JPH09127723A - Toner for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner giving a sharp image, having improved low-temp. fixability and anti-offsetting property, not causing fog even in use over a long period of time and having stable electrostatic chargeability. SOLUTION: This toner is formed with a compsn. contg. at least a polymer, a colorant, a releasing agent and an electrostatic charge controlling agent. The polymer does not practically contain a THF (tetrahydrofuran)-insoluble component and the THF-soluble component of the polymer has a main peak in the mol.wt. region of 3×10<3> -3×10<4> and a sub-peak or a shoulder in the mol.wt. region of 1×10<5> -3×10<6> in its chromatogram by GPC. A polymer part whose mol.wt. is >=1×10<6> in the THF-soluble component accounts for 1-20% by area and a high mol.wt. polymer part whose mol.wt. is >=1×10<5> in the polymer has 0.5-20KOHmg/g acid value. The releasing agent contains polyolefin modified with an arom. vinyl monomer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for visualizing an electrostatic latent image in an image forming method such as electrophotography and electrostatic printing.

[0002]

2. Description of the Related Art US 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 roller has a low temperature, when the recording material passes through the heating roller and is discharged, the recording material and the toner on the recording material are cooled slowly, so that the toner has a high adhesiveness. Therefore, offset or a paper jam due to the winding of the recording material may occur due to the curvature of the roller. Etc. are not fundamentally solved.

In Japanese Patent Laid-Open No. 63-313182, a fixing device for heating a toner image to a recording material and fixing the toner image on a recording material through a heat-resistant sheet which is moved by a heating element of a low heat capacity which is energized and heated in a pulsed manner. An image forming apparatus having a short wait time and low power consumption has been proposed. In JP-A-1-187582, in a fixing device that heat-fixes a visible image of a toner onto a recording material via a heat resistant sheet, the heat resistant sheet has a heat resistant layer and a release layer or a low resistance layer. A fixing device that effectively prevents the offset phenomenon has been proposed.

However, in order to realize a fixing method that has 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.

Based on the above, various attempts have been made to improve the binder resin in the toner.

For example, a method of increasing the glass transition temperature (Tg) and the molecular weight of the binder resin in the toner and improving the melt viscoelasticity of the toner is also known. However, in such a method, when the offset phenomenon is improved, the fixability becomes insufficient, and there arises a problem that the fixability at a low temperature required for high-speed development and energy saving, that is, the low-temperature fixability is deteriorated. .

Generally, in order to improve the low temperature fixability of the toner, it is necessary to lower the viscosity of the toner at the time of melting to increase the adhesion area with the fixing substrate. For this reason, the Tg and molecular weight of the binder resin used Is required to be low.

That is, since the low-temperature fixing property and the offset preventing property are contradictory to each other, it is very difficult to develop a toner satisfying these functions at the same time.

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

Certainly, the toners according to these proposals have a lower fixing temperature (the lowest fixing temperature) and an offset temperature (the temperature at which offset begins to occur), as compared with a toner made of a single resin having a narrow molecular weight distribution. However, if sufficient offset prevention performance is given, the fixing temperature cannot be lowered sufficiently, and if low temperature fixability is emphasized, the offset prevention performance will be insufficient. There was the problem of becoming.

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

Further, in JP-A-56-116043, a vinyl monomer is polymerized in the presence of a reactive polyester resin and polymerized through a crosslinking reaction, an addition reaction and a grafting reaction in the course of the polymerization. Although a toner using such a resin has been proposed and improved in terms of pulverizability, mutual resin functions cannot be fully utilized in terms of low-temperature fixability and offset prevention.

Further, two kinds of gel contents which are simply different from polyester resin (gelation degree of 80% or more and gelation degree of 1
A toner using a resin blended with a vinyl-based resin (less than 0%) is proposed in Japanese Examined Patent Publication No. 1-15063. Although this toner has good low-temperature fixability, it has offset resistance and pulverizability. Not enough yet. 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 offset prevention property is improved, but the low temperature fixing property is remarkably lowered. Also, gelation degree 1
Sufficient grindability cannot be satisfied only by containing less than 0% of vinyl resin.

On the other hand, with respect to the physical properties required for the toner as described above, crosslinking is carried out by reacting a polymer having a carboxylic acid with a metal compound in the binder resin (JP-A-57-57). 178249, 57-17
No. 8250), or a binder containing a vinyl-based resin monomer and a more specific monoester compound as an essential constituent unit and a polyvalent metal compound, and crosslinks via a metal (Japanese Patent Laid-Open No. 61- 110155, 61-110
No. 156) is introduced.

Further, JP-A-63-214760, 63-217362, 63-217363, and 6
In Japanese Patent Laid-Open No. 3-217364, 2 of low molecular weight and high molecular weight is used.
It has a molecular weight distribution divided into groups and crosslinks by reacting carboxylic acid groups contained on the low molecular weight side with polyvalent metal ions (adding a dispersion of a metal compound to a solution obtained by solution polymerization and heating it. However, the reaction between the binder and the metal compound or the dispersion of the metal compound in the binder is not sufficient in any of the methods, and the physical properties required for the toner, particularly the fixing Properties and offset resistance have not yet 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.

