JPH06313992A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To provide a toner for developing electrostatic charge image, with which a high image density can be obtained from the initial stage and the gradual increase in the image density and the decrease in the image density at the time of using the toner for long term duration can be prevented from occurring by adding to the toner a specific urea derivative or a urea oligomer contg. this urea derivative as the constitutional repeating unit. CONSTITUTION:The toner contains a urea derivative that is N,N'-diarylurea, of which two aryl groups have substituents of different kinds and/or in different positions and at least one of the substituents of the two aryl groups is a substituent contg. fluorine, or a urea oligomer contg. the above urea derivative as the constitutional repeating unit. Particularly, the aryl urea derivative, which is represented by the formula and of which two aryl groups have substituents of different kinds and/or in different positions, is preferred. In the formula, each of Y1 and Y2 is a phenyl or naphthyl group; R1 is a fluorine atom or a substituent contg. fluorine such as a fluoroalkyl group; each of R2 to R6 is an alkyl or alkoxyl group, etc.; each of R7 and R8 is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; (a) is a 1 to 3 integer; each of (b) to (f) is any one of integers from 0 to 3.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Toners must have a positive or negative charge, depending on the polarity of the electrostatic latent image being developed.

To retain the electric charge in the toner, it is possible to utilize the triboelectric chargeability of the resin which is a component of the toner. However, in this method, the chargeability of the toner is small, so the image obtained by development is easily fogged. , Becomes unclear. Therefore, in order to impart a desired triboelectric charging property to the toner, a dye, a pigment, or a charge control agent that imparts the charging property is added.

As charge control agents known in the art today, metal complex salts of monoazo dyes, salicylic acid, naphthoic acid, metal complex salts of dicarboxylic acids, copper phthalocyanine pigments, and acid components are used as negative triboelectric charging agents. Resins and the like containing them are known.

However, all of these charge control agents require a certain period of time until they have an appropriate charge amount. For this reason, the charge amount is likely to be insufficient when copying immediately after the copying machine is installed, when copying after being stopped for a long time, and when copying after being left in a high humidity environment. As a result, fogging occurs, and several to several tens of copies are required to obtain an appropriate image density.

When these charge control agents are applied to one-component type developers (magnetic and non-magnetic), such a slow rise of charging causes a ghost [a history of a previous image remains on a developing sleeve or the like. phenomenon. In the sleeve cycle, the same shade as in the previous image may appear (positive ghost), or the reversed shade may appear (negative ghost). ] It seems to be a cause.

In addition to this, the above charge control agents have their respective drawbacks. The metal complex salt of a monoazo dye is colored and cannot be applied to color toners.
A resin containing an acid component is difficult to obtain a sufficient image density in a high humidity environment. In addition, depending on the charge control agent, there are problems in dispersibility in the resin, storage stability, and heat stability.

An example of using a compound similar to a urea derivative as a charge control agent is the thiourea derivative described in JP-A-61-110157. However, the thiourea derivative is
It is difficult to obtain a toner having a desired charge amount.

Further, as a urea derivative, Japanese Patent Application Laid-Open No. 5-3
In Japanese Patent No. 4985, "a diphenylurea derivative having a fluorine-containing substituent symmetrically" and "a diphenylurea derivative having a non-fluorine-containing substituent on one benzene ring" are exemplified. Further, JP-A-3-308282 exemplifies "a diphenylurea derivative having a fluorine atom in one benzene ring and a methyl group in the other benzene ring". However, as a result of a more detailed study by the present inventors, "a urea derivative having symmetrical fluorine-containing substituents"
It was found that the saturated charge amount was sufficient, but the charging speed was not sufficient. Further, when "a urea derivative having a non-fluorine-containing substituent on only one side" is used for the magnetic toner, it has been clarified that neither the saturated charge amount nor the charging speed has reached a sufficiently satisfactory level. became. In addition, "having a fluorine atom on one benzene ring,
The "diphenylurea derivative having a methyl group on the other benzene ring" has a fluorine-containing substituent on only one side, but for some reason it became clear that charging started up slowly. Moreover, this urea derivative had cohesive properties and was difficult to disperse in the resin.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image capable of obtaining an image having high image density, no fog, and no ghost.

It is an object of the present invention to provide a toner for developing an electrostatic charge image which has an appropriate amount of charge very quickly.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which can obtain a high image density from the initial stage, the image density does not gradually increase, and the density does not decrease in long-term durability. .

An object of the present invention is to provide a toner for developing an electrostatic charge image, which can stably obtain a high image density even if it is left under high temperature and high humidity.

An object of the present invention is to provide a color toner having good color reproducibility by using a colorless or light color charge control agent.

[0015]

[Means and Actions for Solving the Problems]
This is achieved by the following configuration.

That is, in N, N ′ diaryl ureas having different kinds and / or positions of the substituents for both aryl groups, a urea derivative in which at least one of the substituents is a fluorine-containing substituent, or the urea derivative as a repeating unit The present invention is achieved by a toner for developing an electrostatic image, which comprises a urea multimer compound having

Among them, arylurea derivatives represented by the following general formula (I) and having different kinds and / or positions of the substituents with respect to both aryl groups are preferable from the viewpoint of easy synthesis.

[0018]

[Chemical 2]

[In the formula, Y ₁ and Y ₂ represent a phenyl group and a naphthyl group. R ₁ represents a fluorine-containing substituent such as a fluorine atom or a fluoroalkyl group. R ₂ , R ₃ , R ₄ ,
R ₅ and R ₆ are an alkyl group, an alkoxy group, a phenyl group which may have a substituent, an aralkyl group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group and a carboxylic acid group. Represents a cyano group, a carbonyl group,
They may be the same or different. R ₇ , R
₈ represents a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms. a is an integer of 1 to 3, and b, c, d, e and f
Is an integer from 0 to 3. However, the case where R ₁ is a fluorine atom and R ₄ , R ₅ and R ₆ represent one methyl group is excluded. ]

The present invention will be described in detail below.

By containing the above-mentioned arylurea derivative, an appropriate charge amount can be quickly obtained.
As a result, a high image density can be obtained from the beginning even if copying is performed immediately after the toner is put in the developing device. Even when the toner is left at high temperature and high humidity, the charge amount temporarily decreases, but the charge amount quickly returns to an appropriate value, so that a high image density can be obtained substantially immediately after restarting.

Further, although the detailed mechanism is unknown, it is considered that the good level of the ghost phenomenon is related to the quick charging. That is, in the present invention, since the charging is performed quickly, the distribution of the amount of charging becomes sharp. It is considered that since the sleeve, which is the toner carrier, is occupied by the toner having an appropriate charge, less toner remains on the sleeve without being developed and ghost is reduced. Further, it is considered that a cause of the ghost is that toner strongly adheres to the surface of the sleeve due to a mirroring force or the like. In other words, the toner of the present invention charges quickly, which means that the toner reaches saturation quickly, and it is considered that the saturation value of the charge amount is not too large. That is, by sufficiently utilizing the charging potential, the toner having a too high charge amount is not generated, and the toner strongly adhered to the sleeve is hardly generated. This is also considered as a mechanism for reducing ghosts.

The fluorine-containing substituent in the above urea derivative is effective in both saturated charge amount and charge speed. In particular, the effect of increasing the charging speed is remarkable, but it has been clarified that the effect of improving the speed cannot be obtained unless the substituent is introduced asymmetrically.

Specific examples of the charge control agent of the present invention represented by the general formula (I) will be shown below, but these are also examples in consideration of easiness of synthesis and the like, which limit the present invention at all. is not.

[0025]

[Chemical 3]

[0026]

[Chemical 4]

In the present invention, a magnetic material may be contained to be used as a magnetic toner. In addition, a high charge amount can be obtained by using magnetic fine powder having a particle size variation coefficient of 30% or less. More preferably, the coefficient of variation is 25% or less.

Although this mechanism is not clear, it is considered as follows. When the particle size distribution is broad, the magnetic fine powder having a large particle size is exposed on the toner surface, and the ratio of the charge control agent to the surface area is reduced. As a result, it seems that the charge control agent cannot come into contact with the charge imparting member such as metal, and the charge amount does not increase. On the contrary, since the magnetic fine powder having an excessively small particle size has a strong cohesive property, it may have the same function as one lump. On the other hand, by using the magnetic fine powder having a sharp particle size distribution with a variation coefficient of 30% or less, the exposed state of the magnetic fine powder on the toner surface becomes uniform, and even if the magnetic fine powder is sufficiently contained, charging is not performed. Hard to block.

The average particle size of the magnetic fine powder is 0.05.
.About.0.5 .mu.m is preferable, and more preferably 0.1 to 0.
4 μm is good. The amount contained in the magnetic toner is preferably 40 to 120 parts by weight with respect to 100 parts by weight of the resin component.

Examples of the magnetic material used in the present invention include iron oxides such as magnetite, γ-iron oxide, ferrite and iron-excessive ferrite; metals such as iron, cobalt and nickel; or metals such as these and aluminum and cobalt;
Examples thereof include alloys with metals such as copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

In the present invention, it is one of the preferable modes to include a wax component in the toner. When present on the toner surface, the wax component reduces the proportion of the charge control agent occupying the surface area, like the magnetic fine powder, and thus has the function of suppressing charging.

Therefore, in order to obtain a sufficient charge amount, it is desirable to reduce the wax content as much as possible. In the present invention, the Mw / Mn of the wax is 3.0 or less, more preferably 2.
By setting it to 0 or less, the wax content can be suppressed without deteriorating the effect of the wax, and as a result, the charge amount can be maintained at a high level.

Further, the action of the wax occurs only when the temperature is such that it passes through the fixing roller, and it is harder than the conventional wax at room temperature, so that the developability is improved. Further, the proportion of wax in the toner surface area does not increase, which is preferable for charging the toner.

The hydrocarbon wax used in the present invention is obtained by, for example, thermally decomposing an alkylene polymer obtained by radically polymerizing alkylene under high pressure, an alkylene polymer polymerized by a Ziegler catalyst under low pressure, and a high molecular weight alkylene polymer. It is possible to use a synthetic hydrocarbon obtained by hydrogenating a distillation residue of a hydrocarbon obtained by the Arge process from a synthetic gas consisting of an alkylene polymer, carbon monoxide, and hydrogen. Of these hydrocarbon waxes,
A hydrocarbon wax obtained by extracting and fractionating specific components is particularly suitable. Those having a low molecular weight removed by a method such as a press perspiration method, a solvent method, and a fractional crystallization method utilizing vacuum distillation, those having a low molecular weight extracted, and those having a low molecular weight component removed therefrom are preferable.

In addition to this, microcrystalline wax,
Carnauba wax, Sazol wax, paraffin wax and the like can also be used.

The preferable range of the molecular weight of these waxes is that the number average molecular weight (Mn) is 500 to 1200.
It is preferable that the weight average molecular weight (Mw) is 800 to 3600. If the molecular weight is smaller than the above range, blocking resistance and developability will be poor, and if the molecular weight is larger than the above range, good fixability and offset resistance will be difficult to obtain.

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 type of the binder resin used in the present invention is, for example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, or a substitution product thereof; styrene-p-chlorostyrene copolymerization. Coal, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester 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-based copolymers such as indene copolymers Combined; polyvinyl chloride, phenol resin, natural modified phenol 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, coumarone indene resin, petroleum resin and the like can be used.

A crosslinked styrene copolymer is also a preferable binder resin.

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

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

When the binder resin is styrene-acrylic,
The toner molecular weight distribution is THF (tetrahydrofuran)
In the molecular weight distribution by GPC (gel permeation chromatogram) of the soluble component, at least one peak exists in the region of molecular weight of 3,000 to 50,000, and at least one peak exists in the region of molecular weight of 100,000 or more. A binder resin is preferable in which the component having a distribution of 100,000 or less becomes 50 to 90%. With such a molecular weight distribution, the charge control agent can be well dispersed, and good fixability and offset resistance can be obtained.

As the colorant used in the present invention, carbon black, lamp black, iron black, ultramarine blue, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow G, rhodamine 6
Conventionally known dyes and pigments such as G, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, monoazo dyes and disazo dyes may be used alone or in combination.

As the magnetic toner using the charge control agent of the present invention, a toner having a weight average particle diameter of 3 to 15 μm can be used. In particular, 12 to 60% by number of magnetic toner particles having a particle size of 5 μm or less are contained, and 8 to 12.7 μm.
The magnetic toner particles having a particle diameter of 1 to 33% by number are contained, and the magnetic toner particles having a particle diameter of 16 μm or more are 2.
The content of the magnetic toner is 0% by weight or less, and the weight average particle diameter of the magnetic toner is 4
From the standpoint of development characteristics, it is more preferably 10 μm.

Further, the toner of the present invention can be mixed with a carrier and used as a two-component toner. As the carrier that can be used in the present invention, known carriers can be used, for example, iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, and the like, and the surface thereof is treated with a resin or the like. What you have done is listed. Further, as the resin for coating the carrier surface, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, acrylic acid ester copolymer, methacrylic acid ester 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.

The following additives are used as the additives used in the present invention for the purpose of imparting various characteristics.

1) Flowability-imparting agent: metal oxide (silica,
Alumina, titania, etc.), carbon black, carbon fluoride, etc. Those that have been subjected to hydrophobic treatment
More preferable.

2) Abrasive: metal oxide (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitride (silicon nitride, etc.), carbide (silicon carbide, etc.), metal salt (calcium sulfate, etc.) , Barium sulfate, calcium carbonate), etc.

3) Lubricants: Fluorine-based resin powders (vinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), etc.

4) Charge control particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, spherical resin fine particles (average particle size 0.05 to 3 μm), etc.

These additives are used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner particles. These additives are
They may be used alone or in combination.

Among the above additives, metal oxides for the purpose of imparting fluidity will be described. In the present invention, it is preferable to externally add fine powder of silica, alumina, or titania treated with a silane coupling agent and / or silicone oil in order to obtain appropriate negative charging property and good developability. .

In addition to anhydrous silicon dioxide (silica), silicates such as aluminum silicate, sodium silicate, potassium silicate, magnesium silicate and zinc silicate can be used as the base fine silica powder to be treated. Applicable. In addition, either a dry method or a wet method can be used.

As the silane coupling agent used in the present invention, conventionally known ones can be used.

For example, dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane,
Benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane and the like can be used.

Further, it is also one of the preferable constitutions to use two kinds of treatment agents, namely, silicone oil (A) and silane coupling agent (B). These two types may be mixed in advance and treated at the same time, or may be treated with the treatment agent (B) and then the treatment agent (A) in this order. It is not preferable to treat the treating agent (B).

When previously treated with silicone oil, the fine silica powder agglomerates, and the treated silica particles are less likely to be fine, which may lower the toner utilization rate.

Further, as the metal oxide fine powder used in the present invention, fine powders of titania and alumina are also preferable, and these may be used in combination including silica and powder.

As the fine powder of titania and alumina as fine powder of metal oxide, fine powder is easily disentangled and less "damage" is obtained. By using such a titania fine powder in the present invention, the toner utilization rate is improved.

Among the above metal oxide fine powders, those having a specific surface area of 40 m ² / g or more (particularly 50 to 400 m ² / g) by nitrogen adsorption measured by the BET method are preferable as the base fine powder, As treated fine powder, 30
m ² / g or more (especially 70~350m ² / g) within the scope of preferred. The applied amount of these fine metal oxide powders shows excellent fluidity and stable chargeability when 0.03 to 5% of the developer weight is added.

Finally, when the degree of hydrophobicity of the fine metal oxide powder is hydrophobized so as to show a value of 30 or more as the degree of hydrophobicity measured by the methanol titration test, the triboelectric charge amount of the toner is It is preferable because it shows a sharp and uniform positive charging property.

In the production of the toner according to the present invention, the toner constituent materials as described above are thoroughly mixed by a ball mill or other mixer, and then well kneaded by using a heat kneader such as a hot roll kneader or an extruder. After cooling and solidification, a method of obtaining a toner by mechanical pulverization and classification is preferable. Alternatively, a method of obtaining a toner by dispersing constituent materials in a binder resin solution and then spray-drying; or a binder resin Polymerization toner production method in which a predetermined material is mixed with a monomer to be constituted to form an emulsion suspension, and then the toner is polymerized; or a so-called microcapsule toner including a core material and a shell material Alternatively, a method of incorporating a predetermined material into the shell material or both of them, and the like can be applied. Further, if necessary, desired additives can be sufficiently mixed with a mixer such as a Henschel mixer to produce the toner according to the present invention.

The measuring methods for each characteristic value used in the present invention will be described below.

In the present invention, the coefficient of variation of the particle size of the magnetic fine powder is measured as follows. Disperse the magnetic fine particles well so that the overlap between them will be as small as possible, and take several 30,000 times transmission electron micrographs without any bias.
From this, 1,000 or more magnetic fine powders are randomly selected, and the horizontal Feret diameter is measured. The coefficient of variation is the ratio of the standard deviation to the average diameter expressed in%.

The particle size distribution of the toner can be measured by various methods, but in the present invention, it is suitable to use a Coulter counter.

That is, a Coulter counter TA-II type (manufactured by Coulter) is used as a measuring device, and an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) are connected. As the electrolytic solution, an approximately 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISOTO
N-II (manufactured by Coulter Scientific Japan) can be used. As the measuring method, the electrolytic aqueous solution 10
A surfactant, preferably 0.1 to 5 ml of alkylbenzene sulfonate is added as a dispersant to 0 to 150 ml, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the volume and number of toners were measured by the Coulter Counter TA-II type using a 100 μm aperture as an aperture. The volume distribution and number distribution of particles of 2 to 40 μm were calculated. Then, the weight-based weight average diameter (D ₄ ) obtained from the volume distribution according to the present invention (the median value of each channel is a representative value for each channel), and the weight-based coarse powder amount obtained from the volume distribution (16 μm or more), and the number-based fine powder ratio (5 μm or less) determined from the number distribution was determined.

In the present invention, the molecular weight distribution by GPC of the THF soluble component of the toner is measured under the following conditions. 40
The column is stabilized in a heat chamber at 0 ° C., THF as a solvent is caused to flow at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected into the column at this temperature for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from a calibration curve (relationship between the logarithmic value of the molecular weight and the count number) prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a standard polystyrene sample having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh or Showa Denko is used, and it is suitable to use a standard polystyrene sample of at least about 10 points. . 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, for example, Shodex GPC KF-801, 802, 80 manufactured by Showa Denko KK
Combination of 3,804,805,806,807,800P and TSKgel G1000H manufactured by Tosoh Corporation
(H _XL ), G2000H (H _XL ), G3000H
(H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ), the combination of TSKguardcolumn can be mentioned. The sample is prepared as follows.

The sample is placed in THF, left to stand for several hours, shaken well and mixed well with THF (until the coalescence of the sample disappears), and then allowed to stand for 12 hours or more. TH at this time
The time for leaving in F should be 24 hours or more. Sample processing filter (pore size 0.45-0.45)
0.5 μm, for example, Mysholydisc H-25-5
A GPC sample is one that has passed through (ex. Tosoh Corp., Excicrodisc 25CR Gelman Science Japan Ltd., etc.). The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

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

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

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

The "methanol titration test" defined in this specification for evaluating the degree of hydrophobicity of fine metal oxide powders is carried out as follows. 0.2 g of the test metal oxide fine powder is added to 50 ml of water in an Erlenmeyer flask having a volume of 250 ml. Methanol is titrated from the burette until the total amount of fine metal oxide powder is wet. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by suspending the total amount of fine metal oxide powder in the liquid and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

[0073]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.
All parts in the following formulations are parts by weight.

Example 1 Styrene / n-butyl methacrylate 100 parts Magnetite 80 parts (average particle size 0.17 μm, coefficient of variation 16%) Low molecular weight polypropylene wax 3 parts (Mn = 780, Mw = 1280, Mw / Mn = 1) .64) Para body of Compound Example (1) 4 parts

After thoroughly mixing the above materials with a blender,
The mixture was kneaded with a twin-screw kneading extruder set at 130 ° C. After cooling the obtained kneaded product, after roughly crushing with a cutter mill,
Finely pulverize using a fine pulverizer with a jet stream, and finely pulverize the resulting fine powder simultaneously with a multi-division classifier (Elbow Jet classifier manufactured by Nittetsu Mining Co., Ltd.) that utilizes the Coanda effect. Weight average particle size 8.3 μm after classification and removal
A black fine powder of

0.6 parts of silica fine powder treated with hexamethyldisilazane and 100 parts of the black fine powder were mixed by a Henschel mixer to obtain a negatively chargeable one-component magnetic toner.

About the above magnetic toner, using a commercially available electrophotographic copying machine NP-6060 (manufactured by Canon Inc.), 23
A copying test was performed on 10,000 sheets in an environment of ° C / 60% RH. As a result, the image density exceeds 1.30 at the 50th copy from the start of copying, and then the image density is 1.35 ± 0.02.
, And a clear image without fog was obtained. The image after copying 10,000 sheets was also clear with a density of 1.36. When the charge amount on the sleeve was measured after copying 10,000 sheets, it was -12.5 μC / g.

Next, when a ghost image was tested in an environment of 20 ° C./10% RH, a weak ghost was seen only for one round of the sleeve, and was at a very good level. The image density was 1.40. Furthermore, 30
Even in an environment of ° C / 80% RH, a good image with an image density of 1.35 was obtained.

Example 2 A one-component magnetic toner was obtained in the same manner as in Example 1, except that the para-form of Compound Example (2) was used instead of Compound Example (1).

With respect to this magnetic toner, as in Example 1, a copying test was performed on 10,000 sheets in an environment of 23 ° C./60% RH. As a result, the image density exceeded 1.30 at the 60th sheet from the start of copying, and then a clear image without fog was obtained. The image after copying 10,000 sheets was also clear with a density of 1.35. When the charge amount on the sleeve was measured after copying 10,000 sheets, it was found to be -12.2 μC / g.

Next, when a ghost image test was carried out in an environment of 20 ° C./10% RH, a weak ghost was seen only for two rounds of the sleeve, and was at a very good level. The image density was 1.42. Furthermore, 30
Even in the environment of ° C / 80% RH, a good image with an image density of 1.33 was obtained.

Comparative Example 1 The procedure of Example 1 was repeated except that 4 parts of the compound example (1) was replaced with 4 parts of the compound represented by the following structural formula (II).
A component magnetic toner was obtained.

[0083]

[Chemical 5]

As with Example 1, this magnetic toner was subjected to a copying test on 10,000 sheets in an environment of 23 ° C./60% RH. As a result, it was necessary to make 200 copies from the start of copying even though the image density exceeded 1.30. After that, a clear image having an image density of 1.40 was obtained. In addition,
When the charge amount on the sleeve was measured after copying 10,000 sheets,
It was -15.2 μC / g.

Next, when a ghost image was tested in an environment of 20 ° C./10% RH, ghosts were seen for 5 rounds of the sleeve.

Comparative Example 2 A one-component magnetic toner was obtained in the same manner as in Example 1 except that 4 parts of the compound example (1) was replaced by 4 parts of the compound represented by the following structural formula (III).

[0087]

[Chemical 6]

With respect to this magnetic toner, a copying test of 10,000 sheets was carried out in the environment of 23 ° C./60% RH as in the case of Example 1. As a result, it was necessary to make 250 copies from the start of copying even if the image density exceeded 1.30. After that, a clear image having an image density of 1.30 was obtained. In addition,
When the charge amount on the sleeve was measured after copying 10,000 sheets,
It was -7.2 μC / g.

Next, when a ghost image was tested in an environment of 20 ° C./10% RH, the ghost was seen for 5 rounds of the sleeve.

Example 3 Styrene / n-butyl methacrylate 100 parts Magnetite 100 parts (average particle size 0.20 μm, coefficient of variation 20%) Low molecular weight polypropylene wax 3 parts (Mn = 910, Mw = 1410, Mw / Mn = 1) .55) Para body of Compound Example (3) 4 parts

Using the above materials, a resin fine powder having a weight average diameter of 6.8 μm was obtained in the same manner as in Example 1. To 100 parts of the resin fine powder obtained, 1.0 part of silica fine powder treated with methyl silicone oil and hexamethyldisilazane was mixed to obtain a toner.

Using this toner, a commercially available laser beam printer LBP-8II (manufactured by Canon Inc.) was modified, and a copying test of 3,000 sheets was carried out in an environment of 23 ° C./60% RH. As a result, the image density exceeds 1.40 at the first copy start, and then the image density is 1.40 ± 0.02.
, And a clear image without fog was obtained. The image after copying 3,000 sheets was also clear with a density of 1.36. When the amount of charge on the sleeve was measured after copying 3,000 sheets, it was -28 μC / g.

Next, when a ghost image test was carried out in an environment of 20 ° C./10% RH, a weak ghost was seen only for one round of the sleeve, and was at a very good level. The image density was 1.45. Furthermore, 30
Even in the environment of ° C / 80% RH, a good image with an image density of 1.41 was obtained.

Example 4 Polyester 100 parts Carbon black 5 parts Meta example of compound example (4) 4 parts

Using the above materials, a resin fine powder having a weight average diameter of 7.8 μm was obtained in the same manner as in Example 1. The set temperature of the biaxial kneader was 110 ° C. To 100 parts of the obtained resin fine powder, 0.5 part of the silica fine powder used in Example 1 and 0.2 part of the alumina fine powder were mixed to obtain a toner.

Next, 95 parts of an acrylic-coated ferrite carrier having an average particle size of 50 μm and 5 parts of the obtained toner were mixed to prepare a developer.

About this developer, a commercially available color electrophotographic copying machine CLC-500 (manufactured by Canon Inc.) was used.
A copying test was performed on 10,000 sheets in an environment of ° C / 60% RH.

As a result, a bright black image having an image density of 1.40 was obtained from the initial stage, and the deterioration of the image quality of 10,000 sheets was not recognized.

Next, when a copy test was performed in an environment of 15 ° C./10% RH, a clear image with a density of 1.38 was obtained, and even if an image with a large amount of toner consumption and an image with a small amount of toner were repeated every tens of sheets. There was almost no change in image density. Furthermore, even under the environment of 30 ° C./80% RH, the concentration is 1.
46 good images were obtained.

Example 5 A cyan toner (7.7 μm), a magenta toner (7.5 μm) and a yellow toner (7.6 μm) were obtained in the same manner as in Example 4 except that the colorants were changed as follows. It was

Cyan Toner: C.I. I. Pigment Blue 15:35 5 parts Magenta Toner: C.I. I. Pigment Red 122 5 parts Yellow toner: C.I. I. Pigment Yellow 17 3rd part

These toners were used together with the black toner of Example 4 to obtain full color. As a result, a clear full-color image excellent in color reproducibility and gradation was obtained.

[0103]

According to the present invention, an appropriate charge amount can be obtained very quickly, a high image density can be obtained from the initial stage, and a stable and clear image can be obtained even at high temperature and high humidity or long-term durability. Further, since the charge control agent according to the present invention is colorless or light-colored, it is suitable for color toner.

Claims (2)

[Claims] 1. An N, N ′ diarylurea having different kinds and / or positions of substituents for both aryl groups, wherein at least one of the substituents is a fluorine-containing substituent, or the urea derivative is used as a repeating unit. A toner for developing an electrostatic charge image, which comprises a urea multimerized product. 2. An electrostatic charge image developing toner containing a compound represented by the following general formula (I), characterized in that the type and / or position of the substituents on both aryl groups of the compound are different. Toner for image development. [Chemical 1] [In the formula, Y ₁ and Y ₂ represent a phenyl group and a naphthyl group. R ₁ represents a fluorine-containing substituent such as a fluorine atom or a fluoroalkyl group. R ₂ , R ₃ , R ₄ , R ₅ and R
₆ is an alkyl group, an alkoxy group, a phenyl group which may have a substituent, an aralkyl group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group, a carboxylic acid group, a cyano group, It represents a carbonyl group and may be the same or different. R ₇ and R ₈ represent a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms. a is
Is an integer of 1 to 3, b, c, d, e and f are 0 to 3
Is an integer. However, the case where R ₁ is a fluorine atom and R ₄ , R ₅ and R ₆ represent one methyl group is excluded. ]