JP3323711B2 - Electrostatic image developing toner and image forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a toner for visualizing an electrostatic latent image such as electrophotography and electrostatic recording, and an image forming method.

[0002]

2. Description of the Related Art Various methods of electrophotography have been described in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748.

[0003] As a toner for electrophotography, fine powder in which a dye or pigment is dispersed in a natural or synthetic resin is used. For example, particles obtained by finely pulverizing a dispersion of a colorant in a binder resin such as polystyrene to about 1 to 30 μm are used as the toner.

[0004] Toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed.

To charge the toner, it is possible to use the frictional charge of the resin which is a component of the toner. However, in this method, since the chargeability of the toner is low, an image obtained by development is easily fogged. , Will be blurred. Therefore, in order to impart appropriate triboelectricity to the toner, a charge control agent is added.

Examples of the negative charge control agent include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, naphthoic acid, and dicarboxylic acid, and polymers having sulfonic acid or carboxylic acid. Phenylmethane dye, quaternary ammonium salt, quaternary
Polymers having quaternary ammonium salts are known.

However, since some of these charge control agents easily contaminate the sleeve or the carrier, the amount of triboelectricity of the toner using them decreases as the number of copies increases, causing a decrease in image density. . In addition, some charge control agents have insufficient triboelectric charge and are susceptible to temperature and humidity, which causes environmental fluctuations in image density. Also, certain charge control agents have poor storage stability,
During long-term storage, triboelectric charging ability decreases. Further, since a certain type of charge control agent has poor dispersibility in a resin, the toner using the same has a non-uniform triboelectric charge amount between particles and is easily fogged. Further, certain charge control agents have poor thermal stability and may be decomposed and deteriorated during the heating and kneading process during toner production. A toner manufactured by reusing a part of the toner using such a charge control agent is liable to generate reversely chargeable particles and easily cause fogging. Further, since certain kinds of charge control agents are colored, they hinder the color tone of the color toner, and therefore cannot be applied to color toner.

At present, there is a strong demand for the development of a charge control agent satisfying all of these requirements.

On the other hand, in general, a corotron or a scorotron is used for a charging device for a photoconductor or a transfer device for transferring a toner image on the photoconductor to a transfer material.
Such a device has a problem in that most of the ions emitted from the wire flow into the casing and are inefficient. Conversely, if there is no casing, it is necessary to supply an extremely high voltage in order to discharge.

If the distance between the thin wire and the member to be charged is reduced in order to solve these problems, charging may become non-uniform due to minute irregularities on the surface of the member to be charged, or spark discharge may occur.

[0011] Further, such a system has a problem in that the wire is deteriorated during use and cuts, and a problem in that the wire is contaminated with inorganic oxide fine powder and the like, leading to image defects.

In order to solve such a problem, a method of applying a voltage to a conductive material which is in direct contact with the photoreceptor has been adopted as a charging method, and a conductive roller is similarly applied to the photoreceptor as a transfer method. A configuration that allows direct contact has been adopted.

[0013] These methods can solve the above-mentioned problems, and furthermore, since a high voltage is not required, miniaturization and cost reduction can be achieved.

However, since the member is in direct contact with the photosensitive member, adverse effects such as fusion of the toner on the photosensitive member occur.

Further, the fact that a voltage is applied to the member promotes this phenomenon. In recent years, not only small-sized copying machines but also high-speed and large-sized copying machines have started to employ a rotating body for contact charging and transfer. At this time, it is necessary to increase the applied voltage and the AC frequency as the copying speed increases in order to stabilize charging and transfer. However, this promotes the fusion of the toner to the photoconductor. Furthermore, a high-speed and large-size copying machine needs to extend the useful number of photoconductors, which also exacerbates the problem.

[0016]

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

That is, an object of the present invention is to provide a high-density, fog-free, missing image during transfer (a phenomenon in which toner at the center of a line image remains on a photoreceptor without being transferred), and ghost (development sleeve cycle due to copy history). It is an object of the present invention to provide a toner for developing an electrostatic image and an image forming method capable of obtaining an image free from density unevenness.

Another object of the present invention is to provide a toner for developing an electrostatic charge image and an image forming method which are less likely to contaminate a contact charging device with toner and which do not cause uneven charging even if contaminated.

Another object of the present invention is to provide a toner for developing an electrostatic charge image and an image forming method, which do not easily contaminate the transfer rotary member with toner and do not cause transfer failure even if it is contaminated.

Another object of the present invention is to provide a toner for developing an electrostatic charge image and an image forming method capable of forming a smooth high-quality color image of a halftone image.

[0021]

The above object can be achieved by incorporating a cyclic quaternary ammonium salt having an anion represented by formula (I) into a toner.

[0022]

Embedded image (However, R ¹ represents an aryl group which may have a substituent, and R ² represents any of hydrogen, an aryl group, an alkyl group, and a cycloalkyl group.)

Further, the toner of the present invention can be applied to an image forming method provided with a contact charging means in contact with the surface of the latent image holding member and / or a transfer rotating member in contact with the surface of the latent image holding member. It is possible to prevent fusion of the toner to the surface.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that a quaternary ammonium salt having an anion represented by the general formula (I) not only has good triboelectrification property but also has a good contact with a photoreceptor. It has been found that, even in an apparatus configuration in which there is a member to be used, the effect of preventing toner fusing can be exhibited by adding the inorganic oxide fine powder to the toner surface.

Particularly, in the cyclic quaternary ammonium salt,
It has been newly found that the use of the anion represented by the general formula (I) provides a more excellent effect of preventing toner fusion.

Since the transfer is basically a process using an electric field, the higher the charge amount of the toner, the stronger the electrostatic force can be exerted. Therefore, a toner having a high chargeability is more effective in transferring, and the amount of residual toner on the photosensitive member is reduced, which is preferable for toner fusion. Conversely, if the amount of charge of the developed toner becomes excessive, the adhesion of the toner to the photoreceptor based on the mirror power increases, making it difficult to remove the toner by the cleaning device.

The reason that the cyclic quaternary ammonium salt of the present invention is more excellent in the effect of preventing toner fusing than the known quaternary ammonium salt is that a proper triboelectric charge is imparted to the toner even under a wide range of copying conditions. It is thought that it is possible to do.

In particular, tetrazolium salts having the general formula (I) as an anion, imidazolium salts, general formulas (II) to
The saturated cyclic quaternary ammonium salt represented by (V) and the polymer having an ammonium ion in the polymer chain are excellent in the effect of preventing fusion.

[0029]

Embedded image (W, X, Y and Z represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group or hydrogen, and may be the same or different.)

Conventionally, the use of an image forming method in which a charging member or a transfer member contacts a photoreceptor surface has been limited to a low-speed machine for fusing toner. For the first time, it can be applied to high-speed machines.

The conventional quaternary ammonium salt has a low charge amount, so that its use as a positive charge control agent for toner has been limited. In the image forming method in which the charging member or the transfer member contacts the surface of the photoreceptor as in the present invention, the amount of toner remaining on the surface of the photoreceptor increases, and the effect of preventing fusion of the toner cannot be expected.

The improvement of the triboelectric charging property of the quaternary ammonium salt is described, for example, in Japanese Patent Publication No. 1-54694 and Japanese Patent Application Laid-Open No. Sho 62-62.
-71968, JP-A-62-87974,
Many proposals have been made, such as JP-A-64-54,
Compared with the cyclic quaternary ammonium salt of the present invention, the toner has insufficient positive triboelectric chargeability and insufficient toner fusing prevention properties.

Japanese Patent Application Laid-Open No. 6-35229 discloses that
Quaternary ammonium salts having an anion represented by the general formula (I) have been proposed.

However, JP-A-6-35229 does not propose the cyclic quaternary ammonium salt of the present invention. When an inorganic oxide fine powder is added to a toner containing a quaternary ammonium salt proposed in Japanese Patent Application Laid-Open No. 6-35229, the toner exhibits anti-fusing properties. However, a high-speed copying machine having a high copying speed does not have a sufficient toner fusion prevention effect. Since the toner containing the cyclic quaternary ammonium salt of the present invention has a more excellent toner fusion preventing effect, the toner fusion can be prevented even when applied to a high-speed machine.

Further, when the present invention is applied to an image forming method in which a rotating member comes into contact with the surface of a photoreceptor as described in the present invention, it exerts particularly excellent effects on developing characteristics such as photoreceptor contamination, development transfer omission, and ghost. I found something new.

The characteristics of the cyclic quaternary ammonium salt of the present invention are that the good charge rate of the conventional quaternary ammonium salt is further improved, and that the cyclic quaternary ammonium salt has remarkably high positive triboelectric chargeability. This characteristic becomes more remarkable when added to a toner having a magnetic compound.

When copying is resumed in a copying machine that has been in a suspended state for a long period of time under high humidity, since the charging performance of many toners is impaired, the charge amount does not return to the state before the suspension, or the return speed does not change. Is significantly reduced. Therefore, under such special conditions, when an image forming method including a transfer rotating body and a charging rotating body that comes into contact with the surface of the photoconductor is used, the phenomenon of toner fusion to the surface of the photoconductor is further deteriorated.

However, in the toner containing the cyclic quaternary ammonium salt of the present invention, the triboelectric charge after being left under high humidity is favorably restored to the charge before being left. Therefore, even if copying is resumed after being left for a long period of time, no transfer failure occurs, so that the amount of toner remaining on the surface of the photoconductor can be extremely reduced. Therefore, the effect of preventing fusion of the toner on the surface of the photoreceptor becomes extremely high.

In the present invention, the return of the triboelectric charge amount under high humidity means that the toner triboelectrically charged under high humidity is left for a long period of time and then shaken with the carrier again before leaving the triboelectric charge amount. Is expressed as a ratio to the charge amount.

Specifically, 2.5 g of toner and carrier 4
7.5 g (in the case of a magnetic toner, 5 g of toner and 45 g of carrier) are collected in a 50 cm ³ polyethylene container, and are left open for 2 days in an environment of a temperature of 30 ° C. and a relative humidity of 80%. After shaking for 240 seconds with a turbula mixer, about 0.5 g is sampled, and the triboelectric charge is measured by a blow-off method. This value is defined as the charge amount under high humidity before being left. Further, after leaving the container in the opened state for 4 days, the frictional charge amount at the time of shaking with the turbula mixer of 0 seconds, 60 seconds, and 240 seconds is measured, and the ratio to the charge amount before leaving is determined.

FIG. 1 shows a charge amount measuring apparatus according to the present invention. A sample is put in a metal measuring container 2 having a conductive screen 3 of 500 mesh (which can be changed to a size that does not allow the passage of carrier particles) at the bottom, and a metal lid 4 is provided. Next, the suction device 1 (at least a portion in contact with the measurement container 2 is an insulator)
, The air is sucked from the suction port 7 and the air volume control valve 6 is adjusted to adjust the pressure of the vacuum gauge 5 to 250 mmH ₂ O. In this state, suction is sufficiently performed (about 1 minute). The voltage of the electrometer 9 at this time is set to V (volt). Here, reference numeral 8 denotes a capacitor, and the capacitance is C (μF). The triboelectric charge (mC / kg) is obtained by dividing the amount of electric charge obtained by the amount of toner (g) removed by suction.

The cyclic quaternary ammonium salt of the present invention is not particularly limited as long as the anion is represented by the general formula (I). Various types of cyclic ammonium salts such as pyridinium salts and piperazinium salts are known,
In particular, tetrazolium salts having the general formula (I) as an anion, imidazolium salts, saturated cyclic quaternary ammonium salts represented by the general formulas (II) to (V), and polymers having a cyclic ammonium ion in the polymer chain Is particularly excellent in the effect of preventing fusion. In the future, as the toner becomes finer for the purpose of improving the image quality, the transfer efficiency of the toner tends to decrease, so that the toner fusion is more likely to occur. In such a case, this particularly excellent fusion preventing effect is as follows.
It becomes a more important characteristic.

[0043]

Embedded image (W, X, Y and Z represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group or hydrogen, and may be the same or different.)

Hereinafter, specific examples of the cyclic quaternary ammonium salt which can be used in the present invention will be shown, but the present invention is not limited thereto.

[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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The cyclic quaternary ammonium salt of the present invention is synthesized by forming a salt with a corresponding ammonium chloride and an acid corresponding to an anion or a metal salt thereof.

For example, Compound Example (1-6) is obtained by dissolving 50 g of N-phenyl J acid in 800 ml of an aqueous solution adjusted to pH 7 with sodium hydroxide and then adding 90 g of 2,3,5-triphenyltetrazolium chloride. By reacting with 150 ml of a dissolved aqueous methanol solution with stirring at 80 ° C. for 1 hour, an off-white powder is obtained.

The method for incorporating the cyclic quaternary ammonium salt of the present invention into a toner includes a method of adding the toner to the inside of the toner and a method of externally adding the toner. The amount of these cyclic quaternary ammonium salts used is determined by the type of the binder resin, the presence or absence of other additives, and the toner manufacturing method including the dispersion method, and is not limited uniquely. However, it is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. When externally added, 0.0 to 100 parts by weight of resin
The amount is preferably 1 to 10 parts by weight, and particularly preferably mechanochemically fixed to the surface of the toner particles.

The quaternary ammonium salt used in the present invention can be used in combination with a conventionally known charge control agent.

External addition of a fine powder of an inorganic oxide such as silica, alumina or titania treated with a silane coupling agent and / or silicone oil to a toner containing a cyclic quaternary ammonium salt of the present invention can be achieved by adding This is effective for improving the charging uniformity and transferability of the toner. The distribution of the triboelectric charge amount of the toner becomes sharper, and the transferability of the toner from the photoreceptor surface is improved. Therefore, the effect of preventing fusion of the toner on the surface of the photoconductor is further improved.

In particular, inorganic fine powders treated with a positively-charged coupling agent having a nitrogen atom and silicone oil are preferred.

As the silicone oil having a nitrogen atom, a silicone oil having at least a partial structure represented by the following formula can be used.

[0065]

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In the formula, R ¹ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ² represents an alkylene group,
R ⁵ represents a compound having a nitrogen-containing heterocyclic ring in its structure; R ³ and R ⁴ represent hydrogen, an alkyl group or an aryl group; However, the above alkyl group, aryl group, alkylene group, and phenylene group may have an organo group having a nitrogen atom, or may have a substituent such as halogen as long as chargeability is not impaired. good.

Examples of the coupling agent having a nitrogen atom include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, Dibutylaminopropyltrimethoxysilane,
Monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxysilyl-γ -Propylbenzylamine, trimethoxysilyl-γ-propylpiperidine, trimethoxysilyl-γ-propylmorpholine, trimethoxysilyl-γ-propylimidazole and the like.

Further, in the present invention, it is preferable to treat the surface of the inorganic fine powder with a silane coupling agent and silicone oil, since charging characteristics, fluidity and transferability are improved. In this case, one of the silane coupling agent and the silicone oil is a nitrogen-containing compound as described above. In particular, when inorganic fine powder treated with a nitrogen-containing silane coupling agent and silicone oil in combination is applied to the toner of the present invention, the charging uniformity of the toner is further improved, which is preferable. Therefore, a beneficial effect is obtained due to a fusion preventing effect, a toner consumption reduction effect, image quality uniformity, and the like.

The silicone oil used in the present invention is:
It may have an alkyl group, an aryl group, or an alkoxy group as a substituent.

The silane coupling agent used in the present invention includes dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane. Examples thereof include silane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

Among the above inorganic oxide fine powders, those having a specific surface area of at least 40 m ² / g (particularly 50 to 400 m ² / g) by nitrogen adsorption measured by the BET method are preferable as the base fine powder, As the processed fine powder, 30
m ² / g or more (especially 70~350m ² / g) within the scope of preferred.

The application amount of these inorganic oxide fine powders is effective when the amount is 0.01 to 20% based on the weight of the developer, and is particularly excellent when 0.03 to 5% is added. Shows fluidity and stable chargeability. In a preferred embodiment, the addition form is 10 to 60 with respect to the toner surface.
%, The effect of preventing fusion of the toner is high when the inorganic oxide fine powder is adhered at an area ratio of%.

Finally, when the hydrophobicity of the inorganic oxide fine powder is increased to a value of 30 or more as the hydrophobicity measured by a methanol titration test, the triboelectric charge amount of the toner is reduced. This is preferable because it exhibits sharp and uniform positive chargeability.

The “methanol titration test” specified in this specification for evaluating the degree of hydrophobicity of the inorganic oxide fine powder is performed as follows. 0.2 g of the test inorganic oxide fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. Methanol is titrated from the burette until the entire amount of the inorganic oxide fine powder is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by the suspension of the entire amount of the inorganic oxide fine powder in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

As for the binder resin used in the present invention, the molecular weight distribution of the toner is a molecular weight distribution by GPC of a THF-soluble component, and at least one peak exists in a molecular weight region of 3,000 to 50,000, 50-90% less than 100,000 components
Is preferable.

The present inventors have found that the use of the above-described binder resin in a configuration in which there is a member that comes into contact with the photosensitive member is effective in preventing toner fusion. Was.

The reason seems to be as follows. In the toner fusion, the toner is deformed by receiving a stress due to heat or pressure. Therefore, if the toner is not easily deformed by heat or pressure, the toner fusion should hardly occur. However, such toner generally has poor fixability. In order to achieve this balance,
It is necessary to consider the temperature dependence of viscoelasticity. That is,
In an environment where toner fusion occurs, heat is mainly generated by friction. For this reason, the temperature is lower than when fixing is performed. Therefore, when the temperature is relatively low, the elasticity is high, and it is difficult to be deformed by pressure. However, when the temperature is high such as at the time of fixing, the elasticity is preferably low. When the binder resin has the above-mentioned molecular weight distribution, the temperature dependency of viscoelasticity becomes preferable.

Although the elastic property is relatively dominated by the high molecular weight component, in the present invention, the content of the component having a molecular weight of 100,000 or more is preferably 10% or more, preferably in the range of 100,000 to 5,000,000. Preferably, there is at least one peak. More preferably, in a region of 300,000 to 2,000,000, it is preferable that there is a maximum peak in a region of 100,000 or more. Further, it is the most preferable form that this peak is the second largest peak in the entire region in order to balance toner fusion and fixing. If the peak of the high molecular weight component is in a region exceeding 5 million, the elasticity is too high.
If the content of 100,000 or more is not present in an amount of 10% or more, the elasticity is too low and the toner is likely to fuse.

In the present invention, at least one peak is preferably present in a region having a molecular weight of 3,000 to 50,000, preferably in a region of 3,000 to 30,000, and more preferably in a region of 5,000 to 20,000. Preferably, at least one peak exists. Further, it is the most preferable form that the peak in this region is the maximum peak in order to obtain good fixability and good dispersibility of the compound added as a charge control agent. If there is no peak in the region of 50,000 or less, the viscosity is insufficient and good viscoelastic properties cannot be obtained. Further, if the peak of the low molecular weight component is less than 3,000 even in the region of 50,000 or less, the dispersion state of the cyclic quaternary ammonium salt of the present invention is deteriorated.

Further, in the present invention, the weight fraction of the polymer having a molecular weight of 100,000 or less is preferably 50 to 90%, particularly preferably 65 to 85%. By being in this range, good viscoelastic temperature dependency is exhibited, and good fixability is exhibited.Also, even if the contact charging device or the transfer rotating body is contaminated with toner, uneven charging and transfer failure do not occur. Become.
It is considered that this is because it is difficult for the toner to become a thick deposit when the toner adheres and becomes contaminated.

Examples of the type of the binder resin used in the present invention include a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and a substituted product thereof; styrene-p-chlorostyrene copolymer. Copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene- Acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile- Styrene copolymers such as indene copolymers Coalescence; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin , Polyvinyl butyral, terpene resin, cumarone indene resin, petroleum resin and the like can be used.

A crosslinked styrene copolymer is also a preferred binder resin.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. A monocarboxylic acid having a heavy bond or a substituted product thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like, and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate;
For example, ethylene-based olefins such as ethylene, propylene, butylene and the like;
Vinyl ketones such as vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether and the like;
And the like, alone or in combination of two or more.

As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used, for example, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene and the like; for example, ethylene glycol diacrylate, Ethylene glycol dimethacrylate,
Carboxylic acid esters having two double bonds such as 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; Are used alone or as a mixture.

In the present invention, M is used to improve the effect of preventing fusion.
It is preferable that w contains 500 to 10,000 wax. Preferably, Mw is 700-5000,
More preferably, Mw is 800-2000. Generally, a wax having a Mw of 500 to 10,000 has a low viscosity when kneaded, and it is difficult to obtain a uniform wax dispersion. On the other hand, it has been found that the toner of the present invention contains the above-mentioned cyclic quaternary ammonium salt, whereby a good wax dispersibility can be obtained. The mechanism is considered to be such that the compatibility between the wax and the above compound is good, and the wax mass once dispersed is hardly re-agglomerated. With good dispersion, Mw is 5
By containing the wax of from 00 to 10000, the surface of the toner particles becomes uniform, and there is no portion that easily contaminates the photosensitive drum.

The present inventors have further found that the use of a wax having an Mw / Mn of 5 or less further enhances the effect of preventing toner fusing. Preferably, Mw / Mn is 3 or less, more preferably 2 or less. Such a wax is preferable because it sharply lowers the viscosity during fixing, but this property is inconvenient during kneading. This is because the resin temperature at the time of kneading is close to the temperature at the time of fixing, so that the wax has the viscosity shown at the time of fixing, and good dispersion force does not work. However, it has been newly found that the quaternary ammonium salt of the present invention improves dispersion of such a wax which is difficult to disperse. It is considered that the presence of the wax which sharply lowers the viscosity in a good dispersion state increases the thermal stability at room temperature and makes the toner less likely to fuse. In addition, it has a good effect on fixing, offset, and blocking.

Examples of the hydrocarbon wax usable in the present invention include an alkylene polymer obtained by radically polymerizing alkylene under high pressure, an alkylene polymer polymerized by Ziegler catalyst under low pressure, and a high-molecular weight alkylene polymer obtained by thermal decomposition. Examples include a synthetic hydrocarbon obtained by hydrogenating a distillation residue of a hydrocarbon obtained by the Age method from a synthesis gas comprising the obtained alkylene polymer, carbon monoxide and hydrogen. Among these hydrocarbon waxes, hydrocarbon waxes obtained by extracting and fractionating specific components are particularly suitable. Pressed sweating, solvent method, fractional crystallization using vacuum distillation, etc.
It is preferable to extract a low molecular weight component and further remove a low molecular weight component therefrom.

In addition, microcrystalline wax,
Carnauba wax, sasol wax, paraffin wax, aliphatic solid alcohol and the like can also be used.

The content of these waxes depends on the binder resin 10
It is effective to use 0.5 to 10 parts by weight with respect to 0 parts by weight.

The coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine, nigrosine compound, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, calco oil blue, and chrome yellow. Conventionally known dyes and pigments such as quinacridone, benzidine yellow, rose bengal, triarylmethane compounds, monoazo and disazo dyes can be used alone or in combination.

As the magnetic material used in the present invention, oxides such as magnetite, γ-iron oxide, ferrite and iron-rich ferrite, metals such as iron, cobalt and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium.

These ferromagnetic materials have an average particle size of 0.1 to
1 μm, preferably about 0.1 to 0.5 μm has good dispersibility, and the amount contained in the magnetic toner is about 40 to 150 parts by weight, particularly 100 parts by weight of the resin component. 60 to 120 parts by weight per part is preferable from the viewpoints of image density stability and charge return speed after being left at high temperature and high humidity.

The toner of the present invention may optionally contain additives. Examples of the additive include a lubricant such as zinc stearate, an abrasive such as cerium oxide and silicon carbide, an anti-caking agent, and a conductivity imparting agent such as carbon black and tin oxide.

Fluorine-containing polymer fine powder such as polyvinylidene fluoride fine powder is also a preferable additive from the viewpoint of fluidity, abrasiveness, charge stability and the like.

Furthermore, the toner of the present invention can be used as a two-component toner by mixing with a carrier. As the carrier that can be used in the present invention, known carriers can be used, for example, iron powder, ferrite powder, powder having magnetic properties such as nickel powder, glass beads, and the like, and the surface thereof is treated with a resin or the like. What was done. Further, as the resin for coating the carrier surface, styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, silicone resin, fluorine-containing resin, A polyamide resin, an ionomer resin, a polyphenylene sulfide resin, or the like, or a mixture thereof can be used.

In producing the toner according to the present invention, the above-mentioned toner constituting materials are sufficiently mixed by a ball mill or other mixer, and then heated roll, kneader,
It is preferable to knead well using an extruder heat kneader, cool and solidify, and then mechanically pulverize and classify the toner to obtain the toner.Alternatively, after dispersing the constituent materials in a binder resin solution, spray drying Or a method for producing a toner by mixing a monomer to form a binder resin with a predetermined material to form an emulsified suspension and then polymerizing to obtain a toner; or a core material In a so-called microcapsule toner composed of a shell material, a method of including a predetermined material in a core material, a shell material, or both of them can be applied. Further, if necessary, the desired additive is sufficiently mixed with a mixer such as a Henschel mixer to produce the toner according to the present invention.

In the present invention, the molecular weight distribution of the THF-soluble portion of the toner by GPC is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and THF was added as a solvent to the column at this temperature.
(Tetrahydrofuran) at a flow rate of 1 ml per minute,
About 100 μl of a THF sample solution is injected and measured. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from a calibration curve (the relationship between the logarithmic value of the molecular weight and the count number) prepared from several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Tosoh Corporation or Showa Denko Co., Ltd. having a molecular weight of about 10 ² to 10 ⁷ , and at least about 10 points, it is appropriate to use a standard polystyrene sample. . An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns.
ex GPC KF-801, 802, 803, 80
4,805,806,807,800P and TSKgelG1000H (H _XL ) manufactured by Tosoh Corporation
_{G2000H (H XL), G3000H (} H XL), G40
_{00H (H XL), G5000H (} H XL), G6000H
(H _XL ), G7000H (H _XL ), TSKguardc
column can be mentioned.

A sample is prepared as follows.

After placing the sample in THF and leaving it to stand for several hours, it is shaken well, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. At this time TH
The time of leaving in F is set to 24 hours or more. Then the sample processing filter (pore size 0.45
0.5 μm, for example, Myshoridisk H-25-5
A sample passed through Tosoh, Exiclodisc 25CR (German Science Japan) can be used as a GPC sample. Further, the sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The molecular weight distribution of the wax is measured by GPC under the following conditions.

Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.1% ionol) Flow rate: 1.0 ml / min Sample: 0.4 ml of about 0.15% sample is injected

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

As a contact charging means applicable to the present invention, a charging roller 12 as shown in FIG. 2 is preferable. As another means, a charging blade 1 as shown in FIG.
There are a method using 2 ′ and a method using a conductive brush. While these contact charging means have the effect of making high voltage unnecessary and reducing the generation of ozone,
Since the member is in direct contact with the photoreceptor, the adverse effect of fusing the toner is likely to occur. The present invention does not limit the method and effect of the contact charging means to which the present invention is applied, and any method of charging a member by directly contacting the member with the photoreceptor is applicable to the present invention. It is possible.

As a preferable process condition when the charging roller is used, the contact pressure of the roller is 5 to 500 g / c.
m, when a voltage obtained by superimposing an AC voltage on a DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 50
５5 kHz, DC voltage = −200 to −1.5 kV, and when DC voltage was used, DC voltage = −200 to −−
5 kV.

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

As the material of the transfer rotary member applicable to the present invention, the same material as that of the charging roller can be used. The preferable transfer process condition is that the contact pressure of the roller is 5 to 500 g / cm. And the DC voltage is 200
〜１０10 kV.

[0108]

EXAMPLES The present invention will be described below in more detail with reference to Examples, which should not be construed as limiting the present invention. still,
All parts in the following formulations are parts by weight.

Example 1 100 parts of a styrene-butyl methacrylate copolymer (peak 1: 10,000, peak 2: 370,000) Magnetic substance 90: Sasol wax (Mw / Mn = 1.6) 3 Part ・ Compound example (1-1) 3 parts

After thoroughly mixing the above materials with a blender,
Kneading was performed with a twin-screw kneading extruder set at 130 ° C. After cooling the obtained kneaded material, it was coarsely pulverized and finely pulverized using a fine pulverizer using a jet stream. Further, the obtained finely pulverized product is strictly classified and removed by a multi-segmentation classifier utilizing a Coanda effect (an elbow jet classifier manufactured by Nittetsu Mining Co., Ltd.) at the same time, and the weight average particle size is 6. A black fine powder of 3 μm was obtained.

Next, silica fine powder (BET = 200 m ²⁾
/ G) 100 parts were treated with 20 parts of a mixture of dibutylaminopropyltrimethoxysilane and dimethyl silicone oil (weight ratio 1: 5). 0.8 part of the treated silica was mixed with 100 parts of the black fine powder using a Henschel mixer to obtain a one-component magnetic toner.

The obtained magnetic toner was transferred to a copying machine (copying speed: 30 sheets / minute at A4) obtained by modifying the developing system of a commercially available electrophotographic copying machine NP-6030 (manufactured by Canon Inc.) as shown in FIG. A copy test was performed using the same. Photoconductor 11
Is in contact with the charging roller 12 made of conductive rubber and connected to the power supply 19, and uniformly charges the surface of the photoconductor. The contact pressure of the charging roller is 50 g / cm and -7
A 600 Hz, 2.6 kVpp AC voltage was superimposed on a 00 V DC voltage. On the downstream side of the developing device, a transfer roller 15 made of the same conductive rubber as the charging roller is used.
Is in pressure contact. A transfer bias is applied to the transfer roller from the power supply 19, and the toner image is transferred from the photoconductor to the transfer material. The contact pressure of the transfer roller is 20 g / cm,
A DC voltage of 4.5 kV was applied.

When 10,000 images were copied at an image ratio of 6% in an environment of 23 ° C./60% (relative humidity), clear images having an image density of 1.40 ± 0.03 were obtained from the beginning. . The resolution of the image also maintained the initial 7.1 lines / mm. The toner consumption after copying 10,000 sheets is 3
It was 76 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 18 mC / k.
g.

Next, under an environment of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 20 mC / kg.

Further, under an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.33 ± 0.03 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.05.

When the charge amount after standing for 2 days was measured,
It was 14 mC / kg. When the return characteristics were subsequently examined, it was 82% for 0 seconds and 100% for 60 seconds.

Further, in any of the copying test environments, no omission phenomenon during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photoreceptor was observed, but no fusion phenomenon of the toner was observed.

Example 2 Compound Example (2-1) was replaced with Compound Example (1-1) in place of Compound Example (1-1).
Except for using a part, a weight average particle size of 6.2 was obtained in the same manner as in Example 1.
A μm one-component magnetic toner was obtained, and the same copying test as in Example 1 was performed.

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The toner consumption after copying 10,000 sheets was 386 g.

The amount of triboelectric charge after leaving the toner powder carrier with the iron powder carrier for 2 days was measured at a toner concentration of 10%.
g.

Next, at a temperature of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

When the amount of charge with the iron powder carrier after being left for 2 days was measured, it was 20 mC / kg.

Further, in a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.33 ± 0.03 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.05.

When the charge amount after standing for 2 days was measured,
It was 15 mC / kg. When the return characteristics were subsequently examined, it was 83% at 0 seconds and 100% at 60 seconds.

In any of the copying test environments, no omission phenomenon during transfer and uneven charging did not occur.

After the completion of the copying test, the photoreceptor was observed, but no fusing phenomenon of the toner was observed.

Example 3 Compound Example (3-1) was replaced with Compound Example (3-1) in place of Compound Example (1-1).
6.4 weight average particle diameter in the same manner as in Example 1 except that
A μm one-component magnetic toner was obtained, and the same copying test as in Example 1 was performed.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The toner consumption after copying 10,000 sheets was 396 g.

The amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, and was found to be 15 mC / k.
g.

Next, at a temperature of 15 ° C./10%, 10.0
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The amount of charge with the iron powder carrier after standing for 2 days was 18 mC / kg.

Further, in an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.32 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.06.

The charge amount after standing for 2 days was measured.
It was 3 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

Further, in any of the copying test environments, the omission phenomenon during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photoreceptor was observed, but no toner fusion phenomenon was observed.

Example 4 Compound Example (5-1) was replaced with Compound Example (5-1) in place of Compound Example (1-1).
6.3 weight-average particle diameter in the same manner as in Example 1 except that
A μm one-component magnetic toner was obtained, and the same copying test as in Example 1 was performed.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The amount of toner consumed after copying 10,000 sheets was 394 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 16 mC / k.
g.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 18 mC / kg.

Further, in a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.32 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.06.

When the charge amount after standing for 2 days was measured,
It was 12 mC / kg. When the return characteristics were subsequently examined, 0% was 81% and 60 seconds was 100%.

In any of the copying test environments, the omission phenomenon during transfer and uneven charging did not occur.

After the completion of the copying test, the photoreceptor was observed, but no toner fusion phenomenon was observed.

Example 5 Instead of compound example (1-1), compound example (7-1) (n
= 100 to 1000), a one-component magnetic toner having a weight average particle diameter of 6.2 µm was obtained in the same manner as in Example 1, and the same copying test as in Example 1 was performed.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The amount of toner consumed after copying 10,000 sheets was 388 g.

The amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10% to be 17 mC / k.
g.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 19 mC / kg.

Further, under a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.32 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.06.

When the charge amount after standing for 2 days was measured,
It was 14 mC / kg. When the return characteristics were subsequently examined, it was 83% at 0 seconds and 100% at 60 seconds.

In any of the copying test environments, no dropout phenomenon during transfer and uneven charging did not occur.

Further, after completion of the copying test, the photoreceptor was observed, but no toner fusion phenomenon was observed.

Example 6 A one-component magnetic toner having a weight average particle size of 6.4 μm was obtained in the same manner as in Example 1 except that 4 parts of the following compound was used instead of Compound Example (1-1). The same copying test was performed.

[0158]

Embedded image

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image with an image density of 1.38 ± 0.05 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The amount of toner consumed after copying 10,000 sheets was 404 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 15 mC / k.
g.

Next, at a temperature of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image of 40 ± 0.05 was obtained.

The amount of charge with the iron powder carrier after standing for 2 days was 19 mC / kg.

Further, under a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 3 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.30 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.08.

When the charge amount after standing for 2 days was measured,
It was 14 mC / kg. When the return characteristics were checked continuously, 0% was 78%, 60 seconds was 95%, and 240 seconds was 10%.
It was 0%.

In any of the copying test environments, no omission phenomenon during transfer and uneven charging did not occur.

After the completion of the copying test, the photosensitive member was observed. As a result, a slight fusion phenomenon of the toner was observed.

Comparative Example 1 A weight average particle diameter of 6.2 μm was obtained in the same manner as in Example 1 except that 4 parts of the following compound example was used instead of compound example (1-1).
And a copying test was conducted in the same manner as in Example 1.

[0168]

Embedded image

When 10,000 images were copied at an image ratio of 6% in an environment of 23 ° C./60%, clear images with an image density of 1.38 ± 0.05 were obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The amount of toner consumed after copying 10,000 sheets was 412 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 14 mC / k.
g.

Next, under a 15 ° C./10% environment,
A copy test of 00 sheets was performed.
A good image of 40 ± 0.05 was obtained.

The amount of charge with the iron powder carrier after being left for 2 days was 17 mC / kg.

Furthermore, under a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 3 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, an image of 1.30 ± 0.04 was obtained,
After about 4,000 sheets, image defects appeared to be caused by toner fusion. The difference between the image densities immediately before and immediately after standing for 4 days was 0.08.

When the charge amount after standing for 2 days was measured,
It was 13 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

In any of the copying test environments, no omission phenomenon during transfer and uneven charging did not occur.

However, when the photoreceptor was observed after the completion of the copying test, a slight fusion phenomenon of the toner was observed.

Comparative Example 2 A weight average particle size of 6.5 μm was obtained in the same manner as in Example 1 except that 4 parts of the following compound examples were used instead of the compound example (1-1).
And a copying test was conducted in the same manner as in Example 1.

[0178]

Embedded image

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60%, an image having an image density of 1.28 ± 0.05 was obtained from the beginning. The resolution of the image also maintained the initial value of 6.3 lines / mm. 10,
After copying 000 sheets, the toner consumption was 445 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was 10 mC / k
g.

Next, under a 15 ° C./10% environment,
A copy test of 00 sheets was performed.
A good image of 32 ± 0.05 was obtained.

The amount of charge with the iron powder carrier after standing for 2 days was 13 mC / kg.

Furthermore, at a temperature of 35 ° C./90%, 5.0
A copy test of 00 sheets was performed. Image density 1.1 from the beginning
5 ± 0.03 images were obtained. Continued in this state 4
After leaving for days, 5,000 copies were made. From the first sheet of the resumption, the image density changed to a low state of 1.00 ± 0.10. The difference in image density immediately before and immediately after standing for 4 days was 0.25.

When the charge amount after standing for 2 days was measured,
It was 7 mC / kg. When the return characteristics were examined continuously, 0 second was 65%, 60 seconds was 76%, and 240 seconds was 80%.
Met.

In any copy test environment,
Image defects and charging unevenness, which are considered to be caused by the phenomenon of omission during transfer and fusion of toner, occurred.

After the completion of the copying test, the photosensitive member was observed. As a result, a fusion phenomenon of the toner was observed.

Comparative Example 3 A weight-average particle size of 6.5 μm was obtained in the same manner as in Example 1 except that the following compound example was used in 4 parts instead of the compound example (1-1).
And a copying test was conducted in the same manner as in Example 1.

[0188]

Embedded image

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60%, an image having an image density of 1.15 ± 0.05 was obtained from the beginning. The resolution of the image also maintained the initial value of 5.6 lines / mm. 10,
After copying 000 sheets, the toner consumption was 434 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was 9 mC / kg.
Met.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
22 ± 0.05 images were obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 1 lmC / kg.

Further, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. Image density 1.1 from the beginning
An image of 0 ± 0.08 was obtained. Continued in this state 4
After leaving for days, 5,000 copies were made. From the first sheet after the resumption, the image density was changed to a low state of 0.95 ± 0.10. The difference between the image densities immediately before and immediately after standing for 4 days was 0.30.

When the charge amount after standing for 2 days was measured,
It was 6 mC / kg. When the return characteristics were continuously examined, 0% was 60%, 60 seconds was 68%, and 240 seconds was 72%.
Met.

In any copy test environment,
Image defects and charging unevenness, which are considered to be caused by the phenomenon of omission during transfer and fusion of toner, occurred.

After the completion of the copying test, the photosensitive member was observed. As a result, a fusion phenomenon of the toner was observed.

Example 7 100 parts of titania fine powder (BET = 120 m ² / g) were treated with 12 parts of a mixture of dibutylaminopropyltrimethoxysilane and dimethyl silicone oil (weight ratio 1: 5). 0.8 part of the treated silica was mixed with 100 parts of the black fine powder of Example 2 using a Henschel mixer to obtain a one-component magnetic toner.

Using the obtained magnetic toner, the same copying test as in Example 1 was performed.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
After 10,000 copies, the toner consumption was 392 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 16 mC / k.
g.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 18 mC / kg.

Further, in an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
A good image of 1.33 ± 0.03 was obtained from the first sheet.
The difference between the image densities immediately before and immediately after standing for 4 days was 0.05.

When the charge amount after standing for 2 days was measured,
It was 14 mC / kg. When the return characteristics were subsequently examined, it was 85% for 0 seconds and 100% for 60 seconds.

In any of the copying test environments, the omission phenomenon during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photosensitive member was observed, but no toner fusion phenomenon was observed.

Example 8 A commercially available electrophotographic copying machine NP-6 was prepared using the magnetic toner of Example 3
030 (manufactured by Canon Inc.), the same copy test as in Example 1 was performed.

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60%, a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. Also,
The resolution of the image also maintained the initial 7.1 lines / mm.
The amount of toner consumed after copying 10,000 sheets was 390 g.

[0209] The amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10% to find that it was 16 mC / k.
g.

Next, at a temperature of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

[0211] The charge amount of the iron powder carrier after standing for 2 days was 18 mC / kg.

Furthermore, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.32 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.06.

When the charge amount after standing for 2 days was measured,
It was 12 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

[0214] In any of the copying test environments, the phenomenon of omission during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photosensitive member was observed, but no fusion phenomenon of the toner was observed.

Example 9 A black fine powder having a weight average particle size of 8.6 μm was obtained in the same manner as in Example 1 except that the amount of the magnetic substance was changed to 80 parts.

Next, 0.6 part of the treated silica of Example 1 was mixed with 100 parts of the black fine powder using a Henschel mixer to obtain a one-component magnetic toner.

The same copying test as in Example 1 was performed on the obtained magnetic toner.

When 10,000 sheets of an image having an image ratio of 6% were copied in an environment of 23 ° C./60% (relative humidity), a clear image having an image density of 1.40 ± 0.03 was obtained from the beginning. . The resolution of the image also maintained the initial value of 6.3 lines / mm. The toner consumption after copying 10,000 sheets is 4
It was 16 g.

When the amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, it was found to be 15 mC / k.
g.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image of 42 ± 0.03 was obtained.

The charge amount of the iron powder carrier after standing for 2 days was 18 mC / kg.

Further, in a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 5 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.33 ± 0.03 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.05.

When the charge amount after standing for 2 days was measured,
It was 12 mC / kg. When the return characteristic was examined continuously, it was 86% at 0 seconds and 100% at 60 seconds.

In any of the copying test environments, the omission phenomenon during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photoreceptor was observed, but no toner fusion phenomenon was observed.

Example 10 A fine black powder having a weight average particle size of 8.5 μm was obtained in the same manner as in Example 6, except that the amount of the magnetic substance was changed to 80 parts.

Next, 0.6 part of the treated silica of Example 1 was mixed with 100 parts of the black fine powder using a Henschel mixer to obtain a one-component magnetic toner.

The same copying test as in Example 1 was performed on the obtained magnetic toner.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60%, a clear image with an image density of 1.38 ± 0.05 was obtained from the beginning. Also,
The resolution of the image also maintained the initial value of 6.3 lines / mm.
The toner consumption after copying 10,000 sheets was 45 lg.

The amount of triboelectric charge after being left with the iron powder carrier for 2 days was measured at a toner concentration of 10%, and was found to be 1 lmC / k.
g.

Next, at a temperature of 15 ° C./10%, the temperature was adjusted to 10.0 or less.
A copy test of 00 sheets was performed.
A good image of 40 ± 0.05 was obtained.

The charge amount of the iron powder carrier after being left for 2 days was measured and found to be 15 mC / kg.

Further, under an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 3 ± 0.03 was obtained. After being left in this state for 4 days, copying was continued for 5,000 sheets. Resume 1
From the first sheet, a good image of 1.30 ± 0.04 was obtained. The difference between the image densities immediately before and immediately after standing for 4 days was 0.08.

When the charge amount after standing for 2 days was measured,
It was 9 mC / kg. When the return characteristics were examined continuously, 0% was 81%, 60 seconds was 95%, and 240 seconds was 100%.
%Met.

In any of the copying test environments, the omission phenomenon during transfer and uneven charging did not occur.

Further, after the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 11 Styrene-butyl methacrylate copolymer 100 parts (peak 1: 15,000, peak 2: 400,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax (Mw / Mn = 2. 5) 2 parts ・ Compound example (1-6) 2 parts

After thoroughly mixing the above materials with a blender,
Kneading was performed with a twin-screw kneading extruder set at 130 ° C. After cooling the obtained kneaded material and coarsely pulverizing with a cutter mill,
Finely pulverize using a fine pulverizer using a jet stream, and then crush the obtained finely pulverized powder at the same time using a Coanda effect, possibly using a soot classifier (Nippon Mining Co., Ltd. elbow jet classifier). Then, a blue fine powder having a weight average particle size of 6.5 μm was obtained.

Next, silica fine powder (BET = 300 m ²⁾
/ G) 100 parts were treated with 30 parts of a mixture of diethylaminopropyltrimethoxysilane and dimethyl silicone oil (weight ratio 2: 5). 1.0 part of the treated silica was mixed with 100 parts of the blue fine powder using a Henschel mixer to obtain a toner.

Next, 7 parts of the obtained toner was mixed with 100 parts of a fluorine-acryl coated ferrite carrier having an average particle diameter of 45 μm to prepare a developer.

A copy test was performed on the obtained magnetic toner using the same modified copier as in Example 1.

When 10,000 images were copied at an image ratio of 6% in an environment of 23 ° C./60% (relative humidity), a vivid blue image having a density of 1.37 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 228
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

After leaving for 2 days, the amount of triboelectric charge
% Was 35 mC / kg.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
It was 40 mC / kg.

Further, under a 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.03 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.30 ± 0.03 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.04. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 33 mC / kg. When the return characteristics were subsequently examined, it was 83% at 0 seconds and 100% at 60 seconds.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 12 Compound Example (2-6) was replaced with Compound Example (2-6) in place of Compound Example (1-6).
Except for using a part, the weight average particle diameter was 6.
A 3 μm blue toner was obtained.

Next, the same carrier 10 as in Embodiment 11 was used.
A developer was prepared using 0 cities.

This developer was subjected to the same copying test as in Example 11.

When copying 10,000 images at an image ratio of 6% in an environment of 23 ° C./60% (relative humidity), a bright blue image having a density of 1.37 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 235
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

After leaving for 2 days, the triboelectric charge
It was 33 mC / kg when measured in%.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
It was 39 mC / kg.

Further, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.03 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.30 ± 0.03 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.04. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 31 mC / kg. When the return characteristics were subsequently examined, it was 85% for 0 seconds and 100% for 60 seconds.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 13 Compound Example (4-1) was replaced with Compound Example (4-1) in place of Compound Example (1-6).
Except for using a part, the weight average particle diameter was 6.
A 3 μm blue toner was obtained.

Next, the same carrier 10 as in Embodiment 11 was used.
A developer was prepared using 0 parts.

This developer was subjected to the same copying test as in Example 11.

When 10,000 images were copied at an image ratio of 6% in an environment of 23 ° C./60% (relative humidity), a bright blue image having a density of 1.33 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 243
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

After leaving for 2 days, the amount of triboelectric charge
It was 30 mC / kg when measured in%.

Next, under a 15 ° C./10% environment,
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
It was 35 mC / kg.

Furthermore, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.05 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.28 ± 0.05 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.07. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 27 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 14 Compound Example (6-1) was replaced with Compound Example (6-1) in place of Compound Example (1-6).
Except for using a part, the weight average particle diameter was 6.
A 5 μm blue toner was obtained.

