JPH05289410A - Electrostatic latent image developing toner - Google Patents

Abstract

PURPOSE:To provide the toner which decreases environmental fluctuations, can maintain a triboelectrostatic charge quantity and hardly splashes the toner and with which always similar images are obtainable by incorporating aryl urea, wax and anionic resin into the toner. CONSTITUTION:The toner obtd. by the suspension polymn. of polymerizable monomers contains at least the aryl urea or the polymerized material of the urea having the aryl urea as a repeating unit, the wax and the anionic resin. The aryl urea is the compd. expressed by the formula. In the formula, Y<1> or Y<2> denotes a phenyl group, naphtyl group; R<1> or R<2> denotes hydrogen atom, an alkyl group, alkoxy group, etc., which may be the same or different; R<3> or R<4> denotes hydrogen atom or a 1 to 8C hydrocarbon group; (j), (k) are any of 1, 2, 3. The m. p. of the wax incorporated into the toner is 55 to 130 deg.C and the content of the wax is 5 to 50phr.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Conventionally, various electrophotographic methods have been described in US Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748.

The developing methods applied to these electrophotographic methods and the like are roughly classified into a dry developing method and a wet developing method. The former is further classified into a method using a two-component developer and a method using a one-component developer.

As a general method for producing these dry developing toners, a coloring agent such as a dye or a pigment and an additive such as a charge control agent are melt-mixed in a thermoplastic resin, and the resulting mixture is dispersed uniformly and then finely mixed. A method of producing a toner having a desired particle diameter by a pulverizer and a classifier is known.

In the toner obtained by the pulverization method, there is a limitation in adding a releasing material such as wax.
That is, in order to obtain a sufficient level of dispersion of the release material and to eliminate the free state, the content of the release material should be such that it is not dissolved and liquid at the kneading temperature with the resin. It is 5 parts by weight or less. Due to such restrictions, there is a limit to the fixability of the toner by the pulverization method.

On the other hand, the toner obtained by suspension polymerization (hereinafter, polymerized toner) does not have the above-mentioned restrictions, and in addition, it can contain a wax, and has good fixing property, anti-offset property, and anti-blocking property. Is obtained.

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, but in this method the toner chargeability is low, so the image obtained by development is easily fogged. , Becomes unclear. Therefore, in order to impart an appropriate triboelectric charging property to the toner, a dye, a pigment or a charge control agent which imparts the charging property is added.

Charge control agents known in the art today include metal complex salts of monoazo dyes, salicylic acid,
Known are metal complex salts of naphthoic acid and dicarboxylic acid, copper phthalocyanine pigments and the like.

[0009]

However, some of these charge control agents are liable to contaminate the sleeve or the carrier, so that the toner using them has a reduced triboelectric charge amount as the number of copies increases. Causes a decrease in image density. Further, a certain type of charge control agent has an insufficient triboelectric charge amount and is easily affected by temperature and humidity, which causes environmental fluctuation of image density. In addition, some charge control agents have poor storage stability, and their triboelectrification ability decreases during long-term storage. Further, since a certain type of charge control agent has a poor dispersibility in a resin, a toner using the charge control agent has a non-uniform triboelectric charge amount between particles and is easily fogged. Also, some charge control agents are colored and cannot be used in color toners.

In the polymerized toner, the charge control agent tends to be localized on the toner surface due to the polarity of water in the suspension process. Therefore, when the amount of addition is changed to obtain an appropriate amount of charge, the amount of charge changes greatly with a slight difference, and control is difficult.

Further, since the charge control agent is localized near the water / oil interface, it affects the particle size distribution of the toner in the suspension process, but good chargeability and a sharp particle size distribution are obtained. Conditions are limited.

An object of the present invention is to provide a toner for developing an electrostatic charge image which has a sufficient triboelectric charge amount and solves the above problems.

[0013]

The present invention provides a toner obtained by suspension polymerization of a polymerizable monomer, which comprises:
At least, the present invention relates to a toner for developing a negative electrostatic image, which contains an arylurea or a urea polymer having arylurea as a repeating unit, a wax, and an anionic resin.

The present invention also provides a toner obtained by suspension polymerization of a polymerizable monomer, which contains at least a guanidine derivative or a guanidine polymer having a guanidine derivative as a repeating unit, a wax and a cationic resin. The present invention relates to a toner for developing a positively charged electrostatic charge image, which is characterized in that

The negative charging toner and positive charging toner of the present invention will be described in detail below.

As the arylurea of the negatively chargeable toner of the present invention, the N, N'-bisarylurea derivative represented by the general formula (I) is preferable in terms of easiness of synthesis.

[0017]

[Chemical 4] (However, Y ¹ and Y ² represent a phenyl group and a naphthyl group.

R ¹ and R ² are a hydrogen atom, 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,
Sulfonic acid derivative group, carboxylic acid derivative group, cyano group,
A carbonyl group, a hydroxyl group, etc. are shown and may be the same or different.

R ³ and R ⁴ are hydrogen atoms or have 1 to 8 carbon atoms.
Shows a hydrocarbon group of.

J and k are one of 1, 2 and 3. Although it is not known to use a urea derivative as a charge control agent, an example of using a similar compound as a charge control agent is a thiourea derivative disclosed in JP-A-61-110157. The present inventors examined the triboelectrification property of the thiourea derivative and found that it had a negative triboelectrification property but was insufficient. Moreover, the thiourea derivative has a relatively small change in the charge amount due to the introduced substituent, and it is difficult to obtain a toner having a desired triboelectric charge amount by changing the type of the thiourea derivative. The present inventors have studied a charge control agent that has sufficient triboelectric chargeability and can change the triboelectric charge amount significantly by changing the kind of the substituent.
A urea derivative was found. Moreover, most of the urea derivatives are colorless, and even if they are colored, they are pale and can be regarded as substantially colorless, so they are also most suitable as charge control agents for color toners. Further, the urea derivative is thermally and mechanically stable and does not decompose by stirring in the developing device. Therefore, a clear image with less fog can always be obtained regardless of the increase in the number of times of copying.

Further, since the urea derivative does not disturb the system in the suspension step during the production of the polymerized toner, the formation of emulsion particles and the broadening of the particle size distribution do not occur. Further, the stability of the suspension process promotes the inclusion of the wax, which improves the anti-blocking property.

As described above, the present inventors have found that the toner containing the urea derivative of the present invention has excellent properties as compared with the toner containing the conventional charge control agent, and the present invention has been completed.

By using the urea derivative of the present invention and the anionic polymer in combination, the chargeability when the external additive is added and the chargeability when the external additive is not added can be brought close to each other. When the charge is imparted only by the anionic polymer, it is strongly affected by the chargeability of the external additive, and the phenomenon in which the charge amount changes when the external additive is deteriorated in a durability test or the like is likely to occur. On the contrary, unless an anionic polymer is used, the suspension process is not stable and a toner having a sharp particle size distribution cannot be obtained.

Specific examples of urea derivatives that can be used in the present invention are shown below, but these are representative examples in consideration of ease of handling and the like, and do not limit the compounds of the present invention.

[0025]

[Chemical 5] The urea derivative of the present invention can be synthesized by a usual method. For example, it can be obtained by reacting an aniline derivative and an isocyanate derivative in a benzene solvent. The parafluoro compound of Compound Example (1) was synthesized as follows.

333 g of 4-fluoroaniline and 2.5 liter of benzene were charged into a four-necked flask, and a solution of 378 g of 4-fluorophenylisocyanate and 0.5 liter of benzene was added dropwise over 40 minutes. Heat was generated during dropping, and the temperature was raised to 55 ° C. After dropping, heat as it is,
The mixture was reacted at reflux (81 ° C) for 1.5 hours. After cooling
It was filtered and washed with methanol until the filtrate was clear.
It was dried with a hot air dryer at 50 ° C. for 24 hours to obtain 805 g of an off-white powder. Compound identification is FTIR (PERKIN
-Manufactured by ELMER) and the results of infrared absorption spectrum are shown in FIG.

On the other hand, as the guanidine derivative of the positively chargeable toner of the present invention, the guanidine derivatives represented by the general formulas (II) and (III) are preferable from the viewpoint of easy synthesis.

[0028]

[Chemical 6] (However, X ¹ and X ² represent a phenyl group, a naphthyl group or a cyclohexyl group which may have a substituent and may be the same or different.

Y ³ and Y ⁴ represent a hydrogen atom, an alkyl group which may have a substituent or a phenyl group, and may be the same or different. Further, Y ³ and Y ⁴ may form a ring.

Z ¹ represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group or a naphthyl group. )

[0031]

[Chemical 7] (However, X ¹ , X ² , X ³ , and X ⁴ represent a phenyl group, a naphthyl group, or a cyclohexyl group, which may have a substituent, and may be the same or different.

Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ represent a hydrogen atom, an alkyl group which may have a substituent or a phenyl group, which may be the same or different. Further, Y ⁵ and Y ⁶ or Y ⁷ and Y ⁸ may form a ring.

Z ² represents a linking group. The guanidine derivative does not disturb the system during the suspension process during the production of the polymerized toner, so that the particle size distribution is not broadened. Further, the stability of the suspension process promotes the inclusion of the wax, which improves the anti-blocking property.

As described above, the toner containing the guanidine derivative of the present invention has excellent properties as compared with the toner containing the conventional charge control agent.

However, upon further study, the combined use of the guanidine derivative of the present invention and a cationic polymer suppresses the formation of emulsified particles in the suspension step, and when an external additive is added. The inventors have found that the chargeability when not having the chargeability can be made close to each other, and have reached the present invention. When the charge is imparted only by the cationic polymer,
The effect of the chargeability of the external additive is strongly influenced, and a phenomenon in which the charge amount changes when the external additive is deteriorated in a durability test or the like is likely to occur.

Specific examples of the guanidine derivative which can be used in the present invention are shown below, but these are representative examples in consideration of ease of handling and the like, and do not limit the compound of the present invention.

[0037]

[Chemical 8]

[0038]

[Chemical 9] As a specific synthesis example, the compound example (13) was synthesized as follows. A 214-head flask equipped with a thermometer, a condenser and a stirrer was charged with 117 g of 2,6-diisopropylaniline and 600 ml of water and stirred. Add 31.8 g of bromcian over a period of about 15 minutes to give 30 ± 5
Stirred at 1.5 ° C for 1.5 hours. Then, the temperature was gradually raised to 90 ° C. and the reaction was continued for 2 hours. After cooling, an aqueous sodium hydroxide solution adjusted to 20% was added dropwise to neutralize. The precipitated crystals were filtered, washed with toluene and water, further washed with methanol, then washed with water and dehydrated. After drying with hot air of 50 ° C. for 48 hours, it was pulverized to obtain 95.0 g of white powder. The results of infrared absorption spectrum are shown in FIG. 2 at a yield of 83.4% and an mp of 256 to 257.7 ° C.

The amount of the above-mentioned arylurea or guanidine derivative used is determined according to the kind of the polymerizable monomer, the presence or absence of additives used if necessary, and the toner production method including the dispersion method. Although it is not uniquely limited, it is preferably used in an amount 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 polymerizable monomer.

These compounds can also be used in combination with a conventionally known charge control agent.

In the present invention, a resin having a polar group is added to the polymerizable monomer system for polymerization. The polar resins that can be used in the present invention are exemplified below.

Examples of the anionic polymer include nitrile monomers such as acrylonitrile, halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and other unsaturated dibasic acids and unsaturated monomers. Saturated dibasic acid anhydride,
Examples thereof include polymers such as nitro-based monomers and copolymers with styrene-based monomers. Among these anionic resins, those having Mw / Mn by GPC of 1.2 to 10 are preferable and those having an acid value of 5 to 100 are preferable.

Examples of the cationic polymers usable in the present invention include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, or copolymers with styrene / unsaturated carboxylic acid ester and the like. Be done. Among these cationic resins, GP
It is preferable that Cw has Mw / Mn of 1.2 to 10,
The amine value is preferably 0.5 to 100.

The amount of the anionic or cationic resin added is 0.1 to 5 with respect to 100 parts by weight of the polymerizable monomer.
It is preferably 0 part by weight.

Next, the molecular weight measuring method of the present invention will be described below.

1) Sample Preparation <Standard Sample> As a standard sample, the following commercially available standard polystyrene (manufactured by Tosoh Corporation) is used. Divide 15 standard polystyrenes into 4 groups as follows:

8.42 × 10 ⁶ 7.06 × 10 ⁵
3.79 × 10 ⁴ 2.98 × 10 ³ 4.48 × 10 ⁶ 3.35 × 10 ⁵ 1.96 × 1
0 ⁴ 8.7 × 10 ² 2.89 × 10 ⁶ 1.9 × 10 ⁵ 9.1 × 10
³ 5.0 × 10 ² 1.09 × 10 ⁶ 9.64 × 10 ⁴ 5.57 × 1
Approximately 3 mg of each sample in the group is placed in a 0 ³ 30 ml sample bottle, 15 ml of THF is added, and the mixture is left at room temperature for 4 hours. Then, it is filtered using a membrane filter (0.50 μm: manufactured by Tosoh Corporation) to obtain a standard sample.

<Unknown sample> 60 mg of a sample is weighed in a sample bottle, and 15 ml of THF is further added. The extraction conditions are such that the initial 3 hours are shaken every 30 minutes and left at room temperature for 24 hours. Insoluble matter is centrifuged (5000 rpm / 20
min), and then the supernatant is filtered using a membrane filter (0.50 μm: manufactured by Tosoh Corporation) to obtain a sample.

2) 150C ALC / GPC manufactured by Waters Co. as a GPC device
Was measured under the following conditions.

1. Solvent: THF (Kishida Chemical's special grade) 2. Column: Shoredex KF-801, KF-80
2, KF-803, KF-804, KF-805, KF
-806, KF-807 7 connections (Showa Denko) 3. Temperature: 40 ° C 4. Flow rate: 1.0 ml / min 5. Injection volume: 1.0 ml 6. Detector: RI 3) GPC data processing method <calibration curve> 1. Take the chromatogram of the standard sample and read the retention time at the peak. When the peaks are divided, it is the time of the main peak.

2. Draw a calibration curve from the molecular weight of the standard sample and the retention time of the peak.

<Unknown sample> A chromatogram of an unknown sample is taken, and the molecular weight is calculated from the retention time using a calibration curve.

In the present invention, for the purpose of improving releasability at the time of heat roll fixing, waxes generally used as a releasing agent such as hydrocarbon compounds are blended in the toner. Examples of waxes used in the present invention include paraffin / polyolefin waxes and modified products thereof, such as oxides and graft-treated products, higher fatty acids, metal salts thereof, and amide waxes. The melting point of these waxes is 55 to 130 ° C., preferably 60 to 1
Those having a temperature of 00 ° C. are desirable, and when the melting point is lower than 55 ° C., the offset resistance of the toner is insufficient and the temperature is 130 ° C.
If it is higher than this, the wax solidifies in the suspension polymerization of the aqueous phase to deteriorate the granulation property.

The melting point of the wax in the present invention is measured by
Temperature rising rate 1 using DSC-7 (manufactured by Perkin Elmer)
The melting point of the wax is defined as the temperature at the apex of the peak showing the maximum endotherm in the DSC curve during the first temperature increase performed at 0 ° C./min.

The content of these waxes is 5 to 5
It is necessary to be 0 phr, preferably 10 to 40 ph
r is good. If the content is less than 5 phr, the releasability effect will be insufficient, and if it is more than 50 phr, the inclusion of the wax will be insufficient.

Examples of the polymerizable monomer that can be used in the above polymerized toner include styrene-based monomers such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene and p-ethylstyrene. , Methyl acrylate / ethyl acrylate / n-butyl acrylate /
Isobutyl acrylate, n-propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, acrylates such as phenyl acrylate, methyl methacrylate, etc. Ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate Examples thereof include methacrylic acid esters such as diethylaminoethyl methacrylate and other monomers such as acrylonitrile, methacrylonitrile and acrylamide.

These monomers may be used alone or in combination. Among the above-mentioned monomers, it is preferable to use styrene or a styrene derivative alone or in a mixture with other monomers, from the viewpoint of developing characteristics and durability of the toner.

As the polymerization initiator, any suitable polymerization initiator, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1, 1'-azobis (cyclohexane-1-
Carbonitrile), 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, azobis or diazo polymerization initiators such as azobisisobutyronitrile, benzoyl peroxide, methyl ethyl ketone peroxide,
Examples thereof include peroxide-based polymerization initiators such as diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide. These polymerization initiators are preferably added in an amount of 0.5 to 20% by weight of the polymerizable monomer.

In the present invention, a crosslinking agent may be added, and the preferable addition amount is 0.001 to 15% by weight.

The toner for developing an electrostatic image of the present invention can also be used as a magnetic toner by containing a magnetic material. Magnetic materials used include magnetite and γ-
Iron oxides such as iron oxides, ferrites, and iron-rich ferrites;
Metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium. Examples thereof include alloys with metals and mixtures thereof.

In particular, in the present invention, since the toner is obtained by the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the magnetic material. Preferably, the surface modification such as the polymerization is performed. It is better to apply a hydrophobic treatment with a substance that does not interfere. These magnetic materials have an average particle size of 0.1.
The amount contained in the magnetic toner is preferably 40 to 150 parts by weight, preferably 60 to 120 parts by weight, based on 100 parts by weight of the binder resin component. Is.

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, rhodamine lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, monoazo dyes and disazo dyes may be used alone or in combination.

In the present invention, since the toner is obtained by the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant, and preferably the surface modification, for example, the polymerization inhibitory property is not exhibited. It is better to give a hydrophobic treatment with a substance. In particular, many dyes and carbon black have a polymerization inhibitory property, so care must be taken when using them.
A preferred method of surface-treating a dye system is a method of polymerizing a polymerizable monomer in the presence of these dyes in advance, and the obtained polymerization colorant is added to the monomer system. Further, the carbon black may be subjected to the same treatment as the above-mentioned dye, or may be subjected to a graft treatment with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane.

The polymerized toner used in the present invention is obtained by the following method. That is, the release agent in the polymerizable monomer
A monomer system in which a colorant, a charge control agent, a polymerization initiator, and other additives are added, and the mixture is uniformly dissolved or dispersed by a homogenizer or an ultrasonic disperser is usually stirred in an aqueous phase containing a dispersion stabilizer. Disperse using a machine or homomixer / homogenizer. Granulation is preferably performed by adjusting the stirring speed and time so that the monomer droplets have a desired toner particle size, generally 30 μm or less. After that, the action of the dispersion stabilizer may be followed by stirring to the extent that the particle state is maintained and the particles are prevented from settling. After completion of the reaction, the dispersion stabilizer is removed, the produced toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, usually 300 parts by weight of water is added to 100 parts by weight of the monomer system.
It is preferable to use 3000 parts by weight as the dispersion medium.

In the above step, the polymerization is carried out at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C.

As the dispersant used in the present invention, a general dispersant can be used, and in some cases, a suitable stabilizer can be used in combination. For example, as an inorganic compound, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate. -Bentonite, silica, alumina, etc. may be mentioned. As organic compounds, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose,
Polyacrylic acid and its salts, starch, etc. can be used by dispersing in an aqueous phase. This dispersant is preferably used in an amount of 0.2 to 20 parts by weight based on 100 parts by weight of the polymerizable monomer. In addition, because of the fine dispersion of these dispersants, 0.0
You may use together 01-0.1 weight part of stabilizers, such as surfactant. This is to promote the desired action of the above dispersant, and specific examples thereof include sodium dodecylbenzene sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, and sodium laurate. Examples thereof include potassium stearate and calcium oleate.

As the 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, toner particles having a particle diameter of 5 μm or less are contained in an amount of 12 to 60% by number, toner particles having a particle diameter of 8 to 12.7 μm are included in an amount of 1 to 33% by number, and an amount of 16 μm is used.
It is more preferable that the toner particles having the above particle diameter are contained in an amount of 2.0% by weight or less, and the weight average particle diameter of the toner is 4 to 10 μm from the viewpoint of developing characteristics.

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 about 1% NaCl aqueous solution is prepared using first-grade sodium chloride. For example, ISOTO
N (R) -II (made by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution in an amount of 0.1 to 5 m.
1 and 2 to 20 mg of the measurement sample are 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 with 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 (D4) obtained from the volume distribution according to the present invention (the central 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 number (5 μm or less) determined from the number distribution was determined.

As the additives used in the present invention for the purpose of imparting various characteristics, the following may be used, for example.

1) Flowability-imparting agents: inorganic oxides (silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. It is more preferable that each is subjected to a hydrophobic treatment.

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, 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 controllable particles: metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black, etc.

These additives are used in an amount of 0.1 to 10 parts by weight, preferably 100 parts by weight of the toner particles.
0.1-5 parts by weight are used. These additives may be used alone or in combination of two or more.

Further, if desired, desired additives can be thoroughly mixed with a mixer such as a Henschel mixer to produce the toner according to the present invention.

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 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 toner of the present invention can be used by any conventionally known means for development for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like.

[0079]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention. still,
All parts in the following formulations are parts by weight.

Example 1 A 0.1 M Na ₃ PO ₄ aqueous solution and a 1 M CaCl ₂ aqueous solution are prepared. TK type homomixer (made by Tokushu Kika Kogyo)
Add 0.1 M Na ₃ PO ₄ to the 20 liter reaction kettle of
51 parts and 709 parts of ion-exchanged water are charged and 9500 rpm
It was stirred at. 68 parts of 1M CaCl ₂ aqueous solution at 60 ° C
The dispersion medium containing Ca ₃ (PO ₄ ) ₂ was gradually added to the above-mentioned flask which was heated above with stirring with a homomixer.

Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Blue 15: 3 10 parts Styrene-methacrylic acid-methyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, acid value = 20) 4 parts of the parafluoro compound of Compound Example (1) Among the above formulations, C.I. I. Pigment Blue 15: 3 and styrene alone were premixed. Next, all of the above formulations were heated to 60 ° C., dissolved and dispersed to obtain a monomer mixture.
Furthermore, while maintaining at 60 ° C., 10 parts of an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

The above monomer composition was added to the dispersion medium prepared in the 20-liter reaction kettle of the homomixer. 6
9500 using a homomixer in a nitrogen atmosphere at 0 ° C
It stirred at rpm for 20 minutes, and granulated the monomer composition. Then, polymerization was carried out at 60 ° C. for 10 hours while stirring with a paddle stirring blade.

After the completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) _2, and the polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured by a Coulter counter to find that the toner had a sharp particle size distribution with a weight average particle size of 8.5 μm.

When the surface of the toner was observed with an electron microscope, almost no adhesion of emulsified fine particles was observed.

BET was added to 100 parts of the obtained toner.
0.6 part of hydrophobic silica having a surface area of 180 m ² / g was externally added.

With respect to 7 parts of this toner, the average particle size is 50 μm.
m acrylic coated ferrite carrier 93
Parts were mixed to obtain a developer.

This developer was subjected to a copying test with a commercially available color electrophotographic copying machine CLC-500 (manufactured by Canon Inc.).

As a result, under the environmental condition of 23 ° C./60%, a vivid image with an image density of 1.51 was obtained from the beginning, and no deterioration was observed after copying 10,000 sheets. The charge amount measured by the blow-off method is -28 μC /
It was g.

Next, when a copying test was carried out under the environmental condition of 15 ° C./10%, a high density image of 1.47 was obtained from the initial stage. Further, even under an environmental condition of 35 ° C./85%, a good image having a density of 1.55 was obtained.

Further, good results were obtained in the blocking test at 50 ° C. for 2 days, and the low temperature fixability was also good.

Example 2 In the same manner as in Example 1, magenta toner, yellow toner and black toner were obtained. Magenta toner styrene 180 parts 2-ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Red 122 12 parts Styrene-methacrylic acid-methyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, acid value = 20) Parafluoro compound of Compound Example (1) 4 parts Weight average Diameter 8.8 μm Charge amount under the same conditions as in Example -25 μC / g Yellow toner Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Yellow 17 7 parts Styrene-methacrylic acid-methyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, acid value = 20) Parafluoro compound of Compound Example (1) 4 parts Weight average Diameter 8.3 μm Charge amount under the same conditions as in Example 1 −29 μC / g Black toner Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts Carbon black 10 parts Styrene-methacrylic acid -Methyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, acid value = 20) Parafluoro compound of compound example (1) 4 parts Weight average diameter 8.1 μm Same as in Example 1 Charge amount under conditions -27 μC / g Each of these toners has a sharp particle size distribution, and almost no emulsified fine particles are observed even when observed with an electron microscope. He was not wearing.

These toners were treated in the same manner as in Example 1,
Used as a developer.

A four-color full-color image was obtained under the same conditions as in Example 1 together with the cyan toner of Example 1, and a vivid full-color image excellent in color mixture and gradation was obtained.

Also, 35 ° C./85% and 15 ° C./10%
A copy test was carried out under the environmental conditions of No. 2 but good results were obtained as in the case of 23 ° C./60%.

Further, these toners gave good results in a blocking test at 50 ° C. for 2 days, and also had good low-temperature fixability.

Example 3 A polymerized toner having a weight average particle diameter of 8.8 μm was obtained in the same manner as in Example 1 except that the formulation of the monomer mixture was as follows.

Although the particle size distribution was affected by the magnetic substance, it was a sharp distribution, and almost no emulsified fine particles were attached.

Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 20 parts Magnetic material (titanium coupling treated product) 160 parts Styrene-methacrylic acid-methyl methacrylate copolymer 10 parts (Mw) = 40,000, Mw / Mn = 3.2, acid value = 20) 6 parts of para-trifluoromethyl compound of compound example (2) This toner was mixed with the same silica as in Example 1 at the same ratio, and a commercial copy was made. Machine (trade name NP-6650, manufactured by Canon Inc.) and applied at 23 ° C / 60% environmental conditions,
As a result of a copying test, a clear image having an image density of 1.41, no fog or roughness and a resolution of 6.3 lines / mm was obtained. Further, when 30,000 sheets were continuously copied and the durability performance was examined, a good image comparable to the initial image was obtained with an image density of 1.39 and a resolution of 6.3 lines / mm. Further, when the triboelectric charge amount of the toner on the developing sleeve was measured, it was -12.5 μC / g in the initial stage, and it was -11.6 μC / g after copying 30,000 sheets, and almost no sleeve contamination was recognized. Then, a copying test was carried out under an environmental condition of 15 ° C./10%, and similarly, an image having a high density and good image quality was obtained. Similarly good results were obtained in the continuous copying test of 30,000 sheets. When the continuous copying test was conducted similarly under the environmental condition of 35 ° C./85%, the result was good. Furthermore, under this environmental condition, the same copying test was conducted after leaving this toner for 1 month, and it was a satisfactory result with no problem.

Also, good results were obtained in a blocking test at 50 ° C. for 2 days, and the low temperature fixability was also good.

Comparative Example 1 4 g of the compound example (1) in Example 1 was replaced by 4 parts of N, N'bis (4-chlorophenyl) thiourea.
By the same method as in Example 1, a fine powder having a weight average particle diameter of 8.4 μm was obtained, and the same silica was mixed at the same ratio to obtain a toner. Further, when the surface of the toner was observed, the adherence of emulsified fine particles was higher than that in Example 1.

A commercially available color electrophotographic copying machine CLC-500 (manufactured by Canon Inc.) was used in the same manner as in Example 1 with this toner.
When a copying test was carried out under the environmental conditions of 23 ° C./60%, the image having an image density of 1.39 was obtained. However, when a continuous copying test was performed to examine durability performance,
The image density was reduced to 1.20 after 2000 sheets, and the background fog was generated, which was a problematic quality in practical use. Also, the toner scattering in the copying machine is severe, and the triboelectric charge amount at this time is -1.
It was 2 μC / g.

Example 4 A 0.1 M Na ₃ PO ₄ aqueous solution and a 1 M CaCl ₂ aqueous solution are prepared. TK type homomixer (made by Tokushu Kika Kogyo)
Add 0.1 M Na ₃ PO ₄ to the 20 liter reaction kettle of
Add 51 parts and 709 parts of ion-exchanged water and 10,000 rp
It was stirred at m. 68 parts of 1M CaCl ₂ aqueous solution was added to 60 parts.
The dispersion medium containing Ca ₃ (PO ₄ ) ₂ was gradually added to the above flask heated to 0 ° C. with stirring with a homomixer.

Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Blue 15: 3 10 parts Styrene-dimethylaminoethyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, amine value = 55) Diolto compound of Compound Example (13) 4 parts Of which, C.I. I. Pigment Blue 15: 3 and styrene alone were premixed. Next, all of the above formulations were heated to 60 ° C., dissolved and dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C, the initiator 2,2'-
10 parts of azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

The above monomer composition was added to the dispersion medium prepared in the 20-liter reaction kettle of the homomixer. 6
1000 using a homomixer in a nitrogen atmosphere at 0 ° C
It stirred at 0 rpm for 20 minutes, and granulated the monomer composition.
Then, polymerization was carried out at 60 ° C. for 10 hours while stirring with a paddle stirring blade.

After completion of the polymerization reaction, the reaction product was cooled, hydrochloric acid was added to dissolve Ca ₃ (PO ₄ ) _2, and the polymerized toner was obtained by filtering, washing with water and drying.

The particle size of the obtained toner was measured with a Coulter counter, and it was found that the toner had a weight average particle diameter of 8.5 μm and a sharp particle size distribution.

When the surface of the toner was observed with an electron microscope, the adhesion of emulsified fine particles was hardly seen.

BET was added to 100 parts of the obtained toner.
0.6 part of silica treated with a silane coupling agent having an amino group having a surface area of 170 m ² / g was externally added.

With respect to 7 parts of this toner, the average particle size is 50 μm.
m-fluorine-acrylic coated ferrite carrier 9
3 parts were mixed to obtain a developer.

The charge amount of this externally added toner was set to 23 ° C./60%.
When measured by the blow-off method under the environmental conditions of
It was 33 μC / g. On the other hand, the charge amount of the toner not externally added was +37 μC / g, and the difference in charge amount was small. This developer is a commercial color electrophotographic copying machine CLC-
A copying test was carried out by a modified machine in which the OPC photosensitive drum of 500 (manufactured by Canon Inc.) was changed to an amorphous silicon drum. As a result, a vivid image with an image density of 1.42 was obtained from the initial stage under the environmental condition of 23 ° C./60%, and no deterioration was observed after copying 10,000 sheets.

Next, when a copying test was carried out under an environmental condition of 15 ° C./10%, a high density image of 1.39 was obtained from the initial stage. Further, even under an environmental condition of 35 ° C./85%, a good image having a density of 1.49 was obtained.

Example 5 In the same manner as in Example 4, magenta toner, yellow toner and black toner were obtained. Magenta toner styrene 180 parts 2-ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Red 122 12 parts Styrene-dimethylaminoethyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, amine value = 55) Diolto compound of Compound Example (13) 4 parts Weight average diameter 8. 8 μm Charge amount under the same conditions as in Example 4 +31 μC / g Yellow toner Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts C.I. I. Pigment Yellow 17 7 parts Styrene-dimethylaminoethyl methacrylate copolymer 10 parts (Mw = 40,000, Mw / Mn = 3.2, amine value = 55) Diolto compound of Compound Example (13) 4 parts Weight average diameter 8. 3 μm Charge amount under the same conditions as in Example 4 +29 μC / g Black toner Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 60 parts Carbon black 10 parts Styrene-dimethylaminoethyl methacrylate co-weight Combined 10 parts (Mw = 40,000, Mw / Mn = 3.2, amine value = 55) Diolt compound of Compound Example (13) 4 parts Weight average diameter 8.1 μm Charge amount under the same conditions as in Example 4 + 36 μC / g These toners each have a sharp particle size distribution, and the emulsified fine particles are Tondo was not attached.

These toners were treated in the same manner as in Example 4,
Used as a developer.

A full-color image of four colors was obtained under the same conditions as in Example 4 together with the cyan toner of Example 4, and a vivid full-color image excellent in color mixture and gradation was obtained.

35 ° C./85% and 15 ° C./10%
A copy test was carried out under the environmental conditions of No. 2 but good results were obtained as in the case of 23 ° C./60%.

Example 6 A polymerized toner having a weight average particle diameter of 8.8 μm was obtained in the same manner as in Example 4 except that the formulation of the monomer mixture was as follows.

The particle size distribution was sharp although it was affected by the magnetic substance, and almost no emulsified fine particles adhered.

Styrene 180 parts 2-Ethylhexyl acrylate 20 parts Paraffin wax (mp 75 ° C.) 20 parts Magnetic material (titanium coupling treated product) 160 parts Styrene-dimethylaminoethyl methacrylate copolymer 10 parts (Mw = 3) 10,000 parts, Mw / Mn = 3.0, amine value = 50) 6 parts of diolt compound of compound example (13) This toner was mixed with the same silica as in Example 4 at the same ratio, and a commercially available copying machine (trade name NP) was used. -4835, Canon Co., Ltd., 23 ° C./60% environmental conditions,
As a result of a copying test, a clear image having an image density of 1.41, no fog or roughness and a resolution of 6.3 lines / mm was obtained. Further, when 30,000 sheets were continuously copied and the durability performance was examined, a good image comparable to the initial image was obtained with an image density of 1.39 and a resolution of 6.3 lines / mm. When the triboelectric charge amount of the toner on the developing sleeve was measured, it was +8.1 μC / g in the initial stage and +7.5 μC / g after copying 30,000 sheets, and almost no sleeve contamination was observed. Then, a copying test was carried out under an environmental condition of 15 ° C./10%, and similarly, an image having a high density and good image quality was obtained. Similarly good results were obtained in the continuous copying test of 30,000 sheets. When the same copying test and continuous copying test were conducted under the environmental conditions of 35 ° C./85%, good results were obtained. Further, under this environmental condition, the toner was allowed to stand for one month, and then the same copying test and continuous copying test were conducted, but it was a satisfactory result with no problem.

Comparative Example 2 A fine powder having a weight average particle diameter of 8.4 μm was obtained in the same manner as in Example 4 except that the styrene-dimethylaminoethyl methacrylate copolymer in Example 4 was not added to the formulation. The same silica was mixed in the same ratio to obtain a toner. Further, when the surface of the toner was observed, the adherence of emulsified fine particles was higher than that in Example 4.

This toner was applied to a commercially available electrophotographic copying machine NP-4835 (manufactured by Canon Inc.) in the same manner as in Example 4, and a copying test was carried out under an environmental condition of 15 ° C./10%. An image of 1.39 was obtained. However, when the continuous copying test was conducted to examine the durability performance, it was found to be 2000
The image density on the sheet decreased to 1.20. At this time, the triboelectric charge amount was +48 μC / g.

[0122]

As described above, the toner containing the urea derivative or guanidine derivative of the present invention as the charge control agent has a sufficient triboelectric charge amount and the triboelectric charge amount between the toner particles is uniform, and there is no fog. Gives a good image. Further, since the dependence of the image density on the temperature and humidity is small, an image of excellent quality is provided under a wide range of environmental conditions. In addition, it has good thermal stability and is less likely to change over time, resulting in excellent quality stability during storage. Further, since there is little color disorder due to the charge control agent, it can be used for color toner. In addition, the urea derivative and the guanidine derivative of the present invention greatly change in triboelectrification property depending on the kind of the substituent, and thus can be applied to various developing methods.

Further, since the polymerized toner can contain a wax containing a much larger amount of wax as compared with the pulverization method in which a wax having a low melting point can be used, good fixability, offset resistance and blocking resistance can be obtained.

Further, since the urea derivative and the guanidine derivative do not disturb the system in the suspension process during the production of the polymerized toner, the generation of emulsion particles and the broadening of the particle size distribution do not occur. Further, the stability of the suspension process promotes the inclusion of the wax, which also improves the blocking resistance.

[Brief description of drawings]

FIG. 1 is a diagram showing an infrared absorption spectrum of a urea derivative (exemplary compound (1)).

FIG. 2 is a diagram showing an infrared absorption spectrum of a guanidine derivative (Exemplary compound (13)).

Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location G03G 9/08 384

Claims (6)

[Claims] 1. A toner obtained by suspension polymerization of a polymerizable monomer, comprising at least arylurea or a urea polymer having arylurea as a repeating unit, a wax, and an anionic resin. Negatively charging toner for developing electrostatic image. 2. The toner for developing an electrostatic charge image according to claim 1, wherein the aryl urea is a compound represented by the following general formula (I). [Chemical 1] (However, Y ¹ and Y ² represent a phenyl group and a naphthyl group.
R ¹ and R ² are a hydrogen atom, 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 derivative group, a carboxylic acid Derivative groups, cyano groups, carbonyl groups, hydroxyl groups, etc. are shown and may be the same or different.
R ³ and R ⁴ represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. j and k are one of 1, 2 and 3. ) 3. The wax contained in the toner has a melting point of 55 to 130 ° C. and a wax content of 5 to 5
The toner for developing an electrostatic charge image according to claim 1, wherein the toner has an amount of 0 phr. 4. A toner obtained by suspension polymerization of a polymerizable monomer, comprising at least a guanidine derivative or a guanidine multimer having a guanidine derivative as a repeating unit, a wax and a cationic resin. Positively-charged toner for developing electrostatic images. 5. The toner for developing an electrostatic charge image according to claim 1, wherein the guanidine is a compound represented by the following general formula (II) or (III). [Chemical 2] (However, X ¹ and X ² represent a phenyl group which may have a substituent, a naphthyl group, and a cyclohexyl group, which may be the same or different. Y ³ and Y ⁴ are hydrogen atoms, It represents an alkyl group which may have a substituent or a phenyl group, which may be the same or different and may form a ring by Y ³ and Y ^4. Z ¹ is a hydrogen atom, It represents an alkyl group, a phenyl group or a naphthyl group which may have a substituent.) (However, X ¹ , X ² , X ³ and X ⁴ represent a phenyl group which may have a substituent, a naphthyl group and a cyclohexyl group, which may be the same or different. Y ⁵ , Y ⁶ and Y ⁷ ,
Y ⁸ represents a hydrogen atom, an alkyl group which may have a substituent or a phenyl group, which may be the same or different. Further, Y ⁵ and Y ⁶ or Y ⁷ and Y ⁸ may form a ring. Z ² represents a linking group. ) 6. The wax contained in the toner has a melting point of 55 to 130 ° C. and a wax content of 5 to 5.
The toner for developing an electrostatic charge image according to claim 4, wherein the toner has an amount of 0 phr.