JP-A-2-168264 and JP-A-2-235.
In JP-A-069, by further polarization of the low molecular weight component and the high molecular weight component in the binder resin and adjusting the content of the carboxyl group, the offset resistance is improved and the productivity and the developability are prevented from being deteriorated. However, although the performance is improved with respect to fixing property and anti-offset property, a developer containing a binder resin is conversely used with the amount of acid described in the specification. The dispersed state of each constituent component inside becomes insufficient, and each component is unevenly distributed inside the developer and is easily released to the outside of the developer, and it is difficult to obtain stable developability. When the developer in such a state is used in a heat fixing method having a fixing film, problems such as fixing of toner to the fixing film and breakage of the fixing film are likely to occur. This phenomenon occurs as the weight average molecular weight (Mw) / number average molecular weight (Mn), which is considered to indicate the degree of polarization of the binder resin, increases, and the difference in specific gravity between constituent components such as magnetic toner increases. The more noticeable it becomes. In particular, a magnetic toner having an Mw / Mn of more than 20 can satisfy the fixing property and the anti-offset property to some extent, but causes a problem in the matching with the developing property and the fixing method as described above.

Further, in JP-A-62-9256,
It discloses a binder composition for toner in which two kinds of vinyl resins having different molecular weights and resin acid values are blended. However, when such a binder resin is used,
In order to improve the compatibility and dispersibility of the toner constituents, the kneading conditions must be strengthened, and the binder resin is easily affected by the breakage of polymer molecules, etc. It will be difficult to demonstrate. Further, if kneading is performed to such an extent that molecular cutting does not occur, dispersion of other additives will occur, which promotes contamination of the surface of the developer bearing member such as the carrier and sleeve, and causes fogging and scattering of the developing property. It causes serious problems. In particular, when a polymer having a weight average molecular weight of 1,000,000 or more is used, these phenomena are likely to become apparent.

Japanese Unexamined Patent Publication (Kokai) No. 3-72505 discloses a vinyl-based toner binder containing a polyfunctional initiator and having a molecular weight of 300,000 or more. However, when such a resin is used, the fixing property can be satisfied to some extent. However, in addition to the above-mentioned problems, the performance of the toner is apt to deteriorate when the toner is left at a high temperature. The cause of this phenomenon is not clear, but since the molecular cleavage of the binder resin is promoted during the production of the toner, the proportion of the high molecular weight resin component in the toner composition becomes low,
It is presumed that this is because the heat resistance is lowered.

Further, the various performances required for the toners listed above are often reciprocal with each other, and it has been increasingly desired in recent years to satisfy both of them with high performance. A comprehensive response that includes characteristics is desired.

Further, in order to increase the speed of the electrophotographic apparatus which has been demanded in recent years, the toughness of the toner having further low temperature fixing property and capable of withstanding high-speed development, and the charging stability capable of withstanding long-term durability are required for the toner. Has been.

However, it is difficult to satisfy both the low temperature fixing property and the toughness of the toner.

Conventionally, a means of incorporating a low softening point release agent (wax) made of polyolefin or the like is known as one of the techniques for imparting low temperature fixing property and anti-offset property to toner.

For example, JP-A-51-14333,
57-148752, 58-97056, 60-247250, and JP-A-4-3629.
No. 53 and JP-A-6-230600,
Solid silicone varnish, higher fatty acid type wax, higher alcohol type wax, vegetable type natural wax (carnauba, rice), montan type ester wax, etc. are known to be added as a release agent, but all of them are low temperature fixability and offset resistance. Not satisfied with sex. Further, these configurations have problems in developability (chargeability) and durability.

In general, when such a low-softening point release agent is contained in the toner, the fluidity is lowered, so the developability and transferability are lowered. In addition, the charging property, the durability, and the storability are also adversely affected.

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

For example, JP-A-59-121052 discloses a polyolefin graft-blocked with an .alpha.-methylene aliphatic monocarboxylic acid ester monomer, and is disclosed in JP-A-56-15470. 59-121053, JP-A-60-93456.
JP-A No. 63-34550 and JP-A No. 63-34550 disclose a polyolefin graft-blocked with an aromatic vinyl monomer, and the polyolefin is improved in fluidity, but the offset resistance is insufficient. , Developability (chargeability) and durability have not been solved yet.

As described above, in order to achieve both fixing and anti-offset properties, it is more difficult to uniformly disperse the release agent inside the toner, such as further polarization of the molecular weight of the low molecular weight component and the high molecular weight component. Therefore, a higher degree of selection of the polymer component and the release agent component of the toner composition has become essential.

[0032]

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

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

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

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

[0036]

The present invention provides a toner for developing an electrostatic charge image, which is formed of a composition containing at least a polymer component, a colorant, a releasing agent and a charge control agent. The polymer component of the product (a) contains substantially no THF-insoluble matter, and (b) the THF-soluble matter of the polymer component is G
In the PC chromatogram, at least a molecular weight of 3 ×
Area of a polymer component having a main peak in the region of 10 ^{3 to} 3 × 10 ⁴ and a sub-peak or shoulder in the region of molecular weight of 1 × 10 ^{5 to} 3 × 10 ⁶ and having a molecular weight of 1 × 10 ⁶ or more. The ratio is 1 to 20%, and (c) the molecular weight is 1 × 1.
0 ⁵ or more of the polymer component is 0.5 or more 20mgKO
The present invention relates to a toner for developing an electrostatic charge image, which has an acid value of H / g or less and the release agent component contains a polyolefin modified with an aromatic vinyl monomer.

The present invention further relates to a toner for developing an electrostatic charge image, wherein the high molecular weight polymer component of the composition has a polymer polymerized with a polyfunctional polymerization initiator.

Further, the present invention is characterized in that the high molecular weight polymer component of the composition has a polymer which is polymerized by using at least a polyfunctional polymerization initiator and a monofunctional polymerization initiator in combination. The present invention relates to a toner for developing a charge image.

