JPH1090939A - Static charge image developing toner, process cartridge, and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having no fog even in long-period durability in which a sharp image can be provided, and low temperature fixing property and offset resistance are improved by setting the acid value of a low molecular weight polymer larger than the acid value of a high molecular weight polymer, and setting the acid value of a wax smaller than the acid value of the low molecular weight polymer. SOLUTION: A polymer component of a composition contains no THF insoluble content. The THF soluble content of the polymer component has a main peak in the molecular weight area of 3×10<3> -3×10<4> , and a sub-peak or shoulder in the molecular weight area of 1×10<5> -3×10<6> . The acid value AVL of the molecular weight area less 5×10<4> in a low molecular weight polymer (the molecular weight area of 5×10<4> in GPC chromatogram) and the acid value AVH of a high molecular weight polymer (the molecular weight area of 5×10<4> or more in GPC chromatogram) satisfies AVL>AVH, and a wax having an acid value AVWax satisfying AVL>AVWax , AVWax >0(mgKOH/g) is contained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for forming a toner image by developing an electrostatic image in an image forming method such as electrophotography and electrostatic printing, and further relates to a process cartridge having the toner and a process cartridge having the toner. The present invention relates to an image forming method using toner.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748. In general, using a photoconductive substance, an electrostatic image is formed on a photoreceptor by various means, and then the electrostatic image is developed using toner, and if necessary, via an intermediate transfer member, or After a toner image is transferred onto a transfer material such as paper without intervening, fixing is performed by heating, pressure, heating and pressurizing, or solvent vapor, etc. to obtain a copy or print. Further, the remaining toner not transferred onto the photosensitive member is cleaned by various methods, and the above-described steps are repeated.

In recent years, such copying apparatuses or printers have been strictly pursued for miniaturization, weight reduction, high speed, and high reliability, and as a result, the performance required for toner has also become higher. . For example, various methods and apparatuses have been developed for a process of fixing a toner image on a sheet such as paper, but the most common method at present is a heat pressure bonding method using a heat roller. The heat compression bonding method using a heat roller performs fixing by allowing the toner image surface of a sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having releasability with respect to toner while contacting the surface under pressure. . In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency when fixing the toner image on the sheet to be fixed is extremely good, and the fixing can be performed quickly, It is very effective in high-speed electrophotographic copying machines.

[0004] However, the following problems are likely to occur in the above-described heat roller fixing which has been frequently used.

(1) There is a so-called wait time during which the image forming operation is inhibited until the heat roller reaches a predetermined temperature; (2) The temperature of the heat roller fluctuates due to the passage of the transfer material or other external factors. It is necessary to maintain the heating roller at an optimal temperature in order to prevent poor fixing due to and the offset phenomenon due to the transfer of the toner to the heating roller.For this purpose, the heat capacity of the heating roller or the heating element must be increased. However, this requires a large amount of electric power and causes a rise in the temperature inside the image forming apparatus. (3) Since the heating roller is at a high temperature, when the transfer material is discharged through the heating roller, The transfer material and the fixed image on the transfer material are cooled slowly, and the toner and the fixed image are tacky, and may be offset or wound around the heating roller. It may cause a paper jam by Mukoto.

Japanese Patent Application Laid-Open No. 63-313182 discloses a fixing device that heats a toner image via a heat-resistant sheet that is moved by a low-heat-capacity heating element that generates heat in a pulsed manner and fixes the toner image on a recording material. 2. Description of the Related Art An image forming apparatus having a short time and low power consumption has been proposed. JP 1
In the fixing device for heating and fixing a toner image to a recording material via a heat-resistant sheet,
A fixing device has been proposed in which the heat-resistant sheet has a heat-resistant layer and a release layer or a low-resistance layer to effectively prevent the offset phenomenon.

There is a need for a toner that realizes a fixing method that has a short wait time and low power consumption while achieving good fixability of a toner image to a recording material and prevention of offset.

Various attempts have been made to improve the binder resin in the toner.

For example, a method is known in which the glass transition temperature (Tg) and the molecular weight of the binder resin in the toner are increased to improve the melt viscoelasticity of the toner. However, in such a method, when the offset phenomenon is improved, the fixing property is reduced, and the low-temperature fixing property required for high-speed development and energy saving is reduced.

In general, in order to improve the low-temperature fixability of a toner, it is necessary to reduce the viscosity of the toner at the time of melting to increase the adhesion area with a recording material. For this purpose, the Tg and molecular weight of the binder resin used are reduced. It is preferred to lower it.

Since the low-temperature fixing property and the offset prevention property of the toner have contradictory aspects, it is difficult to develop a toner that satisfies these functions at the same time.

In order to solve this problem, Japanese Patent Publication No.
No. 23354 discloses a crosslinking agent and a molecular weight modifier,
Toners comprising moderately crosslinked vinyl polymers have been proposed. Japanese Patent Publication No. 55-6805 discloses that the molecular weight distribution is adjusted so that the ratio of the weight average molecular weight to the number average molecular weight using α, β unsaturated ethylenic monomer as a constitutional unit is 3.5 to 4.0. Widened toners have been proposed.

Certainly, these toners have a lower fixing temperature (the lowest temperature at which fixing is possible) and an offset temperature (a temperature at which offset begins to occur), compared to a toner made of a single resin having a narrow molecular weight distribution. Although the fixing temperature range is widened, it is difficult to sufficiently lower the fixing temperature when sufficient offset prevention performance is imparted. Conversely, there has been a problem that if low-temperature fixability is emphasized, the offset prevention performance becomes insufficient.

In place of these vinyl resins, a toner obtained by crosslinking a polyester resin which is considered to be essentially superior to a vinyl resin in terms of low-temperature fixability and further adding an offset preventing agent is disclosed in -208559. Although this toner is excellent in both low-temperature fixing property and offset prevention property, it has a problem in terms of toner productivity (pulverizability).

Further, in Japanese Patent Application Laid-Open No. 56-116043, a vinyl monomer is polymerized in the presence of a reactive polyester resin, and polymerized through a crosslinking reaction, an addition reaction and a grafting reaction in the course of polymerization. A toner using a resin has been proposed. Although the grindability is improved, it is difficult to make full use of the functions of the resins in terms of low-temperature fixability and offset prevention.

[0016] Simply, two types of polyester resin and gel content are different (gel content is 80% or more and gel content is 1
(Less than 0%) is proposed in Japanese Patent Publication No. 1-10663.
This toner has good low-temperature fixability, but needs to be further improved in terms of anti-offset properties and pulverizability. When the proportion of the vinyl resin having a gel content of 80% or more is increased for the purpose of improving the offset resistance, the anti-offset property is improved, but the low-temperature fixability is significantly reduced. Further, it is difficult to obtain sufficient pulverizability of the kneaded material at the time of toner production only by containing a vinyl resin having a gel content of less than 10%.

It has been proposed in JP-A-57-178249 and JP-A-57-178250 to use, as a binder resin, a resin crosslinked by reacting a polymer having a carboxylic acid with a metal compound. Have been. JP-A-61-110155 and JP-A-61-110155 disclose a method in which a binder having a vinyl monomer and a specific monoester compound as essential constitutional units is reacted with a polyvalent metal compound and crosslinked via a metal. It is proposed in Japanese Patent Publication No. 110156.

Further, JP-A-63-214760, JP-A-63-217362, and JP-A-63-2
In JP-A-17363 and JP-A-63-217364, a carboxylic acid group having a molecular weight distribution divided into two groups, a low molecular weight region and a high molecular weight region, reacts with a polyvalent metal ion. There has been proposed a method for causing crosslinking. In any of the methods, the reaction between the binder resin and the metal compound or the dispersion of the metal compound in the binder resin is not sufficient, and the fixing property and the offset resistance required for the toner have not been satisfied. In addition, since it is necessary to mix a large amount of the metal compound with the binder resin, the compounded metal compound shows a catalytic action on the binder resin depending on conditions, and the binder resin is easily gelled, and as a result, the metal compound is mixed. Therefore, it is difficult to determine the manufacturing conditions for obtaining the desired toner, and even if the manufacturing conditions can be determined, there is a problem that it is difficult to obtain reproducibility.

In adjusting the amount of acid in these toners,
It is preferable to further improve the charging characteristics (rise), environmental characteristics (leaving characteristics under high humidity), and image characteristics (fog and density characteristics) of the toner.

Further, JP-A-2-168264, JP-A-2-23569, and JP-A-5-173363
JP-A-5-173366, JP-A-5-172
In Japanese Patent No. 41371, the molecular weight, the mixing ratio, the acid value and the ratio of the low molecular weight component and the high molecular weight component in the binder resin are controlled, and the fixing property, the non-offset property, the image property and the anti-blocking property, and the rising property of charging are controlled. And a toner binder composition improved from the above.

In the above-described toner, poor dispersion of a colorant such as magnetic iron oxide, a charge control agent (charge control agent), and other additives is likely to occur, and contamination of the surface of the developer carrying member such as a carrier or a sleeve is caused. Fog and image density decrease easily occur.

Japanese Unexamined Patent Publication (Kokai) No. 62-9256 proposes a binder composition for a toner in which two kinds of vinyl resins having different molecular weights and acid values are blended. However, when such a binder resin is used, it is necessary to strengthen the kneading conditions in order to improve the compatibility or dispersibility of the toner components. The binder resin is susceptible to the cutting of polymer molecules, and particularly tends to have reduced offset resistance. When kneading is performed to such an extent that polymer molecules are not cut, poor dispersion of additives is likely to occur, and the carrier and the surface of the developer carrier are likely to be contaminated. In particular, when a polymer having a weight average molecular weight of 1,000,000 or more is used, these phenomena are likely to become apparent.

JP-A-3-72505 proposes a vinyl resin having a molecular weight of 300,000 or more using a polyfunctional initiator. When such a resin is used, the fixability is satisfactory to some extent, but the performance of the toner is likely to deteriorate when left at high temperatures. The cause of this phenomenon is not clear, but during the production of the toner, since the molecular cleavage of the binder resin is promoted, the ratio of the high molecular weight resin component in the toner composition is reduced, and the heat resistance is reduced. It is presumed that there is.

On the other hand, it is known that a low softening point release agent (wax) such as polyolefin is contained in the toner in order to improve the low-temperature fixability and the offset resistance of the toner.

JP-A-51-14333, JP-A-5-14333
JP-A-7-148752, JP-A-58-97056, JP-A-60-247250, JP-A-4-36
No. 2953 and JP-A-6-230600,
As a release agent, a solid silicone varnish, a higher fatty acid wax, a higher alcohol wax, a vegetable natural wax (carnauba, rice), and a montan ester wax are described. However, it is necessary to further improve the low-temperature fixability and offset resistance of the toner, and it is also necessary to improve the developability (chargeability) and durability of these toners.

In general, when such a low softening point release agent is contained in a toner, the fluidity of the toner is reduced, so that developability and transferability are reduced. In addition, the chargeability, durability, and storage stability are likely to be adversely affected.

In order to solve these problems, modified waxes obtained by grafting or block copolymerizing with various monomers have been proposed.

JP-A-59-121052 discloses α-
It has been proposed to use a polyolefin grafted / block-copolymerized with a methylene aliphatic monocarboxylic acid ester monomer, as disclosed in JP-A-56-15470, JP-A-59-121053, and JP-A-60-9.
JP-A-3456 and JP-A-63-34550 propose to use a polyolefin obtained by graft / block copolymerization with an aromatic vinyl monomer. These toners are improved in fluidity, but are inferior in offset resistance, and further developable (chargeable),
Further, it is necessary to further improve the durability.

JP-A-62-226260, JP-A-63-139365, JP-A-3-50559 and JP-A-6-208244 contain a polypropylene modified with carboxylic acid or maleic acid. The following toner or resin composition for toner has been proposed. In these toners, the relationship between the release agent and the resin composition is not specified, and it is further desired to maintain fluidity and improve hot offset properties.

In order to enlarge the fixing area (non-offset area), it is necessary to incorporate two or more types of release agents into the toner, as disclosed in JP-A-60-93457, JP-A-4-274247 and JP-A-4-274247. 299357, JP-A-4-33
7737, JP-A-6-208244 and JP-A-7-281478. In these toners, the relationship between the release agent and the resin composition is not specified, and there is still a problem in the uniform dispersion of the release agent in the toner particles.

Furthermore, in recent years, as a technical direction of the copying apparatus, high speed, environmental stability, and high image quality are required.
Further speeding up and long-term use under severe environments (high-temperature, high-humidity or low-temperature, low-humidity environments) tend to cause deterioration of the toner, and easily cause problems such as fogging and image density reduction.
Regarding high image quality, conventional 240 dpi or 300 dpi
What was i, 400 dpi, 600 dpi or 1
It has become 200 dpi.

For this reason, use of a small particle size toner has been proposed. JP-A-1-112253, JP-A-1-19
In Japanese Patent Application Laid-Open Nos. 1156, 2-214156, 2-284158, 3-181952, and 4-162048, a toner having a specific particle size distribution and a small particle size improves image quality. Has been proposed to achieve.

On the other hand, there is an increasing demand for higher quality graphic images. One aspect of the quality of graphic images is the uniformity of image density in solid images.

Regarding the uniformity of density in the solid image, in the one-component developing system, when a halftone solid image is printed, an afterimage of the image printed immediately before appears on the solid image in the rotation cycle of the developing sleeve. There is a phenomenon called “sleeve ghost”, which sometimes lowers the quality of graphic images.

The sleeve ghost means that after a solid white image is continuously formed, as shown in FIG. 8, after a black image portion of a solid black image and a striped image portion of a solid white image on a white background. When an image is formed such that a halftone image portion is formed, an afterimage of the white background portion appears in the halftone image portion adjacent to the white background portion of the striped image portion with a low image density. It is a phenomenon that goes wrong.

Further, a toner fine powder layer is formed on the surface of the developing sleeve, and the toner coated thereon tends to cause poor charging and fog. JP-A-2-284
No. 154 proposes a negatively chargeable magnetic toner in which specific positively chargeable resin particles and specific negatively chargeable hydrophobic silica fine powder are combined with specific negatively chargeable toner particles in order to solve sleeve ghost. ing. However, it is necessary to further improve the formation of a higher resolution and higher definition image with the negatively chargeable magnetic toner.

[0037]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image, which solves the above-mentioned problems.

An object of the present invention is to improve low-temperature fixability and anti-offset properties, to form a high-quality toner image, to have a stable charging performance without fog even in long-term durability, and to improve long-term storage stability. An object of the present invention is to provide an excellent electrostatic image developing toner.

It is a further object of the present invention to provide a toner for developing an electrostatic charge image in which each component is uniformly dispersed in toner particles and has excellent image characteristics similar to those of the initial stage even when used for a long period of time. is there.

It is a further object of the present invention to provide a toner for developing an electrostatic image, which has both low-temperature fixability and high durability of the toner even at a high process speed.

It is a further object of the present invention to provide a toner for developing an electrostatic image, which has no or little "sleeve ghost".

It is a further object of the present invention to provide an electrostatic image developing toner capable of forming a higher resolution and higher definition image.

It is a further object of the present invention to provide a process cartridge having the above toner.

It is a further object of the present invention to provide an image forming method using the above toner.

[0045]

According to the present invention, there is provided a toner for developing an electrostatic image formed from a composition containing at least a polymer component, a colorant, a wax and a charge controlling agent, wherein the polymer component of the composition is , (A) contains substantially no THF-insoluble matter, and (b) THF-soluble matter of the polymer component has a molecular weight of at least 3 × 10 ³ to 3 in the GPC chromatogram.
A main peak in the region of × 10 ⁴ and a molecular weight of 1 ×
(C) an acid value (A _VL ) of a low molecular weight polymer (a region having a molecular weight of less than 5 × 10 ⁴ in a GPC chromatogram) having a subpeak or a shoulder in a region of 10 ^{5 to} 3 × 10 ⁶ ;
And the acid value (A _VH ) of the high molecular weight polymer (region having a molecular weight of 5 × 10 ⁴ or more in the GPC chromatogram) satisfies the following condition A _VL > A _VH , and the wax has the following condition A _VL > A _{The present invention relates} to a toner for developing an electrostatic image, comprising a wax having an acid value (A _VWax ) satisfying _VWax , A _VWax > 0 (mgKOH / g).

Further, the present invention comprises at least an electrostatic image holder and a developing means for developing an electrostatic image formed on the electrostatic image holder using toner, wherein the electrostatic image holder is And the developing means are integrally formed as a cartridge. The process cartridge is detachable from the main body of the image forming apparatus. The toner is formed of a composition containing at least a polymer component, a colorant, a wax and a charge control agent. The polymer component of the composition is (a) substantially free of THF-insoluble components, and (b) the THF-soluble component of the polymer component is G
In the PC chromatogram, at least a molecular weight of 3 × 1
(C) a low molecular weight polymer (having a main peak in a region of 0 ^{3 to} 3 × 10 ⁴ and a subpeak or a shoulder in a region of 1 × 10 ^{5 to} 3 × 10 ⁶ ); 5 × 10 ⁴ less than regions) the acid value of (a _VL) and high molecular weight polymer the acid value of (the molecular weight region of 5 × 10 ⁴ abnormality in GPC chromatogram) (a _VH) and the following conditions a _VL> a _{VH And} a wax having an acid value (A _VWax ) satisfying the following conditions: A _VL > A _VWax , A _VWax > 0 (mg KOH / g).

Further, according to the present invention, an electrostatic charge image is formed on the electrostatic charge image holding member, and the electrostatic charge image is developed with the toner held in the developing means to form a toner image.

The toner is formed of a composition containing at least a polymer component, a colorant, a wax and a charge controlling agent, and the polymer component of the composition is substantially (a) T
Excluding HF insoluble matter, the THF-soluble matter of the polymer component (b) has a main peak at least in a region of a molecular weight of 3 × 10 ^{3 to} 3 × 10 ^{4 in} a GPC chromatogram,
And (c) a low molecular weight polymer (GPC) having a subpeak or a shoulder in a region of a molecular weight of 1 × 10 ^{5 to} 3 × 10 ^6.
(A region with a molecular weight of less than 5 × 10 ⁴ in the chromatogram)
Value of the acid (A _VL) and acid value of the high molecular weight polymer (a region of molecular weight 5 × 10 ⁴ abnormality in GPC chromatogram) (A _VH) and has to satisfy the following condition A _VL> A _VH, the wax _Contains a wax having an acid value (A _VWax ) satisfying the following conditions: A _VL > A _VWax , A _VWax > 0 (mgKOH / g).

[0049]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a polymer component of a toner is a component substantially insoluble in tetrahydrofuran (TH).
F insolubles). Specifically, 5 based on the polymer component
% By weight, preferably 3% by weight or less.

The THF insoluble content indicates the weight ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the polymer component of the toner, and indicates the degree of crosslinking of the polymer component containing the crosslinking component. Can be used as a parameter to indicate The THF-insoluble matter is defined by a value measured as follows.

0.5 to 1.0 g of the toner sample was weighed (w ₁ g), and the sample was filtered with a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.).
R) and run through a Soxhlet extractor, where T
After extracting with 100 to 200 ml of HF for 6 hours and evaporating the soluble component extracted with the solvent, 10
After vacuum drying for several hours at 0 ° C., the amount of the THF-soluble resin component is weighed (w ₂ g). The weight of the components other than the resin components such as the magnetic substance, pigment and wax in the toner is defined as (w ₃ g).
The THF-insoluble content is obtained from the following equation.

THF insoluble matter (%) = [｛w ₁ − (w ₃ +
_{w 2)} / (w 1} -w 3) ] × 100 THF When the insoluble matter content exceeding 5 wt% low-temperature fixing steel is lowered.

Gel Permeation Chromatography (GPC) Measured by THF Soluble Content of Polymer Component
Has a molecular weight of at least 3 × 10 ^{3 to} 3 ×
It has a main peak in the region of 10 ⁴ (more preferably, 5 × 10 ³ to 2 × 10 ⁴ ) and has a molecular weight of 1 × 10 ⁵ to
3 × 10 ⁶ (more preferably, 5 × 10 ⁵ to 1 × 10
It is preferable to have a subpeak or a shoulder in the region ⁶ ).

In the chromatogram of GPC, molecular weight 1
It is preferable that the area ratio of the polymer component showing 1,000,000 or more shows 1 to 20% (more preferably 3 to 10%). The presence of 1 to 20% of a THF-soluble component having a molecular weight of 1,000,000 or more improves offset resistance without hindering low-temperature fixing, and at the same time improves the storage stability of the toner when left at high temperatures. Can be enhanced.

In the present invention, the molecular weight distribution of the polymer component is measured by GPC under the following conditions.

GPC measurement conditions for resin composition and polymer Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Column: Temperature: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 ml / min. Sample: 0.1 m of a sample having a concentration of 0.05 to 0.6% by weight.
l injection

The polymer component used was a low molecular weight polymer component (a molecular weight of 5 × 10 ⁴ in a GPC chromatogram).
(A _VL ) and the high molecular weight polymer component (G
An acid value (A _VH ) of a PC chromatogram having a molecular weight of 5 × 10 ⁴ or more satisfies the following condition A _VL > A _VH and the acid value (A _VWax ) of the wax satisfying the following condition: have.

A _VL > A _VWax , A _VWax > 0 (mgKOH / g)

As a result of intensive studies, the present inventors have found that, in the combination of the polymer component and the wax, both have an acid value, the acid value of the polymer component is A _VL > A _VH , and the acid value of the wax is It has been found that it is preferable for the toner that the relationship between the acid value and the acid value of the low molecular weight polymer satisfy the above conditions.

By controlling the compatibility between the wax and the polymer component, especially the low molecular weight polymer, the low-temperature fixability and the offset resistance can be remarkably improved.

Since the acid value of the polymer component is A _VL > A _VH , the wax having an acid value acts more on the low molecular weight polymer component than on the high molecular weight polymer component, and the low temperature fixation is achieved by its plastic effect. Demonstrate the nature.

Further, in the polymer component, as long as the acid value (A _VWax ) of the wax component satisfies A _VL > A _VWax with respect to the acid value of the low molecular weight polymer, the fluidity and charge stability of the toner are further improved. Became stable for a long time.

When the acid value of the polymer component satisfies A _VL ≦ A _VH , the charge stability of the toner decreases, and even when a wax having an acid value is contained, the low-temperature fixability and the offset resistance are effectively improved. It is difficult.

The acid value of the polymer component is A _VL > A _VH , and the acid value of the wax is A _VL ≦ A with respect to the acid value of the low molecular weight polymer.
_In the case of _VWax , offset resistance and toner chargeability under high humidity are reduced.

More preferably, the acid value of the wax satisfies the following condition with respect to the acid value of the low molecular weight polymer component.

0.5 × A _VL > A _VWax > 0.05 × A _VL

Further, it is preferable to use an acid-modified polyolefin having a wax satisfying the above conditions and having an acid value of 1 to 15 mgKOH / g.

Further, the wax is more preferably a polyolefin whose molecular terminal has been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride.

Further, it is preferable that the wax contains a polypropylene wax whose molecular terminal is modified by an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride.

Further, the acid component in the acid-modified wax and the acid component contained in the low molecular weight polymer component are maleic acid,
More preferably, it is formed from an acid monomer selected from at least one of maleic acid half festers and maleic anhydride.

Examples of the polypropylene wax used in the present invention include a homopolymer of propylene and a copolymer of propylene and another olefin (particularly, ethylene is preferable). The propylene copolymer has a propylene component of 60.
It is preferred that the content be at least 10% by weight.

As the acid monomer used for modifying the wax, those similar to those used for adjusting the acid value of the polymer component can be used.

In the present invention, the acid value (A _VWax ) of the wax is _determined .
Is 1 to 15 mgKOH / g, the acid value (A _VL ) of the low molecular weight polymer component is 21 to 35 mg KOH / g, and the acid value (A _VH ) of the high molecular weight polymer component is 0.5 to
It is preferably 11 mgKOH / g.

Further, the toner has a weight average diameter (D
₄ ) is X (μm), and the number average diameter of the toner is 3.17 μm.
Assuming that the following ratio is Y (%), it is preferable to have a particle size distribution that satisfies the following formula: −5X + 35 ≦ Y ≦ −25X + 180 (1) 3.5 ≦ X ≦ 6.5 (2)

The particle size distribution in the range of the formulas (1) and (2) shown in FIG. 1 has a considerably smaller weight average diameter and a considerably larger amount of fine powder than the particle size distribution of the toner generally used at present. . Rather than suppressing the amount of fine powder that causes "sleeve ghost", rather, by bringing the particle size distribution of the whole toner closer to the fine powder area, the chargeability of the whole toner and its mirroring power are improved to the characteristics of the fine powder. As a result, the chargeability on the toner carrier as a whole of the toner particles was brought into a special state unlike before, and the selective adhesion of the fine powder toner on the toner carrier and the formation of the fine powder layer associated therewith were attempted. Things.

In the present invention, since the toner has a specific particle size distribution that satisfies the above conditions (1) and (2), the particle size is particularly 3.17 μm or less, which tends to increase the charge amount. By bringing the particle size distribution of the entire toner closer to that of the fine toner particles, the difference in charge amount based on the difference in particle size between the fine toner having a particle size of 3.17 μm or less and the entire toner becomes small, so that the toner particles 3.17μ diameter
The toner particles exceeding m are also appropriately attached, making it difficult for the fine powder toner to selectively form the fine powder toner layer on the outermost surface of the developing sleeve, and the charge amount of the toner layer formed on the front surface side of the developing sleeve is made uniform. Therefore, it is considered that the sleeve ghost is suppressed.

Further, in the combination of the above-mentioned polymer component and wax component of the toner, both of them have an acid value,
When the acid value of the polymer component is A _VL > A _VH and the relationship between the acid value of the wax component and the acid value of the low molecular weight polymer satisfies the above conditions, the fixability of the toner having the above particle size is improved. Is done.

Even if the particle size of the toner becomes small, the compatibility between the wax component and the toner polymer component, in particular, the low molecular weight polymer is controlled, whereby the low-temperature fixability and the offset resistance can be significantly improved. Can be

In addition, when the particle size distribution of the toner is within the range of the formulas (1) and (2), effects such as an increase in charge amount and uniformity of charge amount can be obtained. Is likely to decrease. However, the relationship between the molecular weight distribution in GPC and the acid value (A _VWax ) of the polymer component, the wax component, and the acid value of the low molecular weight polymer whose acid value is defined is A _VL >
By combining the wax with _AVWax , the dispersibility of each component in the toner was improved, and the good fluidity of the toner could be maintained. Further, since the charge of the toner rises quickly, the charge amount is hardly reduced in a high-temperature and high-humidity environment, and even if the charge is reduced, the charge is easily recovered. Even in a low-temperature and low-humidity environment, charge-up becomes difficult due to good dispersibility of each component in the toner. Therefore, a synergistic effect of increasing environmental stability and obtaining a toner having stable performance over a long period of time was recognized.

Amount of fine powder in toner (3.17 μm or less) Y
If (%) is less than -5X + 35, the amount of toner coating on the toner carrier tends to be excessive, and "wave-like unevenness" tends to occur.

The amount of fine powder in the toner is (3.17 μm or less)
When Y (%) is more than −5X + 180, the effect of suppressing the formation of the toner fine powder layer on the toner carrier is small, and “sleeve ghost” is likely to occur.

The weight average diameter (D ₄ ) X (μm) is 3.5 μm.
If it is less than m, it is difficult to obtain a sufficient image density.

The weight average diameter (D ₄ ) X (μm) is 6.5 μm.
If it is larger than m, the effect of suppressing the formation of the toner fine powder layer on the toner carrier is small because the particle diameter of the entire toner is different from the particle diameter of the fine powder, and “sleeve ghost” is likely to occur.

Further, the toner preferably has a porosity at the time of tapping of the toner defined by the following formula in the range of 0.40 to 0.70.

Porosity = (true density−tap density) / true density

If the porosity of the toner at the time of tapping is less than 0.40, it is impossible to suppress sleeve ghost and achieve high image quality at the same time. If it exceeds 0.70, the toner coat layer on the toner carrier Is uneven, and the uniformity of the image is reduced.

In the present invention, the true density of the toner is measured as follows.

1 mg of the toner is placed in a tableting machine for 1R measurement, and molded by applying a pressure of about 1.96 MPa (200 kgf / m ² ) for 1 minute. The volume and weight of this sample are measured to determine the true density.

In the present invention, the measurement of the tap density of the toner refers to a value measured by using a powder tester manufactured by Hosokawa Micron Corp. and using a container provided in accordance with the procedure of the instruction manual of the powder tester.

The particle size distribution of the toner of the present invention is measured using a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter), and a 1% aqueous NaCl solution is prepared using primary grade sodium chloride as an electrolytic solution.
As the electrolytic solution, for example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to 150
0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) as a dispersant is added to each ml, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is subjected to dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the volume and the number of toner particles having a size of 2 μm or more are measured by using the measuring device with a 100 μm aperture as a volume distribution. Calculate the distribution.

Then, the weight-based weight average particle diameter (D ₄ : the median value of each channel is a representative value for each channel) obtained from the volume distribution according to the present invention, and the number-based 5 μm or less obtained from the number distribution And 3.17 μm or less, 2.5
Each ratio of 2 μm or less is determined.

The acid value (A _VL ) of the low molecular weight polymer component (region having a molecular weight of less than 5 × 10 ⁴ in the GPC chromatogram) and the acid value of the high molecular weight polymer component (region having a molecular weight of 5 × 10 ⁴ or more in the GPC chromatogram) Value (A _VH ) satisfies the following condition A _VL > A _VH , and the wax component has a weight average molecular weight (Mw _WaxA ) of 8.0 × 10 ³ or more.
A polyolefin (A) having an acid value of 1.4 × 10 ⁴ and a weight average molecular weight (Mw _WaxA ) of 1.0 × 10 4
^{4 to} 4.0 × 10 ⁴ (preferably 1.5 × 10 ⁴ to 2.
More preferably, it contains 5 × 10 ⁴ ) polyolefin (B).

The present inventors have conducted intensive studies and as a result, in the above-mentioned combination of the polymer component and the wax, the polymer component has an acid value of A _VL > A _VH , and two kinds of waxes having specified molecular weights are used as the wax. As a result, it has been found that the object of the present invention is sufficiently satisfied.

By controlling the compatibility between the two types of waxes and the high and low molecular weight polymers in the toner polymer component, the low-temperature fixability and the offset resistance can be remarkably improved.

In the present invention, the molecular weight distribution of the wax is G
It is measured by a PC under the following conditions.

GPC measurement conditions for wax : GPC-15C (Waters) Column: GMH-HT 30 cm, 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1 wt% ionol added) ) Flow rate: 1.0 ml / min Sample: 0.4 ml of 0.15 wt% sample injected

Measurement is performed under the above conditions, and the molecular weight of the sample is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Hou
It is calculated by performing a polypropylene conversion using a conversion formula derived from the win viscosity formula.

When the acid value of the polymer component is A _VL > A _VH , the polyolefin wax (A) having an acid value and having a lower molecular weight as described above has a lower acid value than the high molecular weight polymer component. It acts more on the molecular weight polymer component and exerts low-temperature fixability due to its plasticizing effect. In addition, the polyolefin wax (B) having a higher molecular weight is more affected by the high molecular weight polymer component, and exhibits an effect on high-temperature offset resistance.

The weight-average molecular weight (Mw _WaxA ) of the acid-modified _polyolefin wax (A) is less than 8.0 × 10 ³ ,
When the weight average molecular weight (Mw _wax B) of the polyolefin (B) is less than 1.0 × 10 ⁴ , the high-temperature offset resistance is reduced, and the compatibility between the polymer component and the high / low molecular weight component is not balanced. Collapse, the dispersibility of the wax in the binder resin is reduced, and the developability is likely to be adversely affected.

The weight-average molecular weight (Mw _WaxA ) of the acid-modified polyolefin wax (A) exceeds 1.4 × 10 ^4, and the weight-average molecular weight (Mw) of the polyolefin wax (B)
_{If WaxB} ) exceeds 4.0 × 10 ⁴ , the low-temperature fixability tends to be low, and the dispersibility in the binder resin tends to be low.

When the acid value of the polymer component is A _VL ≦ A _VH , the charge stability of the toner is lowered, and even when a wax having an acid value is contained, the low-temperature fixability and the offset resistance are effectively improved. I can't let it.

The acid-modified polyolefin wax (A)
Preferably has an acid value (A _VWaxA ) satisfying the following conditions.

A _VL > A _VWaxA , A _VWaxA > 0 (mgKO
H / g)

When the acid value of the polymer component is A _VL > A _VH ,
The toner has excellent chargeability, and the acid value of the acid-modified polyolefin wax (A
_VWaxA ) _proved that the fluidity and charge stability of the toner were more stable over a long period of time when the above conditions were satisfied.

More preferably, the acid value of the acid-modified polyolefin wax (A) in the wax is 0.5 × A _VL > A _VWaxA > 0.05 × A with respect to the acid value of the low molecular weight polymer component. It is preferable to satisfy _VL .

Further, the acid-modified polyolefin wax (A) in the wax satisfies the above conditions and has an acid value of 1 to 15.
It is preferably mgKOH / g.

The acid-modified polyolefin wax (A) in the wax is a polypropylene wax whose molecular terminals have been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. Preferably, there is.

Further, acid-modified polyolefin wax (A)
It is more preferred that the acid component and the acid component contained in the low molecular weight polymer component are formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride.

Further, the polyolefin wax (B) in the wax is preferably a polypropylene wax. The polypropylene wax used as the polyolefin wax (B) is a homopolymer of propylene, propylene and another olefin (especially ethylene).
And a copolymer of

In the present invention, the acid value (A _VL ) of the low molecular weight polymer component is 21 to 35 mgKOH / g, and the acid value (A _VH ) of the high molecular weight polymer component is 0.5 to 11 mgK.
OH / g and the relationship is 10 ≦ (A _VL −A _VH )
It is preferred that ≦ 27.

The low-temperature fixability is determined by the Tg of the low molecular weight polymer component.
And the molecular weight distribution, but by containing an acid component in this component and further increasing the acid value of the high molecular weight polymer component by 10 mgKOH / g or more, the same Tg and the same molecular weight distribution can be obtained. The viscosity can be made lower than the resin composition having an acid value outside the above range.

This is because the acid value of the high molecular weight polymer component is set at least 10 mg KOH / g lower than the acid value of the low molecular weight polymer component (acid value 0.5 to 11 mg KOH / g), Entanglement of the molecular chains of the high molecular weight polymer component and the wax with the wax to a certain extent, thus lowering the viscosity on the low temperature side, maintaining the elastic properties on the high temperature side, and further, the wax has a certain domain diameter to form toner particles. It is considered that a sufficient mold release effect can be obtained because of the presence in the metal. This leads to low-temperature fixing in a high-speed machine and improvement in developing characteristics.

On the other hand, the difference in acid value is 27 mgKOH / g
If the ratio exceeds the above range, the miscibility of the low-molecular-weight polymer component and the high-molecular-weight polymer component and the dispersibility of the wax component in the toner will cause problems, and the offset durability and developability tend to decrease.

Further, the acid value of the low molecular weight polymer component is 21
When it is not less than mgKOH / g, the rising property of charging is good.

On the other hand, the acid value of the low molecular weight polymer component is 35 m
If it exceeds gKOH / g, the developability under high humidity tends to decrease.

The acid value of the high molecular weight polymer component is 0.5 mgK
If it is less than OH / g, the low molecular weight polymer component (acid value 2
(1 to 35 mgKOH / g) and miscibility with wax, resulting in reduced offset resistance and fogging.

The polymer component has an acid value / total acid value ratio of:
It is more preferably 0.7 or less (more preferably 0.4 to 0.6). When the value of acid value / total acid value exceeds 0.7, the charge balance of the toner (the frictional charge and the discharge balance of the charge) tends to be charged, and the charge stability of the toner is likely to be reduced. It tends to be up.

The polymer component preferably has a minimum value (Min) in a region having a molecular weight of 3 × 10 ⁴ or more and less than 1 × 10 ⁵ in a GPC chromatogram of a THF-soluble component of the polymer component. In order to achieve both low-temperature fixability and high-temperature offset resistance, it is preferable that the low-molecular-weight polymer component and the high-molecular-weight polymer component have independent molecular weight distributions.

[0119] polymer component of the resin composition of the toner, in relation to the low molecular weight polymer component and a high molecular weight polymer component with respect to the mixing ratio (by _{weight), W L: W H =} 50: 50~90 : 10 is preferably satisfied. The reason is that when the ratio of the low molecular weight polymer component to the high molecular weight polymer component is within this range, the fixability and the offset resistance are improved. If the low molecular weight component is less than 50% by weight, the fixing property is reduced, while the high temperature offset resistance where the high molecular weight component is less than 10% by weight is reduced.

Further, with respect to the relationship between the mixing amount and the acid value,

[0121]

[Outside 40] Is preferably satisfied. The reason is that when the mixing amount of the low molecular weight component and the high molecular weight component and their respective acid values do not satisfy the relationship of the above formula,

[0122]

[Outside 41] The acid value of the low molecular weight component in the whole resin is lower than four times the acid value of the high molecular weight component in the whole resin, the mixing property of the low molecular weight component and the high molecular weight component increases, low viscosity on the low temperature side, high temperature This tends to make it more difficult to emphasize high elasticity on the side.

[0123]

[Outside 42] Is less than 11, the rising characteristics of the charge are deteriorated. On the other hand, when it is more than 30, the developability under high humidity tends to decrease.

In the present invention, the acid value (JIS acid value) of the low molecular weight polymer component and the high molecular weight polymer component of the toner polymer component is determined by the following method.

Dispersion device configuration of each component LC-908 (manufactured by Nippon Kagaku Kogyo Co., Ltd.) JRS-86 (company; repeat injector) JAR-2 (company; autosampler) FC-201 (Gilson; hula cushion collector)

Column configuration JAIGEL-1H to 5H (diameter 20 mm × length 600
mm: preparative column)

Measurement conditions Temperature: 40 ° C. Solvent: THF flow: 5 ml / min Detector: RI

In the sample, additives other than the polymer component are separated in advance. As a fractionation method, an elution time at which the molecular weight becomes 5 × 10 ⁴ is measured in advance, and before and after the elution time, a low molecular weight polymer component and a high molecular weight polymer component are fractionated. The solvent is removed from the sampled sample to obtain an acid value measurement sample.

Measurement of Acid Value (JIS Acid Value) 1) A crushed sample of 0.1 to 0.2 g is precisely weighed, and its weight is defined as W (g).

2) Put the sample in a 20 cc Erlenmeyer flask,
10 cc of a mixed solution of toluene / ethanol (2: 1) is added and dissolved.

3) Add a few drops of an alcohol solution of phenolphthalein as an indicator.

4) Using an alcohol solution of 0.1 N KOH, titrate the solution in the flask with a burette. The amount of the KOH solution at this time is defined as S (ml). At the same time, a blank test was performed, and the amount of the KOH solution
(Ml).

5) The acid value is calculated by the following equation.

[0134]

[Outside 43]

The measurement of the total acid value in the present invention is performed as follows.

Measurement of total acid value 1) A sample is used after removing additives other than the polymer component in advance. About 2 g of the crushed sample is precisely weighed, and its weight is W ′.
(G).

2) A sample was placed in a 200 cc Erlenmeyer flask, and 30 cc of 1,4-dioxane, 10 cc of pyridine,
20 mg of 4-dimethylaminopyridine is added and dissolved for 1 hour.

3) 3.5 cc of ion-exchanged water is added, and the mixture is refluxed for an hour. Then cool.

4) Add a few drops of an alcohol solution of phenolphthalein as an indicator.

5) The solution in the flask is titrated with a 0.1N KOH THF solution using a burette.
The amount of the KOH solution at this time is defined as S ′ (ml). At the same time, a blank test was performed.
l).

6) The total acid value is measured by the following equation.

[0142]

[Outside 44]

As a KOH THF solution, KOH6.
6 g was added to and dissolved in 20 cc of ion-exchanged water.
F720cc and ion-exchanged water 100cc were added, and then methanol was added while stirring until the mixture became transparent.

Examples of the monomer for adjusting the acid value of the polymer component include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid and crotonic acid and α- or β-acrylic acid.
-Alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and monoester derivatives thereof, and maleic anhydride. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired polymer. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value / total acid value.

More specifically, monomethyl maleate,
Α, β-unsaturated dicarboxylic acids such as monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate Monoesters; n-
Monoesters of alkenyl dicarboxylic acids such as monobutyl butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monomethyl phthalate, monomethyl phthalate, monophthalate Monoesters of aromatic dicarboxylic acids such as ethyl ester and monobutyl phthalate are exemplified.

The carboxyl group-containing monomer as described above may be added in an amount of 1 to 20% by weight, preferably 3 to 15% by weight, based on all monomers constituting the polymer side of the binder resin.

The reason that the monoester monomer of dicarboxylic acid is selected as described above is that it is not appropriate to use an acid monomer having high solubility in an aqueous suspension in the suspension polymerization. This is because it is preferable to use the compound in the form of an ester having low solubility.

In the present invention, the carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above method can be saponified by alkali treatment. It is preferable that the carboxylic acid group or the carboxylic acid ester site is changed to a polar functional group by reacting with a cation component of an alkali. Even if the polymer side component of the binder resin contains a carboxyl group that reacts with the metal-containing compound,
This is because the efficiency of the crosslinking reaction is reduced when the carboxyl group is in an anhydrous (ie, ring-closed) state.

This alkali treatment may be carried out after the production of the binder resin, by introducing it as an aqueous alkali solution into the solvent used during the polymerization and stirring. As the alkali, N
hydroxides of alkali metals and alkaline earth metals such as a, K, Ca, Li, Mg, Ba; Zn, Ag, Pb, N
hydroxides of transition metals such as i; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts and pyridium salts. As a particularly preferred example,
NaOH and KOH are mentioned.

The above saponification reaction does not need to be carried out over all of the carboxylic acid groups and carboxylic acid ester sites in the copolymer. The saponification reaction partially proceeds and is converted into a polar functional group. I just need.

The amount of the alkali used in the saponification reaction is difficult to determine unconditionally depending on the type of the polar group in the binder resin, the dispersion method, the type of the constituent monomers, and the like. What is necessary is just 5 times equivalent.
When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction decreases,
As a result, the subsequent crosslinking reaction becomes insufficient. Conversely, when the amount exceeds 5 equivalents, the functional group such as a carboxylic acid ester site is liable to be adversely affected by hydrolysis of the ester and generation of a salt by a saponification reaction.

When an alkali treatment of 0.02 to 5 equivalents of the acid value is performed, the residual cation concentration after the treatment is 5 to 100%.
It is contained between 0 ppm and can be preferably used to regulate the amount of alkali.

The composition constituting the toner has a glass transition temperature (Tg) of 50 to 70 ° C., preferably 55 to 65 ° C., from the viewpoint of storage stability. If the Tg is lower than 50 ° C., it causes deterioration of the toner in a high-temperature atmosphere and offset during fixing. On the other hand, when Tg exceeds 70 ° C., the fixability tends to decrease.

[0154] relationship Tg _H of Tg _L and a high molecular weight polymer component of low molecular weight polymer component of the composition is preferably in the range of _{Tg L ≧ Tg H -5 (℃} ). Tg _L is Tg _H -5
If it is lower than (° C.), the developability tends to decrease.
More preferably, Tg _L ≧ Tg _H is good.

As a method for producing a binder resin composition of a toner, a solution blending method in which a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, then mixed in a solution state, and then the solvent is removed. A dry blending method in which the mixture is melt-kneaded by an extruder or the like; a low-molecular-weight polymer obtained by a solution polymerization method is dissolved in a monomer for constituting a high-molecular-weight polymer, subjected to suspension polymerization, washed with water and dried; A two-stage polymerization method for obtaining the composition is mentioned. However, the dry blending method has problems in terms of uniform dispersion and compatibility, and the two-stage polymerization method has the advantage of uniform dispersibility, but the low molecular weight polymer component is more than the high molecular weight polymer component. In the presence of a low molecular weight polymer component, it is difficult to synthesize a high molecular weight polymer component having a large molecular weight, and unnecessary low molecular weight polymer component is produced as a by-product. Due to problems, the solution blending method is most suitable for application to the present invention. As a method for introducing a predetermined acid value into the low molecular weight polymer component, solution polymerization in which the acid value can be easily set as compared with a polymerization method in an aqueous medium is preferable.

Examples of the method for synthesizing the high molecular weight component of the resin composition include a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
Since it can be easily mixed with a colorant, a charge control agent and other additives, it is advantageous as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is convenient.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). As the dispersant, polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate are used.
It is used in an amount of 0.05 to 1 part by weight based on 0 part by weight. The polymerization temperature is suitably from 50 to 95 ° C., but should be appropriately selected depending on the polymerization initiator used and the target polymer.

As the high molecular weight polymer component of the resin composition, in order to achieve the object of the present invention, it is preferable to use a multitubular polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below. .

Examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-3,3,3.
5-trimethylcyclohexane, 1,3-bis- (t-
Butylperoxyisopropyl) benzene, 2,5-dimethyl-2,5- (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di- (t-butylperoxy) hexyne-3, tris- (t-butylperoxy)
Triazine, 1,1-di-t-butylperoxycyclohexane, 2,2-di-t-butylperoxybutane,
4,4-di-tert-butylperoxyvaleric acid-n-butyl ester, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyazelate, di-tert-butylperoxytrimethyl adipate Two or more peroxide groups in one molecule such as 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides And polyfunctional polymerization initiators having a functional group having a polymerization initiation function such as: diallyl peroxydicarbonate, t-butylperoxymaleic acid, t-butylperoxyallylcarbonate and t-butylperoxyisopropyl fumarate. Functional group having polymerization initiation function such as peroxide group in one molecule Polyfunctional polymerization initiators having both a polymerizable unsaturated group.

Of these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyase And 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for a toner.
Particularly, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a decomposition temperature lower than the decomposition temperature for obtaining a half-life of 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the above-mentioned polyfunctional polymerization initiator. However, in order to maintain the initiator efficiency of the polyfunctional polymerization initiator properly, It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has elapsed under any polymerization conditions.

From the viewpoint of efficiency, these polymerization initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer.

The high molecular weight polymer component of the resin composition used in the present invention is preferably crosslinked with a crosslinkable monomer as exemplified below in order to achieve the object of the present invention.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used.
Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
-Hexanediol acrylate, neopentyl glycol diacrylate, and methacrylates instead of the above compounds; diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol diacrylate). Acrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and methacrylate in place of the acrylate of the above compound); including an aromatic group and an ether bond Diacrylate compounds linked by a chain [for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediakurea , Polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate]; polyester type diacrylate compounds [for example, trade name MANDA (Nippon Kayaku)] Can be As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives: triallyl cyanurate and triallyl trimellitate.

[0169] These cross-linking agents may be used in combination with other monomer components 10
1 part by weight or less, preferably 0.00 part by weight with respect to 0 part by weight
It is preferable to use in the range of 1 to 0.05 part by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of toner fixability and anti-offset property include aromatic divinyl compounds (particularly, divinylbenzene), which are linked by a chain containing an aromatic group and an ether bond. Diacrylate compounds.

On the other hand, as a method for synthesizing the low molecular weight component of the binder resin, a known method can be used. But,
In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In this regard, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent and adjusting the amount of the polymerization initiator and the reaction temperature. ,
It is preferable to obtain a low molecular weight compound in the resin composition used in the present invention. In particular, a solution polymerization method under a pressurized condition is also preferable from the viewpoint of minimizing the amount of the polymerization initiator used and minimizing the influence of the polymerization initiator residue.

The monomers for obtaining the high molecular weight polymer component and the monomers for obtaining the low molecular weight polymer component include:
Examples include the following:

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, p
-N-octylstyrene, pn-nonylstyrene, p
Styrene derivatives such as -n-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene,
Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-methacrylic acid
-Butyl, isobutyl methacrylate, n-methacrylate
Octyl, dodecyl methacrylate, methacrylic acid-2-
Α-methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate; Propyl acrylate, n-octyl acrylate,
Dodecyl acrylate, 2-ethylhexyl acrylate,
Stearyl acrylate, 2-chloroethyl acrylate,
Acrylic esters such as phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole; N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinylnaphthalene;
Acrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide or methacrylic acid derivatives are mentioned. These vinyl monomers are used alone or in combination of two or more.

Of these, a combination of monomers that results in a styrene copolymer or a styrene-acrylic copolymer is preferred.

Further, it is preferable that both the low molecular weight and high molecular weight polymer components contain at least 65 parts by weight of a styrene polymer component or a copolymer component from the viewpoint of miscibility.

As the polypropylene wax used in the present invention, a homopolymer of propylene, a copolymer of propylene and another olefin (particularly, ethylene is preferable) and the like can be used.

As the acid monomer used for modifying the wax component used in the present invention, the same monomers as those used for adjusting the acid value of the polymer component can be used.

In the present invention, a wax having an acid value may be used in combination with a release agent having no acid value.

The weight average molecular weight of the wax (low molecular weight wax) is preferably 30,000 or less, more preferably 10,000 or less, and the addition amount is preferably about 1 to 20 parts by weight based on 100 parts by weight of the binder polymer component.

The wax may be added to and mixed with the binder polymer component in advance in producing the toner. In particular, a method of preliminarily dissolving a low molecular weight wax and a high molecular weight polymer in a solvent at the time of adjusting the polymer component, and then mixing with a low molecular weight polymer solution may be used.

The solid concentration of the polymer solution is 5 to 70% by weight in consideration of dispersion efficiency, prevention of deterioration of resin during stirring, and operability.
The solid concentration of the preliminary solution of the high molecular weight polymer component and the polyolefin polymer is 5 to 60% by weight, and the solid concentration of the low molecular weight polymer solution is 5 to 70% by weight. .

The method of dissolving or dispersing the high molecular weight polymer component and the low molecular weight wax is performed by stirring and mixing, and the stirring may be performed in a batch system or a continuous system.

For example, as a method of mixing a low molecular weight polymer solution, 10 to 1000 parts by weight of the low molecular weight polymer solution is added to 100 parts by weight of the solid content of the preliminary solution, followed by stirring and mixing. Can be In this case, a batch type or a continuous type may be used.

Examples of the organic solvent used when mixing the solution of the resin composition include benzene, toluene, xylol, Solvent Naphtha No. 1, Solvent Naphtha No. 2, Solvent Naphtha No. 3, cyclohexane, ethylbenzene, Solvesso 100, Solvesso 150, and mineral spirits. Hydrocarbon solvents such as methanol, ethanol, iso-
Propyl alcohol, n-butyl alcohol, sec-
Alcohol solvents such as butyl alcohol, iso-butyl alcohol, amyl alcohol and cyclohexanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, n-butyl acetate and cellosolve acetate; Methyl cellosolve, ethyl cellosolve,
Examples include ether solvents such as butyl cellosolve and methyl carbitol. Among these, aromatic, ketone or ester solvents are preferred. They may be used in combination.

The method of removing the organic solvent is preferably a method of heating the organic solvent solution of the polymer, removing 10 to 80% by weight of the organic solvent under normal pressure, and removing the remaining solvent under reduced pressure. At this time, the organic solvent solution is preferably maintained at a temperature of not less than the boiling point of the used organic solvent and not more than 200 ° C. Below the boiling point of the organic solvent, not only is the efficiency at the time of solvent distillation low, but also unnecessary shearing force is applied to the polymer in the organic solvent, and the redispersion of each constituent polymer is promoted, and in a micro state, May cause phase separation. On the other hand, when the temperature is higher than 200 ° C., the polymer is depolymerized, an oligomer is generated by molecular cleavage, and impurities are mixed into the resin composition, which is not preferable.

The present invention may be used as a magnetic toner containing magnetic iron oxide particles.

The magnetic iron oxide particles used in the toner of the present invention are used in an amount of 20 to 2 parts by weight based on 100 parts by weight of the binder resin.
It is preferable to use 00 parts by weight. It is more preferable to use 30 to 150 parts by weight.

In some cases, the magnetic iron oxide particles may be treated with a silane coupling agent, a titanium coupling agent, titanate, aminosilane, or an organosilicon compound.

The silane coupling agent used for the surface treatment of the magnetic iron oxide particles includes hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, and allyldimethylchlorosilane. , Allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilylmercaptan, triorganosilyl acrylate , Vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxa And 1,3-divinyltetramethyldisiloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the titanium coupling agent include isopropoxytitanium triisostearate, isopropoxytitanium dimethacrylate isostearate, isopropoxytitanium tridodecylbenzenesulfonate,
Isopropoxy titanium tris-dioctyl phosphate, isopropoxy titanium tri-N-ethylaminoethyl aminato, titanium bis dioctyl pyrophosphate oxyacetate, bis dioctyl phosphate ethylene dioctyl phosphite, and di-n-butoxy bis triethanol aminato titanium.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils are those having a viscosity of about 30 to 1,000 centistokes at 25 ° C., such as dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil. Silicone oil is preferred.

As a coloring material that can be added to the toner for developing an electrostatic image of the present invention, conventionally known carbon black,
Pigments or dyes such as copper phthalocyanine can be used.

One of the features of the toner for developing an electrostatic image of the present invention is that it contains a metal-containing organic compound as a charge controlling agent. In the case of a negatively chargeable toner, a metal complex compound of a monoazo dye, salicylic acid, and alkyl salicylic acid are used. And a negative charge controlling agent such as a metal complex compound of dialkyl salicylic acid or naphthoic acid.

For example, as the negative charge control agent, there is a metal-containing organic compound represented by the following general formula [I].

[0195]

[Outside 45] [Wherein, M represents a coordination center metal, and Cr having a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group, for example, a phenyl group or a naphthyl group, which may have a substituent, such as a nitro group, a halogen group,
There are a carboxyl group, an anilide group and an alkyl group having 1 to 18 carbon atoms or an alkoxy group. X, X ', Y, and Y' are -O-, -CO-, -NH-, or -NR- (R
Is an alkyl group having 1 to 4 carbon atoms).

[0196]

[Outside 46] Represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium. ]

Next, specific examples of the metal-containing organic compound will be shown.

[0198]

[Outside 47]

[0199]

[Outside 48]

[0200]

[Outside 49]

[0201]

[Outside 50]

[0202]

[Outside 51]

[0203]

[Outside 52]

[0204]

[Outside 53] [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom;
And m ′ represent an integer of 1 to 3, Y ₁ and Y _{3 each} represent a hydrogen atom, C _{1 to} C ₁₈ alkyl, C _{2 to} C ₁₈ alkenyl,
Sulfonamide, mesyl, sulfonic acid, carboxyester, hydroxy, C ₁ -C ₁₈ alkoxy, acetylamino, benzoyl, amino group or halogen atom, n and n ′ represent 1 to 3 integers, Y ₂ and Y ₄ represents a hydrogen atom or a nitro group (X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, and Y ₂ and Y ₄ may be the same or different).

[0205]

[Outside 54] Or a mixed ion thereof. ] A monoazo iron complex compound represented by

[0206]

[Outside 55] (In the formula,

[0207]

[Outside 56] Or a mixed ion thereof. Among them, a monoazo iron complex compound represented by [I] -8 is particularly preferable.

The basic organic acid metal complex compound represented by the following general formula [II] also has negative chargeability and can be used in the present invention.

[0209]

[Outside 57] [Wherein, M represents a coordination center metal, and Cr, a coordination number of 6,
Co, Ni, Mn, or Fe is mentioned. A is

[0210]

[Outside 58] (Alkyl group may have a substituent),

[0211]

[Outside 59] (X represents a hydrogen atom, a halogen atom, or a nitro group) and

[0212]

[Outside 60] (R is a hydrogen atom, an alkyl or alkenyl group of C ₁ -C ₁₈₎ represent.

[0213]

[Outside 61] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or

[0214]

[Outside 62] It is. ]

Next, specific examples of the metal-containing organic compound of the formula [II] will be shown.

[0216]

[Outside 63]

[0219]

[Outside 64]

[0218]

[Outside 65]

These metal complex compounds can be used alone or in combination of two or more.

The amount of the charge control agent to be used is from 0.1 to 100 parts by weight of the binder resin in terms of the charge amount of the toner.
5.0 parts by weight are preferred.

It is preferable that an inorganic fine powder or a hydrophobic inorganic fine powder is externally added to the electrostatic image developing toner of the present invention. For example, fine silica powder, fine titanium oxide powder, or a hydrophobized product thereof may be used. They are preferably used alone or in combination.

Examples of the silica fine powder include a dry method produced by vapor phase oxidation of a silicon halide and a dry method called fumed silica and a wet method produced from water glass and the like. Dry silica with few silanol groups inside and no production residue is preferred.

Further, the silica fine powder is preferably subjected to a hydrophobic treatment. The hydrophobization treatment is provided by chemically treating with an organosilicon compound that reacts or physically adsorbs with the silica fine powder. A preferred method is to treat the dry silica fine powder produced by the vapor phase oxidation of the silicon halide compound with a silane coupling agent or simultaneously with the silane coupling agent and an organic silicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used for the hydrophobic treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldisilane. Chlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilanemercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxy Silane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-di Vinyltetramethyldisiloxane,
1,3-diphenyltetramethyldisiloxane is exemplified.

Examples of the organosilicon compound include silicone oil. As a preferred silicone oil, one having a viscosity at 25 ° C. of about 30 to 1,000 centistokes is used. For example, dimethyl silicone oil, methylphenyl silicone oil, α-
Preferred are methylstyrene-modified silicone oil, chlorophenyl silicone oil, and fluorine-modified silicone oil.

In the method of treating silicone oil, silica fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or the silica oil used as a base may be mixed with silicone oil. The method of injection may be used. Alternatively, it may be prepared by dissolving or dispersing a silicone oil in an appropriate solvent, mixing with a base silica fine powder, and removing the solvent.

As a preferable hydrophobizing treatment of the silica fine powder, there is a method in which the silica fine powder is treated with dimethyldichlorosilane, then treated with hexamethyldisilazane, and then treated with silicone oil.

As described above, it is preferable to treat the silica fine powder with two or more silane coupling agents and then treat it with oil, since the degree of hydrophobicity can be effectively increased.

The above-mentioned silica fine powder which has been subjected to a hydrophobizing treatment and further an oil treatment to the titanium oxide fine powder may be used.
Preferred as well as silica-based.

If necessary, additives other than silica fine powder or titanium oxide fine powder may be externally added to the electrostatic image developing toner of the present invention.

For example, a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing with a hot roll,
These are resin fine particles and inorganic fine particles that function as a lubricant, an abrasive and the like.

The fine resin particles have an average particle size of 0.1.
Those having a thickness of from 03 to 1.0 μm are preferred. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivatives; acrylic acid; methacrylic acid; methyl acrylate , Ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate And acrylates such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, and styrene methacrylate. Lil, phenyl methacrylate, dimethylaminoethyl methacrylate, such as methacrylic acid esters of diethylaminoethyl methacrylate; acrylonitrile, methacrylonitrile, and the like monomers acrylamide.

Examples of the polymerization method include suspension polymerization, emulsion polymerization, and soap-free polymerization. More preferably, particles obtained by soap-free polymerization are good.

In particular, it has been confirmed that the resin fine particles have a great effect in preventing the photosensitive drum from fusing to the photosensitive drum in a contact charging means such as a roller, brush or blade as a primary charging device.

Other fine particles include lubricants such as Teflon, zinc stearate and polyvinylidene fluoride (in particular, polyvinylidene fluoride); abrasives such as cerium oxide, silicon carbide, and strontium titanate (in particular, strontium titanate) Fluidity-imparting agents such as titanium oxide and aluminum oxide (particularly preferably hydrophobic ones); anti-caking agents; and conductivity-imparting agents such as carbon black, zinc oxide, antimony oxide and tin oxide. . Further, a small amount of white fine particles and black fine particles having a polarity opposite to that of the toner may be used as a developing property improver.

The resin fine particles, inorganic fine powder or hydrophobic inorganic fine powder mixed with the toner is used in an amount of 0.1 to 5 parts by weight (preferably 0.1 to 3 parts by weight) based on 100 parts by weight of the toner. Is good.

The toner for developing an electrostatic image of the present invention is prepared by sufficiently mixing a polymer component and a pigment, a dye or a magnetic substance as a colorant, a charge controlling agent, and other additives with a mixer such as a ball mill, and then heating the mixture. It can be produced by melting, kneading, and kneading using a hot kneader such as a roll, kneader, or extruder, and after cooling and solidifying, performing pulverization and strict classification.

As another method for obtaining the toner for developing an electrostatic image of the present invention, the toner can be produced by a polymerization method. The polymerized toner includes a polymerizable monomer, a charge control agent of the present invention, a pigment or dye, a magnetic iron oxide, a polymerization initiator (and a crosslinking agent and other additives as necessary).
Is uniformly dissolved or dispersed into a monomer composition, and then the monomer composition or a prepolymerized version of the monomer composition is added to a continuous phase (eg, water) containing a dispersion stabilizer. The toner particles having a desired particle size are dispersed by using a suitable stirrer and simultaneously subjected to a polymerization reaction. When using magnetic iron oxide in the polymerization method,
It is preferable to perform a hydrophobic treatment in advance.

An example of an image forming method using the present invention will be described with reference to FIG.

The surface of the photosensitive drum (electrostatic image carrier) 1 is negatively charged by the primary charger 742, and a digital latent image is formed by image scanning by exposure to laser light 705, and the magnetic blade 711 and the magnet are included. The latent image is reversely developed with a one-component magnetic toner 710 of a developing device 709 having a developing sleeve 704. In the developing section, the conductive base of the photosensitive drum 1 is grounded, and an alternating bias, a pulse bias, and / or a DC bias are applied to the developing sleeve 704 by bias applying means 712. When the transfer paper P is conveyed and arrives at the transfer section, the transfer paper P is charged by the voltage application means 8 from the back surface (opposite side to the photosensitive drum side) of the transfer paper P by the roller transfer means 2, so that the developed image on the photosensitive drum surface is formed. (Toner image) is transferred onto the transfer paper P by the contact transfer means 2. The transfer paper P separated from the photosensitive drum 1 is subjected to a fixing process by a heating and pressing roller fixing device 707 to fix a toner image on the transfer paper P. The toner image may be later transferred to a transfer sheet via an intermediate transfer member such as an intermediate transfer drum or an intermediate transfer belt.

The one-component magnetic toner remaining on the photosensitive drum after the transfer step is removed by a cleaning device 708 having a cleaning blade. The photosensitive drum 1 after the cleaning is gradually charged by the erase exposure 706, and again
The process starting from the charging process by the primary charger 742 is repeated.

The photosensitive drum has a photosensitive layer and a conductive substrate, and moves in the direction of the arrow. A non-magnetic cylindrical developing sleeve 704 serving as a toner carrier rotates in the developing section so as to advance in the same direction as the surface of the electrostatic image holding member. Inside the non-magnetic cylindrical sleeve 704, a multi-pole permanent magnet (magnet roll) as a magnetic field generating means is arranged so as not to rotate. One-component insulating magnetic toner 710 in developing unit 709
Is applied on a non-magnetic cylindrical surface and the developing sleeve 704
The friction between the surface of the magnetic toner particles and the magnetic toner particles gives the magnetic toner particles, for example, a negative triboelectric charge. Further, an elastic doctor blade 711 is provided so as to press the cylindrical surface, and the thickness of the magnetic toner layer is reduced (from 30 μm to 3 μm).
(Μm) and uniformly regulated to form a magnetic toner layer thinner than the gap between the photosensitive drum 1 and the developing sleeve 704 in the developing section. By adjusting the rotation speed of the developing sleeve 704, the sleeve surface speed is substantially equal to or close to the speed of the photosensitive drum surface. In the developing section, an AC bias or a pulse bias is applied to the developing sleeve 704 by a bias unit 712.
May be applied. This AC bias is f 200
4,000 Hz and Vpp of 500-3,000 V may be used.

At the time of transfer of the magnetic toner particles in the developing section, the toner particles are transferred to the electrostatic image side by the action of the electrostatic force of the electrostatic image holding surface and the AC bias or the pulse bias.

[0244] Instead of the elastic blade 711, a magnetic doctor blade such as iron may be used.

FIG. 2 shows an example of a contact type transfer apparatus.
Reference numeral denotes a transfer roller, which is basically composed of a core 2a at the center and a conductive elastic layer 2b forming the outer periphery thereof. The transfer roller 2 presses the transfer material against the surface of the photosensitive drum 1 with a pressing force, and rotates the photosensitive drum 1 at a constant speed or at a different speed. The transfer material is conveyed between the photosensitive drum 1 and the transfer roller 2 through the guide 4, and a bias having a polarity opposite to that of the toner is applied to the transfer roller 2 from the transfer bias applying unit 3 to thereby transfer the toner image on the photosensitive drum 1. Is transferred to the front side of the transfer material.
Next, the transfer material is fed onto the guide 5.

The conductive elastic layer 2b has a volume resistance of 10 ⁶ to 10 such as polyurethane or ethylene-propylene-diene terpolymer (EPDM) in which a conductive material such as carbon is dispersed.
It is made of an elastic body of 10 ¹⁰ Ωcm.

The preferable transfer process conditions are as follows: the contact pressure of the roller is 5 to 500 g / cm;
0.2 to ± 10 kV.

FIG. 3 shows an example of the charging means. The photosensitive drum 1 has a conductive base layer 1a made of aluminum or the like and a photoconductive layer 1b formed on the outer surface thereof as basic constituent layers.
It is rotated at a predetermined peripheral speed (process speed) clockwise in the drawing.

Reference numeral 42 denotes a charging roller, and the central core 4
2a, and a conductive elastic layer 42b and a surface layer 42c each having the outer periphery formed thereon. Charging roller 4
2 is pressed against the surface of the photosensitive drum 1 with a pressing force,
The photosensitive drum 1 rotates following the rotation of the photosensitive drum 1. A voltage is applied to the charging roller 42 by the bias applying unit E, and the surface of the photosensitive drum 1 is charged to a predetermined polarity / potential by applying a bias to the charging roller 42. Next, an electrostatic charge image is formed by image exposure, and the electrostatic charge image is sequentially visualized as a toner image by a developing unit.

As a preferable process condition when the charging roller is used, the contact of the roller is 5 to 500 g / cm.
In the case where a voltage superimposed on a DC voltage is used, an AC voltage = 0.5 to 5 kVpp, an AC frequency = 50 to 5 kHz,
The DC voltage is ± 0.2 to ± 1.5 kV, and when the DC voltage is used, the DC voltage is ± 0.2 to ± 5 kV.

The material of the charging roller is preferably a conductive rubber, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

The charging roller may be a contact charging means such as a charging blade or a charging brush.

FIG. 7 shows a specific example of the process cartridge. The process cartridge at least integrates the developing unit and the electrostatic image holder into a cartridge, and the process cartridge is formed so as to be detachable from a main body of the image forming apparatus (for example, a copying machine, a laser beam printer, or the like).

In this example, a process cartridge 750 in which a developing means 709, a drum-shaped electrostatic image holder (photosensitive drum) 1, a cleaner 708 having a cleaning blade 708a, and a primary charger (charging roller) 742 are integrated. Is exemplified.

The developing means 709 includes an elastic blade 71
1 and a magnetic toner 710 in a toner container 760. When the magnetic toner 710 is used, the photosensitive drum 1 and the developing sleeve
In order for a predetermined electric field to be formed between the photosensitive drum 1 and the developing sleeve
The distance between the four is very important.

Hereinafter, the present invention will be described with reference to specific examples.

Production Example 1 of Resin Composition Synthesis of Low Molecular Weight Polymer (L-1) 300 parts by weight of xylene was charged into a four-necked flask, and the inside of the vessel was sufficiently purged with nitrogen while stirring. Warmed to reflux.

Under the reflux, a mixture of 75 parts by weight of styrene, 18 parts by weight of n-butyl acrylate, 7 parts by weight of monobutyl maleate and 2 parts by weight of di-tert-butyl peroxide was added dropwise over 4 hours. Thereafter, the mixture was held for 2 hours to complete the polymerization, thereby obtaining a low molecular weight polymer (L-1) solution.

A part of the polymer solution was sampled,
The polymer was dried under reduced pressure, and the obtained low molecular weight polymer (L-1) was obtained.
Was measured for GPC and glass transition point (Tg), the weight average molecular weight (Mw) was 9,600, the number average molecular weight (Mn) was 6,000, and the peak molecular weight (PMw) was 8 , 500 and a Tg of 62 ° C.
The acid value was 25.

At this time, the conversion of the polymer was 97%.

Synthesis of high molecular weight polymer (H-1) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and then 70 parts by weight of styrene and acrylic acid 25 parts by weight of n-butyl, 5 parts by weight of monobutyl maleate, 0.005 parts by weight of divinylbenzene, and 2,2-bis (4,4-di-t
A mixed solution of 0.1 part by weight of tert-butyl per-oxycyclohexyl) propane (half-life 10 hours, temperature: 92 ° C.) was added and stirred to prepare a suspension.

After sufficiently replacing the inside of the flask with nitrogen, 8
The temperature was raised to 5 ° C. to initiate polymerization. After maintaining at the same temperature for 24 hours, 0.1 part by weight of benzoyl peroxide (half-life of 10 hours; temperature of 72 ° C.) was additionally added. Further, the polymerization was completed by holding for 12 hours.

To the suspension after completion of the reaction, an aqueous NaOH solution equivalent to 6 times the acid value (AV = 7.8) of the obtained high molecular weight polymer (H-1) was added, and the mixture was stirred for 2 hours. Was.

The high molecular weight polymer (H-1) was separated by filtration, washed with water, dried, and analyzed. As a result, it was found that Mw was 1.8 million, PMw was 1.2 million, Tg was 62 ° C. The value was 6.

Preparation of Resin Composition In a four-necked flask, 100 parts by weight of xylene and 25 parts by weight of the high molecular weight polymer (H-1) were charged, and the mixture was heated, stirred under reflux, and preliminarily dissolved. went. This state was maintained for 12 hours to obtain a preliminary solution (Y-1).

On the other hand, the low molecular weight polymer (L-
300 parts by weight of the homogeneous solution of 1) was charged and refluxed.

After the above pre-dissolved solution (Y-1) and the low molecular weight polymer (L-1) solution were mixed under reflux, the organic solvent was distilled off, and the obtained resin was cooled, solidified and pulverized. A toner resin composition (I) was obtained.

When the resin composition (I) was analyzed, it was found that P
Mw is 1.1 million, the area ratio in the molecular weight distribution of GPC of the resin composition having a molecular weight of 1,000,000 or more is 9.2%, Tg is 62.5 ° C., and the THF-insoluble content is 2.1% by weight. there were.

Production Examples 2, 3, and 6 of Resin Compositions and Comparative Products
Production Example 2 In the same manner as in Production Example 1 of the resin composition, the amounts of monobutyl maleate, styrene, n-butyl acrylate and the amount of the polymerization initiator were adjusted to obtain low molecular weight polymers (L-2) to (L-4). And (L-6) were obtained, and a predetermined amount of the high molecular weight polymer (H-1) was blended to obtain resin compositions (II), (III) and (V).
I) and (ii) were obtained. Table 1 shows various data.

Production Examples 4, 7 and Comparative Production Examples of Resin Compositions
1 In the same manner as in Production Example 1 of the resin composition, the amounts of monobutyl maleate, styrene, n-butyl acrylate and the amount of the polymerization initiator were adjusted, and the low molecular weight polymer (L-5) and the high molecular weight polymer (H- 2), (H-4) and (H-5) are obtained, and a predetermined amount of the low molecular weight polymer (L-1) or (L-5) is blended to obtain resin compositions (IV), (VII) and (VII). i) was obtained.
Table 1 shows various data.

Preparation Example 5 of Resin Composition Synthesis of High Molecular Weight Polymer H-3 85 parts by weight of styrene and 15 parts by weight of butyl methacrylate were charged into a four-necked flask and subjected to bulk polymerization, followed by 300 parts by weight of xylene and 0.1 parts by weight of benzoyl peroxide was added as a polymerization initiator, and solution polymerization was performed in the presence of a solvent to obtain a high molecular weight polymer (H-3). Table 1 shows the analysis results of the obtained high molecular weight polymer (H-3).

Production of Resin Composition Production Example 1 except that the high molecular weight polymer (H-3) was used.
In the same manner as in the above, a resin composition (V) was obtained. Table 1 shows various data.

[0273]

[Table 1]

Example 1 100 parts by weight of resin composition (I) 100 parts by weight of magnetic iron oxide (average particle size 0.2 μm) ・ Propylene-ethylene copolymer wax copolymerized with maleic anhydride (graph) (Polymerization weight ratio: 92: 8)
(Acid value 3.5, Mw 9000) 4 parts by weight 2 parts by weight of the following negative charge controlling agent

[0275]

[Outside 66]

The above materials were melted and kneaded with a biaxial extruder heated to 140 ° C., and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill.
The obtained finely pulverized powder was classified by a fixed wall type air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed at the same time by a multi-division classifier (Elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) utilizing the Coanda effect to remove the ultrafine powder and the coarse powder at the same time to obtain a weight average particle diameter (D4) 6. As a result, a negatively chargeable magnetic toner having a thickness of 0.1 μm was obtained. Tables 2 and 3 show the physical properties of the obtained toner.
FIG. 5 shows a chart of the PC chromatogram.

100 parts by weight of this magnetic toner, 1.2 parts by weight of hydrophobic silica fine powder (BET 160 m ² / g) treated with dimethyldichlorosilane, treated with hexamethyldisilazane, and then treated with dimethylsilicone oil. And styrene-acrylic fine particles (average particle size: 0.05 μm) obtained by soap-free polymerization were mixed with a Henschel mixer to prepare a magnetic toner (magnetic toner No. A).

Examples 2 to 9 and Comparative Examples 1 to 4 Resin compositions (II) to (VI) were used instead of resin composition (I).
I), (i) and (ii), and a negatively chargeable magnetic toner [Magnetic Toner No. BI
And No. (A) to (d)] were obtained. Tables 2 and 3 show the physical properties of the obtained magnetic toner.

[0279]

[Table 2]

[0280]

[Table 3]

Image output test The above magnetic toner was placed in a process cartridge, and a laser beam printer LBP-A309HII manufactured by Canon was used.
(Using an OPC photosensitive drum) was remodeled by A4 transverse feed from 16 sheets / min to 36 sheets / min, and an image evaluation was performed using a remodeling machine incorporating a transfer device shown in FIG. At this time, the process speed was 165 mm / sec.

As a transfer roller as a contact transfer means,
Transfer roller surface rubber hardness 27 °, transfer current 1μA,
The transfer voltage was +2000 V and the contact pressure was 50 g / cm. The conductive elastic layer of the transfer roller is formed of EPDM in which conductive carbon is dispersed, and has a volume resistance of 10 ⁸ Ω.
Cm.

The charging roller shown in FIG. 3 was set in the process cartridge as a contact charging means, and primary charging was performed. The outer diameter of the charging roller 42 was 12 mm in diameter. EPDM was used for the conductive rubber layer 42b, and nylon resin having a thickness of 10 μm was used for the surface layer 42c. Charging roller 42
Had a hardness of 54.5 ° (ASKER-C). E is a bias power supply for applying a voltage to the charging roller 42,
A predetermined voltage is supplied to the metal core 42 a of the charging roller 42. In FIG. 3, E indicates a system in which an AC voltage is superimposed on a DC voltage. The conditions were as follows.

In the process cartridge, an elastic coating blade made of urethane rubber having a function of frictionally charging the toner was installed so as to press the developing sleeve.

The gap is set so that the primary charge is -700 V, the OPC photosensitive drum is not in contact with the magnetic toner layer on the developing sleeve (including the magnet), and the AC bias (f =
While applying 1800 Hz, Vpp = 1800 V) and a DC bias (V _DC = -500 V) to the developing sleeve, _VL is set to -170 V, and the electrostatic charge image is developed to form a magnetic toner image on the OPC photosensitive drum. did.

The formed magnetic toner image was transferred to plain paper at the above positive transfer potential, and the plain paper having the magnetic toner image was fixed on the plain paper through a heat and pressure roller fixing device.

At this time, the surface temperature of the heating roller of the heating / pressing roller fixing device was set at 190 ° C., the total pressure between the heating roller and the pressure roller was set at 19 kg, and the nip was set at 6 mm.

Under the above set conditions, an image-drawing test was performed in a high temperature and high humidity environment (temperature 32.5 ° C., humidity 85% RH) and a low temperature and low humidity environment (temperature 10 ° C., humidity 15% RH). The obtained images were evaluated for the following items. The print mode was an intermittent mode, 2 sheets / 20 sec.

1) Image density 10,000 ordinary paper for ordinary copying machines (75 g / m ² )
Evaluation was made by maintaining the image density at the end of printing out one sheet. Image density is "Macbeth reflection density" (manufactured by Macbeth)
Was used to measure the relative density of a white background portion with a document density of 0.00 with respect to the printout image.

2) Fog Fog was calculated from a comparison between the whiteness of the transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness on transfer after printing solid white. The environment was low temperature and low humidity (temperature 15 ° C., humidity 10% RH), and the print mode was 2 sheets / 20 sec.

3) Image Quality The pattern shown in FIG. 4 was printed out and its dot reproducibility was evaluated.

A: Very good (2 or less defects / 100) B: Good (3 to 5/100 defects) C: Practical (6 to 10/100 defects) D: Not practical (Less 11 or more / 100)

(4) Uniformity of Image Density A solid black sample image was printed out on A4 size transfer paper, and the image density unevenness was evaluated based on the difference between the maximum value and the minimum value of the image density within one page. . Table 4 shows the image density difference.

Fixability and Offset Resistance Test The above magnetic toner was placed in a process cartridge, and the laser beam printer LBP-309GII manufactured by Canon was remodeled from 16 sheets / min to 24 sheets / min (total pressure 18 kg).
Set the surface temperature of the heating roller of the heating and pressing roller fixing unit to 1
Set the same charging, developing, and transfer conditions as those of the above-described image output tester except that the temperature can be changed from 40 to 230 ° C from the outside, and change the set temperature in 5 ° C increments at room temperature and normal humidity. (Temperature: 20 ° C., Humidity: 60% RH) The image sample was printed out.

1) Fixability The fixability was determined by applying a load of 50 g / cm ² and rubbing the fixed image with soft thin paper. The lowest fixing temperature at which the reduction rate (%) of the image density before and after rubbing was 10% or less was evaluated as the minimum fixing temperature. Table 4 shows the minimum fixing temperature. Plain paper for copiers (75
g / m ² ) paper was used.

2) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image. Table 4 shows the maximum temperature at which no stain on the image occurs.
As the test paper, plain paper for a copying machine (65 g / m ² ) was used.

The results of the evaluation are shown in Table 4.

[0298]

[Table 4]

Example 10 100 parts by weight of resin composition (I) 100 parts by weight of magnetic iron oxide (average particle size 0.2 μm) Maleic anhydride-modified propylene-ethylene copolymer wax (acid value 3.5, (Mw9000) 4 parts by weight 2 parts by weight of negative charge control agent shown below

[0300]

[Outside 67]

The above materials were melt-kneaded with a biaxial extruder heated to 140 ° C., and the cooled kneaded material was roughly pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill.
The obtained finely pulverized powder was classified by a fixed wall type air classifier to produce a classified powder. Furthermore, the ultrafine powder and coarse powder were simultaneously strictly classified and removed by a multi-segment classification device (elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) utilizing the Coanda effect to obtain a weight average particle size (D4) 5. As a result, a negatively chargeable magnetic toner of 0.7 μm was obtained.

100 parts by weight of this magnetic toner, 1.5 parts by weight of hydrophobic silica fine powder (BET 160 m ² / g) treated with dimethyldichlorosilane, hexamethyldisilazane, and then treated with dimethylsilicone oil And 0.08 parts by weight of styrene-acrylic fine particles (average particle size: 0.05 μm) obtained by soap-free polymerization using a Henschel mixer to prepare a magnetic toner (Toner No. A-2).

The magnetic toner No. The particle size distribution of A-2 was measured using a Coulter Multisizer (manufactured by Coulter Inc.), and the data was converted into 16 channels as shown in Table 5, and the particle size distribution was as shown in Table 5. The weight average particle size is 5.71 μm, and the particle size in the number distribution is 2.52.
5.6% for particles of μm or less, 17.5 for particles of 3.17 μm or less.
%, Particle diameter 5.04 μm or less was 69.8%, and porosity was 0.55.

Tables 6 and 7 show the physical properties of the obtained magnetic toner.
Shown in

[0305]

[Table 5]

Examples 11 to 18 and Comparative Examples 5 to 8 Resin compositions (II) to (VI) were used instead of the resin compositions (I).
I), (i) and (ii), and a negatively chargeable magnetic toner [Toner No. (B-
2) to (I-2) and No. (A-2) to (d-2)]
I got Tables 6 and 7 show the physical properties of the obtained toner.

Comparative Example 9 In Comparative Example 5, a magnetic toner (e-2) was obtained by changing the toner production conditions during pulverization and classification.

[0308]

[Table 6]

[0309]

[Table 7]

Image Depth Test The above magnetic toner was placed in a process cartridge, and under the same apparatus and setting conditions as in Example 1, under a high temperature and high humidity environment (temperature 32.5 ° C., humidity 85% RH) and a low temperature and low humidity environment. (1
(0 ° C., 15% RH), and an image obtained was evaluated for the following items. The print mode was 2 sheets / 20 sec.

1) Image density The same procedure as in Example 1 was performed.

2) Fog The fog was carried out in the same manner as in Example 1.

3) Dot Reproducibility An independent one-dot pattern was printed out under an environment of 23 ° C. and 60% RH, and the reproducibility of one dot was evaluated by microscopic observation.

A: The dots are faithfully reproduced. B: The dots are faithfully reproduced, but there is some scattering. C: The image is slightly disturbed. D: The image is disturbed and the reproducibility is poor.

4) Sleeve Coat The sleeve coat was evaluated by continuously printing 10 solid white images in an environment of 15 ° C./10% RH and then printing a solid black black character portion: B and solid as shown in FIG. White white part: An image in which a halftone portion was formed on the entire surface following the stripe pattern portion of A was printed and evaluated visually.

Fixing Property and Offset Resistance Test A test was conducted in the same manner as in Example 11.

The results of the evaluation are shown in Table 8.

[0318]

[Table 8]

Example 19 100 parts by weight of resin composition (I) 100 parts by weight of magnetic iron oxide (average particle size: 0.2 μm) Propylene-ethylene copolymer wax graft-copolymerized with maleic anhydride (copolymerization) Body polymerization ratio 92:
8) (Mw = 9000, acid value 3.5, melting point 123 ° C.)
3 parts by weight ・ Polypropylene (Mw = 20,000) 4 parts by weight ・ Negative charge control agent shown below 2 parts by weight

[0320]

[Outside 68]

The above-mentioned materials were melt-kneaded with a twin-screw extruder heated to 140 ° C., and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The powder was classified with a fixed wall air classifier to produce a classified powder. Further, the obtained classified powder is strictly classified and removed at the same time by a multi-division classifier (Elbow jet classifier manufactured by Nippon Steel Mining Co., Ltd.) utilizing the Coanda effect to remove the ultrafine powder and the coarse powder at the same time to obtain a weight average particle diameter (D4) 6. As a result, a negatively chargeable magnetic toner having a thickness of 0.1 μm was obtained. Tables 10 and 11 show the physical properties of the obtained magnetic toner.

100 parts by weight of this magnetic toner, 1.2 parts by weight of hydrophobic silica fine powder (BET 160 m ² / g) treated with dimethyldichlorosilane, hexamethyldisilazane, and then treated with dimethylsilicone oil And 0.08 parts by weight of styrene-acrylic fine particles (average particle diameter 0.05 μm) obtained by soap-free polymerization were mixed with a Henschel mixer to prepare a magnetic toner (Magnetic Toner No. A-3).

Examples 20 to 29 and Comparative Examples 10 to 14 Instead of the resin composition (I), the resin compositions (II) to (V)
II) and (i), (ii), except that the wax is changed to a different type and acid number as shown in Table 9.
In the same manner as in Example 19, the negatively chargeable magnetic toner [magnetic toner No. (B-3) to (I-3) and (A-3)
~ (D-3)]. Tables 10 and 11 show the physical properties of the obtained magnetic toner.

[0324]

[Table 9]

[0325]

[Table 10]

[0326]

[Table 11]

Image Depth Test The above magnetic toner was placed in a process cartridge, and the same apparatus and setting conditions as in Example 1 were used in a high-temperature, high-humidity environment (3
2.5 ° C, 85% RH) and low temperature and low humidity environment (10 ° C,
(15% RH), and the obtained image was evaluated for the same items as in Example 1. The print mode was 2 sheets / 20 sec.

The results of the evaluation are shown in Table 12.

[0329]

[Table 12]

[0330]

As described above, the toner of the present invention can be prepared by adjusting the molecular weight distribution of the polymer component in the composition, the acid value of the low molecular weight component and the acid value of the high molecular weight component, and the acid value of the wax to be contained. It has better low-temperature fixability and offset resistance than before, and has excellent toner fluidity and charging, reduces fog, is excellent in image quality, and enables long-term durability. Further, the present invention enables long-term charging stability even when applied to increase the speed of the apparatus.

[Brief description of the drawings]

FIG. 1 is a graph showing a particle size distribution range of Expressions (1) and (2).

FIG. 2 is a diagram schematically illustrating a transfer device.

FIG. 3 is a diagram schematically illustrating a charging roller.

FIG. 4 is an explanatory diagram of a checker pattern for testing a developing characteristic of a toner.

FIG. 5 is a chart diagram of a GPC chromatogram of the resin according to Example 1.

FIG. 6 is a schematic diagram illustrating an example of an image forming method in which the present invention is used.

FIG. 7 is a diagram illustrating a specific example of a process cartridge.

FIG. 8 is a schematic diagram illustrating an image pattern used for evaluating a sleeve ghost.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 latent image carrier (photoreceptor) 2 transfer roller 2 a cored bar 2 b conductive elastic layer 3 constant voltage power supply 42 charging roller 704 developing sleeve 742 charging roller

Claims (98)

[Claims] 1. A toner for developing an electrostatic image formed from a composition containing at least a polymer component, a colorant, a wax and a charge control agent, wherein the polymer component of the composition is substantially (a) It contains no THF-insoluble matter, and the THF-soluble matter of the polymer component (b) has a molecular weight of at least 3 × 10 ^{3 to} 3 × 10 ^{4 in} a GPC chromatogram.
And a molecular weight of 1 × 10 ⁵ to
(C) an acid value (A _VL ) of a low molecular weight polymer (a region having a molecular weight of less than 5 × 10 ⁴ in a GPC chromatogram) and a high molecular weight polymer (GPC chromatograph) having a subpeak or shoulder in a 3 × 10 ⁶ region. 5 × 1 molecular weight in grams
0 ⁴ or more regions) the acid value of (A _VH) and has to satisfy the following condition A _VL> A _VH, the wax is satisfying the following condition _{A VL> A VWax, A VWax} > 0 (mgKOH / g) _And a wax having an acid value (A _VWax ). 2. The electrostatic image developing toner according to claim 1, wherein the acid value of the wax satisfies the following condition with respect to the acid value of the low molecular weight polymer component. 0.5 × A _VL > A _VWax > 0.05 × A _VL 3. The toner for developing an electrostatic image according to claim 1, wherein the wax is an acid-modified polyolefin wax having an acid value of 1 to 15 mgKOH / g. 4. The wax according to claim 1, wherein the wax is a polyolefin wax whose molecular terminal has been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. The toner for developing an electrostatic charge image as described in the item (1). 5. The wax according to claim 1, wherein the wax is a polypropylene wax whose molecular terminal is modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. The toner for developing an electrostatic image according to any one of the above. 6. The acid component of the wax and the acid component of the low molecular weight polymer component formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. The toner for developing an electrostatic image according to claim 1, wherein: 7. The wax has an acid value (A _VWax ) of 1 to 15 m.
gKOH / g, the acid value (A _VL ) of the low molecular weight polymer component of the polymer component is 21 to 35 mg KOH / g, and the acid value (A _VH ) of the high molecular weight polymer component is 0.5. ~
The toner for developing an electrostatic image according to claim 1, wherein the toner is 11 mgKOH / g. 8. The low molecular weight polymer having an acid value (A _VL ) of 21 to 21.
35 mgKOH / g, the acid value (A _VH ) of the high molecular weight polymer component is 0.5 to 11 mgKOH / g, and the relationship between the differences is 10 ≦ (A _VL −A _VH ) ≦ 27. The electrostatic image developing toner according to claim 1. 9. A GPC chromatogram of a THF-soluble component of the polymer component, which has a molecular weight of 3 × 10 ⁴ or more to 1 ×.
9. The electrostatic image developing toner according to claim 1, which has a minimum value in a region of less than 10 ⁵ . 10. The composition having a glass transition point (Tg) of 5
0-70 ° C. and the T of the low molecular weight polymer of the composition
g _L and the relationship Tg _H of the high molecular weight polymer, Tg _L ≧ Tg _H toner according to any one of claims 1 to 9 is in the range of -5. Tg of 11. The composition is 55 to 65 ° C., and the relationship of Tg _H of Tg _L and a high molecular weight polymer component of low molecular weight polymer component, wherein in the range of Tg _L ≧ Tg _H Item 11. The electrostatic image developing toner according to any one of Items 1 to 10. 12. The electrostatic image developing toner according to claim 1, wherein a polymer component of the composition satisfies the following formula. [Outside 1] 13. The electrostatic charge according to claim 1, wherein both the low molecular weight polymer component and the high molecular weight polymer component have at least 65% by weight of a styrene monomer component unit. Image developing toner. 14. The electrostatic image developing toner according to claim 1, wherein the high molecular weight polymer component has a polymer polymerized with a polyfunctional polymerization initiator. 15. The electrostatic image according to claim 1, wherein the high molecular weight polymer component has a polymer polymerized by using at least a combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator. Development toner. 16. The electrostatic image developing toner according to claim 1, wherein in a GPC chromatogram of the polymer component, an area ratio of the polymer component having a molecular weight of 1,000,000 or more is 10% or less. 17. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [Wherein, M represents a coordination center metal, and Cr, a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group, which may have a substituent, wherein the substituent is a nitro group,
Halogen group, carboxyl group, anilide group and carbon number 1
To 18 alkyl groups or alkoxy groups. X,
X ', Y and Y' represent -O-, -CO-, -NH- or-
NR- (R is an alkyl group having 1 to 4 carbon atoms). [Outside 3] Represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium. 17. The electrostatic image developing toner according to claim 1, which is a compound represented by the formula: 18. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [Wherein, M represents a coordination center metal, and Cr having a coordination number of 6,
Co, Ni, Mn or Fe. A is [outside 5] (Which may have a substituent of an alkyl group), (X represents a hydrogen atom, a halogen atom, or a nitro group) and (R is a hydrogen atom, an alkyl or alkenyl group of C ₁ -C ₁₈₎ represent. [Outside 8] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or It is. 18. The electrostatic image developing toner according to claim 1, which is a compound represented by the formula: 19. The metal-containing organic compound represented by the following formula [II
I] [Outside 10] [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, m and m ′ each represent an integer of _{1 to 3} , and Y ₁ and Y ₃ represent a hydrogen atom , alkyl of C ₁ ~C _18, C ₂ ~C
_{18 represents} an alkenyl, sulfonamide, mesyl, sulfonic acid, carboxyester, hydroxy, C ₁ -C ₁₈ alkoxy, acetylamino, benzoyl, amino group or halogen atom; n and n ′ represent 1 to 3 integers; Y ₂ and Y ₄ represents a hydrogen atom or a nitro group, (X ₁ and X ₂ above, m and m ', Y ₁ and Y _3, n and n', Y
₂ and Y ₄ may be the same and different. [Outside 11] Or a mixed ion thereof]. The toner for developing an electrostatic image according to claim 17, which is a compound represented by the following formula: 20. The organic compound of the following formula [I]
V] [Outside 12] [Where, Or a mixed ion thereof. 20. The toner according to claim 19, which is a compound represented by the formula: 21. The toner has a toner weight average diameter (D ₄ ) of X (μm) and a toner number average diameter of 3.17.
21. A particle size distribution satisfying the following formula: -5X + 35 ≦ Y ≦ −25X + 180 (1) 3.5 ≦ X ≦ 6.5 (2), where Y (%) is a ratio of μm or less. The toner for developing an electrostatic charge image according to any of the above items. 22. A wax containing at least an acid-modified polyolefin (A) modified with an acid monomer and a polyolefin (B), wherein the acid-modified polyolefin (A) has a weight average molecular weight (Mw).
_WaxA ) is 8.0 × 10 ^{3 to} 1.4 × 10 ⁴ , and the polyolefin (B) has a weight average molecular weight (Mw _WaxB ) of 1.0 × 10 ^{3 to} 1.4 × 10 ⁴ .
0 × 10 ^{4 to} 4.0 × 10 ⁴ , wherein the acid-modified polyolefin (A) has an acid value (A _VWaxA ) satisfying the following conditions: A _VL > A _VWaxA , A _VWaxA > 0 (mgKOH / g) Claims 1 to 21
The toner for developing electrostatic images according to any one of the above. 23. The toner according to claim 22, wherein the polyolefin (B) has a weight average molecular weight (Mw _WaxB ) of 1.5 × 10 ^{4 to} 2.5 × 10 ⁴ . 24. The acid value of the acid-modified polyolefin (A) (A _VWaxA) is, with respect to low molecular weight polymer component of acid value (A _VL), the following conditions _{0.5 × A VL> A VWaxA ×} 0. The electrostatic image developing toner according to claim 22, wherein the toner satisfies 05 × A _VL . 25. The acid-modified polyolefin (A) is 1 to
25. An acid value of 15 mg KOH / g.
The toner for developing electrostatic images according to any one of the above. 26. The acid-modified polyolefin (A) is a polypropylene wax whose molecular terminals have been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. 30. The toner for developing an electrostatic image according to any one of items 25 to 25. 27. The electrostatic image developing toner according to claim 22, wherein the polyolefin (B) is a polypropylene wax. 28. The acid component of the acid-modified polyolefin and the acid component of the low molecular weight polymer component are formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. The electrostatic image developing toner according to any one of claims 22 to 27, wherein the toner is developed. 29. The acid value of the acid-modified polyolefin (A)
_VWaxA ) is 1 to 15 mgKOH / g, and the acid value (A _VL ) of the low molecular weight polymer component is 21 to 23 mgKOH / g.
The electrostatic image developing toner according to any one of claims 22 to 28, wherein the toner has an acid value (A _VH ) of 0.5 to 11 mgKOH / g, which is 5 mgKOH / g. 30. An electrostatic image carrier and at least developing means for developing an electrostatic image formed on the electrostatic image carrier using toner, wherein the electrostatic image carrier and the developing means are The process cartridge is integrally formed into a cartridge, the process cartridge is detachable from the image forming apparatus main body, and the toner is formed of a composition containing at least a polymer component, a colorant, a wax, and a charge control agent, The polymer component of the composition is (a) substantially free of THF-insoluble components, and (b) the THF-soluble component of the polymer component has a molecular weight of at least 3 × 10 ³ to 3 × 10 ³ in a GPC chromatogram. ^Four
And a molecular weight of 1 × 10 ⁵ to
(C) an acid value (A _VL ) of a low molecular weight polymer (a region having a molecular weight of less than 5 × 10 ⁴ in a GPC chromatogram) and a high molecular weight polymer (GPC chromatograph) having a subpeak or shoulder in a 3 × 10 ⁶ region. 5 × 1 molecular weight in grams
0 ⁴ or more regions) the acid value of (A _VH) and has to satisfy the following condition A _VL> A _VH, the wax is satisfying the following condition _{A VL> A VWax, A VWax} > 0 (mgKOH / g) A process cartridge containing a wax having an acid value (A _VWax ). 31. The process cartridge according to claim 30, further comprising contact charging means for charging the electrostatic image holder. 32. The process cartridge according to claim 31, wherein the contact charging means is a charging roller. 33. The process cartridge according to claim 31, wherein the contact charging means is a charging blade. 34. The process cartridge according to claim 31, wherein the contact charging means is a charging brush. 35. The apparatus according to claim 3, further comprising cleaning means for cleaning the surface of the electrostatic image holding member.
35. The process cartridge according to any one of 0 to 34. 36. The process cartridge according to claim 35, wherein the cleaning means has a cleaning blade. 37. The acid value of the wax satisfies the following condition with respect to the acid value of the low molecular weight polymer component.
7. The process cartridge according to any one of 6. 0.5 × A _VL > A _VWax > 0.05 × A _VL 38. The wax according to claim 1, wherein the wax is 1 to 15 mgKOH / g.
The process cartridge according to any one of claims 30 to 37, wherein the process cartridge is an acid-modified polyolefin wax having an acid value of: 39. The wax according to claim 39, wherein the wax is at least one of maleic acid, maleic acid half ester or maleic anhydride.
4. A polyolefin wax whose molecular terminal is modified by an acid monomer selected from at least one species.
9. The process cartridge according to any one of the above items 8. 40. The method according to claim 40, wherein the wax comprises at least one of maleic acid, maleic acid half ester or maleic anhydride.
The process cartridge according to any one of claims 30 to 39, wherein the process cartridge is a polypropylene-based wax whose molecular terminal is modified with an acid monomer selected from at least one kind. 41. An acid component selected from at least one of maleic acid, maleic acid half ester and maleic anhydride, wherein the acid component of the wax and the acid component of the low molecular weight polymer component are formed. The process cartridge according to any one of claims 30 to 40, wherein: 42. The wax has an acid value (A _VWax ) of 1 to 15.
mgKOH / g, and the acid value (A _VL ) of the low molecular weight polymer component of the polymer component is 21 to 35 mgKOH / g, and the acid value (A _VH ) of the high molecular weight polymer component is 0.5.
The process cartridge according to any one of claims 30 to 41, wherein the amount is from 11 to 11 mgKOH / g. 43. The low molecular weight polymer having an acid value (A _VL ) of 21
And the acid value (A _VH ) of the high molecular weight polymer is 0.5 to 11 mg KOH / g, and the relationship between the differences is 10 ≦ (A _VL −A _VH ) ≦ 27. The process cartridge according to any one of claims 30 to 42. 44. GPC of a THF-soluble component of the polymer component
In the chromatogram, the molecular weight is 3 × 10 ⁴ or more and 1 × 1
0 The process cartridge according to any one of claims 30 to 43 to ⁵ below the region having the minimum value. 45. The composition has a glass transition point (Tg) of 5
0-70 ° C. and the T of the low molecular weight polymer of the composition
g _L and process cartridge according to any one of claims 30 to 44 relationship Tg _H of the high molecular weight polymer is in the range of Tg _L ≧ Tg _H -5. 46. a Tg of 55 to 65 ° C. of the composition, and claims relationship Tg _H of Tg _L and a high molecular weight polymer component of low molecular weight polymer component is in the range of Tg _L ≧ Tg _H 45. The process cartridge according to any one of 30 to 45. 47. The process cartridge according to claim 30, wherein the polymer component of the composition satisfies the following formula. [Outside 14] 48. The process cartridge according to claim 30, wherein both the low molecular weight polymer component and the high molecular weight polymer component have at least 65% by weight of a styrene monomer component unit. . 49. The process cartridge according to claim 30, wherein the high molecular weight polymer component has a polymer polymerized with a polyfunctional polymerization initiator. 50. The process cartridge according to claim 30, wherein the high molecular weight polymer component has a polymer polymerized by using at least a combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator. . 51. The process cartridge according to claim 30, wherein in a GPC chromatogram of the polymer component, an area ratio of the polymer component having a molecular weight of 1,000,000 or more is 10% or less. 52. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [Wherein, M represents a coordination center metal, and Cr, a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group, which may have a substituent, wherein the substituent is a nitro group,
Halogen group, carboxyl group, anilide group and carbon number 1
To 18 alkyl groups or alkoxy groups. X,
X ', Y and Y' are -O-, -CO-, -NH-, or -NR- (R is an alkyl group having 1 to 4 carbon atoms). [Outside 16] Represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium. The process cartridge according to any one of claims 30 to 51, which is a compound represented by the following formula: 53. The charge controlling agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [Wherein, M represents a coordination center metal, and Cr having a coordination number of 6,
Co, Ni, Mn or Fe. A is [outside 18] (Optionally having an alkyl group substituent), (X represents a hydrogen atom, a halogen atom, or a nitro group) and (R is a hydrogen atom, an alkyl or alkenyl group of C ₁ -C ₁₈₎ represent. [Outside 21] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or It is. 53. The compound represented by the formula:
The process cartridge according to any one of the above. 54. The metal-containing organic compound represented by the following formula [II
I] [Outside 23] (Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom, m and m ′ each represent an integer of _{1 to 3} , and Y ₁ and Y ₃ represent a hydrogen atom ,
C ₁ -C ₁₈ alkyl, C ₂ -C ₁₈ alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester,
Hydroxy, C ₁ -C ₁₈ alkoxy, acetylamino, benzoyl, an amino group or a halogen atom;
And n 'represents an integer of 1 to 3, Y ₂ and Y ₄ represents a hydrogen atom or a nitro group, (above X ₁ and X _2, m and m', Y
₁ and Y ₃ , n and n ′, and Y ₂ and Y ₄ may be the same and different. [Outside 24] Or a mixed ion thereof. The process cartridge according to claim 52, which is a compound represented by the following formula: 55. The metal-containing organic compound represented by the following formula [I
V] [Outside 25] [In the formula, Or a mixed ion thereof. The process cartridge according to claim 54, which is a compound represented by the following formula: 56. The toner has a toner weight average diameter (D ₄ ) of X (μm) and a toner number average diameter of 3.17.
55. A particle size distribution satisfying the following formula: -5X + 35 ≦ Y ≦ −25X + 180 (1) 3.5 ≦ X ≦ 6.5 (2), where Y (%) is a ratio of μm or less. A process cartridge according to any one of the above. 57. The wax contains at least an acid-modified polyolefin (A) modified with an acid monomer and a polyolefin (B), and the acid-modified polyolefin (A) has a weight average molecular weight (Mw _WaxA ) of 8. 0 × 10 ³
1.4 a × 10 ^{4, and} the ^{weight-average} molecular weight of the polyolefin (B) (Mw _WaxB) is 1.0 × 10 ⁴ ~4.0 ×
10 is ^4, the acid-modified polyolefin (A) is the following condition _{A VL> A VWaxA, A VWaxA} > 0 claims 30 to 5 comprising (mg KOH / g) acid number which satisfies the (A _VWaxA)
7. The process cartridge according to any one of 6. 58. The process cartridge according to claim 57, wherein the polyolefin (B) has a weight average molecular weight (Mw _WaxB ) of 1.5 × 10 ^{4 to} 2.5 × 10 ⁴ . 59. The acid value of the acid-modified polyolefin (A) (A _VWaxA) is, with respect to low molecular weight polymer component of acid value (A _VL), the following conditions _{0.5 × A VL> A VWaxA ×} 0. 59. The process cartridge according to claim 57, wherein the process cartridge satisfies 05 × A _VL . 60. The method according to claim 60, wherein the acid-modified polyolefin (A) is 1 to
60. An acid value of 15 mg KOH / g.
The process cartridge according to any one of the above. 61. The acid-modified polyolefin (A) is a polypropylene wax whose molecular terminals have been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. 61. The process cartridge according to any one of items 60 to 60. 62. The process cartridge according to claim 57, wherein the acid-modified polyolefin (B) is a polypropylene wax. 63. The acid component of the acid-modified polyolefin and the acid component of the low molecular weight polymer component are formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. The process cartridge according to any one of claims 57 to 62, wherein the process cartridge is manufactured. 64. The acid value (A) of the acid-modified polyolefin.
_VWaxA ) is 1 to 15 mgKOH / g, and the acid value (A _VL ) of the low molecular weight polymer component is 21 to 23 mgKOH / g.
64. The process cartridge according to any one of claims 57 to 63, wherein the process cartridge has an acid value (A _VH ) of 0.5 to 11 mgKOH / g. 65. An electrostatic image is formed on the electrostatic image holder,
The electrostatic image is developed with a toner held in a developing unit to form a toner image. The toner is formed of a composition containing at least a polymer component, a colorant, a wax and a charge control agent. The polymer component of the composition is (a) substantially free of THF-insoluble components, and (b) the TH component of the polymer component
In the GPC chromatogram, the F-soluble matter has a main peak at least in a region of a molecular weight of 3 × 10 ^{3 to} 3 × 10 ⁴ and a subpeak or a shoulder in a region of a molecular weight of 1 × 10 ^{5 to} 3 × 10 ^6. (C) the acid value (A _VL ) of the low molecular weight polymer (the region having a molecular weight of less than 5 × 10 ⁴ in the GPC chromatogram) and the acid value (A _VL ) of the high molecular weight polymer (the region having a molecular weight of 5 × 10 ⁴ or more in the GPC chromatogram) the acid value (a _VH) and has to satisfy the following condition a _VL> a _VH, the wax is following condition _{a VL> a VWax, a VWax} > 0 (mgKOH / g) acid number which satisfies (a _VWax) An image forming method characterized by containing a wax having: 66. The image forming apparatus according to claim 65, wherein the toner image is transferred to a transfer material via an intermediate transfer member or not, and the toner image on the transfer material is heated and pressed by a fixing unit. Image forming method. 67. The image forming method according to claim 65, wherein the electrostatic image holder is charged by a charging unit, and an electrostatic image is formed by exposure. 68. The image forming method according to claim 67, wherein the electrostatic image holder is charged by contact charging means. 69. The image forming method according to claim 65, wherein the toner image is transferred to a transfer material by a contact unit to which a bias is applied. 70. The image forming method according to claim 65, wherein after the transfer of the toner image, the surface of the electrostatic image holding member is cleaned by a cleaning unit. 71. The image forming method according to claim 65, wherein the acid value of the wax satisfies the following condition with respect to the acid value of the low molecular weight polymer component.
0.5 × A _VL > A _VWax > 0.05 × A _VL 72. The wax has a concentration of 1 to 15 mgKOH / g.
The image forming method according to any one of claims 65 to 71, wherein the acid-modified polyolefin wax has an acid value of: 73. The wax according to any one of claims 65 to 72, wherein the wax is a polyolefin wax whose molecular terminal has been modified with an acid monomer selected from at least one of maleic acid, maleic acid harfester and acid anhydride. The image forming method as described in the above. 74. The wax according to claim 74, wherein the wax comprises at least one of maleic acid, malefic acid hafester or maleic anhydride.
74. The image forming method according to any one of claims 65 to 73, wherein the wax is a polypropylene wax whose molecular terminal is modified by an acid monomer selected from at least one kind. 75. An acid component contained in the wax and an acid component contained in the low molecular weight polymer component are produced from an acid monomer selected from at least one of maleic acid, maleester maleate, and maleic anhydride. The image forming method according to any one of claims 65 to 74. 76. The acid value (A _VWax ) of the wax is from 1 to 15.
mgKOH / g, and the acid value (A _VL ) of the low molecular weight polymer component of the polymer component is 21 to 35 mgKOH / g, and the acid value (A _VH ) of the high molecular weight polymer component is 0.5.
The image forming method according to any one of claims 65 to 75, wherein the amount is from 11 to 11 mgKOH / g. 77. The acid value (A _VL ) of the low molecular weight polymer is 21.
And the acid value (A _VH ) of the high molecular weight polymer is 0.5 to 11 mg KOH / g, and the relation of the difference is 10 ≦ (A _VL −A _VH ) ≦ 27. Item 78. The image forming method according to any one of Items 65 to 76. 78. GPC of a THF-soluble component of the polymer component
In the chromatogram, the molecular weight is 3 × 10 ⁴ or more and 1 × 1
The image forming method according to any one of claims 65 to 77 having a minimum value 0 less than ⁵ regions. 79. The glass transition point (Tg) of the composition is 5
0-70 ° C. and the T of the low molecular weight polymer of the composition
g _L and the relationship Tg _H of the high molecular weight polymer, an image forming method according to any one of claims 65 to 78 in the range of Tg _L ≧ Tg _H -5. Wherein 80] a Tg of 55 to 65 ° C. of the composition, and claims relationship Tg _H of Tg _L and a high molecular weight polymer component of low molecular weight polymer component is in the range of Tg _L ≧ Tg _H The image forming method according to any one of Items 65 to 79. 81. The image forming method according to claim 65, wherein the polymer component of the composition satisfies the following formula. [Outside 27] 82. The image forming apparatus according to claim 65, wherein both the low molecular weight polymer component and the high molecular weight polymer component have at least 65% by weight of a styrene monomer component unit. Method. 83. The image forming method according to claim 65, wherein the high molecular weight polymer component has a polymer polymerized with a polyfunctional polymerization initiator. 84. The image forming method according to claim 65, wherein the high molecular weight polymer component has a polymer polymerized by using at least a combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator. Method. 85. The image forming method according to claim 65, wherein an area ratio of the polymer component having a molecular weight of 1,000,000 or more is 10% or less in a GPC chromatogram of the polymer component. 86. The charge controlling agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [Wherein, M represents a coordination center metal, and Cr, a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group, which may have a substituent, wherein the substituent is a nitro group,
Halogen group, carboxyl group, anilide group and carbon number 1
To 18 alkyl groups or alkoxy groups. X,
X ', Y, and Y' are -O-, -CO-, -NH-, or -NR- (R is an alkyl group having 1 to 4 carbon atoms). [Outside 29] Represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium. The image forming method according to any one of claims 65 to 85, wherein the compound is a compound represented by the following formula: 87. The charge controlling agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [Wherein, M represents a coordination center metal, and Cr, a coordination number of 6,
Co, Ni, Mn, or Fe. A is [outside 31] (Which may have an alkyl group substituent), (X represents a hydrogen atom, a halogen atom, or a nitro group) and (R is a hydrogen atom, an alkyl or alkenyl group of C ₁ -C ₁₈₎ represent. [Outside 34] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or It is. A compound represented by the formula:
The image forming method according to any one of the above. 88. The metal-containing organic compound represented by the following formula [II
I] [Outside 36] [Wherein, X ₁ and X ₂ represent a hydrogen atom, a lower alkyl group, a lower alkoxy group, a nitro group or a halogen atom;
And m ′ represent an integer of 1 to 3, Y ₁ and Y _{3 each} represent a hydrogen atom, C _{1 to} C ₁₈ alkyl, C _{2 to} C ₁₈ alkenyl,
Sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, C ₁ -C ₁₈ alkoxy, acetylamino, benzoyl, amino group or halogen atom, n and n ′ represent 1 to 3 integers, Y ₂ and Y ₄ represents a hydrogen atom or a nitrile group (X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, and Y ₂ and Y ₄ may be the same or different). [Outside 37] Or a mixed ion thereof. The image forming method according to claim 86, wherein the compound is represented by the following formula: 89. The metal-containing organic compound represented by the following formula [I
V] [Outside 38] [In the formula, Or a mixed ion thereof. The image forming method according to claim 88, wherein the compound is represented by the following formula: 90. The toner has a weight average diameter (D)
₄ ) is X (μm), and the number average diameter of the toner is 3.17 μm.
90. A particle size distribution satisfying the following formula: -5X + 35 ≦ Y ≦ −25X + 180 (1) 3.5 ≦ X ≦ 6.5 (2), where Y (%) is the ratio below. 2. The image forming method according to 1., 91. A wax containing at least an acid-modified polyolefin (A) and a polyolefin (B) modified with an acid monomer, wherein the acid-modified polyolefin (A) has a weight average molecular weight (Mw _WaxA ) of 8. 0 × 10 ³
1.4 a × 10 ^{4, and} the ^{weight-average} molecular weight of the polyolefin (B) (Mw _WaxB) is 1.0 × 10 ⁴ ~4.0 ×
10 is ^4, the acid-modified polyolefin (A) is the following condition _{A VL> A VWaxA, A VWaxA} > 0 claims 65 to 9 with (mg KOH / g) acid number which satisfies the (A _VWaxA)
0. The image forming method according to any one of 0. 92. The image forming method according to claim 91, wherein the weight average molecular weight (Mw _WaxB ) of the polyolefin (B) is 1.5 × 10 ^{4 to} 2.5 × 10 ⁴ . 93. The acid value (A _VWaxA ) of the acid-modified polyolefin (A) is based on the following condition: 0.5 × A _VL > A _VWaxA > 0.5 with _respect to the acid value (A _VL ) of the low molecular weight polymer component. The image forming method according to claim 91 or 92, wherein the image forming method satisfies 05 × A _VL . 94. When the acid-modified polyolefin (A) is 1 to
93. An acid value of 15 mg KOH / g.
The image forming method according to any one of the above. 95. The acid-modified polyolefin (A) is a polypropylene wax whose molecular terminals have been modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. 95. The image forming method according to any one of 91 to 94. 96. The image forming method according to claim 91, wherein the polyolefin (B) is a polypropylene wax. 97. The acid component of the acid-modified polyolefin and the acid component of the low molecular weight polymer component are formed from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride. The image forming method according to any one of claims 91 to 96, wherein the image forming method is performed. 98. The acid value (A) of the acid-modified polyolefin
_VWaxA ) is 1 to 15 mgKOH / g, and the acid value (A _VL ) of the low molecular weight polymer component is 21 to 23 mgKOH / g.
97. The image forming method according to any one of claims 91 to 96, wherein the high molecular weight polymer component has an acid value (A _VH ) of 0.5 to 11 mgKOH / g.