Next, the same carrier 10 as in the eleventh embodiment is used.
A developer was prepared using 0 parts.

This developer was subjected to the same copying test as in Example 11.

When an image having an image ratio of 6% was copied 10,000 times in an environment of 23 ° C./60% (relative humidity), a bright blue image having a density of 1.33 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 252
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

After leaving for 2 days, the amount of triboelectric charge
It was 31 mC / kg when measured in%.

Next, under a 15 ° C./10% environment,
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
It was 36 mC / kg.

Further, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.05 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.28 ± 0.05 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.07. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 28 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 15 In place of compound example (1-6), compound example (7-3) (n
= 100-1000) except that two parts were used.
In the same manner as in the above, a blue toner having a weight average particle size of 6.1 μm was obtained.

Next, the same carrier 10 as in the eleventh embodiment is used.
A developer was prepared using 0 parts.

This developer was subjected to the same copying test as in Example 11.

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60% (relative humidity), a vivid blue image having a density of 1.37 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 240
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

[0284] The amount of triboelectric charge after standing for 2 days
It was 32 mC / kg when measured in%.

Next, at a temperature of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
It was 38 mC / kg.

Further, under an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.03 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.30 ± 0.03 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.04. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 30 mC / kg. When the return characteristics were subsequently examined, it was 83% at 0 seconds and 100% at 60 seconds.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

Example 16 A weight-average particle size of 6.5 μm was obtained in the same manner as in Example 11 except that 2 parts of the following compound was used instead of Compound Example (1-6).
Blue toner was obtained.

[0291]

Embedded image

Next, the same carrier 10 as in the eleventh embodiment is used.
A developer was prepared using 0 parts.

This developer was subjected to the same copying test as in Example 11.

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60% (relative humidity), a bright blue image having a density of 1.33 ± 0.03 was obtained from the beginning. . 266 toner consumption after 10,000 copies
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

[0295] The amount of triboelectric charge after standing for 2 days
It was 32 mC / kg when measured in%.

Next, at a temperature of 15 ° C./10%, a temperature of 10.0
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

When the charge amount after standing for 2 days was measured,
37 mC / kg.

Further, at 35 ° C./90% environment, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.05 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.28 ± 0.05 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.08. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 27 mC / kg. When the return characteristic was examined continuously, it was 80% for 0 seconds and 100% for 60 seconds.

After the completion of the copying test, the photosensitive member was observed. As a result, a very small amount of toner fusion was observed.

Example 17 100 parts of fine silica powder (BET = 300 m ² / g) were treated with 30 parts of silicone oil having an amino group. 1.0 part of the treated silica was added to the blue fine powder 100 of Example 11.
And a Henschel mixer to obtain a toner.

Next, the same carrier 10 as in the eleventh embodiment is used.
A developer was prepared using 0 parts.

This developer was subjected to the same copying test as in Example 11.

When an image having an image ratio of 6% was copied on 10,000 sheets in an environment of 23 ° C./60% (relative humidity), a vivid blue image having a density of 1.37 ± 0.03 was obtained from the beginning. . The toner consumption after copying 10,000 sheets is 251
g. In addition, there was no uneven charging of the photoreceptor or transfer failure of the toner from the photoreceptor onto the transfer paper.

[0305] The amount of triboelectric charge after leaving for 2 days was changed to toner density 5
It was 37 mC / kg when measured in%.

Next, at a temperature of 15.degree.
A copy test of 00 sheets was performed.
A good image having excellent density uniformity of 33 ± 0.03 was obtained.

[0307] The charge amount after being left for 2 days was measured.
It was 42 mC / kg.

Further, in an environment of 35 ° C./90%, 5,0
A copy test of 00 sheets was performed. 1.3 image density from the beginning
A good image of 0 ± 0.03 was obtained. Subsequently, after being left in this state for 4 days, 5,000 copies were made. A good image of 1.30 ± 0.03 was obtained from the first sheet after resumption. The difference between the image densities immediately before and immediately after standing for 4 days was 0.04. No toner scattering was observed during the copying test.

When the charge amount after standing for 2 days was measured,
It was 34 mC / kg. When the return characteristics were subsequently examined, 0% was 81% and 60 seconds was 100%.

After the completion of the copying test, the photosensitive member was observed, but no fusing phenomenon of the toner was observed.

[0311]

According to the present invention, since the quaternary ammonium salt having the anion represented by the above general formula (I) is contained, the toner has good triboelectric charging properties and fuses the toner to the surface of the photoreceptor. Can be prevented.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of a toner charge amount measuring device.

FIG. 2 is a schematic configuration diagram of an electrophotographic apparatus having a charging roller as a contact charging unit.

FIG. 3 is a schematic configuration diagram of an electrophotographic apparatus having a charging blade as a contact charging unit.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 11 Latent image holding body (photoreceptor) 12, 12 'Charging means 13 Exposure part 14 Developing device 15 Transfer roller 16 Cleaning device

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-35229 (JP, A) JP-A-62-87974 (JP, A) JP-A-61-137163 (JP, A) JP-A 61-87163 137164 (JP, A) JP-A-2-73368 (JP, A) JP-A-6-59518 (JP, A) JP-A-1-160966 (JP, A) JP-A-4-121754 (JP, A) JP-A-5-165258 (JP, A) JP-A-4-32851 (JP, A) JP-A-6-123994 (JP, A) JP-A 8-227180 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08 CA (STN)

Claims (6)

(57) [Claims] 1. A toner for developing an electrostatic image, comprising at least a cyclic quaternary ammonium salt having an anion represented by the following general formula (I). Embedded image (However, R ¹ represents an aryl group which may have a substituent, and R ² represents any of hydrogen, an aryl group, an alkyl group, and a cycloalkyl group.) 2. The electrostatic image developing toner according to claim 1, wherein the cyclic quaternary ammonium salt is a tetrazolium salt. 3. The electrostatic image developing toner according to claim 1, wherein the cyclic quaternary ammonium salt is an imidazolium salt. 4. The electrostatic image developing toner according to claim 1, wherein the cation of the cyclic quaternary ammonium salt is represented by the following general formulas (II) to (V). Embedded image (W, X, Y and Z represent an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkyl group or hydrogen, and may be the same or different.) 5. The electrostatic image developing toner according to claim 1, wherein the cyclic quaternary ammonium salt is a polymer having an ammonium ion in a polymer chain. 6. An image forming method comprising a contact charging means in contact with the surface of a latent image holding member and / or a rotating member for transfer in contact with the surface of the latent image holding member, comprises an anion represented by the following general formula (I): An image forming method, comprising using a toner containing at least a cyclic quaternary ammonium salt having the same. Embedded image (However, R ¹ represents an aryl group which may have a substituent, and R ² represents any of hydrogen, an aryl group, an alkyl group, and a cycloalkyl group.)