Further, in the present invention, the toner for developing an electrostatic charge image is characterized in that the content of the aromatic vinyl monomer component in the modified polyolefin is 5 to 60% by weight (preferably 10 to 40% by weight). Regarding

The present invention further relates to a toner for developing an electrostatic charge image, wherein the aromatic vinyl monomer in the modified polyolefin is the same monomer as the constituent component of the polymer.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION The toner composition of the present invention contains substantially no THF insoluble matter. Specifically, it is 5% by weight or less, preferably 3% by weight or less, based on the resin composition.

The THF-insoluble matter in the present invention means the weight ratio of the polymer component (substantially cross-linked polymer) which becomes 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 a toner sample is weighed (w ₁ g), and a cylindrical filter paper (for example, No.
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.
Vacuum-dry at 100 ° C. for several hours, and weigh the amount of the THF-soluble resin component (w ₂ g). The weight of the components other than the resin component such as the magnetic substance or pigment in the toner is (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

If the THF insoluble content exceeds 5% by weight, not only is the fixing property deteriorated, but it is not preferable in terms of matching with the heat fixing device used in the examples of the present invention.

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

In the GPC chromatogram, the area ratio of the polymer component having a molecular weight of 1,000,000 or more is 1 to 1.
It is preferably 20% (more preferably 3 to 10%). The molecular weight is 1,000,000 or more and the soluble component in THF is 1
By the presence of -20%, offset resistance can be improved without impeding low-temperature fixing, and at the same time, storage stability of the developer when left at high temperature can be improved.

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

<GPC measurement conditions of resin composition and polymer> Apparatus: GPC-150C (manufactured by Waters) Column: KF801-7 (manufactured by Showdex) 7 consecutive temperatures: 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

Further, the polymer component used in the present invention is
A high molecular weight polymer component having a molecular weight of 1 × 10 ⁵ or more has an acid value of 0.5 or more and 20 mgKOH / g or less, and the release agent component includes a polyolefin modified with an aromatic vinyl monomer. I am sorry.

As a result of intensive studies, the inventors of the present invention have found that the high molecular weight polymer component has the acid value shown above in a system using a release agent component such as the present invention at low temperature fixability and offset resistance. Furthermore, they have found that it is effective for improving the developability.

This is because the high molecular weight polymer component has an acid value of 0.
By setting it to 5 or more and 20 mgKOH / g, the entanglement of the molecular chains of the polymer component and the releasing agent component of the present invention can be suppressed to some extent, and the releasing agent component exists in the toner with a certain domain diameter, It is considered that a sufficient releasing effect can be obtained.

Further, it has been clarified that the above-mentioned constitution can improve the dispersion of the metal-containing organic compound used in the present invention and can sufficiently exhibit its charging ability.

Extreme polarization of the low molecular weight polymer component and the high molecular weight polymer component is effective for achieving both low temperature fixing and offset resistance, but it is difficult to disperse other internal additives in the toner composition. Tends to become.

The acid value of the high molecular weight polymer component is 20 mg KO
When it exceeds H / g, the dispersibility of the release agent component is deteriorated, the developability (chargeability) and the fluidity are deteriorated, and when the acid value is less than 0.5, offset resistance and developability (chargeability) are obtained. ) Is deteriorated.

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

Further, the polymer component of the toner resin composition of the present invention is, in the relation between the low molecular weight polymer component and the high molecular weight polymer component, with respect to the mixing ratio thereof, W _L : W _H = 50: 50 to 90. It is preferable to satisfy the following condition. The reason is that when the ratio of the low molecular weight polymer component to the high molecular weight polymer component is within this range, the fixability and the offset resistance are improved. That is, if the content of the low molecular weight component is less than 50% by weight, the fixability is deteriorated, whereas if the content of the high molecular weight component is less than 10% by weight, the high temperature offset resistance is deteriorated.

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

<Preparation of Each Component> [Device Configuration] LC-908 (manufactured by Nippon Analytical Industry Co., Ltd.) JRS-86 (the same company; repeat injector) JAR-2 (the same company; autosampler) FC-201 (Gilson Company; Hula cushion collector)

[Column configuration] JAIGEL-1H to 5H
(20φ x 600 mm: preparative column)

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

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

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

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

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

4) Titrate the solution in the flask with a burette using an alcohol solution of 0.1N KOH. The amount of the KOH solution at this time is 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 formula.

[0068]

(Equation 1)

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

More specifically, 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-octenyl succinate, 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 as described above is selected is that it is not appropriate to use it in the form of an acid monomer having high solubility in an aqueous suspension in the suspension polymerization. This is because it is preferable to use it in the form of an ester having low solubility.

In the present invention, the carboxylic acid group and the carboxylic acid ester moiety in the copolymer obtained by the above method can be saponified by alkali treatment. That is, it can be controlled by reacting with an alkali cation component to change the carboxylic acid group or the carboxylic acid ester site into a polar functional group.

This alkali treatment may be carried out after the binder resin is produced, by adding 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 pyridinium salts, and particularly preferable 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 moieties in the copolymer, and the saponification reaction partially proceeds to give polar functional groups. It should be different.

The amount of alkali used in the saponification reaction is difficult to determine depending on the type of polar group in the binder resin, the method of dispersion, the type of constituent monomers, etc. It may be from 02 to 5 times equivalent. When the amount is less than 0.02 times the equivalent, the saponification reaction is not sufficient and the number of polar functional groups generated by the reaction is small, resulting in insufficient post-crosslinking reaction. On the other hand, when the amount exceeds 5 times the equivalent, the functional group such as the carboxylic acid ester moiety is adversely affected by hydrolysis of the ester, formation of a salt by saponification reaction, and the like.

When the alkali treatment is applied in an amount 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 define the amount of alkali.

The modified polyolefin in the release agent component of the present invention has an aromatic vinyl monomer component content of 5 to 6.
It is preferably 0% by weight (preferably 10 to 40% by weight). When the amount of the aromatic vinyl monomer component is less than 5% by weight, the compatibility with the polymer component is poor and the developability and fog are adversely affected, and the toner fluidity is deteriorated. The toner is not uniformly conveyed from the container to the toner carrier, and fading phenomenon that causes uneven image density is likely to occur.

If the amount of the aromatic vinyl monomer component exceeds 60% by weight, the releasing effect becomes small, the offset resistance is adversely affected, and the fixing roller is apt to cause stains.

The aromatic vinyl monomer of the modified polyolefin in the release agent component of the present invention is preferably the same monomer as the polymer constituent component. As a result, the affinity between the release agent component and the polymer component is increased, the impact resistance is excellent, and the durability such as repeated copying can be improved.

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 storability, and when Tg is lower than 50 ° C., in a high temperature atmosphere. Cause deterioration of 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.), When Tg _L is less than Tg _H −5, developability tends to decrease. More preferably, Tg _L ≧ Tg _H is good.

As a method for producing the binder resin composition according to the present invention, a solution in which a high molecular weight polymer and a low molecular weight polymer are separately synthesized by a solution polymerization method, these are mixed in a solution state, and then the solvent is removed. Blending method, also, a dry blending method of melt-kneading with an extruder or the like, further dissolved in a monomer constituting a high molecular weight polymer obtained by dissolving a low molecular weight polymer obtained by a solution polymerization method or the like, suspension polymerization,
Examples thereof include a two-step polymerization method of obtaining a resin composition by washing with water and drying. However, in the dry blend method, uniform dispersion,
There is a problem in compatibility, and although the two-step polymerization method has many advantages such as uniform dispersibility, it is difficult to increase the amount of the low molecular weight polymer component over the high molecular weight polymer component. In the presence of the molecular weight polymer component, not only is it difficult to synthesize a high molecular weight polymer component having a large molecular weight, but there is a disadvantage that an unnecessary low molecular weight polymer component is by-produced, and therefore the present invention The solution blending method is most suitable for application. In addition, as a method for introducing a predetermined acid value into the low molecular weight polymer component, solution polymerization is preferable because the acid value can be easily set as compared with an aqueous polymerization method.

The 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 includes a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Of these, 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 performed using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and the phase in which the polymerization takes place (oil phase consisting of polymer and monomer)
And the aqueous phase are 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,
It is advantageous as a method for producing a binder resin for a toner because it can be easily mixed with a colorant, a charge control agent and other additives.

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

In suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). As dispersants that can be used, polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate and the like are used, and generally 0.05 to 1 part by weight is used with respect to 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.

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

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 , 2-di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-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, t- Both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group are contained in one molecule such as butyl peroxy maleic acid, t-butyl peroxy allyl carbonate and t-butyl peroxy isopropyl fumarate. Selected from polyfunctional polymerization initiators having.

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

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

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

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

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

The high molecular weight polymer component of the resin composition used in the present invention is preferably cross-linked with the following cross-linkable monomers in order to achieve the object of the present invention.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used, and specific examples thereof include aromatic divinyl compounds such as divinylbenzene, divinylnaphthalene and the like; Diacrylate compounds such as ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and methacrylates instead of the above compounds; 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 the acrylates of the above compounds instead of methacrylates 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; and 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 into methacrylate Alternatives; triallyl cyanurate, triallyl trimellitate; and the like.

These cross-linking agents are based on other monomer components 10
1 part by weight or less, preferably 0.00 part by weight with respect to 0 part by weight
It is preferable to use in the range of 1 to 0.05 part by weight.

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

On the other hand, as a method for synthesizing the low molecular weight component of the binder resin according to the present invention, a known method can be used. However, in the bulk polymerization method, although a low molecular weight polymer can be obtained by polymerizing at a high temperature to accelerate the termination reaction rate, there is a problem that the reaction is difficult to control.
In that respect, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer 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 product in the resin composition used in the present invention. In particular, minimize the amount of initiator used,
From the viewpoint of suppressing the influence of the initiator residue as much as possible, the solution polymerization method under pressure is also preferable.

As the monomer for obtaining the high molecular weight polymer component and the monomer for obtaining the low molecular weight polymer component,
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 and its derivatives such as p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene and the like; ethylene. Ethylenically unsaturated monoolefins such as propylene, butylene, 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; vinyl naphthalene compounds; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide; and vinyl monomers used alone or in combination of two or more.

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

Further, both the low molecular weight and high molecular weight polymer components preferably contain at least 65 parts by weight of a styrene polymer component or a copolymer component from the viewpoint of compatibility.

The polyolefin component of the modified polyolefin used as a wax contained in the toner of the present invention is a homopolymer type obtained from a single olefin monomer, or an olefin monomer is copolymerized with another monomer copolymerizable therewith. It may be of any type obtained by copolymerization.

In the olefin monomer, for example, ethylene, propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1 and unsaturated bond positions are different. Isomers thereof, and those having a branched chain consisting of an alkyl group, such as 3-methyl-1-butene, 3-methyl-2-pentene, 3-propyl-5-methyl-2-hexene, and the like. All olefin monomers of are included.

Other monomers that can be copolymerized with the olefin monomer include other olefin monomers,
Vinyl ethers such as vinyl methyl ether, vinyl-n-butyl ether and vinyl phenyl ether;
Vinyl esters such as vinyl acetate, vinyl butyrate; haloolefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, vinyl chloride, vinylidene chloride, tetrachloroethylene; methyl acrylate, ethyl acrylate, n-butyl acrylate Acrylic acid esters or methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, stearyl methacrylate, N, N-dimethylaminoethyl methacrylate and t-butylaminoethyl methacrylate; Acrylonitrile, acrylic acid derivatives such as N, N-dimethylacrylamide; for example, acrylic acid,
Examples thereof include organic acids such as methacrylic acid, maleic acid, fumaric acid and itaconic acid; various ones such as diethyl fumarate and β-pinene.

Therefore, when the polyolefin component is a copolymer type, an olefin copolymer type product obtained by copolymerizing at least two kinds of the above-mentioned olefin monomers, for example, ethylene-
Propylene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, propylene-butene copolymer, propylene-pentene copolymer, ethylene-3-methyl-1-butene copolymer, ethylene-propylene- A copolymer type such as butene copolymer; or an olefin copolymer type obtained by copolymerizing at least one kind of the above-mentioned olefin monomer and at least one kind of monomer other than the above-mentioned olefin monomer,
For example, ethylene-vinyl acetate copolymer, ethylene-vinyl methyl ether copolymer, ethylene-vinyl chloride copolymer, ethylene-methyl acrylate copolymer,
Ethylene-methyl methacrylate copolymer, ethylene-acrylic acid copolymer, propylene-vinyl acetate copolymer, propylene-vinyl ether copolymer, propylene-ethyl acrylate copolymer, propylene-methacrylic acid copolymer, butene -Vinyl methyl ether copolymer, butene-methyl methacrylate copolymer,
It may be a copolymer type such as a pentene-vinyl acetate copolymer, a hexene-vinyl butyrate copolymer, an ethylene-propylene-vinyl acetate copolymer, an ethylene-vinyl acetate-vinyl methyl ether copolymer.

When a monomer other than the olefin monomer is used to obtain the copolymer type, it is preferable to use the copolymer type such that the ratio of the olefin moiety of the olefin monomer in the polyolefin component is, for example, 50 mol% or more. . This is because if the proportion of the olefin portion becomes small, the effect of improving the fixing property of the toner cannot be sufficiently exhibited.

The modified polyolefin comprises a polyolefin component and a modifying component as described above, and the modifying component is blocked or grafted to the polyolefin component.

An aromatic vinyl monomer is used as the modifying component, and specific examples thereof include styrene and
o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenyl styrene,
Preferable examples are styrene monomers such as p-chlorostyrene and 3,4-dichlorostyrene.

A wax composed of a modified polyolefin can be obtained by graft-copolymerizing or block-copolymerizing the above-mentioned aromatic vinyl monomer and the above-mentioned polyolefin according to the usual method and conditions.

The weight average molecular weight of these releasing agents (low molecular weight waxes) is preferably 30,000 or less, more preferably 10,000 or less, and the addition amount is 100% of the binder polymer component 100.
About 1 to 20 parts by weight is preferable with respect to parts by weight.

These low molecular weight waxes may be added and mixed in advance with the binder polymer component during toner production. In particular, a method of pre-dissolving the low molecular weight wax and the high molecular weight polymer in a solvent at the time of preparing the polymer component and then mixing with the low molecular weight polymer solution may be used.

The solid concentration of the polymer solution depends on the dispersion efficiency,
5 to 70 in consideration of deterioration of resin at the time of stirring and operability.
As an example, the solid concentration of the high molecular weight polymer component and the polyolefin polymer is 5 to 60% by weight or less and the low molecular weight polymer solution is 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 carried out by stirring and mixing, and the stirring may be carried out batchwise or continuously.

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

Examples of the organic solvent used at the time of mixing the solution of the resin composition according to the present invention include benzene, toluene,
Hydroxyl solvents such as xylol, solvent naphtha No. 1, solvent naphtha No. 2, solvent naphtha No. 3, cyclohexane, ethylbenzene, Solvesso 100, Solvesso 150, mineral spirits; methanol, ethanol, iso-propyl alcohol, n-butyl alcohol, Alcohol-based solvents such as sec-butyl alcohol, iso-butyl alcohol, amyl alcohol, cyclohexanol; ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester-based solvents such as ethyl acetate, n-butyl acetate, cellosolve acetate Solvents: ether type solvents such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, and methyl carbitol, etc. may be mentioned. Among these aromatic,
Ketone-based and ester-based solvents are preferred. They may be used in combination.

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

The present invention may be a magnetic toner containing magnetic iron oxide particles. As magnetic iron oxide particles,
Those containing a silicon element are preferable because they also have excellent toner fluidity.

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

In some cases, the magnetic iron oxide particles may be treated with a silane coupling agent, a titanium coupling agent, a titanate, an 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 thereof 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 oxyacetate, bis dioctyl phosphate ethylene dioctyl phosphite, di n-butoxy / Examples thereof include bistriethanolaminato titanium.

Examples of the organic silicon 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, as the coloring material which can be added to the toner for developing an electrostatic image of the present invention, conventionally known pigments or dyes such as carbon black and copper phthalocyanine can be used.

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

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

[0128]

[Chemical 6]

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

[0130]

Embedded image

[0131]

Embedded image

[0132]

Embedded image

[0133]

Embedded image

[0134]

Embedded image

[0135]

Embedded image

[0136]

Embedded image Monoazo iron complex compound

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

[0138]

Embedded image

[0139]

Embedded image

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

[0141]

Embedded image

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

[0145]

Embedded image

[0146]

Embedded image

[0147]

Embedded image

[0148]

Embedded image

[0149]

Embedded image

[0150]

Embedded image

In particular, the following equation

[0152]

Embedded image A monoazo iron complex compound represented by is particularly preferable.

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

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

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

As the silica fine powder, both a so-called dry method produced by vapor phase oxidation of a silicon halogen compound or a dry silica called fumed silica and a so-called wet silica produced from water glass can be used. Preference is given to dry silica, which has few silanol groups on its surface and inside and has no production residue.

Further, the silica fine powder is preferably hydrophobized. 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 hydrophobic treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyl. Dichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chlormethyldimethylchlorosilane, triorganosilane mercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldimethyl Examples include siloxane and 1,3-diphenyltetramethyldisiloxane.

Examples of the organic silicon 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.

As the method for treating silicone oil, for example, silica fine powder treated with a silane coupling agent and silicone oil may be directly mixed by using a mixer such as a Henschel mixer. The method of injecting 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 that the silica fine powder is treated with two or more kinds of silane coupling agents and then treated with oil, because the degree of hydrophobicity can be effectively increased.

[0164] The silica fine powder obtained by subjecting titanium oxide fine powder to a hydrophobic treatment and further an oil treatment may also 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 charging auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent at the time of heat roll fixing,
These are resin fine particles and inorganic fine particles that function as a lubricant, an abrasive and the like.

The resin fine particles have an average particle size of 0.
It is preferably from 03 to 1.0 μm, and the polymerizable monomer constituting the resin is styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-ethylstyrene, or the like. Styrene monomer, methacrylic acid 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 and phenyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate
-Octyl / dodecyl methacrylate / methacrylic acid 2-
Examples thereof include methacrylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other monomers such as acrylonitrile, methacrylonitrile, and acrylamide.

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

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

As the other fine particles, lubricants such as Teflon, zinc stearate, polyvinylidene fluoride, and polyvinylidene fluoride are 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, the inorganic fine powder or the hydrophobic inorganic fine powder mixed with the toner is 0.1 to 5 parts by weight (preferably 0.1 to 3 parts by weight) with respect to 100 parts by weight of the toner.
Good to use)

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

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

Further, referring to FIG. 5, an example of an image forming method in which the present invention is used will be described.

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

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

The photosensitive drum has a photosensitive layer and a conductive substrate, and moves in the arrow direction. 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 surface speed of the sleeve is made substantially equal to or close to the speed of the surface of the photosensitive drum. 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.

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

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 device.
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 1.
It is made of an elastic body of 0 ¹⁰ Ωcm.

Preferred transfer process conditions are: a roller contact pressure of 5 to 500 g / cm and a DC voltage of ±.
0.2 to ± 10 kV.

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

Reference numeral 42 denotes a charging roller, which has a central core metal 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.

A preferable process condition when the charging roller is used is that 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.

As the material of the charging roller, conductive rubber is preferable, and a releasing film 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. 6 shows a specific example of the process cartridge. The process cartridge is a cartridge in which the developing device and the electrostatic image holder are at least integrally formed, and the process cartridge is formed so as to be attachable to and detachable from the image forming apparatus main body (for example, a copying machine, a laser beam printer, etc.).

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

The developing means 709 is composed of an elastic blade 71.
1 and a magnetic toner 710 in 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.

[0190]

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 placed in a four-necked flask, and the inside of the container was sufficiently replaced with nitrogen while stirring. The temperature is raised to reflux.

Under this reflux, a mixed solution of 84 parts by weight of styrene, 16 parts by weight of -n-butyl acrylate, and 2 parts by weight of di-tert-butyl peroxide was added dropwise over 4 hours, and then the mixture was kept for 2 hours. Polymerization was completed to obtain a low molecular weight polymer (L-1) solution.

A portion of this polymer solution was sampled,
Low molecular weight polymer (L-1) obtained by drying under reduced pressure
GPC and glass transition point (Tg) were measured, and weight average molecular weight (Mw) = 9,600, number average molecular weight (Mn) = 6,000, peak molecular weight (PMw) =
It was 8,500 and Tg = 62 ° C.

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

Synthesis of high molecular weight polymer (H-1) 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were placed in a four-necked flask, and then 70.5 parts by weight of styrene and acryl. Acid-n-butyl 25 parts by weight, monobutyl maleate 4.5 parts by weight, divinylbenzene 0.005 parts by weight, and 2,2-bis (4,4-
A mixed solution of 0.1 part by weight of di-tert-butylperoxycyclohexyl) propane (half-life: 10 hours, temperature: 92 ° C.) was added and stirred to give a suspension.

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

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

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

Production of Resin Composition 100 parts by weight of xylene and 25 parts by weight of the above high molecular weight polymer (H-1) were placed in a four-necked flask, and the mixture was heated and stirred under reflux to carry out preliminary dissolution. To do. After holding in this state for 12 hours, the preliminarily dissolved solution (Y-) of the polymer (H-1)
1) was obtained.

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

The above-mentioned preliminary solution (Y-1) and the low molecular weight polymer (L-1) solution were mixed under reflux, the organic solvent was distilled off, and the obtained resin was cooled, solidified and then ground. A resin composition I for toner was obtained.

When the resin composition I was analyzed, PMw
= 1.1 million, GPC of a resin composition with a molecular weight of 1 million or more
Area ratio in the molecular weight distribution of 9.2%, Tg = 62
C., THF-insoluble matter was 2.1% by weight.

[Production Examples 2 to 5 of Resin Composition and Comparative Production Examples 2 to 4] As in Production Example 1 of resin composition, styrene,
The amount of n-butyl acrylate and the amount of initiator were adjusted to obtain low molecular weight polymers L-2 and L-3, and the amounts of styrene, n-butyl acrylate, monobutyl maleate, divinylbenzene and the initiator were adjusted. , High molecular weight polymers H-2 to H
-4, H-6 and H-7 were obtained. Next, a predetermined amount of a low molecular weight polymer and a high molecular weight polymer are blended to form a resin composition II to
V and ii-iv were obtained. The results of the molecular weight distribution and the like are shown in Table 1.

