manufactured by NOF)) was added as an additional initiator.

  The mixture was transferred to a propeller type agitator and reacted at 70 ° C. for 5 hours while stirring at 120 r / min, then heated to 80 ° C. and further reacted for 5 hours to produce toner particles. After completion of the polymerization reaction, the slurry containing the particles was cooled, washed with an amount of water 10 times that of the slurry, filtered and dried, and then the particle size was adjusted by classification to obtain black toner particles.

Hydrophobic silica fine powder (primary particle diameter) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts of the black toner particles. : 7 nm, BET specific surface area: 130 m ^{2 /} g) 1.7 parts were mixed with a Henschel mixer (manufactured by Mitsui Miike) at 3000 r / min for 15 minutes to obtain a black toner No. 1 was obtained.

  Black Toner No. The physical properties of 1 are shown in Tables 3 and 4.

(Black toner production example 2)
In black toner production example 1, carbon black no. 1 is carbon black no. No. 2 (described in Table 2) and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was changed to 10.0 parts. 2 was produced. The obtained black toner no. The physical properties of 2 are shown in Tables 3 and 4.

(Black toner production example 3)
In black toner production example 1, carbon black no. 1 is carbon black no. No. 3 (described in Table 2) and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was changed to 12.5 parts. 3 was produced. The obtained black toner no. The physical properties of 3 are shown in Tables 3 and 4.

(Black toner production example 4)
In black toner production example 1, carbon black no. 1 is carbon black no. 4 (described in Table 2), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was changed to 5.5 parts. 4 was produced. The obtained black toner no. The physical properties of 4 are shown in Tables 3 and 4.

(Black toner production example 5)
In black toner production example 1, carbon black no. 1 is carbon black no. No. 5 (described in Table 2), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was changed to 4.5 parts. 5 was produced. The obtained black toner no. The physical properties of 5 are shown in Tables 3 and 4.

(Black toner production example 6)
In the black toner production example 1, FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) to be added was changed to a polymer having a sulfonic acid Ca base shown in the following production example. 1 is polar resin no. No. 2 (described in Table 1), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the addition part of divinylbenzene was changed to 0.25 part. 6 was produced. The obtained black toner no. The physical properties of 6 are shown in Tables 3 and 4.

<Production example of polymer having sulfonic acid Ca base>
500 ml of ethyl acetate was charged into a 3 liter reaction vessel, 100 g of FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) was added over 5 minutes, and the mixture was further stirred for 3 hours. Thereafter, a solution of 10 g of potassium hydroxide in 500 ml of ethanol was added dropwise over 1 hour, and the mixture was further stirred for 3 hours. Subsequently, an aqueous solution of 500 ml of ion-exchanged water containing 10 g of calcium chloride was prepared, added dropwise over 2 hours, and further stirred for 10 hours.

  This was put into 1.5 L of chloroform, 1.0 L of ion exchange water was further added, and the mixture was stirred for 5 hours. Thereafter, the chloroform layer was separated, washed with 2.0 L of ion exchange water three times, and dried under reduced pressure to obtain a polymer having a sulfonic acid Ca base.

  The calcium chloride rate of sulfonic acid was confirmed to be 90% by measuring fluorescent X-rays.

(Black toner production example 7)
In black toner production example 1, FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) to be added was changed to a polymer having a sulfonic acid methyl ester group shown in the following production example. 1 is polar resin no. No. 3 (described in Table 1), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts of divinylbenzene was changed to 0.45 parts. 7 was produced. The obtained black toner no. The physical properties of 7 are shown in Tables 3 and 4.

<Example of production of polymer having sulfonic acid methyl ester group>
A 3-liter reaction vessel was charged with 500 ml of trimethyl orthoformate and heated to 80 ° C. To this, 100 g of FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) was added over 5 minutes, and then stirred for 15 hours. Thereafter, the reaction mixture was added dropwise to 9 liters of n-hexane with stirring. The resin was deposited and allowed to stand for a while. The supernatant was removed by decantation, and 500 ml of chloroform was added to the residue to dissolve it. This was added dropwise to 7.5 liters of n-hexane with stirring, precipitated and precipitated, the supernatant was removed by decantation, and the residue was dried under reduced pressure. This was washed with 300 ml of methanol and further with 300 ml of water. This was dried under reduced pressure to obtain a polymer having a sulfonic acid methyl ester group.

  The esterification rate of sulfonic acid was confirmed to be 85% by measuring the acid value.

(Black toner production example 8)
In black toner production example 1, polar resin no. 1 is polar resin no. 4 (described in Table 1), and carbon black No. 1 is carbon black no. 3 (described in Table 2), the number of added parts was changed to 7.5 parts, and the black toner No. 1 was prepared in the same manner as in the black toner production example 1 except that the reaction temperature at 70 ° C. was changed to 67 ° C. . 8 was produced. The obtained black toner no. The physical properties of 8 are shown in Tables 3 and 4.

(Black toner production example 9)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 5 (described in Table 1) and the black toner no. 9 was produced. The obtained black toner no. The physical properties of 9 are shown in Tables 3 and 4.

(Black toner production example 10)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 6 (described in Table 1), except that the reaction temperature at 70 ° C. was changed to 73 ° C. 10 was produced. The obtained black toner no. The physical properties of 10 are shown in Tables 3 and 4.

(Black toner production example 11)
In black toner production example 1, polar resin no. 1 is polar resin no. 7 (described in Table 1), the number of added parts was changed to 32 parts, and carbon black No. 1 is carbon black no. No. 5 (described in Table 2) and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was also changed to 7.0 parts. 11 was produced. The obtained black toner no. The physical properties of 11 are shown in Tables 3 and 4.

(Black toner production example 12)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 8 (described in Table 1) and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts was changed to 8 parts. 12 was produced. The obtained black toner no. The physical properties of 12 are shown in Tables 3 and 4.

(Black toner production example 13)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 9 (described in Table 1), except that the black toner no. 13 was produced. The obtained black toner no. The physical properties of 13 are shown in Tables 3 and 4.

(Black toner production example 14)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 10 (described in Table 1), except that the black toner no. 14 was produced. The obtained black toner no. The physical properties of 14 are shown in Tables 3 and 4.

(Black toner production example 15)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 11 (described in Table 1), except that the black toner no. 15 was produced. The obtained black toner no. The physical properties of 15 are shown in Tables 3 and 4.

(Black toner production example 16)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 12 (described in Table 1), except that the black toner no. 16 was produced. The obtained black toner no. The physical properties of 16 are shown in Tables 3 and 4.

(Black toner production example 17)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that FCA1001NS (manufactured by Fujikura Kasei Co., Ltd.) was not added. 17 was produced. The obtained black toner no. The physical properties of 17 are shown in Tables 3 and 4.

(Black toner production example 18)
Styrene / n-butyl acrylate copolymer (mass ratio 72/28) 70 parts (Mp = 25000 Mn = 8500 Mw / Mn = 3.0 Tg = 54 ° C.)
Styrene / n-butyl acrylate copolymer (mass ratio 80/20) 30 parts (Mp = 85000 Mn = 50000 Mw / Mn = 3.0 Tg = 64 ° C.)
Bontron E-88 (produced by Orient Chemical Co., Ltd.) 2.0 parts carbon black No. 1 (described in Table 2) 6.5 parts ester wax (endothermic peak = 72 ° C., half width = 4 ° C.) 5.0 parts The above components are melt-kneaded with a Banbury mixer, cooled, and then finely pulverized with a jet mill. Furthermore, a spheroidizing treatment was performed using a surface reforming apparatus using a mechanical impact force to obtain a spherical pulverized raw material. Next, the obtained pulverized raw material was classified by a classifier to obtain black toner particles (18) having an average circularity of 0.949 and a weight average particle diameter of 6.5 μm.

Hydrophobic silica fine powder (1) treated with dimethyl silicone oil (20% by mass) as a fluidity improver and charged to the same polarity (negative polarity) as the toner particles with respect to 100 parts of the black toner particles (18). (Next particle size: 7 nm, BET specific surface area: 130 m ^{2 /} g) 1.7 parts were mixed with a Henschel mixer (manufactured by Mitsui Miike Co., Ltd.) for 15 minutes at 3000 r / min. 18 was obtained.

  Black Toner No. The physical properties of 18 are shown in Tables 3 and 4.

(Black toner production example 19)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1, except that the amount of additional initiator added at 30 minutes during the granulation step was changed to 2.5 parts. 19 was produced. The obtained black toner no. The physical properties of 19 are shown in Tables 3 and 4.

(Black toner production example 20)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that ethylene glycol dimethacrylate was added instead of divinylbenzene. 20 was produced. The obtained black toner no. The physical properties of 20 are shown in Tables 3 and 4.

(Black toner production example 21)
In black toner production example 1, black toner is used except that the additional initiator added at 30 minutes in the granulation process is changed to perbutyl NHP (10-hour half-life temperature 50.6 ° C. (manufactured by NOF Corporation)). No. 1 in black toner No. 21 was produced. The obtained black toner no. The physical properties of 21 are shown in Tables 3 and 4.

(Black toner production example 22)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that 0.2 parts of t-dodecyl mercaptan was newly added to the dissolving step. 22 was produced. The obtained black toner no. The physical properties of 22 are shown in Tables 3 and 4.

(Black toner production example 23)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that trimethylolpropane trimethacrylate was added instead of divinylbenzene. 23 was produced. The obtained black toner no. The physical properties of 23 are shown in Tables 3 and 4.

(Black toner production example 24)
In black toner production example 1, 0.2 part of t-dodecyl mercaptan is newly added to the dissolution process, the reaction temperature is changed to 65 ° C., and no additional initiator is added at the time of the granulation process 30 minutes. In the same manner as in black toner production example 1, black toner no. 24 was produced. The obtained black toner no. The physical properties of 24 are shown in Tables 3 and 4.

(Black toner production example 25)
In black toner production example 1, polar resin no. 1 was added to 15 parts, and carbon black No. 1 was changed. 1 is carbon black no. No. 2 (described in Table 2) and the same procedure as in Black Toner Production Example 1 was performed except that the number of added divinylbenzene was changed to 0.15 part. 25 was produced. The obtained black toner no. The physical properties of 25 are shown in Tables 3 and 4.

(Black toner production example 26)
In the black toner production example 1, the black toner No. 1 was prepared in the same manner as in the black toner production example 1 except that the addition part of divinylbenzene was changed to 0.55 parts. 26 was produced. The obtained black toner no. The physical properties of 26 are shown in Tables 3 and 4.

(Black toner production example 27)
In black toner production example 1, polar resin no. 1 was added to 10 parts, and carbon black No. 1 was changed. 1 is carbon black no. 4 (described in Table 2), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts of divinylbenzene was changed to 0.15 parts. 27 was produced. The obtained black toner no. The physical properties of 27 are shown in Tables 3 and 4.

(Black toner production example 28)
In the black toner production example 1, the black toner No. 1 was prepared in the same manner as in the black toner production example 1 except that the addition part of divinylbenzene was changed to 0.65 parts. 28 was produced. The obtained black toner no. The physical properties of 28 are shown in Tables 3 and 4.

(Black toner production example 29)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that the addition amount of styrene was 69 parts and the addition amount of n-butyl acrylate was 31 parts. 29 was produced. The obtained black toner no. The physical properties of 29 are shown in Tables 3 and 4.

(Black toner production example 30)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that the addition amount of styrene was changed to 73 parts and the addition amount of n-butyl acrylate was changed to 27 parts. 30 was produced. The obtained black toner no. The physical properties of 30 are shown in Tables 3 and 4.

(Black toner production example 31)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that the addition amount of styrene was changed to 68 parts and the addition amount of n-butyl acrylate was changed to 32 parts. 31 was produced. The obtained black toner no. The physical properties of 31 are shown in Tables 3 and 4.

(Black toner production example 32)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1, except that the addition amount of styrene was changed to 74 parts and the addition amount of n-butyl acrylate was changed to 26 parts. 32 was produced. The obtained black toner no. The physical properties of 32 are shown in Tables 3 and 4.

(Black toner production example 33)
In black toner production example 1, carbon black no. 1 is carbon black no. 3 (described in Table 2), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the number of added parts of divinylbenzene was changed to 0.25 parts. 33 was produced. The obtained black toner no. The physical properties of 33 are shown in Tables 3 and 4.

(Black toner production example 34)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 13 (described in Table 1), except that the black toner no. 34 was produced. The obtained black toner no. The physical properties of 34 are shown in Tables 3 and 4.

(Black toner production example 35)
In black toner production example 1, polar resin no. 1 is polar resin no. No. 14 (described in Table 1), except that the black toner no. 35 was produced. The obtained black toner no. The physical properties of 35 are shown in Tables 3 and 4.

(Black toner production example 36)
In black toner production example 1, carbon black no. 1 is carbon black no. No. 6 (described in Table 2), and the black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the added number of parts of divinylbenzene was changed to 0.05 parts. 36 was produced. The obtained black toner no. The physical properties of 36 are shown in Tables 3 and 4.

(Black toner production example 37)
In the black toner production example 1, the black toner No. 1 was prepared in the same manner as in the black toner production example 1 except that the addition part of divinylbenzene was changed to 0.75 parts. 37 was produced. The obtained black toner no. The physical properties of 37 are shown in Tables 3 and 4.

(Black toner production example 38)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1 except that the addition amount of styrene was changed to 67 parts and the addition amount of n-butyl acrylate was changed to 33 parts. 38 was produced. The obtained black toner no. The physical properties of 38 are shown in Tables 3 and 4.

(Black toner production example 39)
In black toner production example 1, black toner No. 1 was prepared in the same manner as in black toner production example 1, except that the addition amount of styrene was changed to 75 parts and the addition amount of n-butyl acrylate was changed to 25 parts. 39 was produced. The obtained black toner no. The physical properties of 39 are shown in Tables 3 and 4.

(Black toner production example 40)
In black toner production example 1, the additional initiator added at 30 minutes in the granulation step was changed to perbutyl NHP (10-hour half-life temperature 50.6 ° C. (manufactured by NOF Corporation)), and the addition timing was changed to the granulation step. The black toner No. 1 was changed in the same manner as in the black toner production example 1 except that the change was made at 40 minutes. 40 was produced. The obtained black toner no. The physical properties of 40 are shown in Tables 3 and 4.

<Examples 1 to 17, Reference Example 18, Examples 19 to 22, Reference Examples 23 and 24, Example 25, Reference Example 26, Example 27, Reference Example 28, Examples 29 to 33 , Comparative Examples 1 to 7 >
The black toners produced in black toner production examples 1 to 33 were evaluated according to the following criteria. Black toner of each embodiment whereas exerted an excellent effect to the developing durability and low-temperature fixing properties, the black toner of Comparative Examples 1 to 7 was the result poor balance of the developing durability and low-temperature fixability . The evaluation results are shown in Table 5.

  The image evaluation method and evaluation criteria of the present invention will be described below.

As an image forming apparatus, a commercially available laser printer LBP-5400 (manufactured by Canon) was used. Unless otherwise specified, Xerox Co., Ltd. was used as an evaluation paper in an environment of a temperature of 23 ° C. and a relative humidity of 50%. business 4200 (75 g / m ² ) was used.

  The remodeling point of the evaluation machine was remodeled so that the process speed was 220 mm / sec by changing the gear and software of the evaluation machine main body.

  The cartridge used for evaluation was a black cartridge. That is, the product toner was extracted from a commercially available black cartridge, the interior was cleaned by air blow, and then 200 g of the toner according to the present invention was filled for evaluation. In the evaluation of the toner kit, a magenta, yellow, and cyan cartridge filled with 200 g of evaluation toner of a color corresponding to each of the magenta, yellow, and cyan stations was inserted, and a fixed image was evaluated by full-color output. .

Low-temperature fixability Using the modified LBP5400 (manufactured by Canon Inc.) described above, the first printout time was set to 20 seconds, and a solid image of 10 mm × 10 mm (toner applied amount 0.50 mg / cm ² ) was obtained from Xerox. The temperature was output on a manufactured Business 4200 (75 g / m ² ), and the minimum fixing temperature at which a stable fixed image was obtained was evaluated according to the following criteria. The stable fixed image of the present invention is obtained by measuring the density of the obtained fixed image and the image density after rubbing the fixed image with Sylbon paper applied with a load of 50 g / cm ² five times. It is defined as a fixing state with a rate of 10% or less.
A: A stable fixed image can be obtained when the minimum fixable temperature is 150 ° C. or more and 160 ° C. or less. B: A stable fixed image can be obtained when the minimum fixable temperature is higher than 160 ° C. but not more than 170 ° C. C: Minimum fixable A stable fixed image can be obtained when the temperature is higher than 170 ° C. and lower than 190 ° C. D: The minimum fixing temperature is higher than 190 ° C. or has no fixing temperature.

(2) Solid black reproducibility Using a modified LBP5400 (manufactured by Canon Inc.) described above, a solid black image (tip margin: 5 mm, toner loading 0.50 mg / cm ² ) was obtained from Xerox Business 4200 (75 g). / M ² ) was output at the fixing temperature showing the maximum gloss on the image, and the solid black reproducibility in the fixed image was evaluated according to the following visual criteria.
A: The density and brightness of a solid black image are vivid and uniform, and there is no problem at all.
B: Although the brightness unevenness or brightness unevenness of the solid black image can be observed slightly, there is no practical problem.
C: Although the density unevenness and brightness unevenness of the solid black image are confirmed, the image density is at a level with no problem.
D: Level at which density unevenness and lightness unevenness of a solid black image are very conspicuous and a density decrease is seen through which paper fibers can be seen through the entire surface.

(3) Fixing gloss A solid whole area image (tip margin: 5 mm, toner applied amount 0.50 mg / cm ² ) on a Xerox business 4200 (75 g / m ² ), set temperature control at 170 ° C., and process speed at 100 mm / The output was changed to sec, and 75 ° gloss of each section obtained by dividing the inside of the fixed image into nine equal parts was measured, and an average value was obtained and evaluated according to the following criteria. The glossiness measuring instrument used in the present invention uses PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd., and the standard surface uses black glass with a glossiness of 96.9. did.
A: 75 ° gloss average value 23.0 or more B: 75 ° gloss average value 18.0 or more but less than 23.0 C: 75 ° gloss average value 13.0 or more but less than 18.0 D: 75 ° gloss average value 13. Less than 0

(4) Fixing stability The offset in the high temperature range from the minimum fixable temperature when the modified LBP5400 (Canon) described above is used and Xerox's business 4200 (75 g / m ² ) is used as the evaluation paper. The temperature up to the temperature at which the toner is generated is defined as a fixing temperature range, and the fixing stability is evaluated according to the following criteria. The offset generation temperature is increased by 5 ° C in order from the lowest fixable temperature, and a 10-mm x 160-mm horizontal gradation image is output to the tip margin of 5 mm to generate offset. It was confirmed visually.
A: Fixable temperature range is 50 ° C. or higher B: Fixable temperature range is 40 ° C. or higher and lower than 50 ° C. C: Fixable temperature range is 30 ° C. or higher and lower than 40 ° C. D: Fixable temperature range is lower than 30 ° C.

(5) Image fog Toner durability was evaluated by performing a durability test using the modified LBP5400 (manufactured by Canon Inc.) described above (set at a process speed of 220 mm / sec and a sleeve peripheral speed of 330 mm / sec). .

  The durability test is performed under high temperature and high humidity environment (30 ° C, 80% RH), normal temperature and normal humidity environment (23 ° C, 50% RH), and low temperature and low humidity environment (15 ° C, 10% RH). An original image with a ratio of 2% was printed out 3000 sheets a day, and a total of 12000 sheets were output in 4 days. The evaluation timing was every 1000 sheets, and a solid white image was output on the first sheet on each evaluation day, and the following evaluation criteria were used.

  Using “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku Co., Ltd.), the reflectance of the white background portion of the standard paper and the printout image was measured, and the fog (reflectance:%) was calculated by the following formula. The filter was measured with a green filter attached.

In addition, the evaluation criteria judged the worst value through durability with the following criteria.
A: Very good Less than 1.0% B: Good 1.0% or more to less than 2.0% C: No practical problem 2.0% or more to less than 3.0% D: Practical problem 3.0 % Or more fog (reflectance;%) = (reflectance of standard paper;%) − (reflectance of sample;%)

(6) Halftone image reproducibility The halftone horizontal direction in which the image density is 0.4, 0.6, 0.8, or 1.2 in the Macbeth reflection densitometer described later with respect to the transfer paper conveyance direction. An original chart with band images arranged is output, and this image is visually observed. Based on the following criteria, the dot reproducibility and the presence or absence of vertical stripes along the transport direction caused by contamination of the developing blade evaluated.

The durability conditions and the sampling timing were determined in accordance with the above (5) Evaluation of image fog.
A: All halftone images are vivid and uniform, and dots are reproduced with high accuracy.
B: Slight dot disturbance is confirmed in some halftone images, but the level is hardly noticed.
C: Although dot disturbance is confirmed on some halftone images, it is difficult to notice on practical images.
D: Levels that greatly impair the quality of practical images, such as poor dot reproducibility on all halftone images, and images with a gritty impression or vertical streak-like image defects due to contamination of the developing blade. .

(7) Solid density stability evaluation Using Xerox's business 4200 (75 g / m ² ), a solid black patch of 20 mm x 20 mm is placed at the center when the image is divided into 3 parts vertically and horizontally (total 9 parts). The original image was output, and the degree of change in the endurance test of the 9-point average density was evaluated as solid density stability.

  The image density was measured by using “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.

Endurance conditions and sampling timing were determined according to the evaluation of (5) Image fogging, and the maximum density difference with respect to the initial density was evaluated according to the following criteria.
A: Very good Less than 0.10 B: Good 0.10 or more and less than 0.20 C: No practical problem 0.20 or more and less than 0.30 D: Practical problem 0.30 or more

  Hereinafter, the evaluation criteria of the toner kit will be described.

(8) Evaluation of Fixing Stability of Full Color Toner Kit Minimum Fixable Temperature for Each Color Using LBP5400 (Canon) Modified Machine Explained above and Xerox Business 4200 (75 g / m ² ) as Evaluation Paper The offset generation temperature in the high temperature range of each color was measured, the temperature range in which all color toners can be fixed was defined as the fixable temperature range, and the fixing stability of the full color toner kit was evaluated according to the following criteria. The offset generation temperature is increased by 5 ° C in order from the lowest fixable temperature, and a 10-mm x 160-mm horizontal gradation image is output to the tip margin of 5 mm to generate offset. It was confirmed visually.
A: Fixable temperature range is 50 ° C. or higher B: Fixable temperature range is 40 ° C. or higher and lower than 50 ° C. C: Fixable temperature range is 30 ° C. or higher and lower than 40 ° C. D: Fixable temperature range is lower than 30 ° C.

(9) Solid Image Reproducibility of Full Color Toner Kit Using the above-described LBP5400 (Canon) remodeling machine, yellow, magenta, cyan, and black single-color solid images and 200% each of red, green, and blue An original image with a secondary color solid image arranged on one side was output, and the solid fixing quality was evaluated according to the following visual criteria at a fixing temperature at which the color image showed the highest gloss.
A: The density and brightness of each color solid image are vivid and uniform, and exhibit a fixing quality excellent in color balance.
B: In a solid image of either color toner or black toner, density unevenness or brightness unevenness can be slightly observed, but there is no practical problem.
C: In a solid image of either color toner or black toner, density unevenness and lightness unevenness are confirmed, but the image density difference is a level that does not matter.
D: Density unevenness and brightness unevenness are very conspicuous in a solid image of either color toner or black toner, and in particular, density unevenness and brightness unevenness of black toner are extremely bad.

(10) Gloss stability of full-color toner kit Using the above-described modified LBP5400 (manufactured by Canon Inc.), yellow, magenta, cyan, and black single-color solid images and 200% each of red, green, and blue Output the original image with the next color solid image on one side, measure the maximum and minimum values of 75 ° gloss in the fixed image, define the difference as the gloss stability of the full color fixed image, and evaluate it according to the following criteria did. The glossiness measuring instrument used in the present invention uses PG-3D (incident angle θ = 75 °) manufactured by Nippon Denshoku Industries Co., Ltd., and the standard surface uses black glass with a glossiness of 96.9. did.
A: Gloss difference of less than 2.0 B: Gloss difference of 2.0 or more and less than 4.0 C: Gloss difference of 4.0 or more and less than 6.0 D: Gloss difference of 6.0 or more

(Yellow toner production example 1)
In the black toner production example 1, the carbon black to be added is C.I. I. Pigment Yellow 74 was replaced with Yellow Toner No. 1 in the same manner as in Black Toner Production Example 1 except that no additional initiator added in the granulation step was added. 1 (Y-1) was produced. The resulting yellow toe No. The physical properties of No. 1 are shown in Table 6.

(Magenta toner production example 1)
In the black toner production example 1, the carbon black to be added is C.I. I. Pigment Red 122 was changed to Magenta Toner No. 1 in the same manner as in Black Toner Production Example 1 except that no additional initiator added in the granulation step was added. 1 (M-1) was produced. The obtained magenta toe no. The physical properties of No. 1 are shown in Table 6.

(Cyan toner production example 1)
In the black toner production example 1, the carbon black to be added is C.I. I. Pigment Blue 15: 3 and cyan toner No. 1 was prepared in the same manner as in Black Toner Production Example 1 except that no additional initiator added in the granulation step was added. 1 (C-1) was produced. The obtained cyan toe No. The physical properties of No. 1 are shown in Table 6.

(Yellow toner production example 2)
In the yellow toner production example 1, the yellow toner No. 1 was changed in the same manner as in the yellow toner production example 1 except that the addition amount of styrene was changed to 75 parts and the addition amount of n-butyl acrylate was changed to 25 parts. 2 (Y-2) was produced. The obtained yellow toner No. Table 6 shows the physical properties of 2.

(Magenta toner production example 2)
In Magenta Toner Production Example 1, the same procedure as in Magenta Toner Production Example 1 was performed except that the addition amount of styrene was changed to 75 parts and the addition amount of n-butyl acrylate was changed to 25 parts. 2 (M-2) was produced. The obtained magenta toner No. Table 6 shows the physical properties of 2.

(Cyan toner production example 2)
In cyan toner production example 1, cyan toner No. 1 was prepared in the same manner as in cyan toner production example 1, except that the addition amount of styrene was changed to 75 parts and the addition amount of n-butyl acrylate was changed to 25 parts. 2 (C-2) was produced. The obtained cyan toner No. Table 6 shows the physical properties of 2.

(Yellow toner production example 3)
In the yellow toner production example 1, the yellow toner No. 1 was changed in the same manner as in the yellow toner production example 1 except that the addition amount of styrene was changed to 68 parts and the addition amount of n-butyl acrylate was changed to 32 parts. 3 (Y-3) was produced. The obtained yellow toner No. The physical properties of 3 are shown in Table 6.

(Magenta toner production example 3)
In Magenta Toner Production Example 1, the same procedure as in Magenta Toner Production Example 1 was performed except that the amount of styrene added was changed to 68 parts and the amount of n-butyl acrylate added was changed to 32 parts. 3 (M-3) was produced. The obtained magenta toner No. The physical properties of 3 are shown in Table 6.

(Cyan toner production example 3)
In cyan toner production example 1, cyan toner No. 1 was prepared in the same manner as in cyan toner production example 1, except that the addition amount of styrene was changed to 68 parts and the addition amount of n-butyl acrylate was changed to 32 parts. 3 (C-3) was produced. The obtained cyan toner No. The physical properties of 3 are shown in Table 6.

(Yellow toner production example 4)
In the yellow toner production example 1, the yellow toner No. 1 was changed in the same manner as in the yellow toner production example 1 except that the addition amount of styrene was changed to 73 parts and the addition amount of n-butyl acrylate was changed to 27 parts. 4 (Y-4) was produced. The obtained yellow toner No. The physical properties of 4 are shown in Table 6.

