JP5241089B2 - Non-magnetic toner - Google Patents

Description

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

  Conventionally, many methods are known as electrophotographic methods. In general, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with toner to form a visible image. After the toner is transferred to the recording material (transfer material), the toner image is fixed on the recording material by heat and pressure to obtain a copy. Toner that is not transferred and remains on the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

  In the electrophotographic method, the step of developing the electrostatic charge image is to form an image on the electrostatic charge image by utilizing electrostatic interaction between the charged toner particles and the electrostatic charge image. There are the following developing methods for developing an electrostatic image using toner. Magnetic one-component development method using magnetic toner in which a magnetic material is dispersed in resin, non-magnetic one-component development method in which non-magnetic toner is charged by a charging member such as an elastic blade and developed, and non-magnetic toner A two-component development method mixed with a magnetic carrier.

  At present, electrostatic latent images have become finer due to the development of techniques for exposing a photosensitive member using a small-diameter laser beam or the like. In order to develop the electrostatic latent image faithfully and obtain a higher quality output, both the toner particles and the carrier particles have been reduced in diameter in any of the development methods described above. In particular, it is often performed to improve the image quality by reducing the average particle diameter of the toner.

  Reducing the average particle diameter of the toner is an effective means for improving the graininess and character reproducibility, particularly among the image quality characteristics. There are problems to be improved in fusing, toner scattering, and the like.

  This is considered to be because the charge amount of the toner decreases due to the following two points. Due to long-term use of the toner, deterioration of the external additive added to the toner particles occurs, and a charging member such as a sleeve and a carrier, and a regulating member for keeping the coatability of the toner on the sleeve at a predetermined amount It is contaminated by toner and external additives, that is, spent. This phenomenon is likely to occur when the diameter of the toner is reduced. More specifically, friction charging is performed by a physical external force such as contact and collision between the toner and the sleeve in the case of a one-component developer and between the toner and the carrier in the case of a two-component developer. (Sleeve carrier) and all the regulating members will be damaged. For example, in the toner, an external additive added to the surface of the toner is embedded in the toner, or the toner component falls off. In the charge imparting member and the regulating member, the toner component including the external additive is contaminated, and the coating component coated on the charge imparting member in order to properly stabilize the charge is worn or destroyed. Furthermore, the photosensitive member and the charging member of the photosensitive member are contaminated by the external additive released from the toner. These damages cannot maintain the initial characteristics of the developer as the number of times of printing increases, and cause fogging, in-machine contamination, and fluctuations in image density.

By the way, a large number of cases in which a release agent is contained in toner particles have been disclosed (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3).
The release agent is used for improving the offset resistance at the time of fixing the toner at a low temperature or at a high temperature and for improving the fixability at the time of fixing at a low temperature. On the other hand, the blocking resistance of the toner is lowered, or the developing property of the toner is lowered by the temperature rise in the developing device. In addition, when the toner is left for a long period of time, the mold release agent oozes out on the surface of the toner particles, so that developability is lowered.

Further, proposals have been made to enable oilless fixing by defining the elastic modulus of the release agent-containing toner (see Patent Document 4 and Patent Document 5). These gazettes describe an invention in which both transparency of OHP and high-temperature offset resistance are achieved by defining viscoelasticity in the vicinity of fixing set temperatures of 150 ° C. and 170 ° C.
Furthermore, it is disclosed that both low temperature fixability and offset resistance can be achieved by defining viscoelasticity in two temperature ranges of 60 to 80 ° C. and 130 to 190 ° C. (Patent Documents 6 and 7). , See Patent Document 8).
Further, with respect to the viscoelastic properties of the toner, by specifying the maximum value and the minimum value of the loss tangent (tan δ), which is the ratio of the storage elastic modulus (G ′) and the loss elastic modulus (G ″), further fixing properties are achieved. It has been disclosed that both improvement in image quality and developability can be achieved (see, for example, Patent Document 9, Patent Document 10, and Patent Document 11).

However, there is still a problem with respect to providing long-term stable developability at the time of temperature rise in the developing device by continuous paper feeding while maintaining good fixability.
Japanese Patent Laid-Open No. 3-50559 Japanese Patent Laid-Open No. 2-79860 JP-A-1-109359 JP-A-6-59502 Japanese Patent Laid-Open No. 8-54750 JP-A-9-34163 JP 2002-13196 A JP 2004-333968 A JP 2004-151638 A JP 2004-157342 A JP 2004-264484 A

An object of the present invention is to provide a toner having excellent fixability and developability.
More specifically, the object of the present invention is to maintain a good low-temperature fixing property and high glossiness even at high speeds, and even if a large number of sheets are continuously printed, the charging member / regulating member, the charging member of the photoreceptor, It is an object of the present invention to provide a toner that is less likely to be contaminated, has a stable image density, and provides an image having excellent durability and stability without fog.

The present invention for solving the above problems is as follows.
<1> In a non-magnetic toner having toner particles containing at least a binder resin, a colorant, and a wax component, and an inorganic fine powder.
The toner particles are
(I) In a water-based medium, a polymerizable monomer composition containing a vinyl polymerizable monomer, a low molecular weight polymer, the colorant, and the wax component is dispersed.
(Ii) granulating the dispersed polymerizable monomer composition;
(Iii) polymerizing the vinyl polymerizable monomer contained in the granulated particles;
It was obtained by
The wax component has a maximum endothermic peak in a temperature range of 60 to 120 ° C. in a DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus,
The low molecular weight polymer may be a low molecular weight polystyrene, a low molecular weight styrene-acrylate copolymer, or a low molecular weight styrene having a weight average molecular weight (Mw) of 2000 to 5000 as measured by gel permeation chromatography (GPC). A methacrylate ester copolymer,
The storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. of the toner is 9.80 × 10 ⁴ to 1.80 × 10 ⁵ dN / m ^2.
The storage elastic modulus (G ′ ₁₅₀ ) at 150 ° C. is 4.50 × 10 ³ to 1.90 × 10 ⁴ dN / m ² ,
In the differential curve obtained by differentiating the temperature-storage elastic modulus curve with temperature, with the horizontal axis representing temperature and the common logarithm Log G ′ of storage elastic modulus G ′ representing the vertical axis,
The temperature that becomes the minimum value of the differential curve in the temperature range of 60 to 130 ° C. is T ₀ .
Draw a straight line connecting the point on the differential curve at temperature T ₀ + a (° C.) and the point on the differential curve at temperature (T ₀ + a) +1 (° C.), where a is an integer from 0 to 9, and the slope is A straight line when it becomes the largest is A,
Points on the differential curve at temperature T ₀ + b (° C.) and temperature (T ₀ + b) +10 (° C.)
b is an integer greater than or equal to 0], a straight line connecting the points on the differential curve is drawn, and the straight line when the slope becomes the smallest is B,
Points on the differential curve at temperature T ₀ + c (° C.) and temperature (T ₀ + c) +10 (° C.)
When c is a straight line connecting points on the differential curve in (an integer larger than b when the straight line B is given)], and the straight line when the inclination is largest is C,
The temperature range ΔT _A from T ₀ to the intersection of the straight lines A and B is 1 ° C. ≦ ΔT _A ≦ 20 ° C.
The temperature T _{BC at} the intersection of the straight line B and the straight line C is 100 ° C. ≦ T _BC ≦ 120 ° C.
A non-magnetic toner characterized by
<2> The loss tangent (tan δ) represented by the ratio (G ″ / G ′) of the loss elastic modulus (G ″) to the storage elastic modulus (G ′) of the non-magnetic toner is in the range of 68 to 85 ° C., and Each has a maximum value (P0 · P1) in the range of 110 to 135 ° C.,
The nonmagnetic toner according to <1>, wherein a difference between a loss tangent maximum value tan δ _p1 existing in a range of 110 to 135 ° C. and a loss tangent tan δ ₁₇₀ of 170 ° C. is 0.60 or more.
<3> are the storage modulus at 80 ° C. of the non-magnetic toner 'storage modulus at 100 ° C. of ₍₈₀ (G G)' ratio _{100) (G '80 / G} ' 100) is 10 to 30,
The storage modulus at 100 ° C. of the non-magnetic toner (G _'100) a storage modulus at 120 ° C. of (G' ratio _{120) (G '100 / G} ' 120) is 5 to 20,
Wherein the storage modulus at 120 ° C. of the non-magnetic toner 'storage modulus at 0.99 ° C. of ₍₁₂₀ (G G)' ratio _{150) (G '120 / G} ' 150) is 3 to 10 The nonmagnetic toner according to <1> or <2>.
<4> the low molecular weight polymer, non-magnetic toner according to any one of the glass transition temperature and wherein a 52 to 58 ° C. der benzalkonium <1> to <3>.
<5> The nonmagnetic toner according to any one of <1> to <4>, wherein the toner particles are produced in an aqueous medium.
<6> The toner particles are prepared by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a wax component in an aqueous medium, and granulating the polymerizable monomer composition. The nonmagnetic toner according to any one of <1> to <5>, which can be obtained by

  By using a toner containing a wax component and having specific rheological properties, it is excellent in low-temperature fixability and high glossiness, and even when a large number of continuous prints are performed, a decrease in developability is suppressed, Contamination of the charge imparting member / regulating member and the charging member of the photosensitive member hardly occurs, the image density is stable, and an image excellent in durability stability without fog is obtained.

The toner of the present invention is a non-magnetic toner having toner particles containing at least a binder resin, a colorant, and a wax component, and an inorganic fine powder. The toner has a storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. of the toner. 2.00 × 10 ^{4 to} 2.00 × 10 ⁵ dN / m ² , and storage elastic modulus (G ′ ₁₅₀ ) at 150 ° C. is 3.00 × 10 ^{3 to} 2.00 × 10 ⁴ dN / m ² , In the differential curve obtained by differentiating the temperature-storage elastic modulus curve with the temperature on the horizontal axis and the common logarithm LogG ′ of the storage elastic modulus G ′ on the vertical axis, the minimum value of the differential curve in the temperature range of 60 to 130 ° C. the composed temperature of _{T 0,} temperature _T 0 + a point and the temperature on the differential curve at _{(℃) (T 0 + a} ) +1 (℃) [provided that, a an integer from 0 to 9] and a point on the differential curve at Draw a straight line, and the slope becomes the largest Straight lines A, the temperature T _{0 +} b point and the temperature on the differential curve at _{(℃) (T 0 + b} ) +10 (℃) [where, b is an integer of 0 or more] when connecting a point on the differential curve at A straight line is drawn, and the straight line when the slope becomes the smallest is B, the point on the differential curve at the temperature T ₀ + c (° C.) and the temperature (T ₀ + c) +10 (° C.), where c is the straight line B The temperature range from T ₀ to the intersection of straight lines A and B, where C is the straight line connecting the points on the differential curve in (an integer greater than b when given) ΔT _A is 1 ° C. ≦ ΔT _A ≦ 20 ° C., and the temperature T _{BC at} the intersection of the straight line B and the straight line C is 100 ° C. ≦ T _BC ≦ 120 ° C.

The toner of the present invention contains a wax component, the storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. of the toner is 2.00 × 10 ⁴ to 2.00 × 10 ⁵ dN / m ² , and the storage elastic modulus at 150 ° C. When (G ′ ₁₅₀ ) is 3.00 × 10 ^{3 to} 2.00 × 10 ⁴ dN / m ² , the toner exhibits good low-temperature fixability and releasability. Furthermore, since the differential curve obtained by differentiating the common logarithm LogG ′ of the storage elastic modulus G ′ with temperature has the characteristics as in the present invention, it is possible to suppress a decrease in developability even when the temperature in the developing device is increased due to continuous paper feeding. be able to.

When G ′ ₁₁₀ is less than 2.00 × 10 ⁴ dN / m ² or G ′ ₁₅₀ is less than 3.00 × 10 ³ dN / m ² , the charge imparting member Toner fusion is likely to occur on the regulating member. On the other hand, when G ′ ₁₁₀ exceeds 2.00 × 10 ⁵ dN / m ² , or when G ′ ₁₅₀ exceeds 2.00 × 10 ⁴ dN / m ² , the external additive released from the toner The charging member / regulating member and the charging member of the photosensitive member are easily contaminated.

Normally, when the temperature inside the developing device rises due to continuous paper passing, the toner is caused by a physical external force such as contact / collision with a charging member or a regulating member for keeping the toner coating amount on the sleeve at a predetermined amount, Often gets damaged.
As shown in FIG. 1, the toner of the present invention has a temperature T at which the differential curve obtained by differentiating the common logarithm LogG ′ of the storage elastic modulus G ′ of the toner with respect to temperature is the minimum value of the differential curve in the temperature range of 60 to 130 ° C. _The straight lines A, B and C as described above can be drawn on the high temperature side from the temperature T ₀ .
Further, in the toner of the present invention, the straight line B and the straight line C have an intersection (T _BC ) at 100 to 120 ° C. That is, having an intersection (T _BC ) in this temperature range means that the storage elastic modulus of the toner is not suddenly reduced unilaterally, but the storage elastic modulus is lowered while suppressing the sudden decrease of the storage elastic modulus. (It may rise slightly). Therefore, T ₀ + ΔT _A ~
In a temperature range of T _BC, will have an area suitable storage modulus G 'is maintained. This temperature range is a temperature range in which the surface temperature of the toner carrier, the photosensitive member, and their peripheral members can be reached when continuous image formation is performed. Will be served. In such a temperature range, the toner is likely to be damaged when subjected to a physical external force. However, since the storage modulus G ′ of the toner of the present invention is moderately high in this temperature range, the toner is not easily damaged by the physical external force. Occurrence of toner component falling off is suppressed. In addition, embedding and separation of the external additive from the toner surface are less likely to occur. Therefore, it is presumed that the toner configuration is effective for preventing contamination of the toner carrier, the photoreceptor, and their peripheral members (charging member, toner regulating member, etc.). Furthermore, since the initial characteristics of the toner and each member can be maintained, the toner of the present invention can provide an image having excellent durability stability without causing fogging and fluctuations in image density.

In the toner of the present invention, 1 ° C. ≦ ΔT _A ≦ 20 ° C., 100 ° C. ≦ T _BC ≦ 120 ° C. When ΔT _A > 20 ° C., the external additive is easily released from the toner, and the charge imparting member / regulating member and the charging member of the photosensitive member are contaminated by the free external additive. When T _BC <100 ° C., the external additive is easily embedded in the toner surface, and when T _BC > 120 ° C., the external additive is easily released from the toner, and the low temperature fixability is deteriorated. End up.

The storage elastic modulus, ΔT _A and T _BC used in the present invention will be described.

In the present invention, the storage elastic modulus G ′ and loss elastic modulus G ″ of the toner are obtained by ordinary dynamic viscoelasticity measurement, and the loss tangent (tan δ) is the storage elastic modulus (G ′) of the loss elastic modulus (G ″). It is calculated by taking the ratio to. For example, in this application, it calculated | required with the following method.
A rotating plate rheometer (trade name: ARES, manufactured by TA INSTRUMENTS) is used as a measuring device. As the measurement sample, a disk-shaped sample of toner having a diameter of 7.9 mm and a thickness of 2.0 ± 0.3 mm is pressure-molded with a tablet molding machine at 25 ° C. Mount the sample on the parallel plate of the measuring device, raise the temperature from room temperature (25 ° C) to 120 ° C in 15 minutes, adjust the shape of the disk, cool to the measurement start temperature of viscoelasticity, and start measurement To do.

The measurement is performed under the following conditions.
1. Use a parallel plate with a diameter of 7.9 mm.
2. The frequency is set to 1.0 Hz.
3. Set the applied strain initial value (Strain) to 0.1%.
4. Measure between 30 and 200 ° C. at a ramp rate of 2.0 ° C./min.
5. Set Max Applied Strain to 20.0%.
6. The maximum torque (Max Allowed Torque) is set to 200.0 g · cm, and the minimum torque (Min Allowed Torque) is set to 0.2 g · cm.
7. Set the strain adjustment to 20.0% of Current Strain.
8. Set Automatic Tension Direction (Auto Tension Direction) as compression (Compression).
9. Set the initial static force (Initial Static Force) to 10.0 g and the automatic tension sensitivity (Auto Tension Sensitivity) to 40.0 g.
10. The operating condition of the automatic tension (Auto Tension) is 1.0 × 10 ³ (Pa) or more for the sample modulus.
11. Capture measurement data at 30 second intervals.

The measurement result of the storage elastic modulus G ′ is plotted on a temperature-storage elastic modulus with the temperature as the horizontal axis and the common logarithm log G ′ of the storage elastic modulus G ′ as the vertical axis. After plotting, the temperature-storage modulus curve is obtained by smoothly connecting the points. Next, the slope of the obtained temperature-storage modulus curve is obtained, and a differential curve obtained by differentiating the common logarithm LogG ′ with temperature is graphed (for example, see FIG. 1). Specifically, the slope of the temperature-storage elastic modulus curve has a certain temperature t (° C.) and t + 1 (° C.) [t is an integer. ], For example, if the slope is between the temperature t (° C.) and t + 1 (° C.), it is used as the differential value at the temperature t + 0.5 (° C.). Then, after the differential value is calculated in the entire temperature range, the differential curve is obtained by plotting the temperature with the horizontal axis and the differential value with the vertical axis and connecting them smoothly. In the obtained differential curve, the temperature that is the minimum value of the differential curve in the temperature range of 60 to 130 ° C. is T ₀ . Next, a straight line connecting the point on the differential curve at the temperature T ₀ + a (° C.) and the point on the differential curve at the temperature (T ₀ + a) +1 (° C.) is drawn, and the straight line when the gradient becomes maximum is drawn. A (where a is an integer of 0 to 9). Furthermore, a straight line connecting a point on the differential curve at temperature T ₀ + b (° C.) and a point on the differential curve at temperature (T ₀ + b) +10 (° C.) is drawn,
A straight line when the inclination becomes the smallest is B (where b is an integer of 0 or more). A straight line connecting the point on the differential curve at the temperature T ₀ + c (° C.) and the point on the differential curve at the temperature (T ₀ + c) +10 (° C.) is drawn, and the straight line when the gradient becomes maximum is C and (Where c is an integer greater than b when the straight line B is given).

  In addition, when it is difficult to tie temperature-storage elastic modulus plot smoothly, you may perform smoothing processing which combined 3 or 5 points | pieces about the measured value, and may make it easy to tie it smoothly. Smoothing that combines three points means that smoothing processing is performed using an average value of three points that are a certain measurement point and one point before and after that.

In addition to the above characteristics, the toner of the present invention has a loss tangent (tan δ) represented by a ratio (G ″ / G ′) of the loss elastic modulus (G ″) to the storage elastic modulus (G ′) of the nonmagnetic toner of 68. It is preferable to have maximum values (P0 · P1) in the range of ˜85 ° C. and in the range of 110 to 135 ° C., respectively.
In the toner of the present invention, the temperature (T _P0 ) at which the loss tangent (tan δ) reaches a maximum in the range of 68 to 85 ° C. corresponds to the temperature at which the resin component of the toner transitions from a glass state to a heat denatureable state. It is closely related to the toner fixability. When it has a maximum value only in a range of less than 68 ° C., the hot offset resistance and storage stability cannot be satisfied, and when it has a maximum value only in a range of more than 85 ° C., low-temperature fixability may not be achieved. In the toner of the present invention, since the loss tangent (tan δ) has a maximum value in the range of 68 to 85 ° C., the hot offset resistance and the low-temperature fixability are compatible, and good fixability is exhibited.
Further, the toner of the present invention has a maximum value in the loss tangent (tan δ) range of 68 to 85 ° C., and further has a maximum value in the range of 110 to 135 ° C. (the temperature at this time is T _P1 ). It is preferable to have. This is because when a physical external force is applied in the vicinity of 110 to 135 ° C., it is easily deformed moderately and hardly deteriorates due to elasticity. When the temperature rises in the developing device remarkably occurs, the toner is damaged by physical external force such as contact / collision with each member and heat generation, particularly at the time of high-speed continuous paper passing in the contact development system. In many cases, for the above reasons, the toner of the present invention has both ease of deformation and resistance to deterioration, so that toner fusion is suppressed, and a charge imparting member / regulating member with a free external additive, and Contamination of the charging member of the photoreceptor can be suppressed.

Further, the toner of the present invention has a maximum value tan of the loss tangent existing in the range of 110 to 135 ° C.
The difference between δ _P1 and the loss tangent tan δ ₁₇₀ at 170 ° C. is preferably 0.60 or more. This is because an image having high glossiness can be provided while maintaining anti-offset property at around 170 ° C. (near the fixing temperature) while suppressing contamination of each member by toner fusion and free external additives. If it is less than 0.60, offset resistance cannot be satisfied.

The toner of the present invention is storage modulus at 80 ° C. of the toner 'storage modulus at 100 ° C. of ₍₈₀ (G G)' ratio _{100) (G '80 / G} ' 100) is from 10 to 30 preferable. If G ′ ₈₀ / G ′ ₁₀₀ is less than 10, the toner may be fused without being able to withstand the pressure and rubbing force in the developing device. If G ′ ₈₀ / G ′ ₁₀₀ is greater than 30, external additives are likely to be released in addition to toner fusion due to the pressure and rubbing force in the developing device, and the charge imparting member and the regulating member are likely to be contaminated.

In the toner of the present invention, the ratio (G ′ ₁₀₀ / G ′ ₁₂₀ ) of the storage elastic modulus (G ′ ₁₀₀ ) at 100 ° C. to the storage elastic modulus (G ′ ₁₂₀ ) at 120 ° C. is 5 to 20. preferable. When G ′ ₁₀₀ / G ′ ₁₂₀ is less than 5, it tends to cause deterioration of low-temperature fixability. When G ′ ₁₀₀ / G ′ ₁₂₀ is greater than 20, the inside of the developing device is significantly contaminated by toner fusion.

The toner of the present invention is storage modulus at 120 ° C. of the toner 'storage modulus at 0.99 ° C. of ₍₁₂₀ (G G)' ratio _{150) (G '120 / G} ' 150) is 3 to 10 preferable. When G ′ ₁₂₀ / G ′ ₁₅₀ is less than 3, it tends to cause deterioration in low-temperature fixability. If G ′ ₁₂₀ / G ′ ₁₅₀ is greater than 10, offset resistance during durability may be reduced.

That is, the toner of the present invention can be controlled to have physical properties of G ′ ₈₀ / G ′ ₁₀₀ = 10 to 30, G ′ ₁₀₀ / G ′ ₁₂₀ = 5 to 20, and G ′ ₁₂₀ / G ′ ₁₅₀ = 3 to 10. preferable. In this way, by controlling the physical properties of the toner, while maintaining low temperature fixability, in addition to suppressing deterioration of developability even when the temperature inside the developing device is increased by continuous paper feeding, offset resistance during durability The toner is also excellent.

The storage elastic modulus (G ′), loss elastic modulus (G ″) and ΔT _A , T _BC defined above are controlled by controlling the prescription of the resin component, the amount of polymerization initiator at the time of polymerization, the reaction temperature, and the like. Adjust as appropriate.

The toner of the present invention is a non-magnetic toner having toner particles containing at least a binder resin, a colorant, and a wax component, and an inorganic fine powder.
The toner particles used in the present invention may be produced by any method, but may be produced by a production method of granulating in an aqueous medium such as a suspension polymerization method, an emulsion polymerization method, or a suspension granulation method. It is preferable to obtain. In the case of a toner manufactured by a general pulverization method, it is very technically difficult to add a large amount of a wax component to toner particles. In the production method of granulating toner particles in an aqueous medium, even if a large amount of a wax component is added to the toner particles, the wax component does not exist on the toner surface and can be encapsulated in the toner particles. Among these production methods, the suspension polymerization method is one of the most preferred production methods from the viewpoint of long-term development stability due to the inclusion of the wax component in the toner particles and the production cost such that no solvent is used.

Hereinafter, the most suitable suspension polymerization method for obtaining the toner particles used in the present invention will be exemplified and the production method of the toner particles will be described. A polymerizable monomer, a colorant, a wax component, and other additives as required are uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. A polymerization initiator is dissolved in to prepare a polymerizable monomer composition. Next, toner particles are manufactured by suspending the polymerizable monomer composition in an aqueous medium containing a dispersant and performing polymerization. As described above, the polymerization initiator may be mixed immediately before being suspended in the aqueous medium, or may be added at the same time when other additives are added to the polymerizable monomer. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction.

  The wax component used in the present invention is preferably a hydrocarbon wax, and the preferred content thereof is 4 to 15 parts by mass, more preferably 5 to 12 parts by mass with respect to 100 parts by mass of the binder resin. When the content of the wax component is less than 4 parts by mass, the effect of releasability at the time of fixing cannot be sufficiently exerted, and when the temperature of the fixing body becomes low, the transfer paper is easily wound. On the other hand, when the amount is larger than 15 parts by mass, the charge imparting member and the photosensitive member due to the wax component are significantly contaminated, and a problem such as fogging and fusion tends to occur.

  The wax component preferably has a maximum endothermic peak in the temperature range of 60 to 120 ° C., more preferably 62 to 110 ° C., in the DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus. More preferably, it is 65-90 degreeC. When the maximum endothermic peak temperature is less than 60 ° C., the storage stability of the toner and the developability such as fogging are deteriorated. On the other hand, when the maximum endothermic peak temperature exceeds 120 ° C., the plastic effect imparted to the toner is small and the low-temperature fixability is poor.

  The wax component preferably has a weight average molecular weight (Mw) of 300 to 4,000, more preferably 500 to 2,000. When Mw is less than 300, the effect as a wax does not work sufficiently, and toner fixation and scratches on the fixing member are likely to occur. When Mw exceeds 4,000, OHP permeability tends to deteriorate.

  Specific examples of hydrocarbon waxes used in the present invention include paraffin wax, microcrystalline wax, petroleum wax such as petrolatum and derivatives thereof, Fischer-Tropsch wax and derivatives thereof by Fischer-Tropsch method, and polyethylene. Examples thereof include polyolefin wax and derivatives thereof. Derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Also included are hardened castor oil and derivatives thereof, vegetable waxes and animal waxes. These wax components may be used alone or in combination of two or more.

  Among these, when the hydrocarbon wax by the Fischer-Tropsch method is used, the high temperature offset property can be kept good particularly while maintaining the developability in contact development well over a long period of time. These hydrocarbon waxes may contain an antioxidant within a range that does not affect the chargeability of the toner.

The wax component used in the present invention preferably includes a hydrocarbon-based wax, but as other wax components, amide wax, higher fatty acid, long chain alcohol, ketone wax, ester wax, and graft compounds and block compounds thereof. Derivatives such as these may be mentioned, and two or more wax components may be used in combination as required.
Among the above wax components, ester waxes represented by the following general formulas (A) to (C) are more preferable.

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ_１及びＲ_２は炭素数が１〜４０の有機基であり、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

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

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ_１は炭素数が１〜４０の有機基を示し、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

(In the formula, a and b represent an integer of 0 to 4, a + b represents 4, R ₁ represents an organic group having 1 to 40 carbon atoms, n and m represent an integer of 0 to 40, and n And m are never 0 at the same time.)

（式中、ａ及びｂは０〜３の整数を示し、ａ＋ｂは１〜３の整数であり、ｋは１〜３の整数であり、ａ＋ｂ＋ｋは４であり、Ｒ_１及びＲ_２は炭素数が１〜４０の有機基であり、Ｒ_３は炭素数が１以上の有機基を示し、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

(Wherein, a and b represent an integer of 0 to 3, a + b is an integer of 1 to 3, k is an integer of 1 to 3, a + b + k is 4, and R ₁ and R ₂ are carbon numbers. Is an organic group having 1 to 40, R ₃ is an organic group having 1 or more carbon atoms, n and m are integers of 0 to 40, and n and m are not 0 at the same time.)

  Examples of the binder resin used in the present invention include commonly used styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, styrene-butadiene copolymers, and the like. As the polymerizable monomer, a vinyl polymerizable monomer capable of radical polymerization can be used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used.

Specific examples of the polymerizable monomer used in the binder resin include styrene; styrene monomers such as o-methylstyrene, m-methylstyrene, p-methylstyrene, m-ethylstyrene, and p-ethylstyrene. Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, dodecyl acrylate, dodecyl methacrylate, acrylic Stearyl acid, stearyl methacrylate, behenyl acrylate, behenyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, diethylaminoethyl acrylate, Acrylic acid ester monomers or methacrylic acid ester monomers such as diethylaminoethyl tacrylate; ene monomers such as butadiene, isoprene, cyclohexene, acrylonitrile, methacrylonitrile, acrylic acid amide, and methacrylic acid amide are preferred. included.

  These may be used alone or in general so that the theoretical glass transition temperature (Tg) described in the publication Polymer Handbook 2nd edition III-p139-192 (John Wiley & Sons) is 40-75 ° C. It is used by appropriately mixing the monomer. When the theoretical glass transition temperature is less than 40 ° C., problems are likely to occur from the viewpoint of storage stability and durability stability of the toner, whereas when it exceeds 75 ° C., the transparency of the OHP image is lowered.

When the toner of the present invention is produced, it is preferable to add a low molecular weight polymer in order to derive the rheological properties of the present invention. The low molecular weight polymer can be added when melt-kneading with other resin components or the like when the toner is produced by a pulverization method. It can be added to the monomer composition. The low molecular weight polymer has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) in the range of 2,000 to 5,000, and Mw / Mn of less than 4.5, preferably Those less than 3.0 are preferred. The low molecular weight polymer preferably has a glass transition temperature of 52 to 58 ° C. The low molecular weight polymer functions as a binder resin.
Examples of the low molecular weight polymer include low molecular weight polystyrene, low molecular weight styrene-acrylic acid ester copolymer, and low molecular weight styrene-methacrylic acid ester copolymer.

In the present invention, a polar resin such as a polyester resin or a polycarbonate resin can be used in combination with the above-described binder resin.
For example, when a toner is directly produced by suspension polymerization or the like, when a polar resin is added during the polymerization reaction from the dispersion step to the polymerization step, a polymerizable monomer composition that becomes toner particles and an aqueous dispersion medium are exhibited. Depending on the polarity balance, the presence state of the polar resin can be controlled so that the added polar resin forms a thin layer on the surface of the toner particles or exists with a gradient from the toner particle surface toward the center. . At this time, by using a polar resin having an interaction with the colorant, it is possible to make the presence state of the colorant in the toner a desirable form.

  A preferable addition amount of the polar resin is 1 to 25 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 1 part by mass, the presence state of the polar resin in the toner particles becomes non-uniform. Conversely, if the amount exceeds 25 parts by mass, the thin layer of the polar resin formed on the surface of the toner particles becomes thick.

  Specific examples of the polar resin used in the present invention include polyester resins, epoxy resins, styrene-acrylic acid copolymers, styrene-methacrylic acid copolymers, and styrene-maleic acid copolymers. In particular, as a polar resin, a polyester resin having a peak molecular weight of 3,000 to 10,000 is preferable because the fluidity, negative frictional charging characteristics, and transparency of toner particles can be improved.

  In the present invention, a crosslinking agent may be used when the binder resin is synthesized in order to increase the mechanical strength of the toner particles and to control the molecular weight of the toner particles.

  As the crosslinking agent used in the present invention, difunctional linking agents such as 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 Japan Drugs), and include those instead dimethacrylate above diacrylate.

  Polyfunctional crosslinkers include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate and its methacrylate, 2,2-bis (4-methacryloxypolyethoxy) Phenyl) propane, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate. The addition amount of these crosslinking agents is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the polymerizable monomer.

Specific examples of the polymerization initiator include 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 1,1′-azobis ( Cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azo or diazo polymerization initiators such as azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, Peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide, lauroyl peroxide, tert-butyl-peroxypivalate are included.
Although the usage-amount of these polymerization initiators changes with the target degree of polymerization, generally it is 3-20 mass parts with respect to 100 mass parts of polymerizable monomers. The kind of the polymerization initiator varies slightly depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

  The toner of the present invention contains 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.

  As the organic pigment or organic dye as the cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, a basic dye lake compound, or the like can be used. Specifically, C.I. 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. And CI Pigment Blue 66.

As organic pigments or organic dyes as magenta colorants, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds are used. . Specifically, C.I. 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. And CI 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. Specifically, C.I. 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. And CI Pigment Yellow 194.

  As the black colorant, carbon black, and one that is toned to black using the yellow / magenta / cyan colorant is used.

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.

In the present invention, when a toner is obtained using a polymerization method, it is necessary to pay attention to the polymerization inhibitory property and water phase transfer property of the colorant, and preferably a material that does not inhibit surface modification, for example, polymerization inhibition. It is better to apply a hydrophobizing treatment to the colorant. In particular, dyes and carbon blacks have many polymerization inhibiting properties, so 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.
Carbon black may be treated with a substance that reacts with the surface functional groups of carbon black, such as polyorganosiloxane, in addition to the same treatment as the above dye.

As the dispersant used in preparing the aqueous dispersion medium, known inorganic and organic dispersants can be used.
Specifically, examples of inorganic dispersants include tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, Examples include calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. 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 sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate.

As the dispersant used when preparing the aqueous dispersion medium, an inorganic poorly water-soluble dispersant is preferable, and it is preferable to use a poorly water-soluble inorganic dispersant that is soluble in an acid.
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 -2.0 mass parts. Moreover, in this invention, it is preferable to prepare an aqueous dispersion medium using 300-3,000 mass parts water with respect to 100 mass parts of polymerizable monomer compositions.

  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. .

  In the toner of the present invention, a charge control agent can be mixed with toner particles and used as necessary. By adding a charge control agent, the charge characteristics can be stabilized, and the optimum triboelectric charge amount can be controlled according to the development system.

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

As examples of charge control agents, organic metal compounds and chelate compounds are effective for controlling the toner to be negatively charged. Monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, Oxycarboxylic acid and dicarboxylic acid metal compounds are included. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Further, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, resin charge control agents, and the like are also included.
Examples of charge control agents that control toner to be positively charged include nigrosine-modified products of nigrosine and fatty acid metal salts; guanidine compounds; imidazole compounds; tributylbenzylammonium-1-hydroxy-4-naphthosulfone. Acid salts, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts and analogs thereof, and lake pigments thereof; triphenylmethane dyes and lake lake pigments (as lake agents) Phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, dicyclo Hexyl tin oxide, and the like of the diorganotin oxide; dibutyl tin borate, dioctyl tin borate, such as diorganotin tin borate such dicyclohexyl tin borate; 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.

An inorganic fine powder is added as a fluidizing agent to the toner particles of the present invention.
Examples of the inorganic fine powder added to the toner particles of the present invention include fine powders such as silica, titanium oxide, alumina, or double oxides thereof. Among the inorganic fine powders, titanium oxide is preferable.

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

  The preferred number average primary particle diameter of the inorganic fine powder is 4 to 80 nm, and the preferred addition amount is 0.1 to 4.0% by mass with respect to the whole toner.

If the number average primary particle diameter of the inorganic fine powder is larger than 80 nm, good toner fluidity cannot be obtained, and the toner particles are likely to be non-uniformly charged, and the triboelectric chargeability under low humidity is poor. It leads to equalization. For this reason, problems such as an increase in fog, a decrease in image density or a decrease in durability are inevitable.
When the number average primary particle size of the inorganic fine powder is smaller than 4 nm, the agglomeration between the inorganic fine particles is strengthened, and the inorganic fine powder is not a primary particle but has a strong agglomeration that is difficult to break even by crushing treatment. It becomes easy to behave as a wide aggregate. Such inorganic fine powder is liable to cause image defects due to development of the aggregates, damage to the image carrier or toner carrier, and the like.
In order to make the charge distribution of the toner particles more uniform, the number average primary particle diameter of the inorganic fine powder is more preferably 6 to 35 nm.

  The number average primary particle size of the inorganic fine powder is determined by the image of the toner magnified by the scanning electron microscope and the elemental analysis means such as an X-ray microanalyzer (XMA) attached to the scanning electron microscope. By measuring 100 or more primary particles of inorganic fine powder adhering to or liberating from the toner surface and comparing the photograph of the toner to which the contained element is mapped, the number average primary particle diameter is obtained. It can be measured.

The addition amount of the inorganic fine powder having a number average primary particle size of 4 to 80 nm is preferably 0.1 to 4.0 parts by mass with respect to 100 parts by mass of the toner particles, and the addition amount is less than 0.1 parts by mass. However, the effect is not sufficient, and if it exceeds 4.0 parts by mass, the fixing property is deteriorated.
The content of the inorganic fine powder can be quantified using a calibration curve prepared from a standard sample using fluorescent X-ray analysis.

  The inorganic fine powder is added to improve the fluidity of the toner and to make the toner base particles uniformly charged. Functions such as toner charge amount adjustment, environmental stability improvement, and characteristics improvement under high humidity environment can be given by treatment such as hydrophobic treatment of inorganic fine powder. It is preferable to use inorganic fine powder. When the inorganic fine powder added to the toner absorbs moisture, the charge amount as the toner is remarkably reduced, and the developability and transferability are easily lowered.

Examples of treatment agents for hydrophobizing inorganic fine powder include unmodified silicone varnish, various modified silicone varnishes, unmodified silicone oil, various modified silicone oils, silane compounds, silane coupling agents, other organosilicon compounds, Organic titanium compounds are included. These treatment agents may be used alone or in combination.
Among these, inorganic fine powder treated with silicone oil is preferable. More preferably, the hydrophobicity-treated inorganic fine powder treated with silicone oil treated with silicone oil simultaneously or after the hydrophobic treatment of the inorganic fine powder with a coupling agent increases the charge amount of the toner particles even in a high humidity environment. It is good for maintaining high and reducing selective developability.

  The toner of the present invention has a weight average molecular weight Mw of 15,000 to 90,000, more preferably 20,000 to 60,000 as measured by gel permeation chromatography (GPC) soluble in tetrahydrofuran (THF). Preferably there is. When Mw exceeds 90,000, the dispersibility of various materials, particularly the colorant, is lowered, and as a result, the coloring power is lowered and the OHP permeability is easily deteriorated.

  In the toner of the present invention, the content of tetrahydrofuran (THF) insoluble in the resin component in the toner is preferably 5.0% by mass or less. When it exceeds 5.0 mass%, the glossiness of the printed image tends to be reduced.

  The toner of the present invention preferably has a weight average particle diameter (D4) of 4.0 to 9.0 μm, and more preferably 4.9 to 7.9 μm. When the weight average particle diameter (D4) is less than 4.0 μm, fog and transferability are deteriorated. When the weight average particle diameter (D4) exceeds 9.0 μm, the characters and line images are likely to be scattered and high resolution is difficult to obtain.

  Hereinafter, various measurement methods other than the storage elastic modulus G ′ according to the present invention will be described.

(1) Measurement of maximum endothermic peak temperature in DSC endothermic curve of wax component For DSC measurement by differential scanning calorimeter of wax component in the present invention, for example, DSC-7 manufactured by PerkinElmer or DSC- manufactured by TA Instruments Japan Co., Ltd. 2920 is available. In the present invention, the maximum endothermic peak temperature of the wax component is measured using DSC-2920 manufactured by TA Instruments Japan, and the maximum endothermic peak temperature of the wax component is obtained from the obtained DSC curve at the time of temperature increase. . An aluminum pan is used as a measurement sample, and an empty pan is set as a control. From 20 ° C. to 180 ° C. at a rate of temperature rise of 2 ° C./min while applying an amplitude of ± 1.5 ° C. and a period of 1 / min. Raise the temperature.
In the present invention, the height ΔH from the baseline to the peak top per unit mass using the DSC measurement method (value obtained by dividing the measured peak height by the mass of the measurement sample (mW / mg) ) Is the endothermic peak intensity.

(2) Measurement of molecular weight of wax component The wax component is measured under the following conditions by gel permeation chromatography (GPC).
Apparatus: GPC-150C (manufactured by Waters)
Column: GMH-MT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% sample Measured under the above conditions. In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

(3) Measurement of molecular weight distribution of toner and low molecular weight polymer soluble in tetrahydrofuran (THF) (measurement of weight average molecular weight of toner)
A specific method for measuring gel permeation chromatography (GPC) of the THF soluble component of the toner is as follows. The toner is extracted with a tetrahydrofuran (THF) solvent for 20 hours in advance using a Soxhlet extractor, and then THF is distilled off with a rotary evaporator. This is dissolved in an appropriate amount of THF, and the obtained solution is filtered through a solvent-resistant membrane filter having a pore diameter of 0.3 μm as a measurement sample. Tosoh HLC-8120GPC, Showa Denko Shodex KF-801, 802, 803, 804, 805, 806, 807 is connected to a standard polystyrene resin (specifically, Tosoh TSK standard polystyrene). Is used to measure the molecular weight distribution of the sample. A weight average molecular weight (Mw) is calculated from the obtained molecular weight distribution.

(4) Measurement of Toner and Tetrahydrofuran (THF) Insoluble Content 1.0 g of toner (W ₁ g) was weighed (W ₁ g), placed in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passed through a Soxhlet extractor, and THF 200 ml as a solvent After evaporating the soluble component extracted with a solvent for 20 hours, it is vacuum-dried for several hours at 40 ° C., and the amount of the THF-soluble resin component is weighed (W ₂ g). The weight of a component other than the resin component such as a pigment in the toner is defined as (W ₃ g). The THF-insoluble content can be obtained from the following formula.

(5) Measurement of toner weight average particle diameter (D4) Using a Coulter Multisizer (manufactured by Coulter), an interface (manufactured by Nikkiki) that outputs number distribution and volume distribution was connected to a PC 9801 personal computer (manufactured by NEC). The electrolyte is adjusted to a 1% NaCl aqueous solution using first grade sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. 100 to 150 ml of the electrolytic aqueous solution is added, and 2 to 20 mg of a measurement sample is further added. The electrolyte solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toner particles of 2.0 μm or more are measured using the Coulter Multisizer with a 100 μm aperture to obtain a weight average. The particle size (D4) is determined.

  EXAMPLES Hereinafter, although a manufacture example and an Example demonstrate this invention concretely, this does not limit this invention at all.

<Toner Production Example 1>
With respect to 100 parts by mass of the styrene monomer, C.I. I. 16.5 parts by mass of Pigment Blue 15: 3 and 3.0 parts by mass of an aluminum compound of 3,5-di-tert-butylsalicylic acid [Bontron E88 (manufactured by Orient Chemical Industries)] were prepared. These were introduced into an attritor (manufactured by Mitsui Mining Co., Ltd.) and stirred at 200 rpm at 25 ° C. for 180 minutes using zirconia beads (140 parts by mass) with a radius of 1.25 mm to prepare a master batch dispersion 1. .

On the other hand, after adding 450 parts by mass of 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 710 parts by mass of ion-exchanged water and heating to 60 ° C., 1.0 mol / liter-CaCl ₂ aqueous solution 67.
7 parts by mass was gradually added to obtain an aqueous medium containing a calcium phosphate compound.

Master batch dispersion 1 40 parts by mass Styrene monomer 28 parts by mass n-butyl acrylate monomer 18 parts by mass Low molecular weight polystyrene 20 parts by mass (Mw = 3,000, Mn = 1,050, Tg = 55 ° C)
Hydrocarbon wax 9 parts by mass (Fischer-Tropsch wax, maximum endothermic peak = 80 ° C., Mw = 750)
Polyester resin 5 parts by mass (bisphenol A-propylene oxide 2 mol adduct: terephthalic acid = 1: 1 polycondensate, Tg = 65 ° C., Mw = 10,000, Mn = 6,000)
-Divinylbenzene 0.01 mass part The said prescription was heated at 65 degreeC, and it melt | dissolved and disperse | distributed uniformly at 5,000 rpm using TK type | mold homomixer (made by Tokushu Kika Kogyo). In this, 10 parts by mass of a 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was dissolved to prepare a polymerizable monomer composition.

The polymerizable monomer composition is charged into the aqueous medium, and at 65 ° C. in an N ₂ atmosphere,
A polymerizable monomer composition is granulated by stirring at 10,000 rpm for 10 minutes with a TK homomixer, and then heated to 67 ° C. while stirring with a paddle stirring blade. When the polymerization conversion rate reached 90%, a 0.1 mol / liter sodium hydroxide aqueous solution was added to adjust the pH of the aqueous dispersion medium to 9. Furthermore, it heated up at 80 degreeC with the temperature increase rate of 40 degreeC / h, and was made to react for 4 hours. After completion of the polymerization reaction, the remaining monomer was distilled off under reduced pressure. After cooling, hydrochloric acid was added to adjust the pH to 1.4, and the mixture was stirred for 6 hours to dissolve the calcium phosphate salt. After filtering and washing with water, it was dried at 40 ° C. for 12 hours to obtain cyan toner particles (A).

  With respect to 100 parts by mass of the toner particles, 1.0 part by mass of hydrophobic silica fine powder surface-treated with hexamethyldisilazane (number average primary particle size: 7 nm), 0.15 part by mass of rutile titanium oxide fine powder ( The toner (A) of the present invention was obtained by dry-mixing the number average primary particle size: 30 nm) with a Henschel mixer (Mitsui Mining Co., Ltd.) for 5 minutes.

<Toner Production Example 2>
<Toner Production Example> Except for changing the addition amount of low molecular weight polystyrene (Mw = 2,800, Mn = 1,000, Tg = 53 ° C.) to 10 parts by mass and the styrene monomer to 38 parts by mass. 1> toner (B) was obtained.

<Toner Production Example 3>
A toner (C) was obtained in the same manner as in <Toner Production Example 1> except that the amount of divinylbenzene added was changed to 0.05 parts by mass.

<Toner Production Example 4>
Toner (D) in the same manner as in <Toner Production Example 1> except that the addition amount of styrene monomer is changed to 23 parts by mass and the addition amount of n-butyl acrylate monomer is changed to 23 parts by mass. Got.

<Toner Production Example 5>
The addition amount of divinylbenzene was changed to 0.05 parts by mass, and the addition amount of 70% toluene solution of a polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate was 7.0 masses. A toner (E) was obtained in the same manner as in <Toner Production Example 1> except that the amount of the toner was changed.

<Toner Production Example 6>
Except that the 70% toluene solution of the polymerization initiator 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate is changed to 12 parts by mass, the same as <Toner Production Example 1> Toner (F) was obtained.

<Toner Production Example 7>
The toner (G) was prepared in the same manner as <Toner Production Example 1> except that the addition amount of divinylbenzene was changed to 0.05 parts by mass and the temperature at which stirring was performed with a paddle stirring blade after granulation was changed to 65 ° C. )

<Toner Production Example 8>
Similar to <Toner Production Example 1> except that 9 parts by mass of ester wax (behenyl behenate: maximum endothermic peak = 75 ° C., Mw = 700) is added without adding hydrocarbon wax. Thus, toner (H) was obtained.

<Toner Production Example 9>
Toner (I) was obtained in the same manner as <Toner Production Example 1> except that the amount of hydrocarbon wax added was changed to 3 parts by mass.

<Example 10 of toner production>
Toner (J) was obtained in the same manner as in <Toner Production Example 1> except that the addition amount of the hydrocarbon wax was changed to 16 parts by mass.

<Toner Production Examples 11, 12, 13, 14>
Toners (K), (L), (M) are the same as <Toner Production Example 1> except that the type of hydrocarbon wax is changed to a hydrocarbon wax having different physical properties as shown in Table 3. ) And (N) were obtained.

<Toner Production Example 15>
The temperature at which 0.05% by weight of divinylbenzene and 8% by weight of 70% toluene solution of 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate are stirred with a paddle stirring blade after granulation A toner (O) was obtained in the same manner as in <Toner Production Example 1> except that was changed to 65 ° C.

<Toner Production Example 16>
A toner (P) was obtained in the same manner as in <Toner Production Example 1> except that the addition amount of divinylbenzene was changed to 0.1 parts by mass.

<Toner Production Example 17>
<Toner except that ion-exchanged water is changed to 613 parts by mass, 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 534 parts by mass, and 1.0 mol / liter-CaCl ₂ aqueous solution to 80.4 parts by mass. In the same manner as in Production Example 1>, toner (Q) was obtained.

<Toner Production Example 18>
<Toner except that ion-exchanged water is changed to 804 parts by mass, 0.1 mol / liter-Na ₃ PO ₄ aqueous solution to 369 parts by mass, and 1.0 mol / liter-CaCl ₂ aqueous solution to 55.0 parts by mass. In the same manner as in Production Example 1>, a toner (R) was obtained.

<Toner Production Example 19>
<Toner except that low molecular weight polystyrene is changed to low molecular weight polymer (styrene-n-butyl acrylate copolymer resin: copolymerization ratio 96: 4, Mw = 3,100, Mn = 1,100, Tg = 48 ° C.) In the same manner as in Production Example 1>, a toner (S) was obtained.

<Toner Production Example 20>
<Production of toner> Except for changing the addition amount of hydrocarbon wax to 5 parts by mass and adding 4 parts by mass of ester wax (behenyl behenate: maximum endothermic peak = 75 ° C., Mw = 700). In the same manner as in Example 1>, toner (T) was obtained.

<Toner Production Example 21>
The low molecular weight polystyrene was changed to a low molecular weight polymer (styrene-n-butyl acrylate copolymer resin: copolymerization ratio 96: 4, Mw = 3,100, Mn = 1,100, Tg = 48 ° C.). A toner (U) was obtained in the same manner as in <Toner Production Example 1> except that the amount of addition was changed to 5 parts by mass and the styrene monomer was changed to 43 parts by mass.

<Toner Production Example 22>
The low molecular weight polystyrene was changed to a low molecular weight polymer (styrene-n-butyl acrylate copolymer resin: copolymerization ratio 96: 4, Mw = 3,100, Mn = 1,100, Tg = 48 ° C.). Was added to 3 parts by mass, 46 parts by mass of styrene monomer, and 5 parts by mass of hydrocarbon wax, and ester wax (behenyl behenate: maximum endothermic peak = 75 ° C., Mw = Toner (V) was obtained in the same manner as <Toner Production Example 1>, except that 4) by mass of 700) was added.

<Production Example 1 of Comparative Toner>
A comparative toner (a) was obtained in the same manner as in <Toner Production Example 1>, except that the addition amount of styrene monomer was changed to 48 parts by mass and that low molecular weight polystyrene was not added.

<Production Example 2 for Comparative Toner>
A comparative toner (b) was obtained in the same manner as <Toner Production Example 1> except that the hydrocarbon wax was not added.

<Production Example 3 for Comparative Toner>
Do not add divinylbenzene, add 10 parts by weight of ester wax (behenyl behenate: maximum endothermic peak = 75 ° C., Mw = 700) without adding hydrocarbon wax, 1,1,3,3- 70 of tetramethylbutylperoxy 2-ethylhexanoate
Comparative Toner (c) in the same manner as in <Toner Production Example 1> except that the% toluene solution is changed to 15 parts by mass, and the temperature at which stirring is performed with a paddle stirring blade after granulation is changed to 70 ° C. Got.

<Production Example 4 for Comparative Toner>
Changing the addition amount of divinylbenzene to 0.5 parts by mass, adding 10 parts by mass of polypropylene wax (maximum endothermic peak = 129 ° C., Mw = 17,000) without adding hydrocarbon wax, 1 , 1,3,3-Tetramethylbutylperoxy 2-ethylhexanoate in 70% toluene solution is changed to 6 parts by mass, granulation temperature is 60 ° C., temperature after stirring with paddle stirring blade A comparative toner (d) was obtained in the same manner as in <Toner Production Example 1> except that was changed to 60 ° C.

<Production Example 5 for Comparative Toner>
The following materials are mixed in advance, the mixture is melt-kneaded with a twin screw extruder, the cooled kneaded product is coarsely pulverized with a hammer mill, the coarsely pulverized product is finely pulverized with a jet mill, and the resulting finely pulverized product is classified. Thus, toner particles (e) were obtained.
-Binder resin 100 parts by mass [styrene-n-butyl acrylate copolymer resin (Mw = 30,000, Tg = 62 ° C.)]
・ C. I. Pigment Blue 15: 3 5 parts by mass, 3,5-di-tert-butylsalicylic acid aluminum compound 3 parts by mass [Orient Chemical Industries, Ltd .: Bontron E88]
Ester wax 10 parts by mass (behenyl behenate, maximum endothermic peak = 75 ° C., Mw = 700)
After obtaining the toner particles (e), a comparative toner (e) was obtained in the same manner as in Toner Production Example 1.

  Tables 1 to 4 summarize the main prescription contents and physical properties of the toner production examples and comparative toner production examples.

<Example 1>
For the toner (A), evaluations (1) to (12) described below were performed.
The results are shown in Tables 5-7. When the durability test was performed and the state at the end of the durability was evaluated, the image density did not decrease and was equal to the initial value, and no image fogging occurred. In addition, no contamination of the charge imparting member / regulating member was observed, and no image defect occurred until the end of the durability evaluation, and a clear image was obtained.

  Examples 2 to 22 and Comparative Examples 1 to 5 are the same as Example 1 except that the toners used are replaced with toners (B) to (V) and comparative toners (a) to (e). Evaluation was performed. The results are shown in Tables 5 to 7 together with the results of Example 1 above.

The specific evaluation method is shown below.
Image evaluation was performed under each environment using LBP-2510 (manufactured by Canon Inc.) as an evaluation machine. In the evaluation, 190 g of each of the toners shown in Tables 1 and 2 was filled in the cartridge and mounted in the cyan station, and dummy cartridges were mounted in the other stations.

(1) Low-temperature fixability Evaluation was performed using Xx64 g / m ² paper in a low-temperature and low-humidity (L / L; 15 ° C., 10% RH) environment. Nine solid 5 cm square images were output on A4 paper. At this time, the amount of toner adhered to the unfixed image was 0.6 mg / cm ² . The image was rubbed back and forth five times with sylbon paper with a load of 4.9 kPa, and the temperature at which the density reduction rate was 20% or more was evaluated as the minimum fixing temperature. A: Fixing lower limit temperature is less than 145 ° C. B: Fixing lower limit temperature is 145 ° C. or more and less than 155 ° C. C: Fixing lower limit temperature is 155 ° C. or more and less than 165 ° C. D: Fixing lower limit temperature is 165 ° C. or more, 175 <° C. E: Minimum fixing temperature is 175 ° C. or higher

(2) Offset resistance after endurance An image with a printing ratio of 2% was printed using 5,000 g / m ² paper in an environment of normal temperature and humidity (N / N; 23.5 ° C., 60% RH). After printing out to the sheet, Xx64 g / m ² paper was used to make a double-sided copy of an A4 landscape image where the entire area 5 cm from the tip was a halftone with an image density of 0.5 and the others were solid white. The level of the offset appearing on the white background at this time was visually confirmed.
A: No offset is generated at all. B: An offset is slightly generated at the end portion other than the portion where the paper is passed in the A4 portrait orientation.
C: A slight offset occurred in the end portion other than the portion that passed through the A4 portrait.
D: Offset occurred in the entire longitudinal direction.
E: An offset occurred from the first surface in the entire longitudinal direction.

(3) Image Glossiness A solid image having a toner paste amount of 0.5 mg / cm ² using Xx75 g / m ² paper in a room temperature and normal humidity (N / N; 23.5 ° C., 60% RH) environment. The image glossiness at a measurement optical part angle of 75 ° was measured using “PG-3D” (manufactured by Nippon Denshoku Industries Co., Ltd.).
A: 25 or more B: 20 or more, less than 25 C: 18 or more, less than 20 D: 15 or more, less than 18 E: less than 15

(4) OHP Transparency Under normal temperature and normal humidity (N / N; 23.5 ° C., 60% RH) environment, the image on the OHP sheet “CG3700” (manufactured by 3M) is displayed as OHP “9550” (manufactured by 3M). The images projected on the white wall surface were visually evaluated in five stages as follows.
A: Transparency is remarkably high and good.
B: Transparency is good.
C: Slightly dull.
D: It is quite dull.
E: Significant disappearance occurred.

(5) Coloring power 0.1 mg / cm ² to 1 in a normal temperature and normal humidity (N / N; 23.5 ° C., 60% RH) environment
. Several types of solid images with different toner paste amounts were created using Xx75 g / m ² paper in the range of 0 mg / cm ² , and their image densities were measured using “Macbeth reflection densitometer RD918” (manufactured by Macbeth). After determining the relationship between the toner amount on the transfer paper and the image density, the coloring power was evaluated relatively with the image density corresponding to the case where the toner paste amount on the transfer paper was 0.5 mg / cm ² .
A: 1.40 or more B: 1.30 or more, less than 1.40 C: 1.20 or more, less than 1.30 D: 1.10 or more, less than 1.20 E: less than 1.10

(6) Image Concentration Xx75g / m ² paper is used under high temperature and high humidity (H / H; 30 ° C, 80% RH) environment and low temperature and low humidity (L / L; 15 ° C, 10% RH) environment. Use an image with a print ratio of 2% to 10,000
In an image printing test for printing out to zero sheets, a solid image was output at the end of durability evaluation, and the density was measured for evaluation. The image density was measured by using a “Macbeth reflection densitometer RD918” (manufactured by Macbeth Co., Ltd.) to measure the relative density with respect to an image of a white background portion having a document density of 0.00.
A: 1.40 or more B: 1.30 or more, less than 1.40 C: 1.20 or more, less than 1.30 D: 1.10 or more, less than 1.20 E: less than 1.10

(7) Image fog Xx75g / m ² paper is used under high temperature and high humidity (H / H; 30 ° C, 80% RH) environment and low temperature and low humidity (L / L; 15 ° C, 10% RH) environment. Image with a print ratio of 2%
In the image printout test that prints up to 0 sheets, an image having a white background is output at the end of the durability evaluation, and the white of the white background of the printout image measured by “REFLECTMETER MODEL TC-6DS” (manufactured by Tokyo Denshoku) The fog density (%) (= Dr (%) − Ds (%)) is calculated from the difference between the brightness (reflectance Ds (%)) and the whiteness of the transfer paper (average reflectance Dr (%)). Image fog at the end of the evaluation was evaluated. An amberlite filter was used as the filter.
A: Less than 0.5% B: 0.5% or more, less than 1.0% C: 1.0% or more, less than 1.5% D: 1.5% or more, less than 5.0% E: 5. 0% or more

(8) Scattering After an endurance test in a high-temperature, high-humidity (H / H; 30 ° C, 80% RH) environment, image quality evaluation (comprehensive evaluation of 5-point text, line images, and solid images) is performed visually and with a magnifying glass. went. The evaluation criteria are as follows.
A: There is no scattering, the line image and the character image are clear, and the solid image is uniform and good.
B: Slight scattering is recognized in the loupe check, but the solid image is uniform and good without any problem in the visual check.
C: Although a part slightly scattered in the line image and the character image is visually confirmed, it is not a level causing a problem in actual use.
D: There are many parts scattered in the line image and the character image by visual observation.
E: Significant scattering occurs in the line image and the character image by visual observation.

(9) Contamination of the charging member (= charging roller) of the photosensitive member ² using Xx75 g / m ² paper in a low temperature and low humidity (L / L; 15 ° C., 10% RH) environment.
In an image printing test for printing out an image with a printing ratio of% up to 10,000 sheets, the charging member (= charging roller) of the photosensitive member was observed after the endurance evaluation.
A: No contamination at all.
B: Slightly contaminated but no image defect occurred.
C: Contamination and slight image defects have occurred.
D: Contamination is conspicuous and image defects are conspicuous.
E: Contamination is severe and significant image defects occur.

(10) Restriction member (= developing blade) contamination ² using Xx75 g / m ² paper in a high temperature and high humidity (H / H; 30 ° C., 80% RH) environment.
In an image forming test in which an image having a printing ratio of% was printed out to 10,000 sheets, the regulating member was observed after the endurance evaluation.
A: No contamination at all.
B: Slightly contaminated but no image defect occurred.
C: Contamination and slight image defects have occurred.
D: Contamination is conspicuous and image defects are conspicuous.
E: Contamination is severe and significant image defects are generated.

(11) Fixing roller winding property Fixing winding property was confirmed at an initial stage in a durability test under a high temperature and high humidity (H / H; 30 ° C., 80% RH) environment. EN100 in (64 g / m ² paper) full tone wet paper, 1m from the transfer sheet tip
From the position of m, a solid image with a toner paste amount of 1.1 mg / cm ² was placed to obtain an unfixed image.
This was fixed using a fixing machine of IRC3200. At this time, when the fixing temperature was lowered from 175 ° C. by 5 ° C. for fixing, the temperature at which the transfer paper was wound around the fixing roller was defined as the fixing roller winding temperature.
A: 155 ° C or lower B: 155 ° C or higher and 160 ° C or lower C: 160 ° C or higher and 165 ° C or lower D: 165 ° C or higher and 170 ° C or lower E: 175 ° C or higher

(12) Blocking test (storability test)
10 g of toner was placed in a 50 cc polycup. The state of the toner when this was left in a constant temperature bath at 53 ° C. for 72 hours was visually judged as follows.
A: No blocking at all, almost the same as the initial state.
B: Although slightly agglomerated, it is in a state of collapsing with the rotation of the polycup, and there is no particular problem.
C: Although it is agglomerated, it is in a state where it is broken by hand.
D: Aggregation is intense.
E: Solidified.

FIG. 4 is a relationship diagram between storage elastic modulus and temperature of the toner of the present invention, and a differential curve diagram obtained by differentiating a common logarithm of storage elastic modulus with temperature.

Claims (6)

In a non-magnetic toner having toner particles containing at least a binder resin, a colorant, and a wax component, and an inorganic fine powder,
The toner particles are
(I) In a water-based medium, a polymerizable monomer composition containing a vinyl polymerizable monomer, a low molecular weight polymer, the colorant, and the wax component is dispersed.
(Ii) granulating the dispersed polymerizable monomer composition;
(Iii) polymerizing the vinyl polymerizable monomer contained in the granulated particles;
It was obtained by
The wax component has a maximum endothermic peak in a temperature range of 60 to 120 ° C. in a DSC curve at the time of temperature rise measured by a differential scanning calorimetry (DSC) apparatus,
The low molecular weight polymer may be a low molecular weight polystyrene, a low molecular weight styrene-acrylate copolymer, or a low molecular weight styrene having a weight average molecular weight (Mw) of 2000 to 5000 as measured by gel permeation chromatography (GPC). A methacrylate ester copolymer,
The storage elastic modulus (G ′ ₁₁₀ ) at 110 ° C. of the toner is 9.80 × 10 ⁴ to 1.80 × 10 ⁵ dN / m ² ,
The storage elastic modulus (G ′ ₁₅₀ ) at 150 ° C. is 4.50 × 10 ³ to 1.90 × 10 ⁴ dN / m ² ,
In the differential curve obtained by differentiating the temperature-storage elastic modulus curve with temperature, with the horizontal axis representing temperature and the common logarithm Log G ′ of storage elastic modulus G ′ representing the vertical axis,
A temperature on the differential curve at a temperature T ₀ + a (° C.) and a temperature (T ₀ + a) +1 (° C.) where T ₀ is the minimum temperature of the differential curve in the temperature range of 60 to 130 ° C. A straight line connecting the points on the differential curve in the integer of 0 to 9], the straight line when the slope becomes the largest is A,
Points on the differential curve at temperature T ₀ + b (° C.) and temperature (T ₀ + b) +10 (° C.)
b is an integer greater than or equal to 0], a straight line connecting the points on the differential curve is drawn, and the straight line when the slope becomes the smallest is B,
Points on the differential curve at temperature T ₀ + c (° C.) and temperature (T ₀ + c) +10 (° C.)
When c is a straight line connecting points on the differential curve in (an integer larger than b when the straight line B is given)], and the straight line when the inclination is largest is C,
The temperature range ΔT _A from T ₀ to the intersection of the straight lines A and B is 10 ° C. ≦ ΔT _A ≦ 16 ° C., and the temperature T _{BC at} the intersection of the straight lines B and C is 105 ° C. ≦ T _BC ≦ 118 ° C. Non-magnetic toner characterized by.
The loss tangent (tan δ) represented by the ratio (G ″ / G ′) of the loss elastic modulus (G ″) to the storage elastic modulus (G ′) of the non-magnetic toner is in the range of 68 to 85 ° C., and 110 to 135. Each has a maximum value (P0 · P1) in the range of
2. The nonmagnetic toner according to claim 1, wherein a difference between a loss tangent maximum value tan δ _p1 existing in a range of 110 to 135 ° C. and a loss tangent tan δ ₁₇₀ of 170 ° C. is 0.60 or more. Wherein Ri _'(100 for the ratio (G' ₈₀ / G _'100) 10 to 30 der storage modulus G) at 100 ° C. ₍₈₀ storage modulus G)' at 80 ° C. of the non-magnetic toner,
The storage modulus at 100 ° C. of the non-magnetic toner (G _'100) a storage modulus at 120 ° C. of (G' ratio _{120) (G '100 / G} ' 120) is 5 to 20,
Wherein the storage modulus at 120 ° C. of the non-magnetic toner 'storage modulus at 0.99 ° C. of ₍₁₂₀ (G G)' ratio _{150) (G '120 / G} ' 150) is 3 to 10 The nonmagnetic toner according to claim 1. The low molecular weight polymer, non-magnetic toner according to claim 1 having a glass transition temperature and wherein a 52 to 58 ° C. der Turkey.
The toner particles are non-magnetic toner according to any one of claims 1 to 4, characterized in that one prepared in an aqueous medium. The toner particles are obtained by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, and a wax component in an aqueous medium, granulating, and polymerizing the polymerizable monomer. non-magnetic toner according to any one of claims 1 to 5, characterized in that as it can be obtained.

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