[Comparative Production Example 1 of Resin Composition] Synthesis of High Molecular Weight Polymer H-5 Into a four-necked flask, 83 parts by weight of styrene, 15 parts by weight of butyl methacrylate and 2 parts by weight of monobutyl maleate were charged, After bulk polymerization, xylene was added and solution polymerization was completed in the presence of a solvent to obtain a high molecular weight polymer (H-5). Table 1 shows the analysis results of the obtained high molecular weight polymer.

Production of Resin Composition A resin composition i was obtained in the same manner as in Production Example 1, except that the high molecular weight polymer was (H-5). The results of the molecular weight distribution and the like are shown in Table 1.

[0206]

[Table 1]

Example 1 Resin composition I 100 parts by weight Magnetic iron oxide 100 parts by weight Polyethylene wax graft-copolymerized with styrene 4 parts by weight (styrene content 20% by weight) Negative charge control agent (following formula) 2 Parts by weight

[0208]

Embedded image

The above mixture was melt-kneaded with a twin-screw extruder heated to 140 ° C., the cooled kneaded product was coarsely pulverized with a hammer mill, and the coarsely pulverized product was finely pulverized with a jet mill. Was classified with a fixed wall type air classifier to produce classified powder. Furthermore, the weight-average particle size (D4) 6 is obtained by strictly classifying ultrafine powder and coarse powder at the same time using a multi-division classifier (Elbowjet classifier manufactured by Nittetsu Mining Co., Ltd.) using the Coanda effect. 0.1 μm (particle size 12.7
A negatively chargeable magnetic toner having a content of magnetic toner particles of 0.2 μm or more) was obtained. The physical properties of the obtained toner are shown in Table 2.
The chart of the GPC chromatogram is shown in FIG.

100 parts by weight of this magnetic toner and 1.2 parts by weight of hydrophobic silica fine powder (BET 300 m ² / g) which was treated with dimethyldichlorosilane, then with hexamethyldisilazane, and then with dimethyl silicone oil. , And 0.08 part by weight of styrene-acrylic fine particles (average particle size: 0.05 μm) obtained by soap-free polymerization were mixed with a Henschel mixer to prepare a magnetic developer (toner No. A).

<Examples 2 to 5> Negatively chargeable magnetic toners were obtained in the same manner as in Example 1 except that the resin compositions II to V were used instead of the resin composition I (toner No. B to No.
E). Table 2 shows the physical properties of the obtained toner.

Example 6 Polyethylene wax graft-copolymerized with styrene (styrene content 50 w
t%) was used to obtain negatively chargeable toner F in the same manner as in Example 1. Table 2 shows the physical properties of the obtained toner.

Example 7 Polyethylene wax graft-copolymerized with pn-dodecylstyrene (p-
A negatively chargeable magnetic toner G was obtained in the same manner as in Example 1 except that the n-dodecylstyrene content rate was 20 wt%). Table 2 shows the physical properties of the obtained toner.

Example 8 Toner H was obtained in the same manner as in Example 1 except that the negative charge control agent in Example 1 was changed to 0.6 part by weight of the following chromium complex compound. Table 2 shows the physical properties of the obtained toner.

[0215]

Embedded image

<Comparative Examples 1 to 4> Resin composition I of Example 1
Magnetic toners having external additives were obtained in the same manner as in Example 1 except that the respective resin compositions i to iv were changed (toner Nos. A to d). Table 2 shows the physical properties of the obtained toner.

<Comparative Example 5> The resin composition of Example 1 was i.
A magnetic toner e having an external additive was obtained in the same manner as in Example 1 except that the release agent was changed to unmodified polyethylene wax. Table 2 shows the physical properties of the obtained toner.

Regarding Example 1 and Comparative Example 5, the dispersion of the fine powder generated in the classification step and the charge control agent at the desired particle size was quantitatively determined by fluorescent X-ray, and the ratio (fine powder / desired particle size) was obtained.
Was measured.

As a result, in Example 1, the dispersion was 1.013, which was good, whereas in Comparative Example 5, the dispersion was 1.150, which was insufficient.

[0220]

[Table 2]

Image Output Test The above magnetic toner is put into a process cartridge, and a laser beam printer A309GII (OPC manufactured by Canon Inc.
Photosensitive drum was used) was changed from 8 sheets / minute to 24 sheets / minute by A4 transverse feed, and image formation was evaluated using a modified machine incorporating the transfer device shown in FIG. The process speed at this time was 108 mm / sec.

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

The charging roller shown in FIG. 2 was installed in the process cartridge to carry out primary charging. The outer diameter of the charging roller 42 is 12 mmφ, and the conductive rubber layer 42b
Was used for EPDM, and a nylon resin having a thickness of 10 μm was used for the surface layer 42c. The hardness of the charging roller 42 is 54.5.
(ASKER-C). E is this charging roller 4
A predetermined voltage is supplied to the cored bar 42a of the charging roller 42 by a power source that applies a voltage to the second roller 2. In FIG. 2, E indicates a system in which an AC voltage is superimposed on a DC voltage. The conditions were as described above.

Further, an elastic blade made of urethane rubber having a function as one of the charging members in the process cartridge was installed so as to press the developing sleeve.

The primary charging is -700 V, the magnetic toner layer on the photosensitive drum and the developing sleeve (including the magnet) sets a non-contact gap, and the AC bias (f = 1800 Hz, V
pp = 1600V) and DC bias (V _DC = −500)
V) is applied to the developing sleeve while V _{L is set} to -170
At V, the electrostatic charge image was developed to form a magnetic toner image on the OPC photoreceptor.

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

At this time, the surface temperature of the heating roller of the heating and pressure roller fixing device was set to 180 ° C., the total pressure between the heating roller and the pressure roller was set to 5.5 kg, and the nip was set to 4 mm.

Under the above setting conditions, under high temperature and high humidity environment (3
2.5 ° C, 85% RH) and low temperature and low humidity environment (10 ° C,
Image development test was performed at 15% RH), and the obtained images were evaluated for the following items. The print mode was 1 sheet / 15 sec.

1) Image density 10,000 on a plain paper for ordinary copying machines (75 g / m ² ).
Evaluation was made by maintaining the image density at the end of printing out one sheet. The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

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

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

⊚: Very good (2 or less defects / 100 defects) ○: Good (3 to 5 defects / 100 defects) Δ: Practical use (6 to 10 defects / 100 defects) ×: Practical use (deficiency) 11 or more / 100)

4) Uniformity of Image Density A solid black sample image was printed out, and unevenness in image density was evaluated by the difference between the maximum value and the minimum value of the image density within one page. Table 4 shows the image density difference.

Fixability and Offset Resistance Test The above magnetic toner was put in a process cartridge, and a Canon laser beam printer LBP-309GII
(16 sheets / min) charging and developing the same as in the above-mentioned image-extracting tester, except that the surface temperature of the heating roller of the heating and pressure roller fixing device is modified to 125 to 230 ° C. from the outside. Set the transfer conditions and change the set temperature in steps of 5 ℃ under normal temperature and normal humidity environment (25 ℃, 60% RH)
An image sample was printed out at.

1) Fixability The fixability is determined by applying a load of 50 g / cm ² and rubbing the fixed image with a soft thin paper. The lowest fixing temperature at which the reduction rate (%) of the image density before and after rubbing was 10% or less was evaluated as the minimum fixing temperature. Table 4 shows the minimum fixing temperature.
As a test paper, plain paper for copiers (90
g / m ² ) paper was used.

2) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and measuring the degree of stain on the image. Table 4 shows the maximum temperature at which no stain on the image occurs.
As the test paper, plain paper (60 g / m ² ) for copiers, which easily causes offset, was used.

Table 3 shows the evaluation results.

[0238]

[Table 3]

[0239]

As described above, the toner of the present invention contains a metal-containing organic compound, adjusts the molecular weight distribution of the polymer component and the acid value of the high molecular weight component in the composition, and uses an aromatic vinyl monomer. By including a modified release agent and adjusting the amount of modification, a lower temperature fixability than before,
It has excellent anti-offset properties, excellent toner fluidity and charging, reduces fog, excellent image quality, and long-term durability. Further, the present invention enables long-term charging stability even when applied to increase the speed of the apparatus.

[Brief description of the drawings]

FIG. 1 is a diagram showing an outline of a transfer device.

FIG. 2 is a diagram showing an outline of a charging roller.

FIG. 3 is an explanatory diagram of a checkered pattern for testing a developing property of toner.

FIG. 4 is a chart of a GPC chromatogram of a resin according to Example 1.

FIG. 5 is a schematic view showing an example of an image forming method in which the present invention is used.

FIG. 6 is a diagram showing a specific example of a process cartridge.

[Explanation of symbols]

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

Claims (10)

[Claims] 1. An electrostatic charge image developing toner formed of a composition containing at least a polymer component, a colorant, a release agent and a charge control agent, wherein the polymer component of the composition is: a) It contains substantially no THF-insoluble matter, and (b) the THF-soluble matter of the polymer component has at least a molecular weight of 3 × 10 ^{3 to} 3 × 1 in the GPC chromatogram.
Having a main peak in the region of 0 ⁴ and a molecular weight of 1 × 10 ⁵
A polymer component having a sub-peak or shoulder in the region of 3 × 10 ⁶ and having a molecular weight of 1 × 10 ⁶ or more and an area ratio of 1 to 20%, and (c) a polymer having a molecular weight of 1 × 10 ⁵ or more. The polymer component is 0.
A toner for developing an electrostatic charge image, which has an acid value of 5 or more and 20 mgKOH / g or less, and the release agent component contains a polyolefin modified with an aromatic vinyl monomer. 2. The toner for developing an electrostatic image according to claim 1, wherein the high molecular weight polymer component of the composition has a polymer polymerized with a polyfunctional polymerization initiator. 3. The high molecular weight polymer component of the composition has a polymer polymerized by using at least a polyfunctional polymerization initiator and a monofunctional polymerization initiator in combination. The toner for developing an electrostatic image as described above. 4. The toner for developing an electrostatic image according to claim 1, wherein the content of the aromatic vinyl monomer component in the modified polyolefin is 5 to 60% by weight. 5. The toner for developing an electrostatic charge image according to claim 1, wherein the content of the aromatic vinyl monomer component in the modified polyolefin is 10 to 40% by weight. 6. The toner for developing an electrostatic charge image according to claim 1, wherein the aromatic vinyl monomer in the modified polyolefin is the same monomer as the polymer constituent component. 7. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [I]: 7. The toner for developing an electrostatic charge image according to claim 1, which is a compound represented by: 8. The charge control agent contains a metal-containing organic compound, and the metal-containing organic compound has the following formula [II]: Embedded image The toner for developing an electrostatic charge image according to claim 1, which is a compound represented by: 9. The metal-containing organic compound has the formula [II
I] The toner for developing an electrostatic charge image according to claim 7, which is represented by: 10. The metal-containing organic compound has the formula [I
V] The toner for developing an electrostatic charge image according to claim 9, which is represented by: