JP3256830B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to electrophotography, electrostatic printing,
In an image forming method such as magnetic recording, the present invention relates to a toner for visualizing a latent electrostatic image.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
A number of methods are known, as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748, but generally, a photoconductive substance is used. An electric latent image is formed on the photoreceptor by various means, then the latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper. The toner is fixed by pressurization or solvent vapor to obtain a copy, and the remaining toner not transferred onto the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

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

However, 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 optimum temperature of the heating roller is set in order to prevent defective fixing due to the fluctuation of the temperature of the heating roller due to the passage of the recording material or other external factors and the transfer of toner to the heating roller, ie, the so-called offset phenomenon. In order to achieve this, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power and causes a rise in the temperature inside the image forming apparatus.

(3) Since the temperature of the roller is low, when the recording material is discharged through the heating roller, the recording material and the toner on the recording material are cooled slowly, so that the toner has high tackiness. In addition, offset or paper jam due to entrainment of the recording material may occur in combination with the curvature of the roller. Etc. are not fundamentally solved.

However, in order to realize a fixing method with a short wait time and low power consumption while achieving excellent fixability of a toner-visible image to a recording material, prevention of offset, and the like, a fixing device as described above is used. In addition, the characteristics of the toner are greatly affected.

Conventionally, in order to prevent the toner from adhering to the surface of the fixing roller, a method of adding a wax such as low molecular weight polyethylene or polypropylene which sufficiently melts upon heating to increase the releasability of the toner has been used. ,
While effective in preventing offset, the cohesiveness of the toner increases, the charging characteristics become unstable, and the durability tends to decrease. Therefore, various attempts have been made to improve the binder resin as another method.

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

In general, in order to improve the low-temperature fixability of a toner, it is necessary to decrease the viscosity of the toner at the time of melting to increase the adhesion area with a fixing base material. Is required to be low.

That is, since the low-temperature fixing property and the offset preventing property have contradictory aspects, it is very difficult to develop a toner that simultaneously satisfies these functions.

In order to solve this problem, for example, Japanese Patent Publication No. 51-23354 discloses a toner comprising a vinyl polymer which is appropriately crosslinked by adding a crosslinking agent and a molecular weight modifier. Japanese Patent No. 6805 discloses a toner having a wide molecular weight distribution such that the ratio between the weight average molecular weight and the number average molecular weight of the α, β unsaturated ethylenic monomer as a constitutional unit is 3.5 to 4.0. Further, a blend-type toner or the like in which Tg, molecular weight, gel content, and the like of a vinyl polymer are combined has been proposed.

Certainly, the toner according to these proposals has a lower fixing temperature (the lowest temperature at which fixing is possible) and an offset temperature (a temperature at which offset starts to occur), compared to a toner made of a single resin having a narrow molecular weight distribution. Although the temperature range that can be fixed is widened, if sufficient anti-offset performance is given, the fixing temperature cannot be lowered sufficiently. There was the problem of becoming.

In place of these vinyl resins, a toner obtained by crosslinking an polyester resin, which is considered to be essentially superior to vinyl resins in terms of low-temperature fixability, and further adding an anti-offset agent, is also a special feature. Kaisho 57-20855
No. 9 proposes this. This is excellent in both low-temperature fixing property and offset prevention property, but has a problem in productivity (pulverizability) as a toner.

In Japanese Patent Application Laid-Open No. 56-116043, a vinyl-based monomer is polymerized in the presence of a reactive polyester resin, and is polymerized through a crosslinking reaction, an addition reaction, and a grafting reaction in the polymerization process. Although a toner using such a resin has been proposed and has been improved in terms of pulverizability, the functions of the resins cannot be sufficiently utilized in terms of low-temperature fixability and offset prevention.

Further, two types of polyester resin and gel content are simply different (gelation degree of 80% or more and gelation degree of 1
(Less than 0%), a toner using a resin blended with a vinyl resin has been proposed in Japanese Patent Publication No. 1-10663. The toner has good low-temperature fixability, but has an anti-offset property and a pulverizability. Not enough yet. Even if the proportion of the vinyl resin having a gelation degree of 80% or more is increased for the purpose of improving the offset resistance, the anti-offset property is improved, but the low-temperature fixability is significantly reduced. Gelation degree 1
Sufficient pulverizability cannot be satisfied only by containing less than 0% of a vinyl resin.

On the other hand, for the physical properties required for the toner as described above, crosslinking is performed by reacting a polymer having a carboxylic acid in a binder resin with a metal compound (Japanese Patent Application Laid-Open No. 57-1982). No. 178249, 57-17
No. 8250), or a binder having a vinyl resin monomer and a more specific monoester compound as essential constitutional units and a polyvalent metal compound are reacted and cross-linked via a metal (Japanese Patent Application Laid-Open No. 61-1986). No. 110155, 61-110
156). further,
JP-A-63-214760 and JP-A-63-217362.
JP-A-63-217363 and JP-A-63-217364 have a molecular weight distribution divided into two groups of a low molecular weight and a high molecular weight, and react a carboxylic acid group contained on the low molecular weight side with a polyvalent metal ion. (A dispersion of a metal compound is added to a solution obtained by solution polymerization, and the mixture is heated and reacted) is disclosed in any method. The dispersion of the metal compound therein is insufficient, and the physical properties required for the toner, in particular, the fixing property and the anti-offset property have not been satisfied. In addition, since it is necessary to mix a large amount of the metal compound with the binder resin, the compounded metal compound shows a catalytic action on the binder resin depending on conditions, and the binder resin is easily gelled, and as a result, the metal compound is mixed. However, it is difficult to determine the manufacturing conditions for obtaining a desired toner, and even if the manufacturing conditions can be determined, there is a problem that reproducibility is hardly obtained.

Further, in the adjustment of the acid amount in these proposals, the charging characteristics (rise), environmental characteristics (leaving characteristics under high humidity), and image characteristics (fog and density characteristics) of the toner are still insufficient.

Further, JP-A-2-168264, JP-A-2-23569, JP-A-5-173363,
In JP-A-5-173366 and JP-A-5-241371, the molecular weight, the mixing ratio, the acid value and the ratio of the low molecular weight component and the high molecular weight component in the binder resin are controlled, and the fixing property, non-offset property, image Toner binder compositions and toners having improved properties, blocking resistance, charging start-up properties, and the like have been proposed, but are still low in perfection.

Particularly, in the adjustment of the acid value disclosed in the above-mentioned publication, poor dispersibility of a coloring agent such as magnetic iron oxide, a charge control agent (charge control agent), and other additives occurs, and a developer or carrier such as a carrier or a sleeve is loaded. Image deterioration such as fogging and density reduction due to contamination on the body surface occurs.

Further, the fixing at a lower temperature is insufficient.

In Japanese Patent Application Laid-Open No. 62-9256,
A binder composition for a toner in which two kinds of vinyl resins having different molecular weights and resin acid values are blended is disclosed. However, when using such a binder resin,
In order to improve the compatibility and dispersibility of the toner components, kneading conditions must be strengthened, and the resin of the binder is affected by cutting of molecules and the like, and exhibits desired performance such as offset resistance. It will be difficult to do. If kneading is performed to the extent that molecular breakage does not occur, poor dispersion of other additives will occur immediately, promoting contamination of the surface of the developer carrier such as a carrier or a sleeve, and fogging and scattering of developability. Cause serious problems. In particular, when a polymer having a weight average molecular weight of 1,000,000 or more is used, these phenomena become apparent.

Japanese Unexamined Patent Publication (Kokai) No. 3-72505 discloses a vinyl-based toner binder having a molecular weight of 300,000 or more using a multifunctional initiator. Although satisfactory, in addition to the above-described problems, the performance of the developer is deteriorated when left at high temperatures. Although the cause of this phenomenon is not clear, according to our investigation, only the molecular cleavage of the binder resin was promoted during the formation of the toner, so that the proportion of the resin component having a sufficient molecular weight in the toner composition was reduced. It is estimated that it became lower and became weaker to thermal shock.

Further, the various properties required for the above-mentioned toners are often reciprocal to each other, and it is more and more desirable in recent years that both of them are satisfied with high performance. Research has been conducted on comprehensive responses that include characteristics, but there is still not enough.

In recent years, the demand for higher speed of the apparatus requires the toner to have a further low-temperature fixing property, a toughness that can withstand high-speed development, and a charging stability that can withstand long-term durability. I have.

However, it is difficult to achieve both the low-temperature fixability described above and the toughness of the toner at the same time, and at present, there is no satisfactory structure in the above-mentioned prior art.

[0027] Further, it has been found that acid anhydrides have a function of improving the chargeability, and examples of applying a resin containing the same are disclosed in JP-A-59-139053 and JP-A-62-2.
80758. These methods employ a method of diluting a polymer having acid anhydride units at a high density into a binder resin, and the dispersion in the toner is poor, and problems such as fogging are likely to occur.

In JP-A-4-181263 and JP-A-3-152555, there is a report that a vinyl copolymer having an acid anhydride group is used to improve the charging stability. It is not yet sufficient as a charge control.

[0029]

SUMMARY OF THE INVENTION An object of the present invention is to significantly improve the drawbacks of the prior art, improve low-temperature fixability and anti-offset properties, and stabilize charging characteristics even during long-term durability. An object of the present invention is to provide a toner for developing an electrostatic charge image which realizes a high quality image and has high durability.

[0030]

SUMMARY OF THE INVENTION The present invention relates to a toner for developing an electrostatic image formed of a composition having at least a polymer component and a colorant, wherein the polymer component of the composition is It has a low molecular weight component and a high molecular weight component, and has a low molecular weight component (a molecular weight of 5.
The acid value / total acid value ratio of the region of less than 0 × 10 ^{4 is} less than 0.6, the acid value is 1 mgKOH / g or more, and the high molecular weight component (GPC chromatogram has a molecular weight of 5.0)
(Region of × 10 ⁴ or more), wherein the acid value / total acid value ratio is 0.6 or more, and the acid value is 1 mgKHO / g or more.

Further, according to the present invention, the polymer component of the toner composition does not substantially contain (i) a THF-insoluble component, and (ii) the THF-soluble component of the polymer component has at least a molecular weight in a GPC chromatogram. It has a peak in a region of 3.0 × 10 ^{3 to} 3.0 × 10 ⁴ and a molecular weight of 1.0 × 10 ⁵ to 3.0.
The present invention relates to a toner for developing an electrostatic image, which has a peak or a shoulder in an area of 0 × 10 ⁶ .

Further, according to the present invention, the acid value of the entire polymer component of the toner composition is at least 11 mgKOH / g and at most 30 mgKO.
H / g or less.

Further, according to the present invention, in a GPC chromatogram of a THF-soluble component of a polymer component of the toner composition, the toner component has a minimum value in a region having a molecular weight of 3.0 × 10 ⁴ or more and less than 1.0 × 10 ^5. And a toner for developing an electrostatic charge image.

Further, the present invention relates to an acid value of the low molecular weight component /
The ratio of the total acid value is less than 0.7, and the acid value of the high molecular weight component /
The present invention relates to a toner for developing an electrostatic image, wherein the ratio of the total acid value is 0.7 or more.

As a result of intensive studies, the present inventor has found that the ratio of acid value / total acid value of the low molecular weight component (region having a molecular weight of less than 5.0 × 10 ⁴ in the GPC chromatogram) of the polymer component of the toner is 0.1. 6, the ratio of acid value / total acid value of the high molecular weight polymer (region having a molecular weight of 5.0 × 10 ⁴ or more in the GPC chromatogram) is 0.6 or more, and both have an acid value of 1 m
It has been found that the toner having an amount of gKOH / g or more has excellent toner charging characteristics and high durability.

Although the cause of the effect is not clear, the balance between the charge and discharge of the toner and the ratio of the acid value / total acid value are deeply involved, and the balance between the low molecular weight component and the high molecular weight component and the acid value / total acid value are further involved. It was found that the toner charging characteristics were excellent when the acid value ratio was in the above range.

In particular, the acid value constitution of the present invention is excellent in charge stability in a high-speed machine.

The toner composition of the present invention substantially contains THF.
Contains no insolubles. Specifically, the content is 5% by weight or less, preferably 3% by weight or less based on the resin composition.

The THF-insoluble component in the present invention indicates the weight ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the resin composition in the toner,
It can be used as a parameter indicating the degree of crosslinking of the resin composition containing the crosslinking component. The THF-insoluble matter is defined by a value measured as follows.

That is, 0.5 to 1.0 g of the toner sample is weighed (w ₁ g), and the sample is filtered with a cylindrical filter paper (for example, No. ₁ made by Toyo Filter Paper).
86R), subjected to a Soxhlet extractor, extracted with 100 to 200 ml of THF as a solvent for 6 hours, and evaporated the soluble components extracted by the solvent.
After vacuum drying at 100 ° C. for several hours, the amount of the THF-soluble resin component is weighed (w ₂ g). The weight of a component other than the resin component such as a magnetic substance or a pigment in the toner is defined as (w ₃ g). T
The HF insoluble content is obtained from the following equation.

THF insoluble matter (%) = [｛w ₁ − (w ₃ + w)
₂ )｝ / (w ₁ −w ₃ )] × 100

When the content of the THF-insoluble component exceeds 5% by weight, not only the fixing property is deteriorated, but also a problem occurs in matching with the heat fixing device used in the embodiment of the present invention.

The T of the polymer component in the toner composition of the present invention
The chromatogram of GPC measured by the HF soluble component has a main peak at least in a region having a molecular weight of 3 × 10 ^{3 to} 3 × 10 ⁴ (more preferably, 5 × 10 ³ to 2 × 10 ⁴ ), and It has a subpeak or shoulder in the region of molecular weight of 1 × 10 ^{5 to} 3 × 10 ⁶ (more preferably, 5 × 10 ⁵ to 1 × 10 ⁶ ).

In the chromatogram of GPC, the area ratio of the polymer component having a molecular weight of 1,000,000 or more is 3 to 3.
It is preferable to show 10%. The presence of 3 to 10% of a THF-soluble component having a molecular weight of 1,000,000 or more improves the offset resistance without inhibiting low-temperature fixing and at the same time improves the storage stability of the developer under high-temperature storage. Can also be increased.

In the present invention, the molecular weight distribution of the polymer component of the toner composition is measured by GPC (gel permeation chromatography) under the following conditions.

<GPC Measurement Conditions for Toner Composition and Resin> Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Column: Temperature: 40 ° C. Solvent: THF (tetrahydrofuran) Flow rate: 1.0 ml / min. Sample: 0.1 m of a sample having a concentration of 0.05 to 0.6% by weight
l injection

In the present invention, both the low molecular weight component and the high molecular weight component of the polymer component need to have an acid value of 1 mgKOH / g or more. If it is not, the rising characteristics of the triboelectric charging of the toner and / or the dispersibility of the toner additive are adversely affected, and fog is likely to be worsened.

Further, according to the present invention, the acid value of the whole polymer component of the toner composition is at least 11 mgKOH / g and at most 30 mgKO.
It is preferably at most H / g. When the acid value of the entire polymer component is less than 11 mgKOH / g, the rising characteristics of toner charging are reduced, while when it exceeds 30 mgKOH / g, the developing characteristics under high humidity tend to be reduced.

The GPC chromatogram of the THF-soluble component of the polymer component of the toner composition of the present invention preferably has a minimum value in a region having a molecular weight of 3.0 × 10 ⁴ or more and less than 1.0 × 10 ^5. . In order to achieve both low-temperature fixability and high-temperature offset resistance, the low-molecular-weight polymer component and the high-molecular-weight polymer component preferably form independent molecular weight distributions.

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.

<Separation of each component> [Apparatus configuration] LC-908 (manufactured by Nippon Kagaku Kogyo Co., Ltd.) JRS-86 (company; repeat injector) JAR-2 (company; autosampler) FC-201 (Gilson; Hula cushion collector)

[Column Configuration] JAIGEL-1H to 5H
(20φ × 600mm: Preparative column)

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

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

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

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

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

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

5) Calculate the acid value by the following equation.

[0060]

(Equation 1)

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

<Measurement of Total Acid Value> 1) A sample is used after removing additives other than the polymer component in advance. Approximately 0.2 g of a crushed sample is precisely weighed, and the weight is
(G).

2) Put the sample in a 20 cc Erlenmeyer flask,
9 cc of 1,4-dioxane, 3 cc of pyridine and 6 mg of 4-dimethylaminopyridine are added and dissolved for 1 hour.

3) Add 1.1 cc of ion-exchanged water and reflux for 4 hours. Then cool.

4) Add 1 to 2 drops of an alcohol solution of phenolphthalein as an indicator.

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

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

[0068]

(Equation 2)

As the KOH THF solution, KOH6.
6 g was added to and dissolved in 20 cc of ion-exchanged water.
720 cc and 100 cc of ion-exchanged water are added, and then methanol is added while stirring until the mixture becomes transparent.

The acid value (JIS acid value, total acid value) of the low molecular weight polymer and the high molecular weight polymer in the resin composition was determined for the low molecular weight polymer and the high molecular weight polymer in accordance with the measurement of the toner polymer component. A resin composite was used as a sample.

The monomers for adjusting the acid value of the polymer component of the present invention include, for example, acrylic acid, methacrylic acid, α
-Acrylic acid such as ethylacrylic acid, crotonic acid and its α- or β-alkyl derivatives, fumaric acid, maleic acid, unsaturated dicarboxylic acids such as citraconic acid and its monoester derivatives or maleic anhydride; A desired polymer can be produced by copolymerizing such monomers alone or in combination with other monomers. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid.

Further, the esterification rate of the monoester derivative of the unsaturated dicarboxylic acid is changed, and further, as a polymer (or a polymer component of the toner composition), dehydration, esterification, dicarboxylic oxidation (degree of ring opening) Control) is preferably performed.

More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate,
Monoesters of α, β-unsaturated dicarboxylic acids such as monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc .; monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, Monoesters of alkenyl dicarboxylic acids such as monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate and monobutyl n-butenyladipate; monomethyl phthalate, monoethyl phthalate, monobutyl phthalate and the like And monoesters of aromatic dicarboxylic acids.

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 monomers constituting the polymer side of the binder resin.

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

In the present invention, the carboxylic acid groups and carboxylic acid ester sites in the copolymer obtained by the above-mentioned method are subjected to an alkali treatment to be saponified.
Acid value / total acid value can also be controlled. That is,
It can be controlled by reacting with a cation component of an alkali to change a carboxylic acid group or a carboxylic acid ester site into a polar functional group.

This alkali treatment may be carried out after the production of the binder resin, by introducing it as an aqueous solution into the solvent used at the time of polymerization and stirring. Examples of the alkali that can be used in the present invention include Na, K, Ca, Li, Mg, and Ba.
Hydroxides of alkali metals and alkaline earth metals such as;
There are hydroxides of transition metals such as Zn, Ag, Pb, and Ni; hydroxides of quaternary ammonium salts such as ammonium salts, alkylammonium salts, and pyridium salts. Particularly preferred examples include NaOH and KOH. .

In the present invention, the saponification reaction does not need to be carried out over all of the carboxylic acid groups and carboxylic acid ester sites in the copolymer. I just need to change.

The amount of the alkali used in the saponification reaction is difficult to determine unconditionally depending on the kind of the polar group in the binder resin, the dispersion method, the kind of the constituent monomer, and the like. What is necessary is just 02-5 times equivalent. When the amount is less than 0.02 equivalent, the saponification reaction is not sufficient, and the number of polar functional groups generated by the reaction is reduced, and as a result, the subsequent crosslinking reaction becomes insufficient. On the other hand, when the amount exceeds 5 times equivalent, the functional group such as a carboxylic acid ester site is adversely affected by hydrolysis of the ester, generation of a salt by a saponification reaction, and the like.

When the alkali treatment is performed at an equivalent of 0.02 to 5 times the acid value, the residual cation concentration after the treatment is 5 to 1%.
It is contained between 000 ppm and can be preferably used to regulate the amount of alkali.

The resin composition according to the present invention has a glass transition temperature (Tg) of 50 to 70 ° C., preferably 55 to 65 ° C. from the viewpoint of storage stability. Causes deterioration of the toner and offset at the time of fixing. On the other hand, when 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 resin composition according to the present invention is preferably in the range of Tg _L ≧ Tg _H -5 (° C.) If Tg _L is less than Tg _H -5, there is a tendency that developing property lowers. More preferably, Tg _L ≧ Tg _H is good.

As a method for producing the binder resin composition according to the present invention, a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, then they are mixed in a solution state, and then the solvent is removed. Blend method, or dry blend method of melt-kneading with an extruder or the like, and further dissolve the low molecular weight polymer obtained by the solution polymerization method or the like in the monomer constituting the high molecular weight polymer and perform suspension polymerization,
A two-stage polymerization method for obtaining a resin composition by washing and drying with water is exemplified. However, with the dry blend method, uniform dispersion,
Although there is a problem in compatibility, and the two-stage polymerization method has many advantages such as uniform dispersibility, it is difficult to increase the amount of low molecular weight polymer components to higher than high molecular weight polymer components. In the presence of a high molecular weight polymer component, not only is it difficult to synthesize a high molecular weight polymer component having a large molecular weight, but also there are disadvantages such as unnecessary low molecular weight polymer components being by-produced. For application, the solution blending method is most preferred. Further, as a method for introducing a predetermined acid value into the low molecular weight polymer component, solution polymerization in which the acid value can be easily set as compared with an aqueous polymerization method is preferable.

As a polymerization method which can be used in the present invention as a method for synthesizing the high molecular weight component of the resin composition according to the present invention, there are a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

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

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

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). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, and calcium phosphate, and are generally used in an amount of 0.05 to 1 part by weight based on 100 parts by weight of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer.

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

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
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-Di-tert-butylperoxybutane, 4,4-di-tert-butylperoxyvaleric acid-n-butyl ester, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxy Azelate, di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-
Butylperoxycyclohexyl) propane, 2,2-
a polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as t-butylperoxyoctane and various polymer oxides, and diallyl peroxydicarbonate; In one molecule such as butylperoxymaleic acid, t-butylperoxyallyl carbonate and t-butylperoxyisopropyl fumarate, both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group are contained. Selected from polyfunctional polymerization initiators having

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

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

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

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

These initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer from the viewpoint of efficiency.

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

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples thereof include aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; Diacrylate compounds, for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and acrylates of the above compounds replaced with methacrylates; diacrylate compounds linked by an alkyl chain containing an ether bond , Such as diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and acrylates of the above compounds instead of methacrylate Diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2,2-bis ( - hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,
2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; further, polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku) . As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

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

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

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

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

For example, styrene; o-methylstyrene, m
-Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
Styrene such as p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene and derivatives thereof; ethylene , Ethylenically unsaturated monoolefins such as propylene, butylene and isobutylene; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; vinyl acetate, vinyl propionate, Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Stearyl, meta Phenyl acrylic acid, dimethylaminoethyl methacrylate, alpha-methylene aliphatic monocarboxylic acid esters such as diethylaminoethyl methacrylate;
Methyl acrylate, ethyl acrylate, acrylic acid n-
Butyl, isobutyl acrylate, propyl acrylate,
Acrylic esters such as n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds of vinyl compounds; vinyl naphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; used alone or in combination of two or more.

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

It is preferable from the viewpoint of miscibility that both the low molecular weight component and the high molecular weight component contain at least 65 parts by weight of a styrene-based polymer component or a copolymer component.

By mixing the high molecular weight polymer constituting the resin composition according to the present invention with a low molecular weight wax in advance, phase separation in the micro region is alleviated, and reaggregation of the high molecular weight component is suppressed. It is preferable because a good dispersion state with the low molecular weight polymer can be obtained.

Examples of the low molecular weight wax applicable to the present invention include compounds such as polypropylene wax, polyethylene wax, microcrystalline wax, carnauba wax, sasol wax, paraffin wax, higher alcohol wax, ester wax and the like, and oxidation thereof. Products and graft-modified products.

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

It is preferable that these low molecular weight waxes are previously added to and mixed with the binder polymer component when producing the toner. In particular, a method in which the low molecular weight wax and the high molecular weight polymer are preliminarily dissolved in a solvent when the polymer component is prepared, and then mixed with the low molecular weight polymer solution.

The solid concentration of the polymer solution is determined by the dispersion efficiency,
In consideration of prevention of deterioration of the resin at the time of stirring, operability, etc., 5 to 70
It is preferable that the solid concentration of the preliminary solution of the high molecular weight polymer component and the polyolefin polymer is 5 to 60% by weight or less, and that the low molecular weight polymer solution has a solid concentration of 5 to 70% by weight or less.

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

Next, as a method of mixing the low molecular weight polymer solution, it is preferable to add 10 to 1000 parts by weight of the low molecular weight polymer solution to 100 parts by weight of the solid content of the preliminary solution and to carry out stirring and mixing. . In this case, a batch type or a continuous type may be used.

The organic solvent used for mixing the solution of the resin composition according to the present invention includes, for example, benzene, toluene,
Xylol, Solvent Naphtha No. 1, Solvent Naphtha No. 2, Solvent Naphtha No. 3, Cyclohexane, ethylbenzene, Solvesso 100, Solvesso 150, Hydrocarbon solvents such as mineral spirits; methanol, ethanol, iso-propyl alcohol, n-butyl alcohol, alcohol solvents such as sec-butyl alcohol, iso-butyl alcohol, amyl alcohol and cyclohexanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate, n-butyl acetate and cellosolve acetate Solvent: ether solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl carbitol. Aromatic in these,
Ketone and ester solvents are preferred. They may be used in combination.

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

In the present invention, magnetic iron oxide particles may be contained to form a magnetic toner.

The magnetic iron oxide particles used in the magnetic toner are preferably used in an amount of 20 to 200 parts by weight based on 100 parts by weight of the binder resin. More preferably 30 to
It is preferable to use 150 parts by weight.

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

Examples of the silane coupling agent used for the surface treatment of the magnetic iron oxide particles include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane,
Trimethylethoxysilane, dimethyldichlorosilane,
Methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α
-Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane,
Triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane,
Examples include dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, and 1,3-diphenyltetramethyldisiloxane.

Examples of the titanium coupling agent include isopropoxytitanium triisostearate, isopropoxytitanium dimethacrylate isostearate,
Isopropoxy titanium tridodecyl benzene sulfonate, isopropoxy titanium tris dioctyl phosphate, isopropoxy titanium tri N-ethylaminoethyl aminato, titanium bis dioctyl pyrophosphate oxy acetate, bis dioctyl phosphate ethylene dioctyl phosphite, di-n-butoxy Bistriethanol aminato titanium and the like can be mentioned.

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

Further, pigments or dyes such as conventionally known carbon black and copper phthalocyanine can be used as coloring materials which can be added to the toner for developing electrostatic images of the present invention.

The toner for developing an electrostatic image of the present invention is characterized in that it contains a charge control agent. In the case of a negatively chargeable toner, a metal complex salt of a monoazo dye, salicylic acid, alkyl salicylic acid, dialkyl salicylic acid or A negative charge control agent such as a metal complex salt of naphthoic acid is used.

For example, as the negative charge control agent,

[0122]

Embedded image

[0123]

Embedded image

[0124]

Embedded image

And the like. The following 3 are more effective as negative charge control agents to be combined with the magnetic iron oxide.
Seeds.

[0126]

Embedded image Monoazo iron complex represented by

[0127]

Embedded image

Compound of aromatic hydroxycarboxylic acid, aromatic diol or aromatic dicarboxylic acid derivative having the above general formula and iron atom

[0129]

Embedded image

[Wherein, Y¹ And Y^Two Is a phenyl group, naphthy
R or a anthryl group;¹And R^TwoIs a halogen field
Nitro group, sulfonic acid group, carboxyl group, carbo
Acid ester group, cyano group, carbonyl group, alkyl
R, an alkoxy group or an amino group;^ThreeAnd R^FourIs water
Having an atomic atom, an alkyl group, an alkoxy group, or a substituent
A good phenyl group, an aralkyl group which may have a substituent or
Represents an amino group;^FiveAnd R⁶Is a hydrogen atom or carbon number 1
And k and j are integers of 0 to 3 (same as above).
Sometimes not 0), and m and n represent 1 or 2.

(The above Y¹ , Y^Two , R¹And R^Two, R^ThreeAnd R^Four,
R^FiveAnd R⁶, K and j, m and n may be the same or different
No. )]

Among the N—N′-bisarylurea derivatives having the above general formula,

[0133]

Embedded image Is preferred.

It has been confirmed that the use of the above-mentioned negative charge control agent and a polymer component whose acid value is adjusted prevents or suppresses image quality characteristics, particularly fog.

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

The toner for developing an electrostatic image of the present invention is preferably mixed with an inorganic fine powder or a hydrophobic inorganic fine powder. For example, fine silica powder, fine titanium oxide powder, or a hydrophobized product thereof may be used. They are preferably used alone or in combination.

As the silica fine powder, both a so-called dry method produced by vapor phase oxidation of a silicon halide and a so-called fumed silica and a so-called wet silica produced from water glass can be used. Dry silica having few silanol groups on the surface and inside and having no production residue is preferable.

It is preferable that the silica fine powder has been subjected to a hydrophobic treatment. The hydrophobizing treatment is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the silica fine powder. A preferred method is to treat the dry silica fine powder produced by the vapor phase oxidation of the silicon halide compound with a silane coupling agent or simultaneously with the silane coupling agent and an organic silicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used for the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyl Dichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chloromethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldi Siloxane and 1,3-diphenyltetramethyldisiloxane.

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

[0141] The silicone oil treatment may be carried out, for example, by mixing silica fine powder treated with a silane coupling agent and silicone oil directly using a mixer such as a Henschel mixer, or adding silicone oil to the base silica. May be injected. Alternatively, it may be prepared by dissolving or dispersing a silicone oil in an appropriate solvent, mixing with a base silica fine powder, and removing the solvent.

Further, as a preferable hydrophobizing treatment of the silica fine powder used in the present invention, a method of preparing by treating with dimethyldichlorosilane, then with hexamethyldisilazane, and then with silicone oil can be mentioned.

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

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

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

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

The fine resin particles have an average particle size of 0.1.
The polymerizable monomer constituting the resin is preferably styrene / o-methylstyrene / m-methylstyrene / p-methylstyrene / p-methoxystyrene / p-ethylstyrene. Styrene monomers, methacrylic acids such as acrylic acid and methacrylic acid,
Methyl acrylate / ethyl acrylate / acrylic acid n-
Butyl, isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate
Acrylic esters such as 2-chloroethyl acrylate / phenyl acrylate, methyl methacrylate / ethyl methacrylate / n-propyl methacrylate / n-butyl methacrylate / isobutyl methacrylate / n-methacrylic acid
-Octyl / dodecyl methacrylate / methacrylic acid 2-
Methacrylates such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other acrylonitrile, methacrylonitrile,
And monomers such as acrylamide.

As the polymerization method, suspension polymerization, emulsion polymerization,
Soap-free polymerization and the like can be used, but more preferably particles obtained by soap-free polymerization are preferred.

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

As other fine particles, for example, lubricants such as Teflon, zinc stearate, and polyvinylidene fluoride are preferable, and polyvinylidene fluoride is particularly preferable. Alternatively, abrasives such as cerium oxide, silicon carbide, and strontium titanate, among which strontium titanate is preferable. Alternatively, for example, a fluidity imparting agent such as titanium oxide and aluminum oxide, particularly a hydrophobic agent is preferable. A small amount of a caking preventing agent or a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide, and tin oxide, or white and black fine particles of opposite polarity can also be used as a developability improver.

The resin fine particles, inorganic fine powder, or hydrophobic inorganic fine powder mixed with the toner may be used as the magnetic toner 100.
0.1 to 5 parts by weight (preferably 0.1 to 5 parts by weight)
To 3 parts by weight).

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

As another method for obtaining the electrostatic image developing toner of the present invention, the toner can be produced by a polymerization method. The polymerized toner is obtained by uniformly dissolving or dispersing the polymerizable monomer, the charge control agent of the present invention, the pigment or dye, the magnetic iron oxide, and the polymerization initiator (and, if necessary, the crosslinking agent and other additives). After preparing the monomer composition by using a suitable stirrer, the monomer composition or a prepolymerized version of the monomer composition is placed in a continuous phase (eg, water) containing a dispersion stabilizer using a suitable stirrer. The toner particles are dispersed and simultaneously subjected to a polymerization reaction to obtain toner particles having a desired particle size. In the case where magnetic iron oxide is used in the polymerization method, it is preferable to perform a hydrophobic treatment in advance.

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

The surface of the photosensitive drum (electrostatic image carrier) 1 is negatively charged by the primary charger 702, and a digital latent image is formed by image scanning by exposure 705 with a laser beam, and the magnetic blade 711 and the magnet 714 are included. The latent image is reversely developed with a one-component magnetic developer 710 of a developing device 709 having a developing sleeve 704. In the developing section, the conductive base of the photosensitive drum 1 is grounded, and an alternating bias, a pulse bias, and / or a DC bias are applied to the developing sleeve 704 by bias applying means 712. When the transfer paper P is conveyed and arrives at the transfer section, the transfer paper P is charged by the voltage application means 8 from the back surface (opposite side to the photosensitive drum side) of the transfer paper P by the roller transfer means 2, so that the developed image on the photosensitive drum surface is formed. (Toner image) is transferred onto the transfer paper P by the contact transfer means 2. The transfer paper P separated from the photosensitive drum 1 is heated and pressed by a roller fixing device 7.
At 07, a fixing process is performed to fix the toner image on the transfer paper P.

The one-component developer remaining on the photosensitive drum after the transfer step is removed by a cleaning device 708 having a cleaning blade. After the cleaning, the photosensitive drum 1 is gradually charged by the erase exposure 706, and the process starting from the charging process by the primary charger 702 is repeated again.

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

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

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

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

The conductive elastic layer 2b 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 1.
It is made of elastic material of 0 ¹⁰ Ωcm.

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

FIG. 2 shows an example of the charging means. The photosensitive drum 1 has a conductive base layer 1a made of aluminum or the like and a photoconductive layer 1b formed on the outer surface thereof as basic constituent layers.
It is rotated at a predetermined peripheral speed (process speed) clockwise in the drawing.

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

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

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

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

FIG. 5 shows a specific example of the process cartridge. The process cartridge at least integrates the developing means and the electrostatic image holder into a cartridge, and the process cartridge is formed so as to be detachable from a main body of an image forming apparatus (for example, a copying machine, a laser beam printer, or the like).

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

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

The toner of the present invention is rapidly charged, has a stable charging property, and is uniformly charged. Therefore, the toner is excellent in transportability of the toner in the developing device, and is charged even if the surface area of the frictional charging member is small. Rise quickly, and the charge amount is quickly made uniform. Therefore, in an image forming method for developing a latent image on an electrostatic latent image holding member with a one-component toner on a developing sleeve carrying one-component toner, the layer thickness of the one-component toner on the developing sleeve is regulated to a thin layer. The toner is preferably used in an image forming method using a developing method having a regulating member. Particularly, no magnetic force can be expected, it is difficult to supply the toner onto the developing sleeve, and the effect is large even in a non-magnetic one-component developing method having a small frictional charging ability.

Next, an example of a developing method in the case of performing non-magnetic one-component development using the toner of the present invention will be described, but the invention is not necessarily limited thereto. FIG. 6 shows an apparatus for developing an electrostatic image formed on a latent image holding member. 80
Reference numeral 8 denotes a latent image holding member, and a latent image is formed by an electrophotographic process unit or an electrostatic recording unit (not shown). 809
Denotes a developing sleeve, which is formed of a non-magnetic sleeve made of aluminum or stainless steel.

As the developing sleeve, a rough tube of aluminum or stainless steel may be used as it is, but preferably the surface is uniformly roughened by spraying glass beads or the like, mirror-finished, or coated with a resin or the like. Those are good, and are the same as those used in the magnetic one-component developing method.

The toner 800 is stored in the hopper 801, and is supplied onto the developer carrier by the supply roller 802. The supply roller is made of a foam material such as polyurethane foam, and rotates in a forward or reverse direction at a relative speed other than 0 with respect to the toner carrier, and together with the toner supply, the developed toner (undeveloped) on the toner carrier. Toner). The toner supplied on the toner carrier is uniformly and thinly applied by the toner application blade 803.

The contact pressure between the toner application blade and the toner carrier is 0.3 to 2 as a linear pressure in the sleeve generatrix direction.
5 kg / m, preferably 0.5 to 12 kg / m is effective. If the contact pressure is less than 0.3 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fogging and scattering. If the contact pressure exceeds 25 kg / m, a large pressure is applied to the toner, and the toner is deteriorated. Further, a large torque is required to drive the toner carrier, which is not preferable. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, the aggregation of the toner of the present invention can be effectively loosened, and the charge amount of the toner can be instantaneously increased. Become.

The toner thinning regulating member conforms to that used in the magnetic one-component developing method. The elastic blade and the elastic roller are preferably made of a material of a triboelectric series suitable for charging the toner to a desired polarity, and are similar to those used in the magnetic one-component developing method. In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber and the like are preferred. In addition, polyamide,
Polyimide, nylon, melamine, melamine cross-linked nylon, phenolic resin, fluororesin, silicone resin,
An organic resin layer such as a polyester resin, a urethane resin, and a styrene resin may be provided. Also, conductive rubber, conductive resin, etc. are used.Fillers such as metal oxides, carbon black, inorganic whiskers, inorganic fibers, etc. and charge control agents are used in the rubber of the blade according to those used in the magnetic one-component developing method. It is preferable because it imparts appropriate conductivity and charge imparting properties such as being dispersed in a resin, and can appropriately charge the toner.

In a system in which a thin layer of toner is coated on a developing sleeve by a blade, the thickness of the toner layer on the developing sleeve is adjusted to match the developing sleeve and the latent image holding member in order to obtain a sufficient image density. It is preferable to make the gap smaller than the gap length and to apply an alternating electric field to the gap. That is, the developing sleeve 8 is controlled by the bias power supply 804 shown in FIG.
By applying a developing bias in which an alternating electric field or a DC electric field is superimposed on the alternating electric field between the photoconductor 09 and the latent image holding member 808, the movement of the toner from the developing sleeve to the latent image holding member is facilitated, and the quality is further improved. Image can be obtained. These conditions also conform to the magnetic one-component developing method.

[0178]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

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

Under reflux, 72 parts by weight of styrene, 19 parts by weight of n-butyl acrylate, 9 parts by weight of butyl maleate half ester (half esterification rate 95%) and 2 parts by weight of di-tert-butyl peroxide Was added dropwise over 4 hours and then maintained for 3 hours to complete the polymerization, thereby obtaining a low molecular weight polymer xylene solution.

The solvent in this solution was removed under reduced pressure and
The temperature was raised to 0 ° C., kept for 2 hours, taken out, cooled, and pulverized to obtain a low molecular weight polymer (L-1).

Synthesis of high molecular weight polymer (H-1) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and 70 parts by weight of styrene and acrylic acid were added. 24 parts by weight of n-butyl, 6 parts by weight of butyl maleate half ester (half esterification rate: 75%), 0.005 part by weight of divinylbenzene, and 2,2-bis (4,4-di-tert-butylperoxy) A mixed solution of 0.1 parts by weight of cyclohexyl) propane was added, and stirred to form a suspension.

After the inside of the flask was sufficiently purged with nitrogen, 0.15 parts by weight of benzoyl peroxide was additionally added.
The polymerization was completed by holding for another 10 hours.

This was separated by filtration, washed with water and dried to obtain a high molecular weight polymer (H-1).

Preparation of Resin Composition (A) In a four-necked flask, 200 parts by weight of xylene, 30 parts by weight of the high molecular weight polymer (H-1) and 4 parts by weight of a low molecular weight polypropylene wax were charged and stirred. To perform pre-mixing.

After maintaining in this state for 20 hours, a uniform premixed liquid (Y-1) of the high molecular weight polymer (H-1) and the low molecular weight polypropylene was obtained.

On the other hand, the low molecular weight polymer (L-
1) 70 parts by weight of xylene and 210 parts by weight of xylene are added and mixed.

After mixing the above preliminary solution (Y-1) and the low molecular weight polymer (L-1) xylene solution, the organic solvent was removed by distillation under reduced pressure, and the obtained resin was cooled, solidified and pulverized. Thus, a resin composition for toner (A) was obtained.

Example 1 Resin Composition (A) 100 parts by weight Magnetic iron oxide 100 parts by weight Monoazo iron complex 2 parts by weight

The mixture was melt-kneaded with a twin-screw extruder heated to 130 ° C., and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. Was classified with a fixed wall type air classifier to produce a classified powder.

Further, the obtained finely pulverized powder was strictly classified and removed by a multi-segment classification device (Elbow Jet Classifier manufactured by Nippon Steel Mining Co., Ltd.) at the same time utilizing the Coanda effect to remove the weight average diameter. (D ₄ ) A negatively chargeable magnetic toner (t-1) of 6.8 μm was obtained.

The physical properties (molecular weight distribution (GP
C), the acid value / total acid value when the polymer component was collected from the toner) and the acid value / total acid value of the used resin are shown in Table 1 below.
FIG. 4 shows a chart of the chromatogram.

100 parts by weight of this magnetic toner (t-1) and 1.2 parts by weight of a hydrophobic silica fine powder treated with dimethyldichlorosilane, treated with hexamethyldisilazane, and then treated with dimethylsilicone oil, A magnetic toner having an external additive mixed with a Henschel mixer (T
-1) was prepared.

[Production Example 2 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-2) In the synthesis of the low molecular weight polymer (L-1) of Production Example 1 of the resin composition, the monomer composition was changed to 71% by weight of styrene. Parts, 20 parts by weight of n-butyl acrylate, 2.5 parts by weight of methacrylic acid, and 5.5 parts by weight of butyl maleate half ester (half esterification rate: 95%). A compound (L-2) was obtained. After pulverization, p
H11.3 in alkaline water to partially open the ring
The total acid number was adjusted.

[0195] L-2 as prepared low-molecular weight polymer component of the resin composition (B), similarly prepared Example 1 of high molecular weight polymer resin composition using H-1 as a component, to obtain a resin composition (B) .

[Production Example 3 of Resin Composition] 80 parts by weight of styrene and acrylic acid were synthesized as a monomer composition of the high molecular weight polymer (H-2).
17 parts by weight of n-butyl, 2 parts by weight of methacrylic acid, and 2 parts by weight of maleic anhydride are preliminarily subjected to bulk polymerization.
Then, a mixture of 0.1 parts by weight of divinylbenzene, 0.5 parts by weight of azobisisobutyronitrile and 100 parts by weight of xylene was continuously added to carry out solution polymerization. After completion of the polymerization, the solvent was removed and pulverized to obtain a high molecular weight polymer (H-2).

[0197] The resulting L-1 as prepared low-molecular weight polymer component of the resin composition (C), the H-2 used as the high molecular weight polymer component, manufacturing examples of the resin composition 1 Similarly, the resin composition (C) Was.

[Production Example 4 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-3) 300 parts by weight of xylene was charged into a four-necked flask, and the inside of the container was sufficiently purged with nitrogen while stirring. The temperature is raised to reflux.

Under the reflux, 80 parts by weight of styrene, 17.5 parts by weight of n-butyl acrylate, 2.5 parts by weight of butyl maleate half ester (half esterification rate 95%), and di-tert-butyl Peroxide 1.7
After dropping 5 parts by weight of the mixture over 4 hours, the mixture was held for 3 hours to complete the polymerization, thereby obtaining a low molecular weight polymer xylene solution.

The solvent in this solution was removed under reduced pressure and pulverized to obtain a low molecular weight polymer (L-3).

Synthesis of High Molecular Weight Polymer (H-3) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, and then 71 parts by weight of styrene and acrylic acid 24 parts by weight of n-butyl, 5 parts by weight of butyl maleate half ester (half esterification rate 70%), 0.005 parts by weight of divinylbenzene, and 2,2-bis (4,4-di-tert-butylperoxy) A mixed solution of 0.1 parts by weight of cyclohexyl) propane was added, and stirred to form a suspension.

After the inside of the flask was sufficiently purged with nitrogen, 0.15 parts by weight of benzoyl peroxide was additionally added.
The polymerization was completed by holding for another 10 hours.

This was filtered off, washed with water and dried to obtain a high molecular weight polymer (H-3).

[0204] Resin composition (D) of manufacturing low molecular weight polymer L-3 as a component, the H-3 used as a high molecular weight polymer component, like Production Example 1 of Resin composition, the resulting resin composition (D) Was.

[Production Example 5 of Resin Composition] Synthesis of Low-Molecular-Weight Polymer (L-4) 300 parts by weight of xylene was charged into a four-necked flask, and the inside of the vessel was sufficiently purged with nitrogen while stirring. The temperature is raised to reflux.

Under the reflux, 67 parts by weight of styrene, 20.5 parts by weight of n-butyl acrylate, 12.5 parts of butyl maleate half ester (half esterification rate: 95%)
A mixture of 2 parts by weight of di-tert-butyl peroxide and 4 parts by weight of di-tert-butyl peroxide was added dropwise over 4 hours, and the mixture was maintained for 3 hours to complete the polymerization, thereby obtaining a low molecular weight polymer xylene solution.

The solvent in this solution was removed under reduced pressure and pulverized to obtain a low molecular weight polymer (L-4).

Production of Resin Composition (D) Using L-4 as the low molecular weight polymer component and H-1 as the high molecular weight polymer component, a resin composition (E) was obtained in the same manner as in Production Example 1 of the resin composition. Was.

[Preparation Example 6 of Resin Composition] Synthesis of Low Molecular Weight Polymer (L-5) After charging 300 parts by weight of xylene into a four-necked flask, and thoroughly stirring the vessel with nitrogen while stirring, The temperature is raised to reflux.

Under the reflux, 74 parts by weight of styrene, 18 parts by weight of n-butyl acrylate, 2 parts by weight of butyl maleate half ester (half esterification rate: 95%), 6 parts by weight of methacrylic acid, and di-tert After dropping a mixed solution of 2 parts by weight of -butyl peroxide over 4 hours, the mixture was maintained for 3 hours to complete the polymerization, thereby obtaining a low molecular weight polymer xylene solution.

The solvent in this solution was removed under reduced pressure and pulverized to obtain a low molecular weight polymer (L-5).

[0212] The resulting L-5 as prepared low-molecular weight polymer component of the resin composition (F), the H-1 used as the high molecular weight polymer component, manufacturing examples of the resin composition 1 Similarly, the resin composition (F) Was.

[Production Example 7 of Resin Composition] A synthetic monomer composition of the high molecular weight polymer (H-4) was prepared by mixing 80 parts by weight of styrene and acrylic acid-n-
17 parts by weight of butyl and 4 parts by weight of butyl maleate half ester (half esterification rate 90%) were previously mixed in a lump, and then 100 parts by weight of xylene was added. Then, 0.1 part by weight of divinylbenzene and azobisisobutyronitrile were added. A solution mixture of 0.5 parts by weight and 100 parts by weight of xylene was continuously added to carry out solution polymerization.

After the completion of the polymerization, the solvent was removed and pulverized to obtain a high molecular weight polymer (H-4).

[0215] The resulting L-1 as prepared low-molecular weight polymer component of the resin composition (G), the H-4 used as a high molecular weight polymer component, manufacturing examples of the resin composition 1 Similarly, the resin composition (G) Was.

<Examples 2 to 5> The resin compositions (A) of Example 1 were used as the resin compositions (B), (C), (D),
In the same manner as in Example 1 except that (E) was used, magnetic toners T-2 to T-5 having an external additive were obtained. Table 1 shows the physical properties of the obtained toner and the physical properties of the resin components used.

<Comparative Examples 1-2> In the same manner as in Example 1 except that the resin composition (A) of Example 1 was changed to resin compositions (F) and (G), respectively, a magnetic toner T having an external additive was prepared. −6
T-7 was obtained. Table 1 shows the physical properties of the obtained toner and the physical properties of the resin components used.

[0218]

[Table 1] [Evaluation] Using a toner T-1 to T-7, a laser beam printer LBP-A309GII manufactured by Canon was modified so as to have the following settings, and image formation evaluation was performed.

The photosensitive drum is primarily charged to V _D = −600 V, and the surface thereof is scanned with a laser beam of a minute spot according to an image pattern to form an electrostatic latent image of V _L = −170 V, and the AC bias is applied. f = 1800Hz, Vp
p = 1400 V and DC bias V _DC = −450 V
While applying between the developing sleeve carrying the toner,
The electrostatic latent image on the OPC surface was developed to form a magnetic toner image.

The formed magnetic toner image is transferred by applying a positive charge from the back of the transfer paper by a transfer device in which a transfer roller having a conductive elastic layer is in contact with an OPC drum at a contact pressure of 50 g / cm. Further, a fixed image was obtained by passing through a heating and pressing roller fixing device.

The fixing temperature was set at 155 ° C.

Under the above set conditions, low temperature and low humidity (15 ° C./1
0% RH, high temperature and high humidity (32.5 ° C / 85% R)
H) Under an environment and a high temperature (severe test) (45 ° C.), a durability image test was performed continuously for 15,000 sheets. still,
The toner container was remodeled to double the capacity, and the main unit was remodeled to accommodate the cartridge. In a high temperature environment, 2000
After printing out images, leave them in the same environment for 7 days, and then
000 images were printed. The photoreceptor was replaced after 5,000 sheets, and durability was performed.

In the durability test, evaluation was made as follows. The results are summarized in Table 2.

The fixing property and the offset resistance were both good, but those using a polyfunctional polymerization initiator having a high molecular weight component were particularly excellent in the high temperature offset resistance.

(1) Image Density Rise In the endurance of each environment, a solid black image was printed at the initial time and at the time of 100 sheets, and the difference in image density was evaluated according to the following criteria.

◎ (excellent): density difference is 0.03 or less ○ (good): density difference is 0.05 or less Δ (good): density difference is 0.1 or less × (impossible): density difference is Δ Less than

(2) Durability Stability (Image Density, Fog) In the durability of each environment, an image of 9 solid blacks of 5 mm square (3 rows, 3 steps), solid black and white on the entire surface is printed every 1000 sheets. Then, image density and fog were measured, and evaluated as follows. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth) to measure the relative density of the white background portion of the printed image having a document density of 0.00 with respect to the printed image, and evaluated based on the criteria shown below. The fog is measured in advance using a "Reflectometer" (manufactured by Tokyo Denshoku Co., Ltd.), and the whiteness of the transfer paper before printing is measured.
The point values were measured and the maximum value recorded throughout the endurance.

Standard of image density durability stability: ； (excellent): 5 mm square, overall solid black density of 1.4 or more through durability （(good): 5 mm square, overall solid black density of 1.35 through durability Above Δ (acceptable): Image density throughout durability was 5 mm × 1.3
5. Solid black 1.3 or more on the entire surface × (impossible): Image density is below the level of Δ

(3) Image quality In the endurance of each environment, 100 μm which is more easily scattered than the splatter in the character line at the initial and 10,000 sheets.
(Latent image) A grid pattern (1 cm interval) at the line was printed, and the scattering and the sharpness of the line were enlarged with an optical microscope and visually evaluated.

◎ (excellent): lines are very sharp and hardly scattered. （(Good): lines are slightly scattered and relatively sharp. （(Acceptable): scattered slightly, lines are blurred. × (impossible): less than level △

[0231]

[Table 2]

[0232]

As described above, the present invention adjusts the molecular weight distribution of the polymer component and the acid value of the low molecular weight component and the high molecular weight component in the fine particle toner composition to thereby improve the fluidity and the charge stability. Improvement is possible, and the pulverizability is good and the pulverized particle size is sharp. Further, it enables lower-temperature fixing than before, excellent offset resistance, reduced fog, and long-term durability. Further, the present invention enables long-term charging stability even when applied to an increase in the speed of the apparatus.

[Brief description of the drawings]

FIG. 1 is a diagram schematically illustrating a transfer device.

FIG. 2 is a diagram schematically illustrating a charging roller.

FIG. 3 is a chart of a GPC chromatogram of a resin according to Example 1.

FIG. 4 is a schematic view illustrating an example of an image forming method in which the present invention is used.

FIG. 5 is a diagram illustrating a specific example of a process cartridge.

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

[Explanation of symbols]

 Reference Signs List 1 latent image carrier (photoreceptor) 2 transfer roller 2a cored bar 2b conductive elastic layer 3 constant voltage power supply 42 charging roller 704 developing sleeve

──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Masaichiro Katada 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) References JP-A-6-348062 (JP, A) JP-A-2 JP-235069 (JP, A) JP-A-5-173366 (JP, A) JP-A-5-53373 (JP, A) JP-A-6-194873 (JP, A) JP-A-6-118701 (JP, A) JP-A-4-190245 (JP, A) JP-A-4-188153 (JP, A) JP-A-6-273975 (JP, A) JP-A-6-313982 (JP, A) 313985 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (13)

(57) [Claims] 1. A toner for developing an electrostatic image formed of a composition having at least a polymer component and a colorant, wherein the polymer component of the composition has a low molecular weight component and a high molecular weight component. The ratio of acid value / total acid value of the low molecular weight component (region having a molecular weight of less than 5.0 × 10 ⁴ in the GPC chromatogram) is less than 0.6 and the acid value is 1 mgKOH / g or more; An electrostatic charge, wherein the ratio of the acid value / total acid value of the component (region having a molecular weight of 5.0 × 10 ⁴ or more in the GPC chromatogram) is 0.6 or more and the acid value is 1 mgKOH / g or more. Image developing toner. 2. The polymer component of the toner composition contains (i) substantially no THF-insoluble component, and (ii) the THF-soluble component of the polymer component has a molecular weight of at least 3.0 in a GPC chromatogram. × 10 ³ ~
It has a peak in the region of 3.0 × 10 ⁴ and has a molecular weight of 1.
The electrostatic image developing toner according to claim 1, wherein the toner has a peak or a shoulder in a region of 0 × 10 ^{5 to} 3.0 × 10 ⁶ . 3. The toner for developing an electrostatic charge image according to claim 1, wherein the acid value of the entire polymer component of the toner composition is 11 mgKOH / g or more and 30 mgKOH / g or less. 4. A GPC chromatogram of a THF-soluble component of a polymer component of the toner composition, wherein the molecular weight is 3.0 ×
The electrostatic image developing toner according to any one of claims 1 to 3, wherein the toner has a minimum value in a region of 10 ⁴ or more and less than 1.0 × 10 ⁵ . 5. The low molecular weight component having an acid value / total acid value ratio of 0.
7, and the ratio of the acid value of the high molecular weight component / total acid value is 0.1.
The toner for developing an electrostatic charge image according to claim 1, wherein the number is 7 or more. 6. The composition has a glass transition point (Tg) of 50.
７０70 ° C. and the Tg of the low molecular weight polymer of the composition
_L and a high molecular weight polymer of Tg _H toner according to any one of claims 1 to 5 related to being in the range of Tg _L ≧ Tg _H -5 of. 7. The composition has a Tg of 55 to 65 ° C.,
And according to any one of claims 1 to 6, characterized in that relationship of Tg _H of Tg _L and a high molecular weight polymer component of low molecular weight polymer component of the composition is in the range of Tg _L ≧ Tg _H An electrostatic image developing toner. 8. The composition according to claim 1, wherein both the low molecular weight polymer component and the high molecular weight polymer component of the composition contain at least 65% by weight of a styrene monomer component unit. 8. The toner for developing an electrostatic image according to any one of 7. 9. The electrostatic charge image developing device according to claim 1, wherein the high molecular weight polymer component of the composition has a polymer polymerized with a polyfunctional polymerization initiator. toner. 10. The composition according to claim 1, wherein the high molecular weight polymer component of the composition has a polymer obtained by polymerizing at least a combination of a polyfunctional polymerization initiator and a monofunctional polymerization initiator. 10. The toner for developing an electrostatic image according to any one of items 9 to 9. 11. The toner according to claim 1, wherein an area ratio of a polymer component having a molecular weight of 1,000,000 or more in a GPC chromatogram of the toner polymer component is 10% or less. Charge image developing toner. 12. The charge control agent represented by the following general formula: The electrostatic image developing toner according to any one of claims 1 to 11, wherein the toner is represented by the following formula. 13. The charge control agent represented by the following general formula: The toner for developing an electrostatic image according to claim 12, wherein: