JPH08184996A - Positively chargeable toner for electrostatic image development - Google Patents

Abstract

(57) [Abstract] [Purpose] To provide a positively chargeable toner for developing an electrostatic charge image, which has a quick charge rise, has a sufficient charge amount, and can obtain a bright chromatic image for a long period of time. is there. [Structure] A positively chargeable toner for developing an electrostatic charge image, comprising a compound represented by the following general formula (I). Embedded image (Wherein, R ₁ and R ₂ independently of one another are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group. In addition R ₁
And R ₂ may combine with each other to form an aromatic condensed ring. Ar ₁ represents an optionally substituted phenyl group, cyclohexyl group, or polycyclic aromatic group. Also, n
Indicates 0 or 1. )

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel positively chargeable toner for developing an electrostatic image in electrophotography, electrostatic recording, electrostatic printing and the like.

[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. They essentially provide a uniform electrostatic charge on the photoconductive insulator layer and form an electrostatic latent image by irradiating the insulator layer with a light image, which is then referred to in the art as toner. After developing with fine powder and transferring the powder image to paper or the like as required, fixing is performed by heating, pressurizing or solvent vapor.

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

Among the two-component developing methods, there are a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using a fur, etc., depending on the type of carrier that carries the toner.

Further, the one-component developing method includes a powder cloud method in which toner particles are sprayed and a contact developing method (contact method in which toner particles are directly brought into contact with an electrostatic latent image surface for development). (Also referred to as development or toner development), without directly contacting the toner particles with the electrostatic latent image surface,
There are a jumping developing method in which toner particles are charged and fly toward the latent image surface by the electric field of the electrostatic latent image, a magnetic dry method in which a magnetic conductive toner is brought into contact with the electrostatic latent image surface to develop the toner. .

As the toner applied to these developing methods, a fine powder in which a dye, a pigment or the like is dispersed in a natural or synthetic resin is conventionally used. For example, 1 to 3 in which a colorant is dispersed in a binder resin such as polystyrene is used.
Particles finely pulverized to about 0 μm are used as a toner. Further, those containing magnetic particles such as magnetite are used as magnetic toners.

These toners have a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

To retain the electric charge in the toner, it is possible to utilize the triboelectric charging property of the resin which is a component of the toner. However, in this method, the charging property of the toner is small, so the image obtained by development is easily fogged. , Becomes unclear. Therefore, in order to impart desired triboelectrification properties to the toner, dyes and pigments imparting the electrification property, and further a charge control agent are added.

The positive charge control agents known in the art today include the following:

Nigrosine, an azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 42-1627),
Benzylmethyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride and other quaternary ammonium salts, dibutyltin oxide and other organotin compounds, higher fatty acid metal salts, EDTA, acetylacetone metal complexes, etc. Polyamine resin such as polymer.

[0011]

These charge control agents are usually added to a thermoplastic resin, thermally melt-dispersed and finely pulverized to prepare an appropriate particle size as required and used.

However, many of these charge control agents have a complicated structure and are not uniform, and have poor stability. In addition, due to decomposition during thermal kneading, mechanical shock, friction, changes in temperature and humidity conditions, etc., decomposition or deterioration is likely to occur, and a phenomenon in which charge controllability is deteriorated is likely to occur.

Therefore, when the toner containing these charge control agents is developed in a copying machine, the charge control agents may be decomposed or deteriorated as the number of copying increases, and the toner may be deteriorated during durability.

Further, since it is extremely difficult to uniformly disperse these charge control agents in the thermoplastic resin, it is fatal that the toner particles obtained by crushing produce a difference in triboelectric charge amount. It has a defect. Therefore, conventionally,
Various methods have been used to achieve more uniform dispersion. For example, a nigrosine dye is used by forming a salt with a higher fatty acid in order to improve the compatibility of a thermoplastic resin,
Often, unreacted fatty acid or salt dispersion product is exposed on the toner surface and contaminates the carrier or the toner carrier, causing the fluidity of the toner, fogging, and reduction in image density. Alternatively, in order to improve the dispersibility of these charge control agents, a method of mechanically pulverizing and mixing the charge control agent powder and the resin powder in advance and then hot-melt kneading is also adopted. However, the original poor dispersibility cannot be avoided, and in the present situation, practically sufficient charging uniformity is not obtained.

Many charge control agents are hydrophilic, and due to poor dispersion in these resins, the charge control agents are exposed to the toner surface when pulverized after melt-kneading, and the charge control agents are exposed under high temperature conditions. Since the charge control agent is hydrophilic, it has a drawback that a high quality image cannot be obtained.

Further, most of the conventionally known positive charge control agents are colored and therefore unsuitable for color toners other than black.

In addition to these, various compounds have been proposed, but none of them have been found to be practically usable because of insufficient charge control effect.

An object of the present invention is to provide a new technique for controlling the charge of positively chargeable toner which overcomes the above drawbacks.

That is, an object of the present invention is to provide a positively chargeable toner which has a sufficient amount of charge, has a fast rise, and has a small change with time of charge and is stable.

Another object of the present invention is to provide a positively chargeable toner which is resistant to changes in temperature and humidity and can withstand long-term storage.

Another object of the present invention is to provide a positively chargeable toner having a bright chromatic color.

Still another object of the present invention is to provide a positively chargeable toner which is excellent in storage stability and maintains desired characteristics even after long-term storage.

[0023]

[Means and Actions for Solving the Problems] In recent years, demands for "higher image quality" and "higher speed" for copying machines have become strict, but at that time, the developer should be "charged quickly". That is, excellent charge rising property is required. However, if the charge rises only quickly, it is difficult to obtain a clear copy image due to toner scattering during paper passing and fog in the copy image.
In addition, it is difficult to obtain a stable image density in a high temperature and high humidity environment.

To solve this problem, JP-A-61-2170
In Japanese Patent Laid-Open No. 55-55, 2-aminobenzimidazole is disclosed as a charge control agent, and it is described that it has excellent thermal / temporal stability and charge stability. However, as will be described below in Examples of the present invention, it is still insufficient to simultaneously satisfy the object of the present invention to "charge quickly" and to have a sufficient amount of charge and maintain charge stability at the same time. there were. On the other hand, in JP-A-5-107814, 2-alkylbenzimidazole is disclosed as a charge control agent, and it is described in Examples that it has a high charge amount and has charge stability. However, as will be specifically described below in Examples of the present invention, if the developer is left for a long time under high temperature and high humidity, the chargeability of the developer is lowered. Further, US Pat. No. 5,102,765 discloses 1-methyl-2-phenylbenzimidazole, but such a compound was still insufficient to satisfy "especially rapid charging".

The inventors of the present invention have conducted various tests and researches in view of such circumstances, and as a result, a novel charge control agent is represented by the following general formula (I) in which the substituent on the nitrogen atom is active hydrogen. It was found that a desired positively chargeable toner for developing an electrostatic image can be obtained by using the compound.

[0026]

Embedded image

(In the formula, R ₁ and R ₂ independently of each other represent a hydrogen atom, an alkyl group, an alkoxy group or an aryl group. Further, R ₁ and R ₂ may be bonded to each other to form an aromatic condensed ring. Ar ₁ represents an optionally substituted phenyl group, cyclohexyl group, or polycyclic aromatic group, and n represents 0 or 1.)

In the general formula (I), it is preferable that at least _one of R ₁ and R ₂ is an alkyl group as it gives a particularly high positive charging property. Specific examples of such an alkyl group include a methyl group, an ethyl group, an i-propyl group and a t-butyl group.

It is generally known that the introduction of an alkyl group increases the positive triboelectrification property, but the effect of the alkyl group in the general formula (I) of the present invention is greater than expected. The reason for this is not necessarily clear, but the introduction of an alkyl group may lower the melting point, which may have modified the dispersion state of the compound represented by the general formula (I) of the present invention in the binder resin. .

Thus, the use of the compound represented by the above general formula (I) having an alkyl group on the benzimidazole ring sufficiently satisfies the intended purpose, but the initial stage even after standing for a long time under high temperature and high humidity. From the viewpoint of satisfying that a clear image without toner scattering can be stabilized, Ar ₁ in the above general formula (I) is preferably a phenyl group substituted with an amino group. Specific examples of the amino group here include a monoalkylamino group, a dialkylamino group,
Examples thereof include a monoarylamino group and a diarylamino group.

The reason why a sharp image can be stably obtained immediately after being left under high temperature and high humidity for a long time by using a phenyl group substituted with an amino group is a phenyl group substituted with an amino group. It is considered that the introduction of the compound further improved the charge imparting property and further increased the charging speed extremely.

The compound represented by the above general formula (I) used in the present invention is generally dehydrated by heating the corresponding o-phenylenediamine compound and carboxylic acid in the absence of solvent or in dilute sulfuric acid or polyphosphoric acid. Is synthesized by performing.

Typical examples of the compounds represented by the general formula (I) are shown below, but the compounds of the present invention are not limited to these.

[0034]

Embedded image

[0035]

[Chemical 4]

[0036]

Embedded image

[0037]

[Chemical 6]

As a method of incorporating the charge control agent according to the present invention into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. If the blending amount of these is too small, a sufficient charge amount is obtained. If it is not obtained and the amount is too large, the charge control effect becomes unstable. When externally added, the amount is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin, and particularly preferably mechanochemically fixed to the surface of the toner particles. The charge control agent of the present invention may be used in combination with a conventionally used positive charge control agent such as a nigrosine dye, a quaternary ammonium salt or a metal salt of a higher fatty acid.

Examples of the binder resin used in the toner using the charge control agent of the present invention include homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and their substitution products; styrene- p-chlorostyrene copolymer, styrene-vinyltoluene copolymer,
Styrene-vinyl naphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene-based copolymers such as copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers Combined; polyvinyl chloride, phenolic resin, natural modified phenolic resin,
Natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum-based Resin etc. can be used.

A crosslinked styrene copolymer is also a preferred binder resin.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate,
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 ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, etc .; These vinyl monomers 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, aromatic divinyl compounds 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.

In particular, in the molecular weight distribution measured by GPC, a styrenic resin having at least one peak in the region of 3 × 10 ^{3 to} 5 × 10 ⁴ and at least one peak or shoulder in the region of 10 ⁵ or more. Copolymers are preferred. As a result, the dispersibility of the charge control agent in the binder resin is improved, and as a result, the distribution of the charge amount is considered to be extremely sharp. Therefore, it is possible to obtain a toner having a particularly rapid rise in charge, which is the object of the present invention. Is.

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

The column was stabilized in a heat chamber at 40 ° C., and tetrahydrofuran (THF) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to obtain T
The measurement is performed by injecting 100 μl of the sample solution dissolved in HF. In measuring the molecular weight of a sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 manufactured by Tosoh or Showa Denko is used.
^It is suitable to use a standard polystyrene sample of at least about 10 points, using a sample of ² to 10 ⁷ . 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 G manufactured by Showa Denko KK
PC KF-801, 802, 803, 804, 80
5,806,807,800P combination, TSKgel G1000H (H _XL ), G200 manufactured by Tosoh Corporation
0H (H _XL ), G3000H (H _XL ), G4000H
(H _XL ), G5000H (H _XL ), G6000H
(H _XL ), G7000H (H _XL ), TSKguard
A combination of columns can be mentioned.

The sample is prepared as follows.

The sample was placed in THF, left for several hours, and shaken well until the samples did not coalesce with THF.
Mix well and leave still for 12 hours or more. This time,
The time of standing in THF should be 24 hours or more. Then sample processing filter (pore size 0.4
5 to 0.5 μm, for example, Mysholydisk H-25
-5 Tosoh Corp. Liquid Chrodisc 25CR Gelman
A sample of GPC is used as a sample of GPC. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

When the pressure-fixing system is used, a binder resin for pressure-fixing toner can be used. Examples thereof include polyethylene, polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acrylate copolymer, ethylene-acetic acid. Examples thereof include vinyl copolymers, ionomer resins, styrene-butadiene copolymers, styrene-isoprene copolymers, linear saturated polyesters and paraffins. Furthermore, polyolefin (low molecular weight polyethylene,
Low molecular weight polypropylene, polyethylene oxide, polytetrafluoroethylene, etc.), epoxy resin, polyester resin,
Styrene-butadiene copolymer (monomer ratio, 5-3
0: 95-70), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride Examples thereof include copolymers, ethylene-vinyl acetate copolymers, ionomer resins), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymers, maleic acid-modified phenol resins, and phenol-modified terpene resins.

