JP2000194161A - Dry electrophotographic toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nonmagnetic one-component dry electrophotographic toner having good stable developing performance, excellent in color reproducibility and also having good fixability by using a specified polyol resin as a resin binder and at least one of specified three additives. SOLUTION: The dry electrophotographic toner contains a polyol resin as a resin binder and at least one of three additives. The polyol resin contains at least one selected from (1) a polyol having an epoxy resin part and an alkylene oxide part in the principal chain and having inert resin ends, (2) a polyol obtained by allowing an epoxy resin to react with an alkylene oxide adduct of dihydric phenol or its glycidyl ether and a compound having two or more active hydrogen atoms which react with epoxy groups in one molecule, etc., as a constituent element. The additives include 0.2-1.0 pt. wt. hydrophobic silica of 0.01-0.03 μm primary particle diameter based on 100 pts.wt. matrix toner.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-magnetic one-component toner for dry electrophotography, and provides a color toner having good and stable developing properties even under long-term stirring.

[0002]

2. Description of the Related Art In a dry electrophotographic method, an electrostatic latent image is formed on a photoreceptor, developed with a dry toner, a toner image is transferred onto a copy sheet, and then thermally fixed to obtain a copy. As is well known, the dry toner used in this method contains a binder resin and a coloring material as main components, and further contains additives such as a charge controlling agent and an offset preventing material as necessary. Here, as the binder resin, polystyrene, in terms of physical properties required for toner, that is, transparency, insulation, water resistance, fluidity (as powder), mechanical strength, gloss, thermoplasticity, pulverizability, etc. Styrene acrylic copolymers, polyester resins, epoxy resins, and the like are generally used, and among them, styrene resins are widely used because of their excellent crushability, water resistance, and fluidity.

However, if a copy obtained with a styrene-acrylic resin toner is brought into close contact with a vinyl chloride resin sheet, the plasticizer contained in the vinyl chloride resin sheet plasticizes the fixed image and fuses the toner to the sheet side. As a result, when the copy is separated from the sheet, a part or all of the toner image is peeled off, and the toner adheres or becomes dirty on the sheet side. Such defects are also observed in the polyester resin-containing toner.

As measures for preventing the transfer to a vinyl chloride resin sheet as described above, JP-A-60-263951 and JP-A-61-263951 describe the method.
JP-A-240252 proposes blending a styrene resin or a polyester resin with an epoxy resin that is not plasticized by a plasticizer for a vinyl chloride resin.

However, when such a blended resin is used particularly for a color toner, offset properties, curl of a fixed image, glossiness, coloring, transparency, and coloring are problematic due to incompatibility between different resins. It is becoming. These problems cannot be all solved by conventional epoxy resins or acetylated modified epoxy resins as proposed in JP-A-61-235852. In recent years, in addition to the silicone rubber-coated roller, a smooth fluororubber-coated roller and a durable Teflon roller have been used as a fixing heat roller. Toners are required to have a wide range of fixing characteristics in terms of curl, gloss and the like of a fixed image.

It is conceivable to solve the above problem by using an epoxy resin alone, but a new problem is that the epoxy resin reacts with amine.
Epoxy resin is a thermoplastic resin, but in general, by reacting an epoxy group with a curing agent to form a crosslinked structure,
It is used as a curable resin with excellent mechanical strength, electrical stability and chemical resistance. Curing agents are broadly divided into amine-based and organic acid anhydride-based curing agents. Of course, the epoxy resin used as an electrophotographic toner is used as a thermoplastic resin.However, there are dyes and pigments that are kneaded with the resin as the toner and amine-based charge control agents. In some cases, a reaction occurs and the toner cannot be used. The chemical activity of this epoxy group is biochemical activity,
That is, toxicity, such as skin irritation, is considered, and its presence requires careful attention.

Further, since the epoxy group shows hydrophilicity,
Water absorption under high temperature and high humidity is remarkable, and causes a decrease in charge, background fouling, poor cleaning, and the like. Also, JP-A-52-86
No. 334 discloses a compound having a positive charge property by reacting an aliphatic primary or secondary amine with a terminal epoxy group of a ready-made epoxy resin. There may be cases where a crosslinking reaction occurs and the toner cannot be used. Although positive chargeability is imparted, it is difficult to set an arbitrary charge level by reaction with an epoxy group.

Japanese Patent Application Laid-Open No. 52-156632 discloses that one or both of terminal epoxy groups of an epoxy resin is reacted with an alcohol, phenol, Grignard reagent, organic acid sodium acetylide, alkyl chloride or the like. However, when an epoxy group remains, problems such as reactivity with an amine, toxicity, and hydrophilicity occur as described above. Some of the reactants are hydrophilic,
In addition, some of them affect the charging and others affect the pulverizability at the time of forming the toner, and are not always effective in the present invention.

On the other hand, with respect to development, non-magnetic one-component development which is excellent in miniaturization and weight reduction without using a carrier has been proposed. In this developing method, since the replenishing property of the toner to the developing roller and the toner holding property of the developing roller are poor, the toner is forcibly rubbed against the developing roller or the amount of toner on the developing roller is regulated by a blade. As a result, the toner tends to be filmed on the developing roller, causing a problem that the life of the developing roller is shortened and the charge amount of the toner becomes unstable. In addition, good development is not performed.
Therefore, in a color toner for non-magnetic one-component development, in addition to the characteristics required for a general color toner,
In many cases, the heat resistance of the binder resin used for the toner is inferior, and the filming of the toner on the developing roller and the like are likely to occur.

JP-A-5-53369 discloses an inorganic fine powder having a BET specific surface area of 1 to 150 m ² / g and treated with a coupling agent having a saturated or unsaturated cyclic or acyclic organic group having 5 or more carbon atoms. And a BET specific surface area of 160 to 40
Although a toner having an inorganic fine powder having a hydrophobicity of 30 or more at 0 m ² / g is disclosed, the charging characteristics of the toner on the developing roller become unstable and the toner may spill or scatter from the developing roller. is there. Also, JP-A-6-20
No. 2374 discloses a non-magnetic one-component toner in which inorganic fine particles having an average particle diameter of 30 nm or more and less than 100 nm are adhered. There are cases.

Japanese Patent Application Laid-Open No. H08-15890 discloses an average particle size of 4
A one-component developer comprising toner particles of about 9 μm and external additives having a small particle diameter (7 to 20 nm) and a large particle diameter (20 to 80 nm), and having 1 to 2% by weight of the small particle diameter external additive is disclosed. However, the charging characteristics of the toner on the developing roller become unstable, and the toner may spill or scatter from the developing roller.

Japanese Patent Application Laid-Open No. 9-288369 discloses a BET specific surface area of 20 to 50 m ² / g, a pH of 6 to 8, and a hydrophobicity of 85%.
Although the toner containing the above silica fine particles is disclosed, the fluidity of the toner is not sufficient, and the toner replenishing property may be insufficient. In Japanese Patent Application Laid-Open No. 9-297424, the softening point (Sp) is 90 to 115 ° C., and the glass transition point (T
g) is Sp + 110 ≦ 4Tg ≦ Sp + 170
A non-magnetic one-component toner having fine particles having a BET specific surface area of 70 m ^{2 on} the surface of a toner having a polyester resin is disclosed. .

[0013]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a color toner used in a one-component developing apparatus, which has good and stable developability even after long-term stirring. . A second object of the present invention is to provide a dry electrophotographic toner having excellent color reproducibility and excellent fixing characteristics.

A third object of the present invention is to provide a dry electrophotographic toner which is stable to amine compounds and is biochemically safe. A fourth object of the present invention is to provide a dry electrophotographic toner having excellent environmental stability. A fifth object of the present invention is to provide a dry electrophotographic toner which does not transfer the toner image to the sheet even when the fixed image surface of the copy is brought into close contact with the vinyl chloride resin sheet and does not peel off the toner image. is there.

[0015]

According to the present invention, (1)
In a dry electrophotographic toner mainly comprising at least a binder resin, a colorant, a charge control agent, and an additive, the binder resin comprises a polyol resin having at least one of the following components: Is a non-magnetic one-component dry electrophotographic toner, characterized by comprising at least one of the following three types I to III.

Binder resin: a polyol having an epoxy resin part and an alkylene oxide part in the main chain and having an inactive resin terminal. A polyol obtained by reacting an epoxy resin, an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof, and a compound having two or more active hydrogens which react with an epoxy group in a molecule.

Alternatively, the epoxy resin constituting the polyol is at least two kinds of bisphenol A type epoxy resins having different number average molecular weights. In at least two or more bisphenol A epoxy resins having different number average molecular weights, the low molecular weight component has a number average molecular weight of 360 to 2,000, and the high molecular weight component has a number average molecular weight of 3,000 to 10,000.

In the above, at least two or more bisphenol A type epoxy resins having different number average molecular weights have a low molecular weight component of 20 to 50% by weight and a high molecular weight component of 5 to 4%.
0% by weight. Wherein the glycidyl ether of an alkylene oxide adduct of a dihydric phenol constituting the polyol is
It is a diglycidyl ether of an alkylene oxide adduct of bisphenol A, and is represented by the following general formula (I).

[0019]

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(Where R is

[0021]

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And n and m are the numbers of repeating units, each being 1 or more and n + m = 2 to 6. Or the alkylene oxide adduct of a dihydric phenol constituting the polyol or its glycidyl ether is added to the epoxy resin in an amount of 10 to 40.
% By weight.

Additives: (I) Hydrophobized silica having a primary particle diameter of 0.01 to 0.03 μm is added in an amount of 0.1 to 100 parts by weight of the base toner.
2 to 1.0 parts by weight. (II) a primary particle size of 0.01 to 0.03 μm and a specific surface area of 6
0 to 140 m ² / g of the hydrophobized titanium oxide,
0.2 to 0.8 parts by weight based on 100 parts by weight of the base toner. (III) Specific surface area 20-50 m ² / g, bulk density 100-2
50 g / l of hydrophobically treated silica is contained in an amount of 0.5 to 2.0 parts by weight based on 100 parts by weight of the base toner.

According to the present invention, (2) the non-magnetic one-component dry electrophotographic toner according to (1), wherein the charge control agent is at least a metal salt compound of a salicylic acid derivative. ) The toner has a volume average particle size of 4 to 13.
It is characterized by having 15 μm or less of toner particles of 5 μm or less in μm, 30 or more of 30 μm of toner particles of 8 to 12.7 μm, and 1.0 vol% or less of toner particles of 16 μm or more. (1) The non-magnetic one-component dry electrophotographic toner according to (2), (4) a developing roller made of at least a metal material, and a developer coating blade having a rubber material on its surface is brought into contact with the developing roller. The non-magnetic one-component dry electrophotographic toner according to (1), (2) or (3), wherein a developing device is used.
(5) The colorant has at least one kind of yellow colorant, at least one of which is a benzimidazolone yellow pigment, and the colorant has been previously treated with the binder resin. (1) or (2)
Or (3) or (4) the non-magnetic one-component yellow toner for dry electrophotography, (6) the colorant has at least one kind of red colorant, at least one of which is a quinacridone pigment or a naphthol type. (1) Non-magnetic one-component dry electrophotographic magenta according to (1), (2), (3) or (4), which is a pigment, and wherein the coloring material has been treated with the binder resin in advance. Toner, (7) the colorant has at least one blue colorant,
(1) or (2) or (3) or (4), wherein at least one of them is a copper phthalocyanine pigment, and the coloring material is previously treated with the binder resin. A magnetic one-component cyan toner for dry electrophotography; (8) the colorant has at least one of a black colorant and a blue colorant, at least one of which is carbon black and a copper phthalocyanine pigment; (1) or (2), (3) or (4), wherein the coloring material is previously treated with the binder resin. Provided.

As a result of the study, the present inventors have found that the use of a polyol resin having a polyoxyalkylene moiety in the main chain and a specific three kinds of additives in combination with the capping of the end of the epoxy resin provides a stable resin. It has been found that component development can be obtained. Furthermore, stable development characteristics, fixing characteristics, prevention of transfer of copy images, chemical stability and biological safety by combination with specific charge control agent and specific colorant, especially when used in color toner , Color reproducibility, stable gloss, stable chargeability, and the like. Furthermore, it has been found that a specific particle size distribution brings about more stable developing characteristics and a vivid color reproducibility in a fixed image.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The binder resin used in the present invention is preferably one obtained by condensing a bisphenol such as bisphenol A or bisphenol F with epichlorohydrin. Epoxy resin is a bisphenol A type epoxy resin of at least two or more different in number average molecular weight, in order to obtain stable fixing properties and gloss, the number average molecular weight of the low molecular weight component is 360-2000, the high molecular weight component It is preferable that the number average molecular weight is 3,000 to 10,000. Further, the low molecular weight component is preferably 20 to 50% by weight, and the high molecular weight component is preferably 5 to 40% by weight. If the low molecular weight component is too large or the molecular weight is lower than 360, the gloss may be too high or the storage stability may be deteriorated. Also, there are too many high molecular weight components or the molecular weight is 10,000
In the case of an even higher polymer, there is a possibility that the gloss is insufficient or the fixability is deteriorated.

As the compound used in the present invention, the following are exemplified as alkylene oxide adducts of dihydric phenol. Examples include reaction products of ethylene oxide, propion oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The obtained adduct may be glycidylated with epichlorohydrin or β-methyl epichlorohydrin before use. Particularly, a diglycidyl ether of an alkylene oxide adduct of bisphenol A represented by the following general formula (1) is preferable.

[0028]

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(Where R is

[0030]

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And n and m are the numbers of repeating units, each being 1 or more, and n + m = 2 to 6. In addition, it is preferable that the alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained in an amount of 10 to 40% by weight based on the polyol resin. Here, if the amount is small, problems such as increased curling may occur, and if n + m in the general formula (1) is 7 or more, gloss may be excessively obtained or storage stability may be deteriorated.

The compound having one active hydrogen which reacts with the epoxy group in the molecule used in the present invention includes monohydric phenols, secondary amines and carboxylic acids. The following are illustrated as monohydric phenols. Examples include phenol, cresol, isopropylphenol, amylphenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like. 2
Secondary amines include diethylamine, dipropylamine,
Examples include dibutylamine, N-methyl (ethyl) piperazine, piperidine and the like. Examples of the carboxylic acids include propionic acid and caproic acid.

In order to obtain a polyol resin having an epoxy resin part and an alkylene oxide part in the main chain of the present invention, various combinations of raw materials are possible. For example, epoxy resin having glycidyl groups at both ends and glycidyl groups having two terminals
It can be obtained by reacting an alkylene oxide adduct of a divalent phenol with dipalide, isocyanate, diamine, diol, polyhydric phenol, or dicarboxylic acid. Of these, the reaction with a dihydric phenol is most preferred in terms of reaction stability. It is also preferable to use a polyhydric phenol or a polycarboxylic acid together with a dihydric phenol within a range not causing gelation. Here, the amount of the polyhydric phenols and polycarboxylic acids is 15% or less, preferably 10% or less based on the total amount.

The compound used in the present invention having two or more active hydrogens which react with the epoxy group in the molecule includes 2
And polyhydric phenols, polyhydric phenols and polyhydric carboxylic acids. Examples of the dihydric phenols include bisphenols such as bisphenol A and bisphenol F. As polyhydric phenols, ortho-cresol novolaks, phenol novolaks, tris (4
-Hydroxyphenyl) methane, 1- [α-methyl-α
-(4-Hydroxyphenyl) ethyl] benzene. Polycarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid,
Examples include phthalic acid, terephthalic acid, trimellitic acid, and trimellitic anhydride.

The following method is used for measuring the softening point of the polyol resin of the present invention. The softening point is measured by the following procedure using a fully automatic dropping device FP5 / EP53 manufactured by Metra Co., Ltd. After the ground sample is placed in a melting crucible and left for 20 minutes, the sample is poured up to the edge of the sample cup (droplet diameter: 6.35 mm), cooled to room temperature, and set in a cartridge.

A predetermined heating rate (1 ° C./min) and a measurement starting temperature (1% of the expected softening temperature) are supplied to the FP5 control unit.
Set at 5 ° C). After mounting the cartridge in the FP53 heating furnace and leaving it for 30 seconds, the start lever is depressed to start measurement. Subsequent measurements are made automatically. When the measurement is completed, remove the cartridge. The softening point (° C.) is calculated as follows.

[Value of Result Display Panel A of FP5] + [Correction Value] The above result is added to the obtained result to correspond to the result of the Duran mercury method. If the difference between the value of the result display panel A and the measurement start temperature (set in, values of panels B and C) is not more than 15 ° C., the measurement start temperature is reset and the measurement is repeated. Examples of the additives used in the present invention include the following three types.

(I) Primary particle size 0.01 to 0.03 μm
(II) a primary particle diameter of 0.01 to 0.03 μm and a specific surface area of 6 to 1.0 part by weight based on 100 parts by weight of the base toner.
0 to 140 m ² / g of the hydrophobized titanium oxide,
0.2 to 0.8 parts by weight based on 100 parts by weight of the base toner (III) Specific surface area 20 to 50 m ² / g, bulk density 100 to 2
50 g / l of the hydrophobized silica is mixed with 0.5 to 2.0 parts by weight, based on 100 parts by weight of the base toner, that is, the hydrophobized silica having a primary particle diameter of 0.01 to 0.03 μm. , With respect to 100 parts by weight of the base toner,
By attaching the toner to the surface of 0.2 to 1.0 parts by weight of the toner, necessary fluidity and chargeability are imparted to the toner, and the developability on the developing roller and from the developing roller to the photoreceptor is improved. The addition amount of this type of silica is
The amount is preferably 0.2 to 1.0 part by weight with respect to 0 part by weight. If the amount is less than 0.2 to 1.0 part by weight, the necessary amount of toner is not supplied to the developing roller or the required amount of toner charge is obtained. May not be possible. If the amount is larger than the above range, the chargeability of the toner may be too high to sufficiently develop the toner or the toner may be scattered from the developing roller.

