JP3428835B2 - Electrostatic image developing toner, process cartridge and image forming method - Google Patents

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art US Pat.
A large number of methods are known as described in the specification of 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on the photoconductor by various means, and then the electrostatic charge image is developed with a toner, and if necessary, via an intermediate transfer body, or A toner image is transferred to a transfer material such as paper without intervening, and then fixed by heating, pressure, heating and pressurizing, solvent vapor or the like to obtain a copy or print. Further, the toner not transferred and remaining on the photosensitive member is cleaned by various methods, and the above steps are repeated.

In recent years, such copying machines or printers have been rigorously pursued to be smaller, lighter, faster, and highly reliable, and as a result, the performance required for toner has become higher. . For example, various methods and apparatuses have been developed for fixing a toner image on a sheet such as paper, and the most general method at present is a heating and pressure bonding method using a heat roller. The heat-pressing method using a heat roller is a method in which fixing is carried out by passing the toner image surface of a fixing target sheet under pressure while contacting the surface of a heat roller having a surface formed of a material having releasability for toner. . In this method, the surface of the heat roller and the toner image on the sheet to be fixed come into contact with each other under pressure, so that the thermal efficiency at the time of fixing the toner image on the sheet to be fixed is extremely good, and rapid fixing can be performed. It is very effective in high speed electrophotographic copying machines.

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 prohibited until the heat roller reaches a predetermined temperature; (2) The temperature of the heat roller fluctuates due to passage of the transfer material or other external factors. It is necessary to maintain the heating roller at an optimum temperature in order to prevent improper fixing due to heat transfer and offset phenomenon due to the transfer of toner to the heating roller. For this purpose, the heat capacity of the heating roller or heating body must be increased. However, this requires a large amount of electric power and causes a temperature rise inside the image forming apparatus. (3) When the transfer material is discharged through the heating roller because the heating roller has a high temperature, The transfer material and the fixed image on the transfer material are cooled slowly, the toner and the fixed image have adhesiveness, and are offset to the heating roller or the transfer material is wound. It may cause a paper jam by Mukoto.

In Japanese Laid-Open Patent Publication No. 63-313182, a weight is applied by a fixing device that heats a toner image through a heat-resistant sheet that is moved by a heating element having a low heat capacity that is energized and heated in a pulse shape to fix the toner image on a recording material. An image forming apparatus that consumes less time and consumes less power has been proposed. JP-A-1
In Japanese Patent Laid-Open No. 187582, a fixing device for heating and fixing a toner image on a recording material via a heat resistant sheet is disclosed.
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 long-felt demand for a toner for realizing a fixing method in which a toner image has a good fixability on a recording material and an offset is prevented, and a wait time is short and power consumption is low.

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 fixability is lowered, and the low temperature fixability required for high-speed development and energy saving is lowered.

Generally, in order to improve the low temperature fixing property of the toner, it is necessary to reduce the viscosity of the toner at the time of melting to increase the adhesive area with the recording material. For this reason, the Tg and the molecular weight of the binder resin used are It is preferable to lower it.

Since the low temperature fixing property and the offset preventing property of the toner are in conflict with each other, it is difficult to develop a toner which satisfies these functions at the same time.

To solve this problem, Japanese Patent Publication No.
In 23354, a cross-linking agent and a molecular weight modifier are added,
Toners made of moderately crosslinked vinyl polymers have been proposed. Japanese Patent Publication No. 55-6805 discloses a molecular weight distribution such that the ratio of the weight average molecular weight and the number average molecular weight of an α, β unsaturated ethylenic monomer as a constituent unit is 3.5 to 4.0. Widened toner has been proposed.

Certainly, these toners have a temperature range between the lower limit fixing temperature (the lowest temperature at which fixing is possible) and the offset temperature (the temperature at which offset begins to occur), as compared with toners made of a single resin having a narrow molecular weight distribution. Although the feasible fixing temperature range is widened, it is difficult to sufficiently lower the fixing temperature when sufficient offset prevention performance is provided. On the other hand, there is a problem that the offset prevention performance becomes insufficient when the low temperature fixability is emphasized.

In place of these vinyl resins, a polyester resin which is essentially superior to vinyl resins in terms of low-temperature fixability is crosslinked, and an offset inhibitor is further added to the toner. -208559 is proposed. Although this toner is excellent in both low-temperature fixability and offset prevention, there is a problem in toner productivity (crushability).

Further, in JP-A-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 the polymerization. A toner using a resin has been proposed. Although it is improved in terms of pulverizability, it is difficult to make full use of the functions of the resins in terms of low-temperature fixability and offset prevention.

Simply, two types of polyester resin and gel content different (gel content 80% or more and gel content 1
A toner using a resin blended with a vinyl resin of less than 0%) is proposed in Japanese Patent Publication No. 1-10663.
Although this toner has good low-temperature fixability, it needs to be further improved in terms of offset prevention 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 offset prevention property is improved, but on the contrary, the low temperature fixing property is remarkably lowered. Further, it is difficult to obtain sufficient pulverizability of the kneaded product at the time of toner production by only adding a vinyl resin having a gel content of less than 10%.

It is proposed in JP-A-57-178249 and JP-A-57-178250 to use, as a binder resin, a resin obtained by reacting a polymer having a carboxylic acid with a metal compound and crosslinking the resin. Has been done. A method of reacting a binder having a vinyl monomer and a specific monoester compound as an essential constitutional unit with a polyvalent metal compound and crosslinking the same through a metal is disclosed in JP-A-61-110155 and JP-A-61-1605. It is proposed in Japanese Patent No. 110156.

Further, JP-A-63-214760, JP-A-63-217362, and JP-A-63-2.
No. 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, is reacted with a polyvalent metal ion contained on the low molecular weight side. A method of cross-linking has been proposed. In either method, 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 offset resistance required for the toner have not been satisfied. Moreover, since it is necessary to mix a large amount of the metal compound with the binder resin, the mixed metal compound exhibits a catalytic action on the binder resin depending on the conditions, and the binder resin easily gels. 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, it is difficult to obtain reproducibility.

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

Further, JP-A-2-168264, JP-A-2-235069, and JP-A-5-173363.
Japanese Patent Application Laid-Open No. 5-173366, Japanese Patent Application Laid-Open No. 5-2
In Japanese Patent No. 41371, the molecular weight, mixing ratio, acid value and ratio of the low molecular weight component and the high molecular weight component in the binder resin are controlled, and the fixability, non-offset property, image property and blocking resistance, and charging rise property are controlled. A binder composition for a toner and a toner having improved the above have been proposed.

In the above toner, the colorant such as magnetic iron oxide, the charge control agent (charge control agent), and other additives are likely to be poorly dispersed, and the surface of the developer carrying member such as the carrier or the sleeve is contaminated. Fog and image density decrease easily occur.

Japanese Patent Application Laid-Open No. 62-9256 proposes a binder composition for 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 constituent components. The binder resin is easily affected by the breakage of polymer molecules, and particularly, the offset resistance is likely to decrease. When kneading is performed to such an extent that polymer molecules are not cleaved, poor dispersion of the additive is likely to occur and contamination of the carrier or the surface of the developer bearing member is likely to occur. 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 containing a polyfunctional initiator and having a molecular weight of 300,000 or more. When such a resin is used, the fixing property can be satisfied to some extent, but the performance of the toner tends to deteriorate when left standing at high temperature. The cause of this phenomenon is not clear, but because the molecular cleavage of the binder resin is promoted during the production of the toner, the proportion of the high molecular weight resin component in the toner composition becomes low, and the heat resistance decreases. It is speculated that there is.

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

Japanese Patent Laid-Open Nos. 51-14333 and 5
7-148752, JP-A-58-97056, JP-A-60-247250, and JP-A-4-36.
2953 and JP-A-6-230600,
As the release agent, solid silicone varnish, higher fatty acid wax, higher alcohol wax, vegetable natural wax (carnauba, rice), montan ester wax are described. However, it is necessary to further improve the low temperature fixability and offset resistance of the toner, and also to improve the developability (chargeability) and durability of these toners.

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

In order to solve these problems, modified waxes grafted or block-copolymerized with various monomers have been proposed.

In Japanese Patent Laid-Open No. 59-121052, α-
It has been proposed to use a polyolefin graft / block copolymerized with a methylene aliphatic monocarboxylic acid ester monomer, which is disclosed in JP-A-56-15470, JP-A-59-121053, and JP-A-60-9.
In Japanese Patent No. 3456 and Japanese Patent Laid-Open No. 34550/1988, it is proposed to use a polyolefin graft / block copolymerized with an aromatic vinyl monomer. Although these toners are improved in fluidity, they are inferior in offset resistance, and further developability (chargeability),
And it is necessary to further improve durability.

In JP-A-62-226260, JP-A-63-139365, JP-A-3-50559 and JP-A-6-208244, polypropylene modified with carboxylic acid or maleic acid is contained. Toners or resin compositions for toners have been proposed. In these toners, there is no regulation on the relationship between the releasing agent and the resin composition, and it is further desired to maintain the fluidity and improve the hot offset property.

In order to expand the fixing area (non-offset area), it is preferable to add two or more releasing agents to the toner in JP-A-60-93457, JP-A-4-274247 and JP-A-4-274247. No. 299357, JP-A-4-33
7737, JP-A-6-208244, and JP-A-7-281478. In these toners, there is no regulation on the relationship between the release agent and the resin composition, and there is still a problem in uniformly dispersing the release agent in the toner particles.

Furthermore, in recent years, high speed, environmental stability, and high image quality have been demanded as the technical direction of the copying machine.
Further speeding up and long-term use in a harsh environment (high-temperature high-humidity or low-temperature low-humidity environment) are likely to cause deterioration of the toner and easily cause problems such as fog and image density reduction.
Regarding high image quality, conventional 240dpi or 300dpi
i was 400dpi, 600dpi or 1
It has become 200 dpi.

For this reason, the use of small particle size toner has been proposed. JP-A-1-112253, JP-A-1-19
In 1156, JP-A-2-214156, JP-A-2-284158, JP-A-3-181952, and JP-A-4-162048, a toner having a specific particle size distribution and a small particle diameter has a high image quality. Have been proposed to achieve.

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

Regarding the uniformity of the density in the solid image, in the one-component developing method, when a halftone solid image is printed, an afterimage of the image printed immediately before the solid image appears in the rotation cycle of the developing sleeve. There is a phenomenon called "sleeve ghost", and there are cases where the quality of graphic images is degraded.

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

Further, a toner fine powder layer is formed on the surface of the developing sleeve, and the toner coated on the toner powder layer is apt to cause poor charging and fogging. JP-A-2-284
In order to solve the sleeve ghost, Japanese Patent 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. ing. However, this negatively chargeable magnetic toner needs to be further improved for the formation of higher resolution and higher definition images.

[0037]

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

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

A further object of the present invention is to provide an electrostatic charge image developing toner in which the respective components are uniformly dispersed in the toner particles and which has the same excellent image characteristics as in the initial stage even after long-term use. is there.

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

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

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

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

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

[0045]

SUMMARY OF THE INVENTION The present invention provides a toner for developing an electrostatic charge image formed of a composition containing at least a polymer component, a colorant, a wax and a charge control agent, and the polymer component of the composition. However, in the GPC chromatogram, (a) substantially no THF-insoluble matter, and (b) the THF-soluble matter of the polymer component have a molecular weight of at least 3 × 10 ³ to 3 × 10 ^3.
4 has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or a shoulder in the region of 3 to 10 ⁶ and (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) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
In the C chromatogram, the acid value (A _VH ) in the molecular weight range of 5 × 10 ⁴ or more) is 0.5 to 11 mgKOH / g.
And the acid value (A _VWax ) of the wax is 1.5 to
7 mgKOH / g, and A _VL , A _VH , A
_Vwax is a toner for developing an electrostatic image, characterized by satisfying the following condition _{0.5 × A VL> A VWax>} 0.05 × A VL 10 ≦ (A VL -A VH) ≦ 27.

Further, the present invention has at least an electrostatic charge image carrier and a developing means for developing the electrostatic charge image formed on the electrostatic charge image carrier with toner, the electrostatic charge image carrier A process in which the developing means and the developing means are integrated into a cartridge.
The process cartridge is removable from the main body of the image forming apparatus, 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 (a) contains substantially no THF insoluble matter, and (b) the THF soluble matter of the polymer component has at least a molecular weight of 3 × 10 ³ to 3 × 10 in a GPC chromatogram.
⁴ has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or a shoulder in the region of 3 to 10 ⁶ and (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) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
In the C chromatogram, the acid value (A _VH ) in the molecular weight range of 5 × 10 ⁴ or more) is 0.5 to 11 mgKOH / g.
And the acid value (A _VWax ) of the wax is 1.5 to
7 mgKOH / g, and A _VL , A _VH , A
_Vwax is a process cartridge which is characterized by satisfying the following condition _{0.5 × A VL> A VWax>} 0.05 × A VL 10 ≦ (A VL -A VH) ≦ 27.

Further, the present invention is an image forming method for forming an electrostatic charge image on an electrostatic charge image carrier and developing the electrostatic charge image with a toner held in a developing means to form a toner image.
The toner contains at least a polymer component, a colorant , and a wax.
And a composition containing a charge control agent,
The polymer component of the composition is (a) substantially free of THF-insoluble matter, and (b) the THF-soluble matter of the polymer component is GPC chromatograph.
In the lamb, the molecular weight is at least 3 × 10 ^{3 to} 3 × 10
⁴ has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or shoulder in the region of ~ 3 x 10 ^6.
And, in (c) low molecular weight polymer (GPC chromatogram
The acid value (A _VL ) of the molecular weight of less than 5 × 10 ⁴ ) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
A region with a molecular weight of 5 × 10 ⁴ or more in the C chromatogram
Area) has an acid value (A _VH ) of 0.5 to 11 mgKOH / g
And the acid value (A _VWax ) of the wax is 1.5 to
7 mgKOH / g, and A _VL , A _VH , A
_{The present} invention relates to an image forming method characterized in that _{Vwax satisfies the following} condition 0.5 × A _VL > A _VWax > 0.05 × A _VL 10 ≦ (A _VL −A _VH ) ≦ 27 .

[0048]

[0049]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the polymer component of the toner is a component (TH) which is substantially insoluble in tetrahydrofuran.
F insoluble matter) is not included. Specifically, it is 5 based on the polymer component.
It is not more than 5% by weight, preferably not more than 3% by weight.

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

A toner sample (0.5 to 1.0 g) was weighed (w ₁ g), and a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd.) was used.
R) and apply it to a Soxhlet extractor, and use T as a solvent.
Extraction was performed for 6 hours with 100 to 200 ml of HF, and the soluble component extracted with the solvent was evaporated.
After vacuum drying at 0 ° C. for several hours, the amount of the THF-soluble resin component is weighed (w ₂ g). The weight of the components other than the resin component such as the magnetic substance, pigment and wax in the toner is (w ₃ g).
The THF insoluble content is calculated from the following formula.

THF insoluble matter (%) = [{w ₁ − (w ₃ +
w ₂ )} / (w ₁ -w ₃ )] × 100 If the THF insoluble component is contained in an amount of more than 5% by weight, the low temperature fixing property is deteriorated.

Gel permeation chromatography (GPC) as measured by the THF solubles of the polymer component
Has a molecular weight of at least 3 × 10 ^{3 to} 3 ×
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 shoulder in the region ⁶ ).

Molecular weight 1 in the GPC chromatogram
It is preferable that the area ratio of the polymer component showing, 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 storage stability of the toner when it is left at high temperature. Can be raised.

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

GPC measurement condition equipment for resin composition and polymer Equipment: GPC-150C (manufactured by Waters) Column: KF801-7 (manufactured by Showdex) 7 continuous temperature: 40 ° C. Solvent: THF (tetrahydrofuran) Flow rate: 1.0 ml / min. Sample: 0.1m of sample with concentration of 0.05-0.6wt%
l injection

The polymer component used is a low molecular weight polymer component (molecular weight 5 × 10 ⁴ in GPC chromatogram).
Oxide (A _VL) and high molecular weight polymer component is less than the area) (G
The acid value (A _VH ) of the molecular weight 5 × 10 ⁴ or more in the PC chromatogram) satisfies the following condition A _VL > A _VH , and the wax has an acid value (A _VWax ) that satisfies the following condition: have.

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

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

By controlling the compatibility between the wax and the polymer component, especially the low molecular weight polymer, the low temperature fixing property and the offset resistance can be dramatically 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 its plasticizing effect allows low temperature fixing. Exert its abilities.

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

When the acid value of the polymer component is A _VL ≦ A _VH , the toner charge stability is lowered, and even if a wax having an acid value is contained, the low temperature fixability and offset resistance are effectively improved. 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 , the offset resistance and the toner chargeability under high humidity are deteriorated.

In the present invention, the acid value of the wax further satisfies the following conditions with respect to the acid value of the low molecular weight polymer component.
It

0.5 × A _VL > A _VWax > 0.05 × A _VL

Further, it is preferable to use an acid-modified polyophine whose wax satisfies the above conditions and whose acid value is 1 to 15 mgKOH / g.

Further, it is more preferable that the wax is a polyolefin whose molecular end is modified by 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 having a molecular terminal modified with 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 produced from an acid monomer selected from at least one of maleic acid half-fester and maleic anhydride.

Examples of the polypropylene wax used in the present invention include homopolymers of propylene and copolymers of propylene and other olefins (especially ethylene is preferred). The propylene copolymer contains 60 parts of propylene component.
It is preferable that the content is at least wt%.

As the acid monomer used for modifying the wax, the same acid monomer as used for adjusting the acid value of the polymer component can be used.

In the present invention, the acid value of the wax (A _VWax )
Is 1.5 to 7 mgKOH / g, 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.
5~11mgKOH / g Ru der.

Further, the toner has a weight average diameter (D
₄ ) is X (μm), the number average diameter of the toner is 3.17 μm
When 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 distributions in the ranges of the formulas (1) and (2) shown in FIG. 1 have a considerably smaller weight average diameter and a considerably larger amount of fine powder than the particle size distribution of toners generally used at present. . Instead of suppressing the amount of fine powder that is the cause of "sleeve ghost," rather, by making the particle size distribution of the entire toner closer to the fine powder region, the chargeability of the entire toner and its mirroring power can be made into the characteristics of the fine powder. In order to prevent the electrification on the toner carrier as a whole of the toner particles from being brought to a special state as never before, the selective adhesion of the fine powder toner on the toner carrier and the formation of the fine powder layer associated therewith were prevented. It is a thing.

In the present invention, since the toner has a specific particle size distribution satisfying the above conditions (1) and (2), the particle size is 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 powder toner particles, the difference in the charge amount based on the particle size difference between the fine powder toner having a particle size of 3.17 μm or less and the entire toner becomes small, and therefore the particles on the surface of the developing sleeve are reduced. Diameter 3.17μ
Toner particles exceeding m are also appropriately attached, and it becomes difficult for the fine toner to selectively form a fine toner layer on the outermost surface of the developing sleeve, and the charge amount of the toner layer formed on the surface side of the developing sleeve becomes uniform. Therefore, it is considered that the sleeve ghost is suppressed.

Further, in the combination of the polymer component and the wax component of the toner, both 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 fixing property of the toner having the above particle size is improved. To be done.

Even when the particle diameter of the toner becomes small, the compatibility between the wax component and the toner polymer component, especially the low molecular weight polymer is controlled to dramatically improve the low temperature fixability and the offset resistance. To be

Moreover, when the particle size distribution of the toner is within the range of the formulas (1) and (2), the effect of increasing the charge amount and the uniformity of the charge amount can be obtained, but on the contrary, deterioration of fluidity and environmental stability Is a concern. However, the relationship between the polymer component and the wax component acid value (A _VWax ) whose molecular weight distribution and acid value are regulated by GPC and the acid value of the low molecular weight polymer is A _VL >
By combining with the wax which is _AV Wax, the dispersibility of each component in the toner was improved, and the good fluidity of the toner could be maintained. Furthermore, since the charge of the toner rises quickly, it is difficult for the amount of charge to drop in a high temperature and high humidity environment, and even if it drops, it is easy to recover. Even in a low temperature and low humidity environment, the dispersibility of each component in the toner is good, and it is difficult to charge up. Therefore, the environmental stability was increased, and a synergistic effect that a toner having stable performance over a long period of time was obtained was recognized.

Amount of fine powder in toner (3.17 μm or less) Y
When (%) is less than −5 × + 35, the toner coat amount on the toner carrier is likely to be excessive, and “wavy unevenness” is likely to occur.

The amount of fine powder in the toner is (3.17 μm or less)
When Y (%) is more than −5 × + 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.

Weight average diameter (D ₄ ) X (μm) is 3.5 μ
When it is less than m, it is difficult to obtain a sufficient image density.

Weight average diameter (D ₄ ) X (μm) is 6.5 μm.
If it is larger than m, the particle size of the entire toner is far from the particle size forming the fine powder, so that 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.

Further, it is preferable that the toner 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

When the porosity at the time of tapping the toner is less than 0.40, it becomes impossible to suppress the sleeve ghost and the high image density at the same time, and when it exceeds 0.70, the toner coat layer on the toner carrier. Becomes non-uniform and the uniformity of the image deteriorates.

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

1 mg of the toner is put into a tablet molding machine for 1R measurement, and is pressed at a pressure of about 1.96 MPa (200 kgf / m ² ) for 1 minute to mold. The volume and weight of this sample are measured to determine the true density.

In the present invention, the tap density of the toner is measured by using a powder tester manufactured by Hosokawa Micron Co., Ltd. and using a container attached thereto according to the procedure of the instruction manual of the powder tester.

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

Then, the weight-based weight-average particle size (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
The respective ratios of 2 μm or less are obtained.

Acid value (A _VL ) of low molecular weight polymer component (region of molecular weight less than 5 × 10 ⁴ in GPC chromatogram) and high molecular weight polymer component (region of molecular weight 5 × 10 ⁴ or more in GPC chromatogram) acid 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 to
Polyolefin (A) having an acid value of 1.4 × 10 ⁴ and weight average molecular weight (Mw _WaxA ) of 1.0 × 10
^{4 to} 4.0 × 10 ⁴ (preferably 1.5 × 10 ⁴ to 2.
It is more preferable that the polyolefin (B) of 5 × 10 ⁴ ) is contained.

As a result of intensive studies, the inventors of the present invention used two kinds of waxes having an acid value A _VL > A _VH of the polymer component in the combination of the polymer component and the wax and having a molecular weight defined as the wax. Therefore, it was found that the object of the present invention was sufficiently satisfied.

By controlling the compatibility of the two kinds of waxes with the high and low molecular weight polymers in the toner polymer component, the low temperature fixing property and the offset resistance can be dramatically improved.

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

Wax GPC measurement condition equipment: GPC-15C (Waters) Column: GMH-HT 30 cm, 2 stations (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1 wt% ionol added) ) Flow rate: 1.0 ml / min Test material: 0.4 ml of 0.15 wt% sample injected

The molecular weight calibration curve prepared from the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the sample measured under the above conditions. In addition, Mark-Hou
It is calculated by performing polypropylene conversion using a conversion formula derived from the wink viscosity formula.

Since 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 defined as described above is lower 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. Further, the polyolefin wax (B) having a higher molecular weight is more effectively acted by the high molecular weight polymer component and exerts an effect on high temperature offset resistance.

The weight average molecular weight (Mw _WaxA ) of the acid-modified _polyophine wax (A) is less than 8.0 × 10 ³ ,
When the weight average molecular weight (Mw _waxB ) of the polyolefin (B) is less than 1.0 × 10 ⁴ , the high temperature offset resistance is lowered, and the compatibility of the polymer component with high and low molecular weight components is balanced. Crumbling, the dispersibility of the wax in the binder resin decreases, 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) is
_{When WaxB} ) is more than 4.0 × 10 ⁴ , the low temperature fixability is lowered and the dispersibility in the binder resin is apt to be lowered.

When the acid value of the polymer component is A _VL ≦ A _VH , the charge stability of the toner is lowered, and even if a wax having an acid value is contained, the low temperature fixability and offset resistance are effectively improved. I can't let you do 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 in this polymer component, the acid value (A
It has been clarified that the fluidity and charging stability of the toner are more stable in the long term within the range where _VWaxA ) satisfies the above conditions.

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.

Further, the acid-modified polyolefin wax (A) in the wax is a polypropylene wax having a molecular terminal 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 preferable that the acid component contained in the low molecular weight polymer component and the acid component in the above are produced 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 polypropylene wax. The polypropylene wax used as the polyolefin wax (B) is a homopolymer of propylene, propylene and other olefins (especially ethylene is preferable).
Copolymers of

In the present invention, the low molecular weight polymer component has an acid value (A _VL ) of 21 to 35 mgKOH / g, and the high molecular weight polymer component has an acid value (A _VH ) of 0.5 to 11 m.
gKOH / g, and the relationship is 10 ≦ (A _VL −
A _VH) ≦ 27 Ru der.

The low temperature fixability is determined by the Tg of the low molecular weight polymer component.
And, the same Tg and the same molecular weight distribution can be obtained by including 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, though it is affected by the molecular weight distribution. The viscosity can be made lower than that of the resin composition having an acid value outside the above range.

This is because by setting the acid value of the high molecular weight polymer component to be 10 mgKOH / g or more lower than the acid value of the low molecular weight polymer component (acid value 0.5 to 11 mgKOH / g), the low molecular weight polymer component And the high molecular weight polymer component and entanglement of the wax molecular chains are suppressed to a certain degree, and thus the viscosity is reduced on the low temperature side, the elastic property is maintained on the high temperature side, and the wax has a certain domain diameter so that the toner particles have a certain size. Since it exists inside, it is considered that a sufficient releasing effect can be obtained. This leads to low-temperature fixing and improvement of developing characteristics in high-speed machines.

On the other hand, the difference in acid value was 27 mgKOH / g.
If it exceeds the range, problems occur in the mixing property of the low molecular weight polymer component and the high molecular weight polymer component and the dispersibility of the wax component in the toner, and the durability offset property and the developability tend to be deteriorated.

Furthermore, the acid value of the low molecular weight polymer component is 21.
When it is more than mgKOH / g, the rising property of charging becomes 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 the wax are not compatible, the offset resistance is lowered, and fog is likely to occur.

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). If the acid value / total acid value exceeds 0.7, the toner charging balance (friction charging and charge discharging balance) tends to become a charging tendency, and the toner charging stability tends to decrease, resulting in toner charging. Tends to up.

The polymer component preferably has a minimum value (Min) in the region where the molecular weight is 3 × 10 ⁴ or more and less than 1 × 10 ⁵ in the GPC chromatogram of the 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 each have independent molecular weight distributions.

The polymer component of the resin composition of the toner is: W _L : W _H = 50: 50 to 90 in terms of the mixing ratio (weight basis) of the low molecular weight polymer component and the high molecular weight polymer component. It is preferable to satisfy the following condition. The reason is that when the ratio of the low molecular weight polymer component and the high molecular weight polymer component is within this range, the fixability and the offset resistance are improved. When the content of the low molecular weight component is less than 50% by weight, the fixability is deteriorated, and on the other hand, when the content of the high molecular weight component is less than 10% by weight, the high temperature offset resistance is deteriorated.

Further, regarding the relationship between the mixed amount of these and the acid value,

[0121]

[Outside 40] It is preferable to satisfy The reason is that when the mixing amount of the low molecular weight component and the high molecular weight component and the 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 less than 4 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 is increased, and the low viscosity at the low temperature side, the high temperature It tends to be more difficult to emphasize high elasticity on the side.

[0123]

[Outside 42] When it is less than 11, the rising characteristics of charging are deteriorated, while when it exceeds 30, the developability under high humidity tends to be deteriorated.

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.

Dispersing device configuration of each component LC-908 (manufactured by Nippon Analytical Industry Co., Ltd.) JRS-86 (the same company; repeat injector) JAR-2 (the same company; autosampler) FC-201 (Gilson company; Hula cushion collector)

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

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

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

Measurement of acid value (JIS acid value) 1) 0.1-0.2 g of a ground product of a sample 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) Titrate the solution in the flask with a burette using an alcohol solution of 0.1N KOH. The amount of the KOH solution at this time is S (ml). A blank test is performed at the same time, and the amount of KOH solution at this time is set to B
(Ml).

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

[0134]

[Outside 43]

The total acid value in the present invention is measured as follows.

Measurement of Total Acid Value 1) Samples are used after removing additives other than polymer components in advance. Precisely weigh about 2 g of crushed sample and weigh it with W '
(G).

2) A sample was put into a 200 cc Erlenmeyer flask, 30 cc of 1,4-dioxane, 10 cc of pyridine,
Add 20 mg of 4-dimethylaminopyridine and dissolve for 1 hour.

3) Add 3.5 cc of ion-exchanged water and reflux for an hour. Then cool.

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

5) Titrate the solution in the flask with a burette using 0.1N KOH in THF.
The amount of the KOH solution at this time is S '(ml). At the same time, a blank test was performed, and the amount of KOH solution at this time was changed to B '(m
l).

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

[0142]

[Outside 44]

As a THF solution of KOH, KOH6.
6 g was added to 20 cc of ion-exchanged water to dissolve, then TH
F720cc and 100cc of ion-exchanged water were added, and then methanol was added with stirring until it 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 its α- or β-acid.
-Alkyl derivatives; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and their monoester derivatives or maleic anhydride. A desired polymer can be produced by copolymerizing such monomers alone or in combination with other monomers. Among these, it is particularly preferable to use a monoester derivative of unsaturated dicarboxylic acid in order to control the acid value / total acid value.

More specifically, monomethyl maleate,
Of 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 alkenyldicarboxylic acids such as monobutyl butenyl succinate, monomethyl n-octenyl succinate, monoethyl n-butenyl malonate, monomethyl n-dodecenyl glutarate, monobutyl n-butenyl adipate; monomethyl phthalate, monophthalate Examples include monoesters of aromatic dicarboxylic acids such as ethyl ester and monobutyl phthalate.

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

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

In the present invention, the carboxylic acid group and the carboxylic acid ester moiety in the copolymer obtained by the above method can be saponified by alkali treatment. It is preferable to change the carboxylic acid group or the carboxylic acid ester moiety into a polar functional group by reacting with an alkali cation component. 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 decreases when the carboxyl group is in a dehydrated (that is, closed) state.

This alkali treatment may be carried out after the binder resin has been produced, by adding it as an aqueous alkali solution into the solvent used during the polymerization and stirring it. As an alkali, N
Hydroxides of alkali metals and alkaline earth metals such as a, K, Ca, Li, Mg, Ba; Zn, Ag, Pb, N
Examples thereof include hydroxides of transition metals such as i; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts, and pyridinium salts. As a particularly preferred example,
Examples include NaOH and KOH.

The above-mentioned saponification reaction does not have to be carried out over all of the carboxylic acid groups and carboxylic acid ester moieties in the copolymer, and the saponification reaction may partially proceed to change to polar functional groups. Good.

The amount of alkali used in the saponification reaction is difficult to determine depending on the type of polar group in the binder resin, the method of dispersion, the type of constituent monomers, etc., but the acid value of the binder resin is 0.02 to 0.02. It may be 5 equivalents.
If the amount is less than 0.02 times the equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction is reduced,
As a result, the subsequent crosslinking reaction becomes insufficient. On the other hand, when the amount exceeds 5 times the equivalent, the functional group such as a carboxylic acid ester moiety is likely to be adversely affected by hydrolysis of the ester and formation of a salt by a saponification reaction.

When the alkali treatment was carried out in an amount of 0.02 to 5 times the acid value, the residual cation concentration after the treatment was 5 to 100.
It is contained between 0 ppm and can be preferably used for defining the amount of alkali.

The composition of the toner has a glass transition temperature (Tg) of 50 to 70 ° C., preferably 55 to 65 ° C., from the viewpoint of storability. If the Tg is lower than 50 ° C., it may cause deterioration of the toner in a high temperature atmosphere and offset at the time of fixing. Further, if Tg exceeds 70 ° C., the fixability tends to decrease.

The relationship between Tg _L of the low molecular weight polymer component and Tg _H of the high molecular weight polymer component of the composition is preferably in the range of Tg _L ≧ Tg _H −5 (° C.). Tg _L is Tg _H -5
If it is less than (° C.), the developability tends to decrease.
More preferably, Tg _L ≧ Tg _H.

As a method for producing a binder resin composition for 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, these are mixed in a solution state, and then a solvent is removed. A dry blending method of melt-kneading with 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, suspension polymerization is carried out, washed with water and dried to obtain a resin. There may be mentioned a two-stage polymerization method for obtaining the composition. However, the dry blending method has problems in uniform dispersion and compatibility, and the two-step polymerization method has an advantage of uniform dispersibility, but the low molecular weight polymer component is more than the high molecular weight polymer component. It is difficult to increase the amount, and in the presence of a low molecular weight polymer component, not only is it difficult to synthesize a high molecular weight polymer component having a large molecular weight, but also unnecessary low molecular weight polymer components are by-produced. 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 is preferable because the acid value can be easily set as compared with the polymerization method in an aqueous medium.

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, it is easy to control the heat of reaction, and the phase in which the polymerization takes place (oil phase consisting of polymer and monomer)
And the aqueous phase are different, the termination reaction rate is low, and as a result, the polymerization rate is high and the polymerization degree is high. Further, in the production of toner, due to the relatively simple polymerization process and the fine particles of the polymerization product,
Since it is easy to mix with a colorant, a charge control agent and other additives, it is advantageous as a method for producing a binder resin for toner.

However, the polymer produced is liable to become impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer, and suspension polymerization is convenient in order to avoid this inconvenience.

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) is preferable. As the dispersant, polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate are used. Generally, the aqueous solvent 10
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 50 to 95 ° C., but it should be appropriately selected depending on the polymerization initiator used and the target polymer.

For 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. .

As the polyfunctional polymerization initiator having a polyfunctional structure, 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-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate, di-t-butylperoxytrimethyladipate , 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-butylperoxyoctane and various polymer oxides, and two or more peroxide groups in one molecule. A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as; and diallyl peroxydicarbonate, t-butyl peroxymaleic acid, t-butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate. Such as a functional group having a polymerization initiation function such as a peroxide group in one molecule Polyfunctional polymerization initiators having both a polymerizable unsaturated group.

Of these, more preferred are 1,1
-Di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyase Rate 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 toner.
In particular, it is preferable to use together with a polymerization initiator having a decomposition temperature lower than the decomposition temperature for obtaining the half-life of 10 hours of the polyfunctional polymerization initiator.

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, diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the initiator efficiency of the polyfunctional polymerization initiator proper. It is preferably added after the polymerization time has passed the half-life indicated by the polyfunctional polymerization initiator under arbitrary polymerization conditions.

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

The high molecular weight polymer component of the resin composition used in the present invention is preferably cross-linked with the following cross-linkable monomers 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 those in which the acrylate of the above compounds is replaced with methacrylate); 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 the above compounds in which acrylate is replaced by methacrylate); containing aromatic groups and ether bonds Chain-bonded diacrylate compounds [for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediaclay] , Polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate, and those in which the acrylates of the above compounds are replaced by methacrylates]; polyester type diacrylate compounds [eg, trade name MANDA (Nippon Kayaku)] To be As the polyfunctional cross-linking agent, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethane tetraacrylate, oligoester acrylate, and acrylates of the above compounds into methacrylate. Substituted: triallyl cyanurate and triallyl trimellitate.

These cross-linking agents are used as the other monomer component 10
0 parts by weight or less, preferably 1 part by weight or less, preferably 0.00
It is preferably used in the range of 1 to 0.05 parts by weight.

Of these crosslinkable monomers, those which are preferably used from the viewpoints of toner fixability and anti-offset property are those having a chain containing an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and an ether bond. Diacrylate compounds mentioned above.

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 low molecular weight polymer can be obtained by polymerizing at a high temperature to accelerate the termination reaction rate, but there is a problem that the reaction is difficult to control. In that respect, 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 due to the solvent and by adjusting the amount of the polymerization initiator and the reaction temperature. ,
It is preferable to obtain a low molecular weight product in the resin composition used in the present invention. In particular, the solution polymerization method under pressure is also preferable in that the amount of the polymerization initiator used is minimized and the influence of the polymerization initiator residue is suppressed as much as possible.

The monomer for obtaining the high molecular weight polymer component and the monomer for obtaining the low molecular weight polymer component include
Some examples are as follows.

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethyl styrene, pn-butyl styrene, p-te
rt-butyl styrene, pn-hexyl styrene, p
-N-octyl styrene, pn-nonyl styrene, 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, vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate; Methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid n
-Butyl, isobutyl methacrylate, n-methacrylic acid
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, vinyl isobutyl ether; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl compounds such as N-vinylindole and N-vinylpyrrolidone; vinylnaphthalene;
Examples thereof include acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. These vinyl monomers are used alone or in combination of two or more.

Of these, a combination of monomers that forms a styrene copolymer or a styrene-acrylic copolymer is preferable.

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

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

The acid monomer used for modifying the wax component used in the present invention may be the same as the one used for adjusting the acid value of the polymer component.

In the present invention, it is possible to use a release agent having no acid value in combination with the wax having an 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 with respect to 100 parts by weight of the binder polymer component.

The wax may be added to and mixed with the binder polymer component in advance during the production of the toner. In particular, a method of pre-dissolving the low molecular weight wax and the high molecular weight polymer in a solvent and then mixing with the low molecular weight polymer solution may be used when adjusting the polymer components.

The solid concentration of the polymer solution is 5 to 70% by weight in consideration of dispersion efficiency, prevention of deterioration of the 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 carried out by stirring and mixing, and the stirring may be carried out batchwise or continuously.

For example, as a method of mixing the 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, and the mixture is stirred and mixed. To be In this case, a batch system or a continuous system may be used.

The organic solvent used for mixing the solution of the resin composition includes 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, cyclohexanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester solvents such as ethyl acetate, n-butyl acetate, 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. Moreover, these may be mixed and used.

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 then removing the residual solvent under reduced pressure. At this time, it is preferable to keep the organic solvent solution at a temperature not lower than the boiling point of the used organic solvent and not higher than 200 ° C. If the boiling point of the organic solvent is lower than the efficiency of solvent distillation, the polymer in the organic solvent is subjected to unnecessary shearing force, redispersion of each constituent polymer is promoted, and in a micro state. May cause phase separation. Further, if the temperature exceeds 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 contain magnetic iron oxide particles and be used as a magnetic toner.

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

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

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

Examples of the titanium coupling agent include isopropoxytitanium / triisostearate, isopropoxytitanium / dimethacrylate / isostearate, isopropoxytitanium / tridodecylbenzenesulfonate,
Examples thereof include 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 organic silicon compound include silicone oil. As a preferable silicone oil, one having a viscosity of about 30 to 1,000 centistokes at 25 ° C. is used, and for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified. Silicone oil is preferred.

As the 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 feature of the toner for developing an electrostatic image of the present invention is that it contains a metal-containing organic compound as a charge control agent. In the case of a negatively chargeable toner, a metal complex compound of a monoazo dye, salicylic acid, or alkylsalicylic acid is used. A negative charge control agent such as a metal complex compound of dialkyl salicylic acid or naphthoic acid is used.

Examples of the negative charge control agent include metal-containing organic compounds represented by the following general formula [I].

[0195]

[Outside 45] [In the formula, M represents a coordination center metal, 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, and the substituent is 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. ]

Specific examples of the metal-containing organic compound are shown below.

[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
And m'represent an integer of 1 to 3, Y ₁ and Y ₃ are hydrogen atoms, 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 integer, Y ₂ and Y ₄ represents a hydrogen atom or a nitro group (the above X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, Y ₂ and Y ₄ may be the same or different).

[0205]

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

[0206]

[Outside 55] [In the formula,

[0207]

[Outside 56] Or a mixed ion thereof. Among these, 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 a negative charging property and can be used in the present invention.

[0209]

[Outside 57] [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn, or Fe may be 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 represents a hydrogen atom or a C ₁ -C ₁₈ alkyl or alkenyl group).

[0213]

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

[0214]

[Outside 62] Is. ]

Specific examples of the metal-containing organic compound of the formula [II] are shown below.

[0216]

[Outside 63]

[0217]

[Outside 64]

[0218]

[Outside 65]

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

The amount of these charge control agents used is 0.1 to 100 parts by weight of the binder resin in view of the amount of charge of the toner.
5.0 parts by weight is preferred.

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

Examples of the silica fine powder include dry silica produced by vapor phase oxidation of a silicon halogen compound or dry silica called fumed silica and wet silica produced from water glass. Preference is given to dry silica, which has few silanol groups inside and has no production residues.

Further, the silica fine powder is preferably hydrophobized. The hydrophobic treatment is applied by chemically treating with an organosilicon compound that reacts with or physically adsorbs on the silica fine powder. As a preferred method, a method of treating dry silica fine powder produced by vapor phase oxidation of a silicon halogen compound with a silane coupling agent, or simultaneously treating with a silane coupling agent and an organosilicon compound such as silicone oil Is mentioned.

As the silane coupling agent used for the hydrophobic treatment, hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldisilane. Chlorsilane, benzyldimethylchlorosilane, brommethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxy Silane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-di Vinyl tetramethyldisiloxane,
1,3-diphenyltetramethyldisiloxane may be mentioned.

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

The silicone oil treatment may be carried out by directly mixing the silica fine powder treated with the silane coupling agent and the silicone oil with a mixer such as a Henschel mixer, or by using the silica-based silicone oil as the base. It may be a method of jetting. Alternatively, it may be produced by dissolving or dispersing silicone oil in an appropriate solvent, mixing with silica fine powder of the base, and removing the solvent.

As a preferable hydrophobic treatment for the silica fine powder, there may be mentioned a method in which it is prepared by treating it with dimethyldilychlorosilane, then with hexamethyldisilazane, and then with silicone oil.

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

[0229] The silica fine powder may be subjected to a hydrophobizing treatment, and further, an oil treatment may be applied to the titanium oxide fine powder,
It is preferable as well as silica type.

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

For example, a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a releasing agent at the time of heat roll fixing,
Resin fine particles or inorganic fine particles that act as a lubricant, an abrasive, etc.

The resin fine particles have an average particle size of 0.
It is preferably from 03 to 1.0 μm. As the polymerizable monomer constituting the resin, styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene derivative; 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 Acrylic acid esters such as; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl 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. Particles obtained by soap-free polymerization are more preferable.

In particular, it has been confirmed that the above-mentioned resin fine particles have a great effect in preventing the toner from being fused on the photosensitive drum in a contact charging means such as a roller, a brush or a blade as a primary charging device.

Other fine particles include lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride (polyvinylidene fluoride is preferred); abrasives such as cerium oxide, silicon carbide, and strontium titanate (among others, strontium titanate). Fluidity-imparting agents such as titanium oxide and aluminum oxide (particularly preferably hydrophobic ones); anti-caking agents; 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, the inorganic fine powder or the 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) per 100 parts by weight of the toner. Is good.

The toner for developing an electrostatic image of the present invention is heated by thoroughly mixing a polymer component, a pigment as a colorant, a dye or a magnetic material, a charge control agent and other additives with a mixer such as a ball mill. It can be produced by melting, kneading and kneading using a heat kneader such as a roll, a kneader and an extruder, cooling and solidifying, pulverizing and strict classification.

As another method for obtaining the electrostatic image developing toner of the present invention, the toner can be produced by a polymerization method. This polymerization toner includes a polymerizable monomer, the charge control agent of the present invention, a pigment or a dye, magnetic iron oxide, a polymerization initiator (and a crosslinking agent and other additives as necessary).
In a continuous phase (for example, water) containing a dispersion stabilizer after uniformly dissolving or dispersing the above to prepare a monomer composition. Are dispersed by using a suitable stirrer, and at the same time, a polymerization reaction is performed to obtain toner particles having a desired particle diameter. When using magnetic iron oxide in the polymerization method,
It is preferable to perform a hydrophobic treatment in advance.

Further, with reference to FIG. 6, an example of the image forming method in which the present invention is used will be described.

The surface of the photosensitive drum (electrostatic image holder) 1 is negatively charged by the primary charger 742, a digital latent image is formed by image scanning by exposure 705 with a laser beam, and a magnetic blade 711 and a magnet are included. The latent image is reversely developed with the one-component magnetic toner 710 of the developing device 709 having the developing sleeve 704. In the developing section, the conductive substrate of the photosensitive drum 1 is grounded, and the developing sleeve 704 is applied with the alternate bias, pulse bias and / or DC bias by the bias applying means 712. When the transfer paper P is conveyed and reaches the transfer portion, the roller transfer means 2 charges the transfer paper P from the back surface (the surface opposite to the photosensitive drum side) by the voltage applying means 8 to develop a developed image on the surface of the photosensitive drum. The (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 fixed by a heating and pressure roller fixing device 707 to fix the toner image on the transfer paper P. The toner image may be transferred to a transfer paper later 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 process is removed by a cleaning device 708 having a cleaning blade. The photosensitive drum 1 after cleaning is gradually discharged 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 arrow direction. The non-magnetic cylindrical developing sleeve 704, which is a toner carrier, rotates so as to move in the same direction as the surface of the electrostatic image carrier in the developing section. Inside the non-magnetic cylindrical sleeve 704, a multi-pole permanent magnet (magnet roll) that is a magnetic field generating means is arranged so as not to rotate. One-component insulating magnetic toner 710 in developing unit 709
Is coated on the 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 to reduce the thickness of the magnetic toner layer (30 μm to 3 μm).
(00 μm) and regulated uniformly 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 surface speed of the sleeve is made substantially equal to or close to the speed of the surface of the photosensitive drum. An AC bias or a pulse bias is applied to the developing sleeve 704 in the developing section by a bias means 712.
May be applied. This AC bias f is 200
˜4,000 Hz, Vpp may be 500 to 3,000 V.

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

A magnetic doctor blade such as iron may be used instead of the elastic blade 711.

FIG. 2 shows an example of a contact type transfer device.
Is a transfer roller, and has a basic structure including a cored bar 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 peripheral surface of the photosensitive drum 1 at a constant speed or with a different peripheral 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 means 3 to form a toner image on the photosensitive drum 1. Is transferred to the surface side of the transfer material.
Then, the transfer material is sent onto the guide 5.

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

As preferable transfer process conditions, the contact pressure of the roller is 5 to 500 g / cm, and the DC voltage is ±.
It is 0.2 to ± 10 kV.

FIG. 3 shows an example of 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 clockwise at a predetermined peripheral speed (process speed) in the drawing.

Reference numeral 42 denotes a charging roller, which has a central core metal 4
2a, a conductive elastic layer 42b having its outer periphery formed, and a surface layer 42c have a basic configuration. Charging roller 4
2 is pressed against the surface of the photosensitive drum 1 with a pressing force,
It rotates following the rotation of the photosensitive drum 1. A voltage is applied to the charging roller 42 by the bias applying means E, and a bias is applied to the charging roller 42, so that the surface of the photosensitive drum 1 is charged to a predetermined polarity and potential. Then, an electrostatic charge image is formed by image exposure, and the electrostatic charge image is sequentially visualized as a toner image by the developing means.

A preferable process condition when using a charging roller is that the contact of the roller is 5 to 500 g / cm.
Then, when the one superimposed on the DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 50 to 5 kHz,
DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to ± 5 kV.

The material of the charging roller is preferably a conductive rubber, and a release film may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), etc. 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 is a cartridge in which the developing unit and the electrostatic image holder are at least integrally formed, and the process cartridge is formed so as to be attachable to and detachable from the image forming apparatus main body (for example, a copying machine, a laser beam printer, etc.).

In this example, a process cartridge 750 having a developing means 709, a drum-shaped electrostatic image carrier (photosensitive drum) 1, a cleaner 708 having a cleaning blade 708a, and a primary charger (charging roller) 742 is integrated. It is illustrated.

The developing means 709 is composed of an elastic blade 71.
1 and a magnetic toner 710 in the toner container 760, the magnetic toner 710 is used, and at the time of development, the photosensitive drum 1 and the developing sleeve 7 are biased by a bias from a bias applying unit.
04, a predetermined electric field is formed between the photosensitive drum 1 and the developing sleeve 70 so that the developing process can be performed properly.
The distance to 4 is very important.

The present invention will be described below 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 placed in a four-necked flask, and the inside of the container was sufficiently replaced with nitrogen while stirring. Warmed to reflux.

Under this reflux, a mixed solution 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. After that, the mixture was held for 2 hours to complete the polymerization, and a low molecular weight polymer (L-1) solution was obtained.

A portion of this polymer solution was sampled,
Low molecular weight polymer (L-1) obtained by drying under reduced pressure
GPC and glass transition point (Tg) were measured. 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, Tg is 62 ° C.,
The acid value was 25.

At this time, the polymer conversion rate 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 placed in 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).
ert-Butylpa-oxycyclohexyl) propane (half-life: 10 hours, temperature: 92 ° C) (0.1 parts by weight) was added and the mixture was stirred to prepare a suspension.

After thoroughly replacing the inside of the flask with nitrogen,
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 10 hours temperature; 72 ° C.) was added additionally. Further, it was kept for 12 hours to complete the polymerization.

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

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

Production of Resin Composition 100 parts by weight of xylene and 25 parts by weight of the above high molecular weight polymer (H-1) were placed in a four-necked flask, and the temperature was raised and the mixture was stirred under reflux to carry out preliminary dissolution. went. This state was maintained for 12 hours to obtain a preliminary solution (Y-1).

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

The above-mentioned preliminary 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 then ground. A resin composition (I) for toner was obtained.

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

Production Examples 2, 3, 6 of Resin Composition and Comparative Production
Production Example 2 Low molecular weight polymers (L-2) to (L-4) were prepared by adjusting the amounts of monobutyl maleate, styrene, n-butyl acrylate and the amount of polymerization initiator in the same manner as in Production Example 1 of resin composition. And (L-6) are obtained, and a predetermined amount of the high molecular weight polymer (H-1) is blended to obtain resin compositions (II), (III) and (V
I) and (ii) were obtained. Various data are shown in Table 1.

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

Production Example 5 of Resin Composition Synthesis of High Molecular Weight Polymer H-3 Into a four-necked flask, 85 parts by weight of styrene and 15 parts by weight of butyl methacrylate were charged, and bulk polymerization was carried out. Then, 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 carried out 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.
A resin composition (V) was obtained in the same manner as. Various data are shown in Table 1.

[0273]

[Table 1]

Example 1 Resin composition (I) 100 parts by weight Magnetic iron oxide (average particle size 0.2 μm) 100 parts by weight Propylene-ethylene copolymer wax (copolymerized with maleic anhydride) Polymerization weight ratio 92: 8)
(Acid value 3.5, Mw 9000) 4 parts by weight 2 parts by weight of negative charge control agent shown below

[0275]

[Outside 66]

The above materials were melt-kneaded with a twin-screw extruder heated to 140 ° C., the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill.
The finely pulverized powder obtained was classified by a fixed wall type air classifier to produce classified powder. Furthermore, the weight-average particle size (D4) 6 is obtained by strictly classifying ultrafine powder and coarse powder at the same time using a multi-division classifier (Elbowjet classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. A negatively chargeable magnetic toner of 0.1 μm was obtained. The physical properties of the obtained toner are shown in Tables 2 and 3 and G
A PC chromatogram chart is shown in FIG.

100 parts by weight of this magnetic toner and 1.2 parts by weight of hydrophobic silica fine powder (BET 160 m ² / g) which was treated with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. And 0.08 part by weight of 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).

Instead of the resin compositions (I) of Examples 2 to 9 and Comparative Examples 1 to 3 , the resin compositions (II) to (VI) were used.
I), (i), and (ii) are used, and the negatively chargeable magnetic toner [Magnetic Toner No. 1] is used in the same manner as in Example 1 except that the type and acid value of the wax are changed. BI
And No. (Aj to (c)) were obtained. The physical properties of the obtained magnetic toner are shown in Tables 2 and 3. In addition, Examples 3, 6, 7
9 and 9 are shown as reference examples.

[0279]

[Table 2]

[0280]

[Table 3]

Image Generation Test The above magnetic toner was put in a process cartridge, and a laser beam printer LBP-A309HII manufactured by Canon was used.
(Using an OPC photosensitive drum) was modified from 16 sheets / minute to 36 sheets / minute by A4 transverse feed, and image development was evaluated using a modified machine incorporating the transfer device shown in FIG. The process speed at this time was 165 mm / sec.

As a transfer roller which is 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 made of EPDM in which conductive carbon is dispersed, and has a volume resistance of 10 ⁸ Ω.
・ Has cm.

As the contact charging means, the charging roller shown in FIG. 3 was installed in the process cartridge to carry out the primary charging. The outer diameter of the charging roller 42 is 12 mm, EPDM is used for the conductive rubber layer 42b, and nylon resin having a thickness of 10 μm is used for the surface layer 42c. Charging roller 42
Hardness was 54.5 ° (ASKER-C). E is a bias power source for applying a voltage to the charging roller 42,
A predetermined voltage is supplied to the cored bar 42a 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 primary charge is -700 V, the gap is set so that the OPC photosensitive drum and the magnetic toner layer on the developing sleeve (including the magnet) are not in contact with each other, and the AC bias (f =
1800 Hz, Vpp = 1800 V) and DC bias (V _DC = −500 V) are applied to the developing sleeve, _VL is set to −170 V, an electrostatic charge image is developed, and a magnetic toner image is formed on the OPC photosensitive drum. did.

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

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

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

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

2) Fog was calculated by comparing the whiteness of the transfer paper measured with a fog reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness on the transfer after printing solid white. The environment was low temperature and low humidity (temperature 15 degrees, 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.

[0292] A: Very good (2 defects or less / 100 defects) B: Good (3-5 defects / 100 defects) C: Practical use possible (6 to 10 defects / 100 defects) D: Not practical (11 or more defects / 100 defects)

(4) Uniformity of Image Density A solid black sample image was printed out on A4 size transfer paper, and unevenness in image density was evaluated by 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 Anti-Offset Test The above magnetic toner was put in a process cartridge, and Canon laser beam printer LBP-309GII was modified from 16 sheets / min to 24 sheets / min (total pressure 18 kg).
Heating and pressing roller The surface temperature of the heating roller of the fixing device is set to 1
Except for modification so that it can be changed from 40 to 230 ° C from the outside, the same charging, development and transfer conditions as those of the above-mentioned image development tester are set, and the set temperature is changed in steps of 5 ° C under normal temperature and normal humidity environment. The image sample was printed out at a temperature of 20 ° C. and a humidity of 60% RH.

1) Fixability The fixability is obtained by applying a load of 50 g / cm ² and rubbing the fixed image with a soft thin paper. The lowest temperature at which the reduction rate (%) of the image density before and after rubbing was 10% or less was evaluated as the lowest 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 measuring the degree of stain on the image. Table 4 shows the maximum temperature at which no stain is generated on the image.
Plain paper for copiers (65 g / m ² ) was used as the test paper.

Table 4 shows the evaluation results.

[0298]

[Table 4]

Example 10 Resin composition (I) 100 parts by weight Magnetic iron oxide (average particle size 0.2 μm) 100 parts by weight 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 by a twin-screw extruder heated to 140 ° C., the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized material was finely pulverized by a jet mill.
The finely pulverized powder obtained was classified by a fixed wall type air classifier to produce classified powder. Further, the weight-average particle size (D4) of the obtained classified powder is strictly removed at the same time using a multi-division classifier utilizing the Coanda effect (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) A negatively chargeable magnetic toner of 0.7 μm was obtained.

100 parts by weight of this magnetic toner and 1.5 parts by weight of hydrophobic silica fine powder (BET160 m ² / g) which was treated with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. , And 0.08 part 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 (toner No. A-2).

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. The particle size distribution shown in Table 5 was obtained. Weight average particle size is 5.71 μm, particle size distribution is 2.52
5.6% below μm, 17.5 below 3.17 μm
%, The particle size was 5.04 μm or less was 69.8%, and the porosity was 0.55.

The physical properties of the obtained magnetic toner are shown in Tables 6 and 7.
Shown in.

[0305]

[Table 5]

Instead of the resin compositions (I) of Examples 11 to 18 and Comparative Examples 4 to 7 , the resin compositions (II) to (VI) were used.
I) and (i) and (ii) are used, and the negatively chargeable magnetic toner [toner No. (B-
2) to (I-2) and (a-2) to (d-2)] were obtained. Physical properties of the obtained toner are shown in Tables 6 and 7. still,
Examples 12, 15, 16 and 18 are given as reference examples.
It is a thing.

Comparative Example 8 In Comparative Example 4, magnetic toner (e-2) was obtained by changing the toner manufacturing conditions at the time of pulverization and classification.

[0308]

[Table 6]

[0309]

[Table 7]

Image Output Test The above magnetic toner was put in a process cartridge, and the same apparatus and setting conditions as in Example 1 were used, in a high temperature and high humidity environment (temperature 32.5 ° C., humidity 85% RH) and a low temperature and low humidity environment. (1
An image development test was performed at 0 ° C. and 15% RH), and the obtained images were evaluated for the following items. The print mode was set to 2 sheets / 20 sec.

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

2) Fog The same procedure as in Example 1 was performed.

3) Dot reproducibility An independent 1-dot pattern was printed out under the environment of 23 ° C. and 60% RH, and the reproducibility of 1 dot was evaluated by microscopic observation.

A: Dots are reproduced faithfully B: Dots are reproduced faithfully, but there is some scattering C: There is some disturbance in the image D: There are many disturbances in the image and poor reproducibility

4) Sleeve coat The sleeve coat was evaluated by continuously printing ten solid white images in an environment of 15 ° C./10% RH, and then solid black black characters as shown in FIG. White portion of white: An image in which a halftone portion on the entire surface is formed next to the striped portion A is printed and visually evaluated.

Fixability and Offset Resistance Test The same procedure as in Example 11 was carried out.

The evaluation results are shown in Table 8.

[0318]

[Table 8]

Example 19 Resin composition (I) 100 parts by weight Magnetic iron oxide (average particle size 0.2 μm) 100 parts by weight 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 = 20000) 4 parts by weight 2 parts by weight of negative charge control agent shown below

[0320]

[Outside 68]

The above materials were melt-kneaded with a twin-screw extruder heated to 140 ° C., 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 by a fixed wall type air classifier to produce classified powder. Furthermore, the weight-average particle size (D4) 6 is obtained by strictly classifying ultrafine powder and coarse powder at the same time using a multi-division classifier (Elbowjet classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. A negatively chargeable magnetic toner of 0.1 μm was obtained. The physical properties of the obtained magnetic toner are shown in Tables 10 and 11.

100 parts by weight of this magnetic toner and 1.2 parts by weight of hydrophobic silica fine powder (BET 160 m ² / g) which was treated with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. A magnetic toner (magnetic toner No. A-3) was prepared by mixing 0.08 part by weight of styrene-acrylic fine particles (average particle diameter: 0.05 μm) obtained by soap-free polymerization with a Henschel mixer.

Examples 20 to 29 and Comparative Examples 9 to 13 Resin compositions (II) to (V) instead of resin compositions (I).
II) and (i) and (ii) are used, and the wax is changed to those having different kinds and acid values shown in Table 9 except that
In the same manner as in Example 19, negatively chargeable magnetic toner [magnetic toner No. (B-3) to (I-3) and No. (A-3)
~ (D-3)] was obtained. The physical properties of the obtained magnetic toner are shown in Tables 10 and 11. In addition, Examples 21, 24, 25 and
And 27 are shown as reference examples.

[0324]

[Table 9]

[0325]

[Table 10]

[0326]

[Table 11]

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

Table 12 shows the evaluation results.

[0329]

[Table 12]

[0330]

As described above, the toner of the present invention is 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 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, excellent toner fluidity and charging, reduced fog, excellent image quality, and long-term durability. Further, even when it is applied to speeding up of the apparatus, long-term charge stability is possible.

[Brief description of drawings]

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

FIG. 2 is a diagram showing an outline of a transfer device.

FIG. 3 is a diagram showing an outline of a charging roller.

FIG. 4 is an explanatory diagram of a checkered pattern for testing a developing property of toner.

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

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

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

FIG. 8 is a schematic diagram showing an image pattern used for evaluation of a sleeve ghost.

[Explanation of symbols]

1 Latent image carrier (photoreceptor) 2 Transfer roller 2a core metal 2b conductive elastic layer 3 constant voltage power supply 42 Charging roller 704 Development sleeve 742 charging roller

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-173366 (JP, A) JP-A-6-194873 (JP, A) JP-A-3-168652 (JP, A) JP-A-6- 93026 (JP, A) JP 7-43935 (JP, A) JP 63-139365 (JP, A) JP 7-281478 (JP, A) JP 63-138259 (JP, A) JP-A-6-138701 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08-9/097

Claims (80)

(57) [Claims] 1. An electrostatic charge image developing toner formed of 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 (a) substantially In the GPC chromatogram, the THF-soluble component (b) containing no THF-insoluble component has a molecular weight of at least 3 × 10 ³ to 3 × 10 ^3.
4 has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or a shoulder in the region of 3 to 10 ⁶ and (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) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
In the C chromatogram, the acid value (A _VH ) in the molecular weight range of 5 × 10 ⁴ or more) is 0.5 to 11 mgKOH / g.
And the acid value (A _VWax ) of the wax is 1.5 to 7 mgK.
An OH / g, _{and, A VL, A VH, A} Vwax is following condition _{0.5 × A VL> A VWax>} 0.05 × A VL 10 ≦ (A VL -A VH) satisfying the ≦ 27 A toner for developing an electrostatic charge image, characterized by: 2. The toner for developing an electrostatic charge image according to claim 1, wherein the wax is an acid- modified polyolefin wax. Wherein said wax is maleic acid, according to claim 1 or 2 molecular terminal by an acid monomer selected from at least one or more of the maleic acid half ester or maleic anhydride is modified polyolefin waxes Toner for developing electrostatic image. Wherein said wax is maleic acid, to claim 1 or 2 is a polypropylene wax having a molecular terminal modified with an acid monomer selected from at least one or more of the maleic acid half ester or maleic anhydride The toner for developing an electrostatic image as described above. 5. The acid component of the wax and the acid component of the low molecular weight polymer component are produced 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 charge image according to any one of claims 1 to 4 , wherein 6. The GPC chromatogram of the THF-soluble component of the polymer component has a molecular weight of 3 × 10 ⁴ or more to 1 ×.
The toner according to any one of claims 1 to 5 having a minimum value 10 of less than ⁵ regions. 7. The glass transition point (Tg) of the composition is 50.
˜70 ° C. and Tg of the low molecular weight polymer of the composition
_L and relationship between Tg _H of the high molecular weight polymer, Tg _L ≧ _Tg H toner according to any one of claims 1 to 6 in the range of -5. 8. The composition has a Tg of 55 to 65 ° C.,
8. The electrostatic image developing toner according to claim 7 , wherein the relationship between Tg _{L of the} low molecular weight polymer component and Tg _H of the high molecular weight polymer component is in the range of Tg _L ≧ Tg _H. 9. polymer component toner according to any one of claims 1 to 8 are satisfied the following formula of the composition. [Outer 1] 10. Both the low-molecular weight polymer component and high-molecular polymer components, electrostatic charge according to any one of claims 1 to 9 has at least a styrene monomer component unit 65 wt% or more Toner for image development. 11. High molecular weight polymer component, a polyfunctional polymerization toner according to any one of claims 1 to 10 initiator having a polymer produced by. 12. The electrostatic image according to any one of claims 1 to 11 having a high molecular weight polymer component is a polyfunctional polymerization initiator and a monofunctional polymerization initiator at least in combination with polymer produced Toner for development. 13. A GPC chromatogram of the polymer components, toner according to any one of claims 1 to 12 area ratio of the polymer component showing a molecular weight of 1,000,000 or more is 10% or less. 14. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group and may have a substituent, and 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 3] Represents hydrogen, sodium, potassium, ammonium or aliphatic ammonium. ] The toner for developing an electrostatic charge image according to any one of claims 1 to 13 , which is a compound represented by the formula: 15. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn or Fe. A is [outside 5] (May have a substituent of an alkyl group), (X represents a hydrogen atom, a halogen atom, or a nitro group) and [Ex. 7] (R represents a hydrogen atom or a C _{1 to} C ₁₈ alkyl or alkenyl group). [Outside 8] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or [External 9] Is. ] The toner for developing an electrostatic charge image according to any one of claims 1 to 13 , which is a compound represented by the formula: 16. The metal-containing organic compound has the following formula [II
I] [Outside 10] [In the formula, 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 ′ represent an integer of _{1 to 3} , and Y ₁ and Y ₃ represent a hydrogen atom. , C ₁ -C ₁₈ alkyl, C
_{2 to} C ₁₈ alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, C _{1 to} C
_{18 represents} an alkoxy, acetylamino, benzoyl, amino group or a halogen atom, n and n'represent an integer of 1 to 3, Y ₂ and Y ₄ represent a hydrogen atom or a nitro group, (the above X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, Y ₂ and Y ₄ may be the same and different.) [Ex. 11] Or a mixed ion thereof]. 15. The toner for developing an electrostatic charge image according to claim 14 , which is a compound represented by: 17. The metal-containing organic compound has the formula [I
V] [Outer 12] [In the formula, [Outer 13] Or a mixed ion thereof. ] The toner for developing an electrostatic charge image according to claim 16 , which is a compound represented by: 18. The toner has a weight average diameter (D ₄ ) of X (μm) and a toner number average diameter of 3.17.
Any of claims 1 to 17 having 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 not more than μm. The toner for developing an electrostatic image as described in 1. 19. The wax contains at least an acid-modified polyolefin (A) and a polyolefin (B) modified with an acid monomer, and the weight-average molecular weight (Mw) of the acid-modified polyolefin (A).
_WaxA ) is 8.0 × 10 ^{3 to} 1.4 × 10 ⁴ ,
Weight average molecular weight (Mw) of the polyolefin (B)
_WaxB ) is 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , and the acid-modified polyolefin (A) has an acid value of 1.5 to 7 mgK.
It has OH / g, and has an acid value (A _VWaxA ) satisfying the following condition 0.5 × A _VL > A _VWaxA × 0.05 × A _VL.
19. The toner for developing an electrostatic charge image according to any one of 18 . 20. The polyolefin (B) has a weight average molecular weight (Mw _Wax B) of 1.5 × 10 ^{4 to} 2.5 × 10.
20. The toner for developing an electrostatic charge image according to claim 19 , which is ⁴ . 21. acid-modified polyolefin (A) is maleic acid, maleic acid half esters, claim molecular terminal by an acid monomer selected from at least one or more of maleic anhydride is modified polypropylene wax 19 Or the toner for developing an electrostatic charge image according to item 20 . 22. The polyolefin (B) is an electrostatic image developing toner according to any one of claims 19 to 21 is a polypropylene wax. 23. The acid component contained in the acid-modified polyolefin and the acid component contained in the low molecular weight polymer component are produced 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 charge image according to any one of claims 19 to 22 , which has been obtained. 24. An electrostatic charge image carrier, and at least developing means for developing the electrostatic charge image formed on the electrostatic charge image carrier with toner, the electrostatic charge image carrier and the developing means .
Process cartridge with integrated cartridge
The process cartridge is attachable to and detachable from the main body of the image forming apparatus, and the toner is formed of a composition containing at least a polymer component, a colorant, a wax, and a charge control agent. In the GPC chromatogram, the component has (a) substantially no THF-insoluble matter, and (b) the THF-soluble matter of the polymer component has at least a molecular weight of 3 × 10 ^{3 to} 3 × 10 5.
⁴ has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or a shoulder in the region of 3 to 10 ⁶ and (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) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
In the C chromatogram, the acid value (A _VH ) in the molecular weight range of 5 × 10 ⁴ or more) is 0.5 to 11 mgKOH / g.
And the acid value (A _VWax ) of the wax is 1.5 to 7 mgK.
An OH / g, _{and, A VL, A VH, A} Vwax is following condition _{0.5 × A VL> A VWax>} 0.05 × A VL 10 ≦ (A VL -A VH) satisfying the ≦ 27 Process cartridge characterized by. 25. The process cartridge according to claim 24 , further comprising a contact charging unit for charging the electrostatic image holder. 26. The process cartridge according to claim 25 , wherein the contact charging means is a charging roller. 27. The process cartridge according to claim 25 , wherein the contact charging means is a charging blade. 28. The process cartridge according to claim 25 , wherein the contact charging means is a charging brush. 29. A claim further comprising a cleaning means for cleaning the electrostatic image holding member surface 2
29. The process cartridge according to any one of 4 to 28 . 30. The process cartridge according to claim 29 , wherein the cleaning means has a cleaning blade. 31. A process cartridge according to any one the wax is an acid-modified polyolefin wax der Ru請 Motomeko 24 to 30. 32. The wax is at least one of maleic acid, maleic acid half ester or maleic anhydride.
24. to 3 molecular terminal by an acid monomer selected from a species or a modified polyolefin wax
1. The process cartridge according to any one of 1 . 33. The wax is at least one of maleic acid, maleic acid half ester or maleic anhydride.
24. to the molecular terminal is modified polypropylene wax with an acid monomer selected from the species above
31. The process cartridge according to any one of 31 . 34. The acid component of the wax and the acid component of the low molecular weight polymer component are produced from an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. 34. The process cartridge according to any one of claims 24 to 33 , wherein 35. GPC of a THF-soluble component of the polymer component
In the chromatogram, the molecular weight is 3 × 10 ⁴ or more 1 × 1
0 The process cartridge according to any one of claims 24 to 34 to ⁵ below the region having the minimum value. 36. The glass transition point (Tg) of the composition is 5.
0 to 70 ° C. and T of the low molecular weight polymer of the composition
g _L and process cartridge according to any one of claims 24 to 35 relationship Tg _H of the high molecular weight polymer is in the range of _{Tg L} ≧ Tg H -5. 37. 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 36. The process cartridge according to 36 . 38. A process cartridge according to any one of claims 24 to 37 polymer component of the composition satisfies the following formula. [Outside 14] 39. Both the low-molecular weight polymer component and a high molecular weight polymer component, the process cartridge according to any one of claims 24 to 38 has at least a styrene monomer component unit 65 wt% or more . 40. A process cartridge according to any one of claims 24 to 39 having a polymer produced by the high molecular weight polymer component is a polyfunctional polymerization initiator. 41. A high molecular weight polymer component, the process cartridge according to any one of claims 24 to 40 having a polyfunctional polymerization initiator and a monofunctional polymerization initiator at least in combination with polymer produced . 42. In GPC chromatogram of the polymer component, the process cartridge according to any one of claims 24 to 41 area ratio of the polymer component showing a molecular weight of 1,000,000 or more is 10% or less. 43. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group and may have a substituent, and 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 24 to 42 , which is a compound represented by the above formula. 44. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn or Fe. A is [outer 18] (May have a substituent of an alkyl group), (X represents a hydrogen atom, a halogen atom, or a nitro group) and [Ex. 20] (R represents a hydrogen atom or a C _{1 to} C ₁₈ alkyl or alkenyl group). [Outside 21] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or [External 22] Is. ] Is a compound represented by the claims 24 to 42
The process cartridge according to any one of 1. 45. The metal-containing organic compound is represented by the following formula [II
I] [23] (In the formula, 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 ′ represent an integer of _{1 to 3} , and Y ₁ and Y ₃ represent a hydrogen atom. , C ₁ -C ₁₈ alkyl, C
_{2 to} C ₁₈ alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, C _{1 to} C
_{18 represents} an alkoxy, acetylamino, benzoyl, amino group or a halogen atom, n and n ′ represent an integer of 1 to 3, Y ₂ and Y ₄ represent a hydrogen atom or a nitro group, (the above X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, Y ₂ and Y ₄ may be the same or different. Or a mixed ion thereof. The process cartridge according to claim 43 , which is a compound represented by the formula (4). 46. The metal-containing organic compound has the formula [I
V] [Outer 25] [In the formula, Or a mixed ion thereof. 46. The process cartridge according to claim 45 , which is a compound represented by: 47. The toner has a weight average particle diameter (D ₄ ) of X (μm) and a toner number average particle diameter of 3.17.
Any of claims 24 to 46 having a particle size distribution satisfying the following formula: -5X + 35? The process cartridge described in. 48. The wax contains at least the acid-modified polyolefin (A) and the polyolefin (B) modified with an acid monomer, and the weight-average molecular weight (Mw) of the acid-modified polyolefin (A).
_WaxA ) is 8.0 × 10 ^{3 to} 1.4 × 10 ⁴ ,
Weight average molecular weight (Mw) of the polyolefin (B)
_WaxB ) is 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , and the acid-modified polyolefin (A) has an acid value of 1.5 to 7 mgK.
OH / g, and according to any one of claims 24乃<br/> optimum 47 having the following conditions _{0.5 × A VL> A VWaxA ×} 0.05 × acid value satisfying _{A VL} of _{(A VWaxA)} Process cartridge. 49. The weight average molecular weight (Mw _Wax B) of the polyolefin (B) is 1.5 × 10 ^{4 to} 2.5 × 10.
49. The process cartridge according to claim 48 , which is ⁴ . 50. A acid-modified polyolefin (A) is maleic acid, claim maleic acid half ester, a molecular terminal by an acid monomer selected from at least one or more of maleic anhydride is modified polypropylene wax 48 Or the process cartridge described in 49 . 51. A acid-modified polyolefin (B) A process cartridge according to any of claims 48 to 50 is a polypropylene wax. 52. The acid component contained in the acid-modified polyolefin and the acid component contained in the low molecular weight polymer component are produced 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 58 to 51 , which has been processed. 53. An electrostatic charge image is formed on the electrostatic charge image carrier,
An image forming method of developing an electrostatic charge image with a toner held in a developing means to form a toner image, wherein the toner is a composition containing at least a polymer component, a colorant, a wax and a charge control agent. And the polymer component of the composition is (a) substantially free of THF-insoluble matter, and (b) the THF-soluble matter of the polymer component has at least a molecular weight of 3 × 10 5 in a GPC chromatogram. ^{3 to} 3 x 10
⁴ has a main peak in the region of ⁴ and has a molecular weight of 1 × 10 ⁵
Has a sub-peak or a shoulder in the region of 3 to 10 ⁶ and (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) is 2
1 to 35 mgKOH / g, which is a high molecular weight polymer (GP
In the C chromatogram, the acid value (A _VH ) in the molecular weight range of 5 × 10 ⁴ or more) is 0.5 to 11 mgKOH / g.
And the acid value (A _VWax ) of the wax is 1.5 to 7 mgK.
An OH / g, _{and, A VL, A VH, A} Vwax is following condition _{0.5 × A VL> A VWax>} 0.05 × A VL 10 ≦ (A VL -A VH) satisfying the ≦ 27 And an image forming method. 54. The toner image according to claim 53 , which is transferred onto a transfer material with or without an intermediate transfer member, and the toner image on the transfer material is heated and fixed by a fixing unit. Image forming method. 55. The image forming method according to claim 53 or 54 , wherein the electrostatic charge image carrier is charged by a charging means and an electrostatic charge image is formed by exposure. 56. The image forming method according to claim 55 , wherein the electrostatic image carrier is charged by contact charging means. 57. A toner image according to claim 53 or bias is transferred to the transfer material by contact means being applied
57. The image forming method according to any one of 56 . 58. After the toner image has been transferred, the image forming method according to any one of claims 53 to 57 an electrostatic image bearing member surface is cleaned by the cleaning means. 59. The image forming method according to any one of claims 53 to 58 wherein the wax is an acid-modified polyolefin wax. 60. wherein said wax is maleic acid, either of claims 53 to 59 molecular terminal by an acid monomer selected from at least one or more of the maleic acid half an ester or acid anhydride is modified polyolefin waxes An image forming method according to claim 1. 61. the wax is at least one of maleic acid, maleic acid half an ester or maleic anhydride
53 through claim molecular terminal is modified polypropylene wax with an acid monomer selected from the species above
59. The image forming method according to any one of 59 . 62. The acid component having an acid component and a low molecular weight polymer component wax has is generated, maleic acid, maleic acid half an ester, an acid monomer selected from at least one or more maleate Lee phosphate anhydride the image forming method according to any one of claims 53 to 61 in which is. 63. GPC of a THF-soluble component of the polymer component
In the chromatogram, the molecular weight is 3 × 10 ⁴ or more 1 × 1
The image forming method according to any one of claims 53 to 62 having a minimum value 0 less than ⁵ regions. 64. The glass transition point (Tg) of the composition is 5
0 to 70 ° C. and 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 53 to 63 in the range of _{Tg L} ≧ Tg H -5. 65. 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 64. The image forming method according to 64 . 66. The image forming method according to any one of the polymer according to claim 53 or 65 components satisfies the following formula in the composition. [Outside 27] 67. The image formation according to any one of claims 53 to 66 , wherein both the low molecular weight polymer component and the high molecular weight polymer component have at least 65% by weight of a styrenic monomer component unit. Method. 68. The image forming method according to any one of claims 53 to 67 having a polymer produced by the high molecular weight polymer component is a polyfunctional polymerization initiator. 69. A high molecular weight polymer component, the image formation according to any one of claims 53 to 68 having a polyfunctional polymerization initiator and a monofunctional polymerization initiator at least in combination with polymer produced Method. In GPC chromatogram of claim 70] polymer components, the image forming method according to any one of claims 53 to 69 area ratio of the polymer component showing a molecular weight of 1,000,000 or more is 10% or less. 71. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn or Fe. Ar is an aryl group and may have a substituent, and 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 53 to 70 , which is a compound represented by the above formula. 72. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: [In the formula, M represents a coordination center metal, Cr having a coordination number of 6,
Co, Ni, Mn, or Fe. A is [outside 31] (May have a substituent of an alkyl group), (X represents a hydrogen atom, a halogen atom, or a nitro group) and (R represents a hydrogen atom or a C _{1 to} C ₁₈ alkyl or alkenyl group). [Outside 34] Represents hydrogen, sodium, potassium, ammonium, or aliphatic ammonium. Z is -O- or [external 35] Is. ] The compound shown by these] 53 to 70
The image forming method according to any one of 1. 73. The metal-containing organic compound has the formula [II
I] [Outer 36] [In the formula, 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 ′ represent an integer of _{1 to 3} , and Y ₁ and Y ₃ represent a hydrogen atom. , C ₁ -C ₁₈ alkyl, C
_{2 to} C ₁₈ alkenyl, sulfonamide, mesyl, sulfonic acid, carboxy ester, hydroxy, C _{1 to} C
_{18 represents} an alkoxy, acetylamino, benzoyl, amino group or a halogen atom, n and n'represent an integer of 1 to 3, Y ₂ and Y ₄ represent a hydrogen atom or a nitol group, (the above X ₁ and X ₂ , m and m ′, Y ₁ and Y ₃ , n and n ′, Y ₂ and Y ₄ may be the same or different. Or a mixed ion thereof. The image forming method according to claim 71 , which is a compound represented by 74. The metal-containing organic compound has the formula [I
V] [Outside 38] [In the formula, Or a mixed ion thereof. The image forming method according to claim 73 , which is a compound represented by the formula: 75. The toner has a weight average particle diameter (D ₄ ) of X (μm) and a toner number average particle diameter of 3.17.
75. Any of claims 53 to 74 having a particle size distribution satisfying the following formula: -5X + 35? An image forming method according to claim 1. 76. The wax contains at least the acid-modified polyolefin (A) and the polyolefin (B) modified with an acid monomer, and the weight-average molecular weight (Mw) of the acid-modified polyolefin (A).
_WaxA ) is 8.0 × 10 ^{3 to} 1.4 × 10 ⁴ ,
Weight average molecular weight (Mw) of the polyolefin (B)
_WaxB ) is 1.0 × 10 ^{4 to} 4.0 × 10 ⁴ , and the acid-modified polyolefin (A) has an acid value of 1.5 to 7 mgK.
An OH / g, according to any one of claims 53乃<br/> optimum 75 having the following conditions _{0.5 × A VL> A VWaxA>} 0.05 × A VL acid number which satisfies the _{(A VWaxA)} Image forming method. 77. The polyolefin (B) has a weight average molecular weight (Mw _WaxB ) of 1.5 × 10 ^{4 to} 2.5 × 10.
⁴ The image forming method according to claim 76. 78. The acid-modified polyolefin (A) is a polypropylene wax having a molecular terminal modified with an acid monomer selected from at least one of maleic acid, maleic acid half ester and maleic anhydride. 76. The image forming method described in 76 or 77 . 79. The polyolefin (B) The image forming method according to any one of claims 76 to 78 is a polypropylene wax. 80. The acid component of the acid-modified polyolefin and the acid component of the low molecular weight polymer component are produced from an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic acid aqueous solution. any image forming method according to claim 76 or 79 in which is.