When the toner of the present invention is used as a two-component developer, it is used as a mixture with carrier powder.

The carrier powder used in the present invention includes:
All known materials can be used, and examples thereof include magnetic powder such as iron powder, ferrite powder, and nickel powder, glass beads, and those whose surface is coated with a resin. Here, as the resin for coating the surface of the carrier, a styrene-acrylic acid ester copolymer, a styrene-methacrylic acid ester copolymer, an acrylic acid ester copolymer, a methacrylic acid ester copolymer, a silicone resin, a fluorine-containing resin Polyamide resin, ionomer resin, polyphenylene sulfide resin, etc., or a mixture thereof can be used.

Further, the toner of the present invention can be used as a magnetic toner by containing a magnetic material. The magnetic material contained in the magnetic toner of the present invention includes magnetite, hematite, iron oxides such as ferrite, metals such as iron, cobalt, nickel, or aluminum of these metals,
Examples thereof include alloys with metals such as cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof. It is desirable that these ferromagnetic materials have an average particle size of about 0.1 to 2 μm, and the amount contained in the toner is preferably about 40 to 150 parts by weight with respect to 100 parts by weight of the resin component.

In addition, it is highly preferable to add an inorganic oxide fine powder to the toner of the present invention for the purpose of charging stability, imparting fluidity, improving transferability, and the like. It is preferable to use the oxide fine powder without impairing the charging stability.

As a method for obtaining a fine powder of a positively chargeable inorganic oxide, there is a method of treating with a silane coupling agent having at least one organo group having at least one nitrogen atom and / or a silicone oil. Is preferable because it improves not only the charging stability and transferability but also the recovery characteristic of the charge amount when the toner is left in a high temperature and high humidity environment for a long period of time.

Examples of the untreated inorganic oxide fine powder include silica, titanium oxide, aluminum oxide, cerium oxide and the like.

Examples of the silane coupling agent containing a nitrogen atom include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane. Silane, dibutylaminopropyltrimethoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ- Propylphenylamine, trimethoxysilyl-γ-propylbenzylamine, trimethoxysilyl-γ-propylpiveridine, trimet Shishiriru -γ- propyl morpholine, trimethoxysilyl -γ- propyl imidazole.

Examples of the silane coupling agent containing no nitrogen atom include dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, and vinyltrichloride. Examples include ethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane.

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

[0058]

[Chemical 7]

(Wherein R ¹ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ² represents an alkylene group or a phenylene group, R ⁵ represents a compound having a nitrogen-containing heterocycle in its structure, R ³ and R ⁴ represent hydrogen, an alkyl group or an aryl group, provided that the above-mentioned alkyl group, aryl group, alkylene group and phenylene group may have an organo group having a nitrogen atom, and have a charging property. It may have a substituent such as halogen within a range that does not impair the above.)

The silicone oil containing no nitrogen atom is generally represented by the following formula.

[0061]

Embedded image

(In the formula, R represents an alkyl group (eg, methyl group), and n represents an integer.)

A preferred silicone oil is 25
Viscosity at about 5 × 10 ^{2 to} 5 × 10 ⁵ cm ² /
s., such as methyl silicone oil,
Dimethyl silicone oil, phenyl methyl silicone oil, chlorophenyl methyl silicone oil, alkyl modified silicone oil, fatty acid modified silicone oil, polyoxyalkylene modified silicone oil, amino modified silicone oil and the like are preferable.

In the present invention, "rise of charge"
Property, charge stability, and charge amount recovery characteristics can be obtained by the following methods. 2.5 g of toner and 47.5 g of carrier (5 g of toner and 45 g of carrier in the case of magnetic toner) were collected in a polyethylene container of 50 cm ³ ,
Leave open for 2 days. After shaking this for 240 seconds with a Turbula mixer, about 0.5 g was sampled, and the triboelectric charge amount was measured by the blow-off method. The remaining sample was left unopened for another 4 days and then shaken with a turbuler mixer for 0 seconds, 6
The triboelectric charge amount at 0 seconds and 240 seconds was measured, and the respective values were designated as Q ₀ , Q ₆₀ , and Q ₂₄₀ . At this time, the charge stability of the toner is represented by a decrease amount (Q ₀ -Q) of the charge amount immediately after being left, and the smaller the value, the better. Specifically 0-
It is preferably in the range of 3.0 [mC / kg]. The charge recovery characteristic is represented by (Q ₆₀ -Q), and this value is-
The range of 1.0 to +2.0 [mC / kg] is preferable for the toner having excellent recovery characteristics. Particularly preferably-
The range of 0.2 to +0.5 [mC / kg] is preferable. Also represented in the amount of change in charge amount due to shaking the "charging rise" of (Q ₂₄₀ -Q _60), good smaller the value. Specifically, the range of ± 1.0 [mC / kg] is preferable as a toner excellent in charging rise. Particularly preferably, it is in the range of ± 0.3 [mC / kg]. If it exceeds 1.0 [mC / kg], charge-up of the charge occurs, and if it is less than -1.0 [mC / kg], the charge deteriorates. In any case, it is uniform and stable in long-term paper feeding durability. It is difficult to obtain a good image.

FIG. 1 shows a charge amount measuring device of the present invention. A sample is put in a metal measuring container 2 having a conductive screen 3 of 500 mesh at the bottom (the size can be appropriately changed so that carrier particles do not pass), and the metal lid is closed. Next, in the suction device 1 (at least the portion in contact with the measurement container 2 is an insulator), suction is performed from the suction port 7 and the air flow rate adjusting valve is adjusted to set the pressure of the vacuum gauge 5 to 250 mmH ₂ O. Suction sufficiently in this state (for about 1 minute). The voltage of the electrometer at this time is V
(Volts). Here, 8 is a condenser, and the capacity is C (μF). The amount of charge obtained from these is
The triboelectric charge amount (mC
/ Kg).

In the present invention, the transferability is specifically represented by the transfer rate. That is, a solid black image is developed and transferred, and can be expressed by the following formula by the toner amount (per unit area) on the photoconductor and the toner amount on the transfer material.

Transfer rate (%) = (amount of toner on transfer material) /
(Amount of toner on the photoconductor before transfer) × 100

The image quality is represented by the resolution, and the resolution is measured by the following method. That is, in a pattern composed of five fine lines having the same line width and spacing, 2.8, 3.2, 3.6, 4.0, 4.5, 5.0,
Make an original image that is drawn to have 5.6, 6.3, 7.1, 8.0, 9.0, 10.0 lines. This one
An image obtained by copying an original document having two types of line images under appropriate copying conditions is observed with a magnifying glass, and the number of images (lines / mm) in which fine lines are clearly separated is used as the resolution value. . The higher this number is, the better the image quality is.

In producing the electrostatic image developing toner using the charge control agent of the present invention, known additives for improving image characteristics can be used, if necessary, in addition to the above compounds. For example, abrasives such as strontium titanate and silicon carbide, lubricants such as metal stearate,
In addition, a conductivity-imparting agent such as tin oxide may be contained.

The electrostatic image developing toner according to the present invention is
The charge control agent according to the present invention is a binder resin, and a pigment or dye as a colorant, and if necessary, a magnetic material,
By a well-known method such as mixing the additives and the like by a ball mill and other mixers sufficiently, and then melt-kneading using a heat kneader such as a heating roll, kneader, and extruder, and then performing coarse pulverization and fine pulverization. Particle size 45 μm or less,
Desirably, particles having a particle size of 4 to 20 μm are sampled to obtain an average particle size of 7 to
It can be manufactured as a 15 μm toner.

Alternatively, a method in which a material is dispersed in a binder resin solution and spray-dried, or a predetermined material is dispersed in a monomer that constitutes the binder resin to form an emulsified suspension and then polymerized A method such as a polymerization method for obtaining a toner and a toner manufacturing method can be applied.

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

[0073]

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

Example 1 Styrene-acrylic acid-n-butyl copolymer 100 parts (Peak 1: 11,000, Peak 2: 230,000) Magnetic material (magnetite) 80 parts Low molecular weight polyethylene 2 parts Compound (18) 4 Department

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,
It was pulverized by a pulverizer using a jet stream, and the obtained pulverized product was classified by a fixed wall type air classifier. Further, the finely divided powder and the coarse powder are strictly removed at the same time with a multi-division classifier (Elbowjet classifier manufactured by Nittetsu Kogyo Co., Ltd.) using the Coanda effect to obtain the classified powder, and the weight average particle diameter is 8.5 μm.
A fine powder of

Next, 100 parts of the obtained fine powder was mixed with 0.6 part of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil by a Henschel mixer to prepare a one-component magnetic toner.

As shown in Table 1, the rising of the charge of this toner is very fast and the charge amount is high. It is also found that the charging stability is also excellent.

Next, this toner was used as NP-3 manufactured by Canon Inc.
Evaluation was carried out using 525. As can be seen from the results in Table 1, the image density, the image quality (resolution), and the transfer rate were good after running 10,000 sheets under a normal temperature and normal humidity environment of 23 ° C./60%.

The recovery characteristics of the triboelectric charge amount of the toner under the environment of high temperature and high humidity of 35 ° C./85% were very good as can be seen from Table 1.

Also, the image density, image quality (resolution) and transfer rate were good after 10,000 sheets were passed under high temperature and high humidity conditions of 35 ° C./85%.

Example 2 A fine powder having a weight average of 8.0 μm was produced in the same manner as in Example 1 except that the compound (18) was changed to the compound (15), and 100 parts of this fine powder was mixed with dibutylaminopropyl. 0.6 part of silica powder surface-treated with trimethoxysilane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a one-component magnetic toner.

When this product was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 1.

Example 3 A fine powder having a weight average of 8.2 μm was prepared in the same manner as in Example 1 except that the compound (18) was changed to the compound (2), and 100 parts of this fine powder was mixed with dibutylaminopropyl. 0.6 part of silica powder surface-treated with trimethoxysilane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a one-component magnetic toner.

When this product was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 1.

Example 4 100 parts of the fine powder obtained in Example 1 was mixed with 0.6 part of silica powder surface-treated only with dibutylaminopropyltrimethoxysilane with a Henschel mixer to prepare a one-component magnetic toner. did.

When this product was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 1.

Example 5 Styrene-acrylic acid-n-butyl copolymer was added to styrene-
Butyl methacrylate copolymer (peak 1: 12,10
0, peak 2: 300,000) except that the fine powder having a weight average of 8.4 μm was prepared in the same manner as in Example 1, and 100 parts of this fine powder was mixed with dibutylaminopropyltrimethoxysilane and dimethyl silicone. 0.6 part of silica powder surface-treated with oil was mixed with a Henschel mixer to prepare a one-component magnetic toner.

When this product was evaluated in the same manner as in Example 1, good results were obtained as shown in Table 1.

Example 6 Styrene-butyl acrylate copolymer 100 parts (peak 1: 9,500, peak 2: 260,000) carbon black 4 parts low molecular weight polyethylene wax 4 parts compound (19) 4 parts

The above materials were subjected to the same steps as in Example 1 to obtain fine powder having a weight average particle diameter of 8.7 μm.

Next, 100 parts of the obtained fine powder was mixed with 1.0 part of titanium oxide powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil with a Henschel mixer to prepare a one-component non-magnetic toner. did. Next, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 55 μm to prepare a developer.

As shown in Table 1, it can be seen that the rising of the charge of this developer is very fast and the charge amount is also high. It is also found that the charging stability is also excellent.

Next, this developer was used as NP-3 manufactured by Canon Inc.
Evaluation was performed using the developing device of 525 modified to the one shown in FIG. As can be seen from the results in Table 1, 23
The image density, the image quality (resolution), and the transfer rate were good after 10,000 sheets were passed in a normal temperature and normal humidity environment of ° C / 60%.

The recovery characteristics of the triboelectric charge amount of the toner under a high temperature and high humidity environment of 35 ° C./85% were very good as can be seen from Table 1.

Further, the image density, image quality (resolution) and transfer rate after 10,000 sheets were passed under conditions of high temperature and high humidity of 35 ° C./85% were good.

Example 7 A fine powder having a weight average of 8.5 μm was produced in the same manner as in Example 6 except that the compound (19) was changed to the compound (37), and 100 parts of this fine powder was mixed with dibutylaminopropyl. A one-component magnetic toner was prepared by mixing 1.0 part of titanium oxide powder surface-treated with trimethoxysilane and dimethyl silicone oil with a Henschel mixer.

Then, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 55 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 6, good results were obtained as shown in Table 2.

Example 8 Styrene-acrylic copolymer 100 parts (Peak 1: 14,800, Peak 2: 250,000) Copper phthalocyanine blue pigment 5 parts Compound (18) 4 parts

Fine powders having a weight average particle diameter of 8.2 μm were obtained from the above materials by the same steps as in Example 1.

Next, 100 parts of the obtained fine powder was mixed with 0.6 part of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil with a Henschel mixer to prepare a blue toner. Then, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

As shown in Table 1, it can be seen that the rising of the charge of this developer is very fast and the charge amount is also high. It is also found that the charging stability is also excellent.

Next, this developer was used as CLC5 manufactured by Canon Inc.
The evaluation was performed using a modified machine in which 50 OPC photosensitive drums were replaced with amorphous silicone drums. As can be seen from the results in Table 2, 1 in a normal temperature and normal humidity environment of 23 ° C / 60%
The image density, image quality (resolution), and transfer rate after the endurance of 10,000 sheets were good.

The recovery characteristics of the triboelectric charge amount of the toner under a high temperature and high humidity environment of 35 ° C./85% were extremely good as can be seen from Table 1.

The image density, the image quality (resolution) and the transfer rate after 10,000 sheets of paper had passed under high temperature and high humidity conditions of 35 ° C./85% were good.

Example 9 A fine powder having a weight average of 8.1 μm was prepared in the same manner as in Example 8 except that the compound (18) was changed to the compound (36), and 100 parts of this fine powder was mixed with dibutylaminopropyl. 1.0 part of silica powder surface-treated with trimethoxysilane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a color toner.

Next, the carrier 100 having an average particle diameter of 59 μm is used.
5 parts of the toner was mixed with 1 part to prepare a developer.

When this product was evaluated in the same manner as in Example 8, good results were obtained as shown in Table 2.

Example 10 GP of styrene-acrylic acid copolymer in Example 8
With respect to the molecular weight distribution by C, a fine powder having a weight average of 7.8 μm was produced by the same process as in Example 1 except that only the peak was changed to 250,000, and 100 parts of the obtained fine powder was mixed with dibutylaminopropyltrimethoxy. 1.0 part of silica powder surface-treated with silane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a color toner.

Then, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 8, good results were obtained as shown in Table 2.

Example 11 A fine powder having a weight average of 8.4 μm was prepared in the same manner as in Example 8 except that the quinacridone type pigment (CI Pigment Red 122) was used instead of the copper phthalocyanine blue pigment. 0.6 parts of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil was mixed with 100 parts of the body with a Henschel mixer to prepare a red toner.

Next, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 8, good results were obtained as shown in Table 2.

Example 12 A copper phthalocyanine blue pigment was used as C.I. I. Pigment Yellow 17 was used, except that the fine powder having a weight average of 8.3 μm was produced in the same manner as in Example 8.
0.6 parts of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a yellow toner.

Next, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 8, good results were obtained as shown in Table 2.

Comparative Example 1 Example 1 except that the compound (18) was changed to the quaternary ammonium salt decyl-trimethylammonium chloride.
A fine powder having a weight average of 7.8 μm was prepared in the same manner as described above, and 0.6 part of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil was added to 100 parts of the fine powder using a Henschel mixer. A one-component magnetic toner was prepared by mixing.

When this product was evaluated in the same manner as in Example 1, as shown in Table 3, the rising of charging was fast, but
It does not satisfy high charge amount and charge stability. In addition, since the charging recovery characteristics under high temperature and high humidity environment are not satisfied, the image density, image quality (resolution) and transfer rate after 10,000 sheets have been passed are unsatisfactory regardless of environmental conditions.

Comparative Example 2 A weight average of 8. was carried out in the same manner as in Example 1 except that the compound (18) was changed to 2-t-butylbenzimidazole.
A 1 μm fine powder was prepared, and 100 parts of the fine powder was mixed with 0.6 part of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil by a Henschel mixer to prepare a one-component magnetic toner. did.

When this product was evaluated in the same manner as in Example 1, as shown in Table 3, the recovery characteristic of the triboelectric charge amount was particularly poor under high temperature and high humidity, and therefore, the high temperature high of 35 ° C./85% was obtained. Deterioration in image density, image quality (resolution) and transfer rate was observed after running 10,000 sheets under humidity.

Comparative Example 3 A weight average of 8.5 μm was obtained in the same manner as in Example 6 except that the compound (19) was changed to 2-aminobenzimidazole.
m fine powder was prepared, and 100 parts of this fine powder was mixed with 1.0 part of titanium oxide powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil with a Henschel mixer to prepare a one-component non-magnetic toner. Was produced. Then, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 6, as shown in Table 3, the charge amount and the charge stability were satisfied, but the charge rising characteristics, particularly the charge return characteristics in a high temperature and high humidity environment, were evaluated. I'm not satisfied, so 1 regardless of environmental conditions
Deterioration of image density, image quality (resolution) and transfer rate was observed after the endurance of 10,000 sheets.

Comparative Example 4 A fine powder having a weight average of 8.7 μm was produced in the same manner as in Example 8 except that the compound (18) was changed to 1-methyl-2-phenylbenzimidazole.
0.6 parts of silica powder surface-treated with dibutylaminopropyltrimethoxysilane and dimethyl silicone oil was mixed with a Henschel mixer to prepare a color toner. Then, 5 parts of the toner was mixed with 100 parts of an acrylic-coated ferrite carrier having an average particle diameter of 59 μm to prepare a developer.

When this product was evaluated in the same manner as in Example 8, as shown in Table 3, the rise of charging was particularly bad, and therefore, the image density and image quality ( The resolution) and the transfer rate were deteriorated.

[0126]

[Table 1]

[0127]

[Table 2]

[0128]

[Table 3]

[0129]

According to the present invention, the charge rises quickly and has a sufficient amount of charge, and a bright chromatic image can be obtained for a long period of time.

[Brief description of drawings]

FIG. 1 is a schematic view of an apparatus used for measuring a toner charge amount.

FIG. 2 is a schematic view showing an example of a developing device.

[Explanation of symbols]

 11 Latent Image Holder 12 Developer Carrier 13 Hopper 14 Supply Roller 15 Developer Coating Blade 16 Developer

Claims (3)

[Claims] 1. A positively chargeable toner for developing an electrostatic charge image, comprising a compound represented by the following general formula (I). Embedded image (Wherein, R ₁ and R ₂ independently of one another are a hydrogen atom, an alkyl group, an alkoxy group, an aryl group. In addition R ₁
And R ₂ may combine with each other to form an aromatic condensed ring. Ar ₁ represents an optionally substituted phenyl group, cyclohexyl group, or polycyclic aromatic group. Also, n
Indicates 0 or 1. ) 2. R ₁ and R ₂ in the above general formula (I)
2. The positively chargeable toner for developing an electrostatic charge image according to claim 1, wherein at least one of them is an alkyl group. 3. In the above general formula (I), Ar ₁ is an aminophenyl group.
A positively chargeable toner for developing an electrostatic charge image according to item 1.