JP2000330339A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To ensure superior electrostatic chargeability by any of a wet granulation method and a kneading and comminuting method by incorporating a resin binder, a colorant and a metallic complex of salicylic acid having a specified loss on heating. SOLUTION: The electrostatic charge image developing toner contains at least a resin binder, a colorant and a metallic complex of salicylic acid having <=12 wt.%, preferably <=10 wt.%, further preferably <=8 wt.% loss on heating at 200 deg.C. Since the metallic complex having such a relatively small loss on heating at 200 deg.C is used, the toner excellent in electrostatic chargeability is easily obtained even by a wet granulation method. In the case of >12 wt.% loss on heating, the toner having the desired electrostatic chargeability is not obtained when the wet granulation method is adopted. Stable electrostatic chargeability is not ensured owing to an environmental change and stability of an initial charged state deteriorates.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used for electrophotography, electrostatic printing and the like.

[0002]

2. Description of the Related Art A toner for developing an electrostatic image used in a system such as an electrophotographic system or an electrostatic printing system is conventionally manufactured by a wet granulation method represented by a kneading-pulverizing method or a suspension polymerization method. .

[0003] Further, with respect to toner characteristics, recently, there has been a demand for a copying machine and a printer that can achieve higher image quality from the initial stage to the endurance time than before. For example, by improving the reproducibility of one dot, the reproducibility of halftone images can be improved, and the rattling of lines can be improved (improved radiance).
Various requests have been made, such as improvement in reproducibility due to the above. To meet these requirements, it is effective to reduce the diameter of the toner, make it spherical, and make the shape uniform, and it is known that a wet granulation method is effective in obtaining such a toner.

[0004] As a toner material, various charge control agents are generally used for the purpose of controlling chargeability. Among the charge control agents, in particular, a developer having a high ability to adjust the chargeability of the toner, exhibiting a stable chargeability in an environment from low temperature / low humidity to high temperature / high humidity, and having excellent durability. A salicylic acid metal complex is well known as a charge control agent having characteristics. However, even if such a salicylic acid metal complex is used in the above-mentioned wet granulation method, there is a problem that a toner having excellent charging performance as obtained by a pulverization method cannot be obtained. That is, since it is not effective to use a salicylic acid metal complex having excellent chargeability in the wet granulation method, it is difficult to obtain a toner having a small particle diameter having excellent chargeability.

[0005]

That is, an object of the present invention is to provide a toner having excellent chargeability which can be obtained by any of a wet granulation method and a kneading and pulverizing method.

Another object of the present invention is to provide a toner having a small particle size and excellent chargeability.

Another object of the present invention is to provide a toner having excellent chargeability and image quality.

[0008]

The present invention comprises at least a binder resin, a colorant and a metal salicylate complex, and the metal salicylate complex has a heat loss at 200 ° C. of 1%.
The present invention relates to a toner for developing an electrostatic image, wherein the content is 2% by weight or less.

The inventors of the present invention pay attention to the weight loss of the salicylic acid metal complex used at 200 ° C., and if the weight loss is less than a certain value, the charging is performed even if a so-called wet granulation method is employed. It has been found that a toner having excellent properties can be obtained. The weight loss component is considered to be mainly salicylic acid, which is a raw material when synthesizing a salicylic acid metal complex, and the salicylic acid is dissolved in a solution such as water, which is a dispersion medium when producing a toner by a wet granulation method. High in nature. For this reason, when the content of the residual salicylic acid in the salicylic acid metal complex is large, when the toner composition is granulated in the dispersion medium, salicylic acid becomes a trigger, and the salicylic acid metal complex itself elutes into the dispersion medium, or the toner composition It is considered that the dispersion state of the metal salicylate complex in the product particles, particularly the dispersion state in the toner particle surface layer, becomes inhomogeneous, and the desired chargeability cannot be obtained satisfactorily.

The salicylic acid metal complex contained in the toner of the present invention is not particularly limited as long as it is a complex comprising salicylic acid, alkylsalicylic acid or a derivative thereof and a metal.
The following general formula (I);

Embedded image (Wherein R ₁ , R ₂ , R ₃ and R ₄ each independently represent hydrogen or an alkyl group having 1 to 9 carbon atoms. M is Zn,
Indicates Cr, Al, Fe or B. X ⁺ represents a counter ion, and represents any of a hydrogen ion, an alkali metal ion, NH ₄ ^{+ and} various ammonium ions. n represents an integer of 1 or 2. It is preferable to use a salicylic acid metal complex represented by the formula (1). The counter ion can be changed depending on the conditions of post-treatment of the precipitate after synthesis. For example, if the precipitate is washed with dilute sulfuric acid until the pH of the solution becomes 6 to 7 level, the counter ion becomes hydrogen ion, and if the pH is adjusted to about 9 to 10 with caustic soda aqueous solution instead of dilute sulfuric acid, it becomes sodium ion. Become. Further, if the treatment is carried out with hydrochlorides of various amines, sodium ions can be replaced with various ammonium ions.

Particularly preferred salicylic acid metal complexes in the present invention are those wherein M is Zn, R _{1 to} R ₄ are -tC ₄ H ₉ and X is H (general formula (ii)), and M is Cr. R ₁ ~
R ₄ is -tC ₄ H ₉ and X is H (general formula (i)). These general formulas are shown below.

[0012]

Embedded image

The salicylic acid metal complex contained in the toner of the present invention has a loss on heating at 200 ° C. of 12% by weight or less, preferably 10% by weight or less, more preferably 8% by weight or less. That is, the weight loss of the salicylic acid metal complex of the present invention when heated at 200 ° C. is preferably as small as possible. in this way
By using a metal salicylate complex having a relatively small loss on heating at 200 ° C., a toner having excellent chargeability can be easily obtained even by a wet granulation method. For this reason, the toner of the present invention not only reduces the shape variation of each particle, but also improves the homogeneity of the toner particles themselves. It is considered that since the distribution is sharpened, noise such as fog is reduced and image quality (image quality) is improved. If the above-mentioned heating loss exceeds 12% by weight, a toner having a desired chargeability cannot be obtained when the wet granulation method is employed, that is, stable chargeability cannot be obtained due to environmental changes, or initial charge stability deteriorates. I do.

In the present specification, the "loss on heating at 200 ° C."
TG / DT4 according to G method (thermogravimetry)
The value measured by -200 (manufactured by Seiko Instruments Inc.) is used, but it does not mean that it is measured only by the device, that is, 200 ° C or less when the sample is gradually heated to 200 ° C. Any device may be used as long as the device can recognize the accumulated weight reduced by the above.
Therefore, “the loss on heating at 200 ° C.” means “cumulative weight lost at 200 ° C. or less”. Similarly, “a component that loses weight at 200 ° C.” also means “a component that loses weight at 200 ° C. or lower”. In the present specification, the heating loss is expressed as a ratio (% by weight) to the weight of the metal salicylate complex before heating, that is, at room temperature.

It is considered that one of the components of the salicylic acid metal complex that loses its weight at a temperature of 200 ° C. or less is residual moisture and a residue of a salicylic acid component which is a raw material during synthesis. Salicylic acid has the property of losing almost 100% at 200 ° C. (see FIG. 2). In addition, since salicylic acid is easily dissolved in water and the like, when a salicylic acid metal complex containing a large amount of this component is present during wet granulation, particularly in the vicinity of the toner particle surface layer, the salicylic acid migrates to the medium solvent together with salicylic acid under the influence of salicylic acid. It is considered that the charging characteristics of the obtained toner are impaired. In the present invention, "20 containing salicylic acid"
The use of a metal salicylate complex having a reduced "heat loss component at 0 ° C." can prevent the transfer of the metal salicylate complex in the vicinity of the toner particle surface layer to the medium solvent, so that the charge density on the toner particle surface is uniform. The chargeability, in particular, the charge rising performance and the charge stability (environmental stability during durability) can be improved. Such characteristics are particularly effective for a small particle diameter toner having low fluidity and making it difficult to uniformly contact the charging member. Further, since salicylic acid has a stimulating property, the toner of the present invention using the salicylic acid metal complex containing a small amount of the component is
It is excellent in safety when prepared by either a wet granulation method or a kneading and pulverizing method.

The TG curves of the salicylic acid metal complex and salicylic acid usable in the present invention are shown in FIGS. 1 and 2, respectively. FIG. 2 shows that when the temperature is gradually increased, salicylic acid causes a significant weight loss at about 100-200 ° C.
Indicates that weight loss is almost 100%. On the other hand, FIG.
When the temperature is gradually increased, the salicylic acid metal complex of the present invention loses weight from about 100 ° C., but it is relatively slow, and the weight loss on heating at 200 ° C. is 1
It is less than 0% by weight. From these figures, it is considered that the components of the salicylic acid metal complex lost by heating at 200 ° C. are salicylic acid and water. In addition,
In each of the figures, the TG curve is based on the weight loss ratio (simply referred to as TG in the figures) on the right axis, and the line indicating the time-dependent change in temperature is on the left axis.

The salicylic acid metal complex used in the present invention may be produced by any method as long as the above-mentioned loss on heating can be ensured. For example, it is obtained by obtaining a salicylic acid metal complex by a known method, washing the obtained precipitate of the complex with water, preferably warm water at 40 to 80 ° C, and drying. Preferably, a vacuum drying treatment is further performed. Specifically, for example, 2 moles of the desired salicylic acid or salicylic acid derivative is dissolved in methanol, and 1 mole of chromic disulfide is added thereto. Further, a 25% aqueous solution of caustic soda is added to adjust the pH to 4 to 5. The liquid obtained here is refluxed for 3 hours. The solution containing the precipitate obtained here is filtered while keeping the temperature at about 50 ° C. to collect the precipitate.
Next, the obtained cake is washed with diluted sulfuric acid, and further p
Water washing and filtration are repeatedly performed with purified hot water at 60 ° C. until H 6 to 7, preferably 7. Alternatively, the counter ion may be changed to Na ⁺ by adjusting the pH to 9 to 10 with an aqueous solution of caustic soda instead of dilute sulfuric acid. In the present invention, the pH is 6 to
7, and the counter ion is preferably H ⁺ . Thereafter, after drying, if necessary, further vacuum drying is performed, whereby the metal salicylate complex used in the present invention is obtained.