(Magenta toner production example 4)
In the magenta toner production example 1, the magenta toner No. 1 was prepared in the same manner as in the magenta toner production example 1 except that the addition amount of styrene was changed to 73 parts and the addition amount of n-butyl acrylate was changed to 27 parts. 4 (M-4) was produced. The obtained magenta toner No. The physical properties of 3 are shown in Table 6.

(Cyan toner production example 4)
In cyan toner production example 1, cyan toner No. 1 was prepared in the same manner as in cyan toner production example 1, except that the addition amount of styrene was changed to 73 parts and the addition amount of n-butyl acrylate was changed to 27 parts. 4 (C-4) was produced. The obtained cyan toner No. The physical properties of 4 are shown in Table 6.

<Example 34 , Reference Example 35, Example 36, and Comparative Example 8>
The black toner manufactured in black toner manufacturing examples 1, 28, and 25, and the color toners manufactured in yellow, magenta, and cyan toner manufacturing examples 1 to 3 are refilled into corresponding color cartridges, respectively, as shown in Table 6. As a combined toner kit, the quality of the full color fixed image was evaluated according to the following criteria.

The toner kit of Example 34 exhibited an excellent effect in a stable fixing region, solid image quality, and gloss balance. The toner kits of Reference Example 35 and Example 36 also showed a generally excellent full color fixed image quality, whereas the toner kit of Comparative Example 8 showed a difference in the optimal fixing temperature range between the color toner and the black toner. The solid black image has a problem of conspicuous uneven density and uneven brightness. Table 7 shows the evaluation results.

It is explanatory drawing showing temperature (P1) which shows the minimum value of the loss tangent (tan-delta) calculated | required by the dynamic viscoelasticity test of the toner of this invention. When the common logarithm (log [Iv]) of viscosity Iv is plotted against the common logarithm (log [Mw]) of absolute molecular weight (Mw) in 135 ° C. GPC-RALLS-viscosimeter analysis of the toner of the present invention. FIG. FIG. 4 is a cross-sectional explanatory view of a process cartridge according to the present invention. It is a schematic block diagram of an example of the apparatus which implements the image forming method of this invention. It is a schematic block diagram of the other fixing apparatus which concerns on this invention. It is a schematic block diagram of the other fixing apparatus which concerns on this invention.

Explanation of symbols

Pa, Pb, Pc, Pd Image forming station 1 (1a to 1d) Photosensitive drum (image carrier)
2 (2a to 2d) Charging means 3 (3a to 3d) Scanner unit 4 (4a to 4d) Developing means 4A Developing unit 5 Electrostatic transfer device 6 (6a to 6d) Cleaning means 7 (7a to 7d) Process cartridge 11 Static Electrotransfer belt 12 (12a to 12d) Transfer roller 13 Belt drive rollers 14a and 14b Driven roller 15 Tension roller 16 Feeding unit 17 Cassette 18 Feeding roller 19 Registration roller 20 Fixing unit 21a Heating roller 21b Pressure roller 22 Adsorption roller 23 Paper discharge roller 24 Paper discharge unit 31 Cleaning frame (cartridge frame)
35 Removal toner storage chamber 40 Developing roller (toner carrier)
41 Toner container (developer storage part)
42 Toner transport mechanism 43 Toner supply roller 44 Toner regulating member (blade)
45 (45a, 45b, 45e) Development frame (cartridge frame)
47, 48 Coupling hole 50 Cleaner unit 51, 64 Heating body 52, 64a Heater substrate 53, 64b Energizing heating resistor (heating element)
54, 64d Temperature detecting element 55, 65 Heat resistant film 56, 57 Belt support roller 58 Support roller 60 Cleaning blade 62 Support roller (rotating body)
63 Belt support 64c Surface protective layer 100 Image forming apparatus main body S Recording medium (recording material sheet)

Claims (14)

A black toner having a toner particle containing a styrene-based binder resin, carbon black, a wax component, and a polar styrene-based resin, and an inorganic fine powder,
In the measurement by the dynamic viscoelasticity test of the black toner,
(I) the maximum value of the loss elastic modulus G ″ is 50 ° C. or more and 62 ° C. or less,
(Ii) When the temperature at which the loss tangent tan δ exhibits the minimum value is the temperature P1, the temperature P1 is 120 ° C. or higher and 155 ° C. or lower,
(Iii) The value tan δ (P1) of tan δ at the temperature P1 is 0.50 or more and 5.00 or less,
(Iv) The value G ′ (P1) of the storage elastic modulus at the temperature P1 is 7.0 × 10 ² Pa or more and 1.0 × 10 ⁴ Pa or less,
(V) When the storage elastic modulus at temperature (P1-20) ° C. is G ′ (P1-20) and the storage elastic modulus at temperature (P1 + 20) ° C. is G ′ (P1 + 20), {LogG ′ ( P1-20) -LogG meets the relationship '(P1)} <{LogG ' (P1) -LogG '(P1 + 20)}, and,
The absolute molecular weight Mw measured by high-temperature GPC-RALLS-viscosity analysis of the orthodichlorobenzene (ODCB) soluble component of the black toner is 4.0 × 10 ⁴ or more and 2.0 × 10 ⁵ or less,
The common logarithm (log [Iv (s)]) of the viscosity Iv (s) of the resin component (s) having an absolute molecular weight (Mw) logarithm (log [Mw]) of 5.00 or more in the analysis is expressed as the absolute molecular weight. When the slope when plotted against the common logarithm of Mw (s) (log [Mw (s)]) is a (s), a (s) is 0.30 or more and 0.70 or less,
The common logarithm (log [Iv (a)]) of the viscosity Iv (a) of all the resin components (a) in the chromatogram detected by the viscometer in the analysis is the common logarithm (log [Mw] of the absolute molecular weight Mw (a). A (s) / a (a) is 0.20 or more and 0.80 or less, where a (a) is the slope when plotted against (a)])
Black toner characterized by the above. The relationship between the storage elastic modulus G ′ (P1-20) and the storage elastic modulus G ′ (P1) is
0.10 ≦ {LogG ′ (P1-20) −LogG ′ (P1)} ≦ 0.65
The black toner according to claim 1, wherein: The black toner according to claim 1, wherein the storage elastic modulus G ′ (P1 + 20) has a value of 1.0 × 10 ² Pa or more and 5.0 × 10 ³ Pa or less. The tan δ (P1 + 20) -tan δ (P1)} is 0.10 or more and 3.00 or less when the loss tangent at the temperature (P1 + 20) ° C. is tan δ (P1 + 20). The black toner according to any one of the above. The value of the storage elastic modulus G ′ (P1), the storage elastic modulus G ′ (P1-20), and the storage elastic modulus G ′ (P1 + 20) are
{G ′ (P1) / G ′ (P1 + 20) −G ′ (P1-20) / G ′ (P1)}> 1.0
Black toner according to any one of claims 1 to 4, satisfy the relationship. The polar styrene resin has an Mw of 8000 to 50,000, an acid value or a hydroxyl value of 3 mgKOH / g to 30 mgKOH / g, and 3.0 parts by mass to 30 parts by mass with respect to 100 parts by mass of the binder resin. black toner according to any one of claims 1 to 5, characterized in that it is contained below 2.0 parts by weight. The black loss modulus G "of the toner has a maximum value at 60 ° C. less than a temperature 52 ° C., one of claims 1 to 6, characterized in that it has a minimum value below 0.99 ° C. temperature of 125 ° C. or higher The black toner according to item 1 . The relationship of the storage modulus of the black toner is
0.05 <[{LogG ′ (P1) −LogG ′ (P1 + 20)} − {LogG ′ (P1-20) −LogG ′ (P1)}] <0.40
The toner according to any one of claims 1 to 7, characterized in that. The relationship of the storage modulus of the black toner is
0.15 ≦ {LogG ′ (P1-20) −LogG ′ (P1)} ≦ 0.60
Black toner according to any one of claims 1 to 8, characterized in that. The loss tangent relationship of the black toner is
0.20 ≦ {tan δ (P1 + 20) −tan δ (P1)} ≦ 2.00
Black toner according to any one of claims 1 to 9, characterized in that. The storage elastic modulus G ′ (P1) is 8.0 × 10 ² Pa or more and 8.0 × 10 ³ Pa or less,
Black toner according to any one of claims 1 to 10 reservoir modulus G '(P1 + 20) is equal to or less than 1.0 × 10 ² Pa or more 1.0 × 10 ³ Pa. Black toner according to any one of claims 1 to 11 wherein the toner a (a), characterized in that 0.50 to 1.40. Black toner according to any one of claims 1 to 12 in the toner a (s) / a (a ) is characterized in that 0.30 to 0.60. Yellow toner having yellow toner particles and inorganic fine powder containing yellow colorant and binder resin, magenta toner having magenta colorant and binder resin, and magenta toner having inorganic fine powder; Full-color image having cyan toner particles containing cyan colorant and binder resin and cyan toner having inorganic fine powder, black toner particles containing carbon black and binder resin, and black toner having inorganic fine powder A toner kit for forming,
The black toner is the black toner according to any one of claims 1 to 13 ,
The maximum values of the loss modulus G ″ measured by the dynamic viscoelasticity test of the yellow toner, the magenta toner, and the cyan toner are all in the range of 50 ° C. to 62 ° C. Is (P1-10), and a temperature higher by 10 ° C. is (P1 + 10), the loss tangent tan δ in the temperature range of (P1-10) to (P1-10) is less than the tan δ of black toner A toner kit for forming a full-color image, which is large and 0.70 or more and 10.00 or less.

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