The primary particle diameter is 0.01 to 0.03 μm.
The titanium oxide subjected to hydrophobic treatment having a specific surface area of 60 to 140 m ² / g was added in an amount of 0.2 to 100 parts by weight of the base toner.
By adhering to the surface of the 0.8 parts by weight toner, the chargeability of the toner is stabilized, and in particular, the charge rising property and the charge-up are prevented. If the amount of this type of titanium oxide is less than this, the toner may have too high a chargeability to sufficiently develop the toner. If the amount is larger than the above range, the chargeability of the toner may be too low, and the toner may be scattered from the developing roller or may cause stain on the background. Hydrophobized silica having a specific surface area of 20 to 50 m ² / g and a bulk density of 100 to 250 g / l is added to 0.5 to 2.
By attaching the toner to the surface of the 0 parts by weight toner, the thin layer of the toner on the developing roller becomes uniform, the unevenness of the thin layer is greatly improved, and furthermore, by stirring the developing roller for a long time,
The generation of white stripes due to the fusion of the toner to the stirring developer coating blade is prevented. If the amount of silica of this type is smaller than this, the thin layer of the toner on the developing roller becomes non-uniform and uniform development of the toner and an image cannot be obtained. White streaks may occur due to fusion of the toner to the toner. When added in an amount larger than this, the silica of this type is excessively present and may not adhere to the surface of the toner, which may impair the charging stability of the toner.

The two types of silica used in the present invention are generally produced by a wet method or a dry method. In particular, a so-called fume produced by a dry method (vapor phase oxidation of a silicon halide compound) is used. What is called silica is preferred from the viewpoint of fluidity.

As the charge control agent used in the present invention, all known charge control agents can be used, and one or more charge control agents may be mixed and used. However, one of the charge control agents used is a salicylic acid derivative metal salt compound. In the toner composition comprising the binder resin and the additive, a metal compound of a salicylic acid derivative, for example, a zinc salt of salicylic acid, a calcium salt of salicylate, a sodium salt of salicylate, or the like, is dispersed in the binder resin, so that the toner is dispersed on a developing roller in one-component development. A uniform thin layer can be formed, and a charge stable one can be obtained. Other charge control agents include, for example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts, fluorine-modified quaternary ammonium salts, Both positive and negative polarities such as alkyl amide, phosphorus simple substance or compound, tungsten simple substance or compound, fluorine-based surfactant and the like can be mentioned. The content of these charge control agents is generally 100
It is 0.1 to 10 parts by weight based on parts by weight.

The toner according to the present invention has a volume average particle size of 4
It is characterized in that the toner particles have a particle size of up to 13 μm, 15% or less of toner particles of 5 μm or less, 30% or more of toner particles of 8 to 12.7 μm, and 1.0% by volume or less of toner particles of 16 μm or more. I do.

The toner according to the present invention is suitable for a toner for a full-color image formed by additive color mixing, but this method performs various color reproductions by superposing two or more colors of toner. According to the study of the present inventors, in the toner of the present invention, when two or more toner particles having a volume average particle diameter larger than 13 μm are superimposed on each other, the toner particles at the edge portion where the electric field strength is strong in the electrostatic latent image on the photoreceptor. Scattering will occur. In addition, the degree of halftone coloring is reduced, and color reproducibility is deteriorated. If the volume average particle size is smaller than 4 μm, or if the toner particles having a volume average particle size of 5 μm or less are more than 15% by number, the toner charge amount becomes too high, the development amount becomes insufficient, and an ID cannot be obtained. Also, since there are many fine toners, the reproducibility of the electrostatic latent image is deteriorated, and adverse effects such as fusion of the toner to the carrier occur. In addition, toner particles of 8 to 12.7 μm
If the number is less than 0% by number, toner particles which should most contribute to the development of the electrostatic latent image will be insufficient, and it will be difficult to faithfully reproduce the image. Occurs.

As the particle size measuring device in the present invention,
A Coulter Counter TAII and a Coulter Multisizer (all manufactured by Coulter Inc.) are used. Measurement is 100 μm
An aperture is used, and a 1% aqueous solution of sodium chloride is used as an electrolyte. For the sample, a surfactant is dropped into 50 ml of the electrolytic solution, and toner particles are added thereto. This solution is applied to an ultrasonic cleaner for about 1 minute to prepare a toner dispersion solution. This is set in a measuring tank of the measuring device so as to have a constant concentration and measured.

The toner according to the present invention has stable developing characteristics by using at least a developing roller made of a metal material and a developing device in which a developer coating blade having a rubber material on its surface is brought into contact with the developing roller. It is characterized by being obtained. The binder resin according to the present invention, a specific charge control agent, a toner comprising a specific additive, a combination of a metal developing roller and a blade, friction,
The toner thin layer on the developing roller, such as triboelectric charging property and uniform thin layer forming property, becomes uniform, the unevenness of the thin layer is greatly improved, and the toner amount on the developing roller is stable even by long-term stirring of the developing roller Become In addition, it shows stable charging performance irrespective of environmental conditions. The material of the developing roller may be any conventionally known one, for example, aluminum, SUS, or the like, and may have a roughened surface such as a sanding process or a sandblasting process.

FIG. 1 shows an outline of a developing apparatus suitable for carrying out the present invention. A toner supply roller made of a polyurethane material that comes into contact with a development roller of a development device (a development roller mainly made of a silicone resin or a metal material as a surface layer), and a blade made of a urethane material that comes into contact with the main development roller Is set as shown in FIG. 1). In FIG. 1, 1 is a latent image carrier (belt photoreceptor), 2 is a developing roller, 2-1 is a metal core, 2-2 is a resin coat layer, 3 is a toner supply member,
Is a developer application blade, 5 is an agitator, and 6 is a development area.

The measurement of the amount of charge and the amount of adhesion are performed as follows. The toner on the developing roller is sucked through a Faraday cage having a filter layer on the exit side, and the charge amount is measured by a suction method specific charge measuring device that measures the specific charge of the toner trapped in the Faraday cage. Do.
At the same time, the toner adhesion amount is calculated from the relationship between the weight of the trapped toner and the area of the sucked developing roller. Appropriate values of these characteristics vary depending on the linear velocity (ratio) of the developing roller and the photoreceptor, but are generally as follows. This is preferable from the viewpoint of stabilizing the amount of toner to be developed. The charge amount is 10 to 25 (μC / g) in absolute value, and the adhesion amount is 0.4 to 1.2.
(Mg / cm ² ) is desirable. The evaluation of the toner thin layer property of the developing roller is as follows.

The thin layer property of the toner on the developing roller was visually observed. After the developing roller was stirred for a long period of time, the developing unit was disassembled, and after removing the toner, the state of filming of the toner on the developing roller and the state of fixation of the toner to the developer application blade were visually observed.

For the toner according to the present invention, all dyes and pigments known as colorants can be used. However, the yellow toner contains one or more yellow colorants, at least one of which is a benzimidazolone yellow pigment, and the colorant is previously treated with the binder resin. . By using a specific yellow colorant treated with the binder resin for the toner comprising the binder resin, the charge control agent, and the additive according to the present invention, a yellow toner having stable chargeability and excellent coloring power can be obtained. The total content of the yellow colorant in the toner is preferably 4 to 10 parts by weight.

The magenta toner contains at least one red colorant, at least one of which is a quinacridone pigment or a naphthol pigment, and furthermore, the colorant has been previously treated with the binder resin. Features. By using a specific red colorant treated with the binder resin for the toner comprising the binder resin, the charge control agent, and the additive according to the present invention, a magenta toner having stable chargeability and excellent coloring power can be obtained.
The total content of the red colorant in the toner is preferably 3 to 10 parts by weight.

The cyan toner contains at least one blue colorant, at least one of which is a copper phthalocyanine pigment, and the colorant is previously treated with the binder resin. .
By using a specific blue colorant treated with the binder resin for the toner comprising the binder resin, the charge control agent, and the additive according to the present invention, a cyan toner having stable chargeability and excellent coloring power can be obtained. The total content of the blue colorant in the toner is preferably 1 to 8 parts by weight.

The black toner has at least one kind of a black colorant and a blue colorant, at least one of which is carbon black or copper phthalocyanine. The colorant is previously treated with the binder resin. It is characterized by having. The binder resin according to the present invention, a charge control agent, a toner comprising additives,
By using the specific black and blue colorants treated with the binder resin, a black toner having stable chargeability and excellent coloring power can be obtained. The content of the coloring material other than carbon black is 0.1 to 0.3 of the carbon black content.
Parts, and the total content of carbon black and other coloring materials is preferably 3 to 12 parts by weight. In black toner, carbon black and other coloring materials are used in combination. This is because the electrical resistance of the toner becomes too low with carbon black alone, and it may not be possible to hold a sufficient charge. For this reason, the amount of carbon black is adjusted for resistance adjustment, and another coloring material is added to obtain a degree of coloring. The toner resistance is determined in relation to the developing system. In order to obtain an arbitrary resistance, carbon black is selected in consideration of various characteristics such as different resistance, different acidity, different particle size, different specific surface area, and the like. By pre-treating the coloring material with the binder resin,
Increase the dispersibility of the pigment in the binder resin, obtain sufficient coloring power with the above content, increase the transparency and color development of the toner, facilitate the charge control, and form a thin layer on the developing roller for one-component development. Can be made uniform. In the pretreatment with a resin, a binder resin and a coloring material are melt-kneaded at a fixed ratio and coarsely pulverized. Generally, the mixing ratio is desirably 1 to 5 parts by weight of the resin to 1 part by weight of the coloring material. If the colorant is less than 1 part by weight per 1 part by weight of the resin, the colorant cannot be sufficiently dispersed. If the amount of the resin is more than 5 parts by weight per 1 part by weight of the coloring material, the dispersing force does not act on the coloring material and the resin cannot be sufficiently dispersed. When two or more kinds of coloring materials are used, the treatment may be performed individually, or the treatment may be performed after mixing a pigment in advance.

Specific examples of the colorant used in the present invention include yellow colorants such as naphthol yellow S, Hanza yellow 10G, Hanza yellow 5G, Hanza yellow G, cadmium yellow, yellow iron oxide, loess, and graphite. , Titanium yellow, polyazo yellow, oil yellow, Hanza yellow GR, Hanza yellow A, Hanza yellow RN, Hanza yellow R, Pigment yellow L, Benzidine yellow G, Benzidine yellow GR,
Permanent Yellow NCG, Vulcan Fast Yellow 5G, Vulcan Fast Yellow R, Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Benzimidazolone Yellow, Isoindolinone Yellow and the like. Examples of red-based coloring materials include red, red lead, red lead, cadmium red, cadmium mercury red, antimony red, permanent red 4R, para red, phisay red parachlor orthonitroaniline red, lithol fast scarlet G, brilliant fast scarlet, Brilliant Carmin BS, Permanent Red F2R, Permanent Red F4R, Permanent Red FRL, Permanent Red FRLL, Permanent Red F4R
H, Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Lisor Rubin G
X, permanent red F5R, permanent red F
BB, Brilliant Carmine 6B, Pigment Scarlett 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Museum,
Eosin lake, rhodamine lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil red, quinacridone red, villazolone red, polyazo red, crawl permillion, benzidine orange, perinone orange, oil orange, etc. can give. Examples of blue colorants include cobalt blue, cerulean blue, alkali blue lake, peacock blue lake, Victoria blue lake, metal-free phthalocyanine blue, phthalocyanine blue, fast sky blue, indanthrene blue RS, indanthrene blue BC, and indigo. , Ultramarine,
Navy blue, anthraquinone blue, fast violet B, methyl violet lake, cobalt purple, manganese purple, dioxane violet, anthraquinone violet, chrome green, zinc green, chromium oxide,
Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green lake, malachite green lake, phthalocyanine green, anthraquinone green and the like. Other coloring materials include titanium oxide, zinc white,
Litobon, nigrosine dye, iron black and the like. In the toner according to the present invention, wax may be dispersed in the binder resin.

As a result of further studies, the present inventors have found that by finely dispersing wax in the binder resin,
The offset resistance can be improved without applying a releasing oil to a fixing roller such as a fluoro rubber coated roller or a Teflon roller. The wax used in the present invention is preferably an ester type or an olefin type. These waxes are incompatible with the binder resin and are easily finely dispersed in the binder resin. The ester wax has an ester bond and includes, for example, natural waxes such as carnauba wax, candelilla wax and rice wax, and montan wax. On the other hand, examples of the olefin wax include synthetic waxes such as polyethylene wax and polypropylene wax.

The average dispersion diameter of the wax in the binder resin is desirably 0.2 to 5.0 μm. 0.2
If it is smaller than μm, the effect of exuding the wax cannot be obtained and the offset resistance cannot be improved. In order to disperse the binder resin to a particle size of less than 0.2 μm, it is necessary to apply excessive dispersion energy to the binder resin at the time of melt-kneading. On the other hand, if it is larger than 5.0 μm, the fixing property, the fluidity, the storability and the durability of the toner are deteriorated.

The average dispersion diameter of the wax is determined by observing the toner with a transmission electron microscope. This is a result obtained by arbitrarily selecting and measuring 100 points of dispersed wax from an enlarged photograph of 100,000 times magnification and averaging. The toner of the present invention may be a magnetic toner containing a magnetic material. Fundamental materials include iron oxides (magnetite, ferrite, hematite, etc.), metals (iron, cobalt, nickel, etc.), aluminum and cobalt, copper, lead, magnesium, tin, zinc, antimony,
Examples include alloys or mixtures of beryllium, bismuth, calcium, cadmium, manganese, selenium, titanium, tungsten, vanadium, and the like. These magnetic materials preferably have a volume average particle size of about 0.1 to 2.0 μm, and the amount contained in the toner is 5 to 150 parts based on 100 parts by weight of the binder resin.

The toner of the present invention may contain other additives in addition to the above additives. For example, Teflon, fluoropolymer, low molecular weight polyolefin, fatty acid metal salt (zinc stearate, aluminum stearate, calcium stearate, etc.), conductivity-imparting agent (carbon black, tin oxide, etc.), magnetic substance, and their additives It may contain a treated product. However, excessive additives are considered to greatly affect the formation of a thin layer on the developing roller for one-component development, the occurrence of dust due to transfer, and the failure of fixing. Careful selection is required.

[0058]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. ◎ Synthesis example of binder resin Synthesis example 1 378.4 g of low-molecular bisphenol A type epoxy resin (number average molecular weight about 360) and 378.4 g of high molecular bisphenol A type epoxy resin in a separable flask equipped with a stirrer, thermometer, nitrogen inlet, and condenser. (Number average molecular weight about 2700) 8
6. Og, a diglycidylation product of a bisphenol A type propylene oxide adduct (n + m in the general formula (1))
About 2.1) 191. Og, bisphenol F274.5
g, p-cumylphenol 70.1 g, xylene 200
g was added. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, and the temperature was further raised to 160 ° C. , Softening point 109 ° C, Tg
1000 g of a polyol resin at 58 ° C. was obtained (hereinafter referred to as binder resin 1).

Synthesis Example 2 252.6 g of a low-molecular bisphenol A type epoxy resin (number average molecular weight of about 360) and a high molecular weight bisphenol A type epoxy resin (number average molecular weight of about 100) were added to the apparatus of Synthesis Example 1.
00) 112. Og, 336.0 g of a diglycidylation product of bisphenol A type ethylene oxide adduct (n + m about 5.9 in the general formula (1)), bisphenol A2
55.3 g, p-cumylphenol 44.1 g, and xylene 200 g were charged. 70-100 ° C under nitrogen atmosphere
The temperature was raised to 0.183 g of lithium chloride, and
The temperature was raised to 60 ° C., and xylene was distilled off under reduced pressure to remove 18
Polymerization is performed at a reaction temperature of 0 ° C. for 6 to 9 hours,
1000 g of a polyol resin having a Tg of 58 ° C and a Tg of 58 ° C (hereinafter referred to as binder resin 2).

Synthesis Example 3 289.9 g of a low-molecular bisphenol A type epoxy resin (number average molecular weight of about 2400) and a high molecular weight bisphenol A type epoxy resin (number average molecular weight of about 10
000) 232. Og, diglycidylated product of bisphenol A type ethylene oxide adduct (n + m about 6.0 in general formula (1)) 309. Og, bisphenol A
117.5 g, p-cumylphenol 51.6 g, and xylene 200 g were charged. 70-100 under nitrogen atmosphere
° C, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization is performed at a reaction temperature of 80 ° C. for 6 to 9 hours, and a softening point of 11
1000 g of a polyol resin having a temperature of 6 ° C. and a Tg of 61 ° C. was obtained (hereinafter referred to as a binder resin 3).

Synthesis Example 4 421.5 g of a low-molecular bisphenol A type epoxy resin (number average molecular weight of about 680) and a high molecular weight bisphenol A type epoxy resin (number average molecular weight of about 650) were added to the apparatus of Synthesis Example 1.
0) 107.0 g, 214.0 g of diglycidylated bisphenol A-type ethylene oxide adduct (n + m about 2.0 in the general formula (1)), bisphenol F21
0.0 g, p-cumylphenol 47.5 g, and xylene 200 g were charged. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
The temperature was raised to 0 ° C., and xylene was distilled off under reduced pressure.
C. for 6 to 9 hours at a reaction temperature of 114.degree.
Thus, 1000 g of a polyol resin having a Tg of 60 ° C and a Tg of 60 ° C was obtained (hereinafter referred to as a binder resin 4).

Synthesis Example 5 In the apparatus of Synthesis Example 1, 370.6 g of a low molecular weight bisphenol A type epoxy resin (number average molecular weight: about 680) and a high molecular weight bisphenol A type epoxy resin (number average molecular weight: about 650)
0) 306.0 g, 102.0 g of a diglycidylated bisphenol A-type ethylene oxide adduct (n + m about 5.8 in the general formula (1)), bisphenol All
0.2 g, p-cumylphenol 111.2 g, and xylene 200 g were charged. 70-100 ° C under nitrogen atmosphere
The temperature was raised to 0.183 g of lithium chloride, and
The temperature was raised to 60 ° C., and xylene was distilled off under reduced pressure to remove 18
Polymerization is carried out at a reaction temperature of 0 ° C. for 6 to 9 hours to obtain a softening point of 118.
1000 g of a polyol resin having a Tg of 62 ° C and a Tg of 62 ° C was obtained (hereinafter referred to as a binder resin 5).

Examples of additives (I) Hydrophobized silica having a primary particle size of 0.01 to 0.03 μm

[0064]

[Table 1]

(II) Primary particle size 0.01 to 0.03 μm
Treated titanium oxide with a specific surface area of 60 to 140 m ² / g

[0066]

[Table 2]

(III) Hydrophobized silica having a specific surface area of 20 to 50 m ² / g and a bulk density of 100 to 250 g / 1

[0068]

[Table 3]

Example 1 A coloring material was treated according to the following formulation.

Yellow colorant formulation: 200 parts by weight of binder resin 1 I. Pigment Yellow 180 (benzimidazolo yellow) 100 parts by weight Red colorant formulation: 200 parts by weight of binder resin 1 I. Pigment Red 122 (quinacridone) 100 parts by weight Blue colorant formulation: Binder resin 1 200 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Black colorant formulation: 200 parts by weight of binder resin 1 100 parts by weight of carbon black The above materials are put into a hen shell mixer for each color and mixed. Into a heated two-roll mill, and melt-kneaded for 30 minutes after the introduction. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized by a hammer mill to obtain a binder resin 1-treated coloring material. Next, a toner was prepared according to the following formulation.

Yellow toner prescription: Binder resin 1 88 parts by weight Binder resin 1 treated yellow colorant 18 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Magenta toner prescription: Binder resin 1 88 parts by weight Red colorant treated with binder resin 1 18 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical) 4 parts by weight Cyan toner formulation: 94 parts by weight of binder resin 1 94 parts by weight of binder resin 1 treated blue color Material 9 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight Black toner formulation: 87 parts by weight of binder resin 1 1 part by treatment of binder resin 1 part by weight of blue colorant 1.5 parts by weight of binder resin 1 treatment Black colorant 18 parts by weight salicylic acid Conductive zinc salt (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight The above-mentioned materials were put into a Henschel mixer for each color and mixed, and the obtained mixture was charged into a roll mill heated to 110 ° C. and then 30 minutes after charging. It was melt-kneaded. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0072]

[Table 4]

The following three kinds of additives were mixed with 100 parts by weight of the obtained toners of each color using a Henschel mixer to obtain a one-component developer.

I-1 Hydrophobized silica 0.5 part by weight II-1 Hydrophobized titanium oxide 0.5 part by weight III-1 Hydrophobized silica 1.5 part by weight The obtained one-component developer was commercially available. Digital full color printer (IPSiO Color 200 manufactured by Ricoh Company)
0), and an image was formed for each single color of yellow, magenta, cyan, and black and for full color. When the charge amount on the developing roller and the toner adhesion amount were measured by a suction method, the yellow developer was −20.5 μC / g,
0.72 mg / cm ² , magenta developer is −19.5 μm
C / g, 0.78 mg / cm ² , -2 for cyan developer
^{0.1μC / g, 0.70mg / cm 2} , the black developer -19.0μC / g, was 0.83 mg / cm ^2. The thin layer property on the developing roller was uniform and good. The obtained printed image was clear in both single color and full color. The image edge portion was observed with a 30-fold loupe, but was sharp without any dust. There was no unevenness in the gloss of the image, and a calm and high-quality image was obtained. The average gloss was 28%. The obtained full-color image was adhered to a vinyl chloride sheet and subjected to a storage test at room temperature for 180 hours. As a result, the full-color image was favorably maintained and no transfer to the sheet was observed. 2 by full color image
When a durability test was performed on up to 10,000 sheets, no remarkable change was observed in the fixed image, and the image on the 20,000th sheet was a clear image without background smear. Observation of the developing roller revealed that the thin layer was uniform and had no streaks and was good. The amount of charge and the amount of adhesion are also yellow developer—19.1 μC / g, 0.78 mg / c
m ² , magenta developer—18.2 μC / g, 0.85 m
g / cm ² , cyan developer—19.5 μC / g, 0.8
0 mg / cm ² , black developer −18.1 μC / g,
It was stable at 0.81 mg / cm ² .

Example 2 A coloring material was treated according to the following formulation. Yellow colorant formulation: 100 parts by weight of binder resin 3 I. Pigment Yellow 180 (benzimidazolone yellow) 100 parts by weight Red colorant formulation: Binder resin 3 100 parts by weight C.I. I. Pigment Red 57: 1 (naphthol type) 100 parts by weight Blue colorant formulation: Binder resin 3 100 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Black colorant formulation: 100 parts by weight of binder resin 3 100 parts by weight of carbon black The above materials are put into a hen shell mixer for each color and mixed, and then the mixture is air-cooled. And then kneaded for 15 minutes. Thereafter, the kneaded material was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a binder resin 3 treated colorant.
Next, a toner was prepared according to the following formulation.

Yellow toner formulation: Binder resin 3 94 parts by weight Binder resin 3 treated yellow colorant 12 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Magenta toner formulation: Binder resin 3 94 parts by weight Binder resin 3 treated red colorant 12 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Cyan toner formulation: 97 parts by weight of binder resin 3 97 parts by weight of binder resin 3 treated blue color Material 6 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Black toner formulation: 93 parts by weight of binder resin 3 93 parts by weight of binder resin 3 blue colorant 2 parts by weight of binder resin 3 black color Colorant 12 parts by weight Salicylic acid derived Zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight The above-mentioned materials were put into a Henschel mixer for each color and mixed. The obtained mixture was put into a roll mill heated to 120 ° C. And melt-kneaded. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0077]

[Table 5]

The following three types of additives were mixed with 100 parts by weight of the obtained color toners using a Henschel mixer to obtain a one-component developer.

I-2 Hydrophobized silica 0.8 parts by weight II-2 Hydrophobized titanium oxide 0.8 parts by weight III-2 Hydrophobized silica 1.6 parts by weight 1, a commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Company)
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
8.8 μC / g, 0.85 mg / cm ² , magenta developer: −17.0 μC / g, 0.89 mg / cm ² , cyan developer: −19.5 μC / g, 0.79 mg / c
m ² , black developer −17.7 μC / g, 0.91
mg / cm ² . The thin layer property on the developing roller was uniform and good. In addition, the obtained print image was sharp in both single color and full color, and no dust was observed. There was no unevenness in the gloss of the image, and a calm and high-quality image was obtained. The average gloss was 16%.
When the obtained full-color image was subjected to a vinyl chloride sheet preservation test, the full-color image was favorably maintained and no transfer to the sheet was observed. When a durability test was performed on up to 20,000 sheets of a full-color image, no remarkable change was observed in the fixed image, and the image on the 20,000th sheet was a clear image without background contamination. Observation of the developing roller revealed that the thin layer was uniform and had no streaks and was good. The amount of charge and the amount of adhesion are also yellow developer-17.9 μC / g, 0.90 mg / g
cm ² , magenta developer—16.4 μC / g, 0.90
mg / cm ² , cyan developer-18.6 μC / g, 0.1 mg / cm ²
87 mg / cm ² , black developer—17.2 μC /
g and 0.95 mg / cm ² .

Example 3 A coloring material was treated according to the following formulation.

Yellow colorant formulation A: 200 parts by weight of binder resin 2 I. Pigment Yellow 180 (benzimidazolone yellow) 100 parts by weight Yellow colorant formulation B: 200 parts by weight of binder resin 2 C.I. I. Pigment Yellow 17 (benzidine yellow) 100 parts by weight Red colorant formulation A: 200 parts by weight of binder resin 2 I. Pigment Red 57: 1 (naphthol type) 100 parts by weight Red colorant formulation B: 200 parts by weight of binder resin 2 I. Pigment Red 122 (quinacridone type) 100 parts by weight Blue colorant formulation: Binder resin 2 200 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Black colorant formulation: Binder resin 2 200 parts by weight 100 parts by weight Carbon black 100 parts by weight For each color, the above materials are put into a Henschel mixer and mixed. And then kneaded for 30 minutes. Thereafter, the kneaded material was rolled and cooled, and coarsely pulverized by a hammer mill to obtain a binder resin 2 treated colorant. Next, a toner was prepared according to the following formulation.

Yellow toner formulation: 88 parts by weight of binder resin 2 12 parts by weight of yellow colorant A treated with binder resin 2 6 parts by weight of yellow colorant B treated with binder resin 2 Salicylic acid derivative zinc salt (BONTRON E-84, Orient Chemical) 4 parts by weight Magenta toner prescription: 88 parts by weight of binder resin 2 9 parts by weight of red colorant A treated with binder resin 2 9 parts by weight of red colorant B treated with binder resin 2 Salicylic acid derivative zinc salt (BONTRON E-84, Orient Chemical Co., Ltd.) 4 parts by weight Cyan toner prescription: 93 parts by weight of Binder Resin 2 9 parts by weight of blue colorant treated with Binder Resin 2 Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemicals) 4 parts by weight Black Toner formulation: 86 parts by weight of binder resin 2 binder Fat 2 treated blue colorant 3 parts by weight Binder resin 2 treated black colorant 18 parts by weight (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight The above materials were put into a hen shell mixer for each color and mixed. The obtained mixture was put into a twin-screw continuous kneader heated to 80 ° C. and melt-kneaded. After that, the kneaded material is rolled and cooled,
It was roughly pulverized by a hammer mill and finely pulverized by a mechanical pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0083]

[Table 6]

The following three kinds of additives were mixed with 100 parts by weight of the obtained toners of each color using a Henschel mixer to obtain a one-component developer.

I-4 Hydrophobized silica 1.0 part by weight II-4 Hydrophobized titanium oxide 1.0 part by weight III-4 Hydrophobized silica 2.0 part by weight 1 and a commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Co., Ltd.).
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
7.9 μC / g, 0.92 mg / cm ² , magenta developer at −16.4 μC / g, 0.9 mg / cm ² , cyan developer at −20.0 μC / g, 0.75 mg / cm ² ,
Black developer was -18.9 μC / g, 0.84 mg / g
cm ² . The thin layer property on the developing roller was uniform and good. In addition, the obtained print image was clear and sharp, with no dust at the image edge portion in both the single color and the full color. In addition, there was no unevenness in image gloss, and an image having a calm quality was obtained. The average gloss was 24%. When the obtained full-color image was subjected to a vinyl chloride-based sheet storage test, the full-color image was favorably maintained and no transfer to the sheet was observed. In addition, when a durability test was performed on up to 20,000 sheets using full-color images,
No remarkable change was observed in the fixed image, and the image on the 20,000th sheet was a clear image without background smear. Observation of the developing roller revealed that the thin layer was uniform and had no streaks and was good. The amount of charge and the amount of adhesion are also as follows: yellow developer-16.5 μC / g;
98 mg / cm ² , magenta developer—15.1 μC /
g, 0.97 mg / cm ² , cyan developer-18.8 μm
C / g, 0.80 mg / cm ² , black developer-1
It was stable at 7.6 μC / g and 0.92 mg / cm ² .

Example 4 A coloring material was treated according to the following formulation. Yellow colorant formulation: 100 parts by weight of binder resin 4 I. Pigment Yellow 180 (benzimidazolone yellow type) 100 parts by weight Red colorant formulation: Binder resin 4 100 parts by weight C.I. I. Pigment Red 57: 1 (naphthol) 100 parts by weight Blue colorant formulation A: Binder resin 4 100 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Blue colorant formulation B: Binder resin 4 100 parts by weight C.I. I. Solvent Blue 111 (anthraquinone) 100 parts by weight Black colorant formulation: 100 parts by weight of binder resin 4 100 parts by weight of carbon black The above materials were put into a hen shell mixer for each color and mixed, and then the mixture was air-cooled. It was charged into a roll mill and kneaded for 15 minutes after the charging. Thereafter, the kneaded material was rolled and cooled, and coarsely pulverized by a hammer mill to obtain a binder resin 4 treated colorant.
Next, a toner was prepared according to the following formulation.

Yellow toner formulation: Binder resin 4 94 parts by weight Binder resin 4 treated yellow colorant 12 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Magenta toner formulation: Binder resin 4 94 parts by weight Red colorant treated with binder resin 4 12 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical) 4 parts by weight Cyan toner formulation: 97 parts by weight of binder resin 4 97 parts by weight of binder resin 4 treated blue coloration Material A 4 parts by weight Binder resin 4 treated blue colorant B 2 parts by weight Salicylic acid zinc conductor (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Black toner prescription: Binder resin 4 93 parts by weight Binder resin 4 2 parts by weight of treated blue colorant A binder Fat 4 treated black colorant 12 parts by weight Metal-containing azo dye (Spilon Black TRH-1, manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.1 part by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Company) 3 parts by weight Part The above materials were put into a Henschel mixer for each color and mixed, and the obtained mixture was put into a continuous kneader heated to 85 ° C. and melt-kneaded. Thereafter, the kneaded material was cooled, roughly pulverized by a hammer mill, and finely pulverized by a mechanical pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0088]

[Table 7]

The following three types of additives were mixed with 100 parts by weight of the obtained color toners using a Henschel mixer to obtain a one-component developer. I-4 Hydrated silica 0.6 parts by weight II-4 Hydrophobized titanium oxide 0.3 parts by weight III-4 Hydrophobized silica 1.2 parts by weight The obtained one-component developer was used in the same manner as in Example 1. Commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Company)
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
0.5 μC / g, 0.71 mg / cm ² , magenta developer at −19.5 μC / g, 0.70 mg / cm ² , cyan developer at −21.3 μC / g, 0.70 mg / c
m ² , black developer -22.0 μC / g, 0.69
mg / cm ² . The thin layer property on the developing roller was uniform and good. The obtained print image was clear and sharp without any dust in both monochrome and full-color images. There was no unevenness in the gloss of the image, and a calm and high-quality image was obtained. The average gloss was 14%. When the obtained full-color image was subjected to a vinyl chloride-based sheet storage test, the full-color image was favorably maintained and no transfer to the sheet was observed. When a durability test was performed on up to 20,000 sheets of full-color images, no remarkable change was observed in the fixed images, and the 20,000th image was a clear image with no background smear. Observation of the developing roller revealed that the thin layer was uniform and had no streaks and was good. The amount of charge and the amount of adhesion are also yellow developer-18.9 μC / g, 0.81 mg / c.
m ² , magenta developer—18.8 μC / g, 0.78 m
g / cm ² , cyan developer—19.5 μC / g, 0.7
1 mg / cm ² , black developer-23.1 μC / g,
It was stable at 0.67 mg / cm ² .

Example 5 A coloring material was treated according to the following formulation. Binder resin 5 100 parts by weight C.I. I. Pigment Yellow 180 (benzimidazolone yellow) 100 parts by weight Red colorant formulation: Binder resin 5 100 parts by weight C.I. I. Pigment Red 57: 1 (naphthol) 100 parts by weight Blue colorant formulation: Binder resin 5 100 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Black colorant formulation: Binder resin 5 100 parts by weight Carbon black 100 parts by weight The above materials were put into a Henschel mixer for each color and mixed, and then the mixture was rolled and air-cooled. It was charged into a two-roll mill and kneaded for 15 minutes after the charging. Thereafter, the kneaded product was rolled and cooled, and coarsely pulverized by a hammer mill to obtain a binder resin 5 treated colorant. Next, a toner was prepared according to the following formulation.

Yellow toner formulation: 94 parts by weight of binder resin 5 12 parts by weight of yellow colorant treated with binder resin 5 0.5 part by weight of fluorinated quaternary ammonium salt compound (FT-310, manufactured by Neos) salicylic acid derivative zinc salt ( BONTRON E-84, manufactured by Orient Chemical Co.) 3 parts by weight Magenta toner formulation: 97 parts by weight of binder resin 5 6 parts by weight of red colorant treated with binder resin 5 6 parts by weight fluorinated quaternary ammonium salt compound (FT-310, Neos) 0.5 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 3 parts by weight Cyan toner formulation: 97 parts by weight of binder resin 5 97 parts by weight of binder resin 5 Blue colorant treated with 6 parts by weight Fluorine 4 Grade ammonium salt compound (FT-310, manufactured by Neos) 0.5 parts by weight Salichi Acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 3 parts by weight Black toner formulation: 93 parts by weight of binder resin 5 2 parts by weight of blue colorant treated with binder resin 5 12 parts by weight of black colorant treated with binder resin 5 Part Fluorine-based quaternary ammonium salt compound (FT-310, manufactured by Neos) 0.5 part by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 3 parts by weight Henschel mixer for each color , And the resulting mixture was put into a twin-screw continuous kneader heated to 100 ° C. and melt-kneaded. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0092]

[Table 8]

The following three additives were mixed with 100 parts by weight of the obtained toners of each color using a Henschel mixer to obtain a one-component developer. I-5 Hydrophobized silica 0.7 parts by weight II-5 Hydrophobized titanium oxide 0.4 parts by weight III-5 Hydrophobized silica 0.7 parts by weight The obtained one-component developer was the same as in Example 1. Commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Company)
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
3.1 μC / g, 0.65 mg / cm ² , magenta developer -20.9 μC / g, 0.70 mg / cm ² , cyan developer -21.7 μC / g, 0.68 mg / c
m ² , black developer 22.4 μC / g, 0.65 m
g / cm ² . The thin layer property on the developing roller was uniform and good. The obtained print image was clear and sharp without any dust in both monochrome and full color images. There was no unevenness in the gloss of the image, and a calm and high-quality image was obtained. The average gloss was 35%. When the obtained full-color image was subjected to a vinyl chloride-based sheet storage test, the full-color image was favorably maintained and no transfer to the sheet was observed. When a durability test was performed on up to 20,000 sheets of full-color images, no remarkable change was observed in the fixed images, and the 20,000th image was a clear image with no background smear. Observation of the developing roller revealed that the thin layer was uniform and had no streaks and was good. The charge amount and the adhesion amount are also yellow developer-21.9 μC / g, 0.70 mg / c.
m ² , magenta developer—18.9 μC / g, 0.75 m
g / cm ² , cyan developer-20.2 μC / g, 0.7
4 mg / cm ² , black developer-21.0 μC / g,
It was stable at 0.71 mg / cm ² .

Comparative Example 1 The following additives were mixed with 100 parts by weight of the toner selected in Example 1 using a Henschel mixer to obtain a one-component developer. I-1 Hydrophobized silica 0.5 part by weight II-1 Hydrophobized titanium oxide 0.5 part by weight The obtained one-component developer was used in the same manner as in Example 1 to obtain a commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Company).
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
4.1 μC / g, 1.02 mg / cm ² , magenta developer: −12.6 μC / g, 1.10 mg / cm ² , cyan developer: −14.1 μC / g, 1.00 mg / c
m ² , black developer -12.6 μC / g, 1.06
mg / cm ² . The thin layer on the developing roller was uniform. In the obtained print image, dust was slightly observed at an edge portion. There is no uneven image gloss and the average gloss is 28%
Met. In the preservation test of the obtained full-color image on a vinyl chloride sheet, the image was well maintained and no transfer to the sheet was observed. However, when a durability test was performed on up to 20,000 sheets of a full-color image, background stains became noticeable from the 10,000th sheet. Observation of the developing roller revealed that the thin film was non-uniform, and toner was fixed to the roller and the developer application blade. Charge amount,
Amount of adhesion: yellow developer-9.8 μC / g, 0.29 m
g / cm ² , magenta developer—7.5 μC / g, 0.3
1 mg / cm ² , cyan developer-8.7 μC / g,
36 mg / cm ² , black developer-7.1 μC / g,
It was deteriorated to 0.26 mg / cm ² .

Comparative Example 2 The following three additives were mixed with 100 parts by weight of each color toner obtained in Example 2 using a Henschel mixer to form a one-component developer. II-2 Hydrophobized titanium oxide 1.2 parts by weight III-2 Hydrophobized silica 1.6 parts by weight
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of attached toner were measured by a suction method.
0 μC / g, 1.10 mg / cm ² , magenta developer -5.8 μC / g, 1.20 mg / cm ² , cyan developer -6.1 μC / g, 1.12 mg / cm ² , black developer Was -6.6 μC / g, 1.91 mg / cm ² . The thin layer property on the developing roller was not uniform, and the toner was not retained on the developing roller and fell off. The obtained printed images were very dirty, unclear, and dusty in both monochrome and full-color images.

Comparative Example 3 A toner was prepared according to the following formulation using the colorant treated with binder resin 5 prepared in Example 5.

Yellow toner prescription: Binder resin 5 94 parts by weight Binder resin 5 treated yellow colorant 12 parts by weight Fluorinated quaternary ammonium salt compound (FT-310, manufactured by Neos) 2 parts by weight Magenta toner prescription: Binder resin 5 97 parts by weight Binder resin 5 treated red colorant 6 parts by weight Fluorinated quaternary ammonium salt compound (FT-310, manufactured by Neos) 2 parts by weight Cyan toner formulation: 97 parts by weight of binder resin 5 97 parts by weight of binder resin 5 treated blue coloration Material 6 parts by weight Fluorinated quaternary ammonium salt compound (FT-310, manufactured by Neos) 2 parts by weight Black toner formulation: 93 parts by weight of binder resin 5 5 parts of blue colorant treated with binder resin 5 2 parts by weight of black colorant treated with binder resin 5 Colorant 12 parts by weight Fluorinated quaternary ammonium salt compound (FT-3 0, the above materials were mixed placed in a Henschel mixer for each Neos Co., Ltd.) 2 parts by weight of each color, and melt-kneaded was charged to the resulting mixture biaxial continuous kneader heated to 100 ° C.. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0098]

[Table 9]

The following three kinds of additives were mixed with 100 parts by weight of the obtained toners of each color by a Henschel mixer to obtain a one-component developer.

I-5 Hydrophobized silica 0.7 parts by weight II-5 Hydrophobized titanium oxide 0.4 parts by weight III-5 Hydrophobized silica 0.7 parts by weight 1 and a commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Co., Ltd.).
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
8.0 μC / g, 0.74 mg / cm ² , magenta developer: −16.7 μC / g, 0.80 mg / cm ² , cyan developer: −19.5 μC / g, 0.75 mg / c
m ² , black developer −16.9 μC / g, 0.82
mg / cm ² . The thin layer property on the developing roller was uniform and good. The obtained print image was clear and sharp without any dust in both monochrome and full color images. There was no unevenness in the gloss of the image, and a calm and high-quality image was obtained. The average gloss was 35%. When the obtained full-color image was subjected to a vinyl chloride-based sheet storage test, the full-color image was favorably maintained and no transfer to the sheet was observed. However, when a durability test was performed on up to 20,000 sheets of full-color images, soiling became severe on thousands of sheets, and images were not formed. Observation of the developing roller revealed that the thin layer was non-uniform and toner fell off the roller. The charge amount and the adhesion amount are also as follows: yellow developer-7.1 µC / g, 0.23 mg / cm ² , magenta developer-6.8 µC / g, 0.21 mg / cm ² , cyan developer-6.9 µC / g, 0.18 mg / cm ² ,
Black developer—6.0 μC / g, 0.12 mg / cm
² , and had deteriorated.

Comparative Example 4 A coloring material was treated with the binder resin 4 according to the formulation of Example 4, and kneading was performed according to the same toner formulation. Thereafter, the kneaded material was cooled, roughly pulverized by a hammer mill, and finely pulverized by a mechanical pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0102]

[Table 10]

The following three types of additives were mixed with a Henschel mixer to 100 parts by weight of each color toner thus obtained to obtain a one-component developer.

I-4 Hydrated silica 0.6 parts by weight II-4 Hydrophobized titanium oxide 0.3 parts by weight III-4 Hydrophobized silica 1.2 parts by weight The obtained one-component developer was used in Examples. 1 and a commercially available digital full-color printer (IPSiO Co manufactured by Ricoh Co., Ltd.).
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. When the charge amount on the developing roller and the toner adhesion amount were measured by a suction method, the yellow developer was -3.
0.4 μC / g, 0.45 mg / cm ² , magenta developer at −25.5 μC / g, 0.59 mg / cm ² , cyan developer at −35.2 μC / g, 0.49 mg / c
m ² , black developer is −32.4 μC / g, 0.60
mg / cm ² . The thin layer on the developing roller was slightly uneven. When the obtained print image was observed, it was slightly colored and found to have many dusts at the edges, and was unclear and lacked sharpness. When a durability test was performed on up to 20,000 sheets of full-color images, thousands of sheets showed severe dust and reduced image density. Observation of the developing roller revealed that the thin layer was uneven and had many streaks. The amount of charge and the amount of adhesion are yellow developer—35.1 μC.
/ G, 0.45 mg / cm ² , magenta developer-33.
4 μC / g, 0.49 mg / cm ² , cyan developer-3
8.1 μC / g, 0.37 mg / cm ² , and black developer −33.6 μC / g, 0.43 mg / cm ² .

Comparative Example 5 A toner was prepared according to the following recipe without performing the colorant treatment with the binder resin.

Yellow toner formulation: 100 parts by weight of binder resin 3 I. Pigment Yellow 180 (benzimidazolone yellow) 6 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Magenta toner formulation: 94 parts by weight of binder resin 3 I. Pigment Red 57: 1 (naphthol) 6 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical) 4 parts by weight Cyan toner formulation: 97 parts by weight of binder resin 3 C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 3 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight Black toner formulation: 93 parts by weight of binder resin 3 I. Pigment Blue 15: 3 (copper phthalocyanine) 1 part by weight Carbon black 6 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight The obtained mixture was charged into a roll mill heated to 120 ° C., and was melt-kneaded for 30 minutes after the charging. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0107]

[Table 11]

The following three types of additives were mixed with a Henschel mixer to 100 parts by weight of each color toner thus obtained to obtain a one-component developer. I-2 Hydrophobized silica 0.8 parts by weight II-2 Hydrophobized titanium oxide 0.8 parts by weight III-2 Hydrophobized silica 1.6 parts by weight The obtained one-component developer was used in the same manner as in Example 1. Commercially available digital full-color printer (IPSiO Co., manufactured by Ricoh Company)
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
3.8 μC / g, 1.10 mg / cm ² , magenta developer at −12.6 μC / g, 1.12 mg / cm ² , cyan developer at −14.9 μC / g, 1.09 mg / c
m ² , black developer -13.6 μC / g, 1.20
mg / cm ² . The thin layer on the developing roller was uniform. However, the obtained printed images were unclear and had no coloring power in both monochrome and full-color images. Image gloss was also uneven. When a durability test was performed on up to 20,000 sheets of full-color images, thousands of sheets showed severe dust and soiling.

Comparative Example 6 A coloring material was treated according to the following formulation. Yellow colorant formulation: 200 parts by weight of styrene acrylic resin (St / n-BMA, Mn 5000, Mw 12000, Tg 61 ° C.) I. Pigment Yellow 180 (benzimidazolone yellow) 100 parts by weight Red colorant formulation: Styrene acrylic resin (St / n-BMA, Mn 5000, Mw 12000, Tg 61 ° C.) 200 parts by weight C.I. I. Pigment Red 122 (quinacridone) 100 parts by weight Blue colorant formulation: Styrene acrylic resin (St / n-BMA, Mn 5000, Mw 12000, Tg 61 ° C.) 200 parts by weight C.I. I. Pigment Blue 15: 3 (copper phthalocyanine) 100 parts by weight Black colorant formulation: Styrene acrylic resin (St / n-BMA, Mn 5000, Mw 12000, Tg 61 ° C.) 200 parts by weight Carbon black 100 parts by weight The above materials are used for each color. After mixing in a Henschel mixer, the mixture was charged into a two-roll mill heated to 100 ° C., and melt-kneaded for 30 minutes after charging. Thereafter, the kneaded material was rolled and cooled, and coarsely pulverized with a hammer mill to obtain a styrene acrylic resin-treated coloring material. Next, a toner was prepared according to the following formulation.

Yellow toner formulation: Styrene acrylic resin 88 parts by weight Styrene acrylic resin-treated yellow colorant 18 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Magenta toner formulation: Styrene acrylic resin 88 parts by weight Styrene acrylic resin-treated red colorant 18 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight Cyan toner formulation: 94 parts by weight of styrene acrylic resin Blue coloration of styrene acrylic resin treatment Material 9 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co., Ltd.) 4 parts by weight Black toner formulation: Styrene acrylic resin 87 parts by weight Styrene acrylic resin treatment Blue colorant 1.5 parts by weight Styrene acrylic resin treatment Black coloring material 18 parts by weight Salicylic acid derivative zinc salt (BONTRON E-84, manufactured by Orient Chemical Co.) 4 parts by weight The above materials were put into a Henschel mixer for each color and mixed, and the resulting mixture was heated to 110 ° C. The mixture was charged into a roll mill and melt-kneaded for 30 minutes after charging. Thereafter, the kneaded material was rolled and cooled, coarsely pulverized by a hammer mill, and finely pulverized by an air jet mill pulverizer. Further, fine powder was removed by an air classifier to obtain toner of each color having the following particle size distribution.

[0111]

[Table 12]

The following three kinds of additives were mixed with 100 parts by weight of the obtained toners of each color by a Henschel mixer to obtain a one-component developer. I-1 Hydrophobized silica 0.5 part by weight II-1 Hydrophobized titanium oxide 0.5 part by weight III-1 Hydrophobized silica 1.5 part by weight The obtained one-component developer was used in the same manner as in Example 1. Commercially available digital full-color printer (IPSiO Co., manufactured by Ricoh Co., Ltd.)
lor 2000), yellow, magenta,
An image was formed for each of a single color of cyan and black and a full color. The amount of charge on the developing roller and the amount of adhered toner were measured by a suction method.
2.5 μC / g, 0.65 mg / cm ² , magenta developer: −30.5 μC / g, 0.69 mg / cm ² , cyan developer: −32.2 μC / g, 0.60 mg / c
m ² , black developer is −29.1 μC / g, 070 m
g / cm ² . The thin layer on the developing roller had many streaks and unevenness. The resulting print image had a slightly lower image density in both single color and full color, and noticeable unevenness in image gloss. When the obtained full-color image was subjected to a vinyl chloride sheet preservation test, the full-color image was transferred to the sheet. When a durability test was performed on up to 20,000 sheets of full-color images, streaks began to appear on the entire image after about 10,000 sheets. When the developing roller was observed, streaks ran in front of the thin layer, and the roller surface and blade surface In both cases, toner sticking occurred.

[0113]

According to the present invention, stable one-component development can be obtained by using a polyol resin having a polyoxyalkylene moiety in the main chain and three specific additives in combination with capping the end of the epoxy resin. Toner. In addition, a specific charge control system, stable development characteristics by combination with a specific colorant, fixing characteristics, copy image transfer prevention, chemically stable and biologically safe,
In particular, when used in a color toner, it has effects on color reproducibility, stable gloss, stable chargeability, and the like. Furthermore, a more stable development characteristic due to a specific particle size distribution and vivid color reproducibility due to a fixed image are provided.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a developing device suitable for the gist of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Latent image carrier 2 Developing roller 2-1 Core metal 2-2 Resin coat layer 3 Toner supply member 4 Developer coating plate 5 Agitator 6 Development area

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) G03G 15/00 (72) Inventor Keiko Shiraishi 1-3-6 Nakamagome, Ota-ku, Tokyo Ricoh Co., Ltd. (72) Inventor Yoichiro Watanabe 1-3-6 Nakamagome, Ota-ku, Tokyo F-term in Ricoh Co., Ltd. (reference) 2H005 AA01 AA08 AA21 CA07 CA15 CA21 CA25 CA26 CB07 CB13 CB18 DA02 DA04 EA05 EA06 EA07 EA10 FA07

Claims (8)

[Claims] 1. A dry electrophotographic toner comprising at least a binder resin, a colorant, a charge controlling agent, and an additive, wherein the binder resin is a polyol resin having at least one of the following components: Become
A non-magnetic one-component dry electrophotographic toner, wherein the additive comprises at least one of the following three types I to III. Binder resin: a polyol having an epoxy resin part and an alkylene oxide part in the main chain, and having an inactive resin terminal. A polyol obtained by reacting an epoxy resin, an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof, and a compound having two or more active hydrogens which react with an epoxy group in a molecule. Alternatively, the epoxy resin constituting the polyol is at least two or more bisphenol A epoxy resins having different number average molecular weights. In at least two or more bisphenol A epoxy resins having different number average molecular weights, the low molecular weight component has a number average molecular weight of 360 to 2,000, and the high molecular weight component has a number average molecular weight of 3,000 to 10,000. In at least two or more bisphenol A type epoxy resins having different number average molecular weights, the low molecular weight component is 20 to 50% by weight, and the high molecular weight component is 5 to 40% by weight. Wherein the glycidyl ether of an alkylene oxide adduct of a dihydric phenol constituting the polyol is
Diglycidyl ether of an alkylene oxide adduct of bisphenol A and represented by the following general formula (1). Embedded image (Where R is And n and m are the numbers of repeating units, each being 1 or more, and n + m = 2 to 6. Or the alkylene oxide adduct of a dihydric phenol constituting the polyol or its glycidyl ether is added to the epoxy resin in an amount of 10 to 40.
% By weight. Additives: (I) Hydrophobized silica having a primary particle diameter of 0.01 to 0.03 μm is added in an amount of 0.1 to 100 parts by weight of the base toner.
2 to 1.0 parts by weight. (II) a primary particle size of 0.01 to 0.03 μm and a specific surface area of 6
0 to 140 m ² / g of the hydrophobized titanium oxide,
0.2 to 0.8 parts by weight based on 100 parts by weight of the base toner. (III) Specific surface area 20-50 m ² / g, bulk density 100-2
50 g / l of hydrophobically treated silica is contained in an amount of 0.5 to 2.0 parts by weight based on 100 parts by weight of the base toner. 2. The non-magnetic one-component dry electrophotographic toner according to claim 1, wherein the toner contains at least one kind of charge controlling agent, at least one of which is a metal salt compound of a salicylic acid derivative. 3. The toner has a volume average particle size of 4 to 13 μm.
And having 15% by number or less of toner particles of 5 μm or less,
30% by number or more of toner particles having a particle size of
3. The non-magnetic one-component dry electrophotographic toner according to claim 1, wherein the toner has 1.0% by volume or less of toner particles of 6 μm or more. 4. A developing device in which a developing roller made of at least a metal material and a developer applying blade having a rubber material on its surface are brought into contact with the developing roller. 2. The non-magnetic one-component dry electrophotographic toner according to claim 1. 5. The colorant has at least one kind of yellow colorant, at least one of which is a penzimidazolone yellow pigment, and the colorant is previously treated with the binder resin. Claim 1
Or the nonmagnetic one-component yellow toner for dry electrophotography according to 2 or 3 or 4. 6. The colorant has at least one kind of red colorant, at least one of which is a quinacridone pigment or a naphthol pigment, and the colorant is previously treated with the binder resin. And
The non-magnetic one-component magenta toner according to claim 1, 2, 3, or 4. 7. The colorant has at least one kind of blue colorant, at least one of which is a copper phthalocyanine pigment, and the colorant is previously treated with the binder resin. 5. The non-magnetic one-component dry electrophotographic cyan toner according to claim 1, 2, 3 or 4. 8. The colorant has at least one of a black colorant and a blue colorant, at least one of which is carbon black, and a copper phthalocyanine pigment, wherein the colorant is previously contained in the binder. The non-magnetic single-component dry electrophotographic black toner according to claim 1, wherein the black toner is processed with a resin.