The preferred particle size of the metal salicylate complex used in the toner of the present invention varies depending on the size of the toner particles and is not particularly limited. However, the particle size of the complex fine particles is preferably as small as possible. Specifically, for example, it is desired that the volume average particle size is less than 1 μm, more preferably 0.001 to 0.5 μm, and still more preferably 0.005 to 0.5 μm.
The particle size of the salicylic acid metal complex can be controlled by the stirring conditions during the synthesis, the reaction time, the concentration of the reactants in the solvent, and the like.

In the toner of the present invention, the salicylic acid metal complex is used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the binder resin.
Parts by weight, preferably 0.5 to 5 parts by weight. If the content is less than 0.1 part by weight, the effect of the addition of the metal salicylate complex is ineffective, that is, the desired charge rising property, charge stability, and charge environment stability cannot be obtained. On the other hand, if the content is more than 10 parts by weight, the toner cannot be uniformly dispersed in the toner, which may impair the charging stability or cause the charge controlling agent having a poor dispersion state to separate from the toner and cause the charge applying member (carrier, Blades, developing rollers, etc.) and cause charging deterioration.

The metal salicylate complex as described above has a high charge control effect even when the toner is obtained by a kneading and pulverizing method. Further, there is a great effect even when used by being contained in a charge imparting member such as a carrier, a toner thin layer regulating member or a developing roller (sleeve).

The binder resin for the toner of the present invention is not particularly limited, and those usually used in toners are preferable. For example, styrene resin, (meth) acrylic resin, styrene- (meth) acrylic resin Resins, polyamide resins, polyester resins, polyurethane resins, epoxy resins and other known resins can be used alone or as a mixture. good.
For example, when adjusting a color toner, it is preferable to use a polyester resin, and when adjusting a black toner, it is preferable to use a polyester resin, a styrene-acrylic resin, or a combination thereof.

When the physical properties of the binder resin are adjusted as a full-color toner, the glass transition temperature is 50 to 50%.
It is preferable to use a binder resin having a temperature of 75 ° C., a softening point of 80 to 120 ° C., a number average molecular weight of 2500 to 30,000 and a weight average molecular weight / number average molecular weight of 2 to 20. When adjusting as a black toner, a binder resin having a glass transition temperature of 50 to 75 ° C., a softening point of 80 to 150 ° C., a number average molecular weight of 1,000 to 10,000, and a weight average molecular weight / number average molecular weight of 30 to 100 is used. Is preferred.

When the toner of the present invention is prepared by a wet granulation method, in particular, an emulsification dispersion granulation method or a suspension method, an acid value as a main component of the binder resin is 3 to 50 KOH mg / g, preferably 5 to 50 KOH mg / g.
It is particularly preferred to use a polyester resin of 4040 KOH mg / g. By using a polyester resin having such an acid value, it is possible to improve the dispersibility of various pigments including carbon black and a charge control agent including a salicylic acid metal complex, and to effectively provide a toner having negative chargeability. Can be. When the acid value is less than 3 KOHmg / g, the above-mentioned effects are reduced, and when the acid value is more than 50 KOHmg / g, the stability of the toner charge amount with respect to environmental fluctuations, especially humidity fluctuations, is likely to be impaired.

When the toner of the present invention is prepared by a wet granulation method, in particular, a suspension polymerization method or an emulsion dispersion granulation method, the following raw material monomers are used as a resin monomer or a monomer constituting a binder resin. Is particularly preferred.

Examples of the raw material monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene and p-tert-butylstyrene. Styrene or a styrene derivative such as p-chlorostyrene; ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; methyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, methacrylic Isobutyl acid, t-butyl methacrylate, n-methacrylic acid
Alkyl methacrylates such as pentyl, isopentyl methacrylate, neopentyl methacrylate, 3- (methyl) butyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate; Methyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, t-butyl acrylate, n-pentyl acrylate, isopentyl acrylate, neopentyl acrylate, 3- (methyl) butyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, acrylic Alkyl acrylates such as undecyl acid and dodecyl acrylate; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid; acrylonitrile, maleic ester, itaconic ester, vinyl chloride, vinyl acetate,
Examples include vinyl benzoate, vinyl methyl ethyl ketone, vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether.

As the colorant for the full-color toner, known pigments and dyes are used. For example, carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, Dupont oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, CI pigment red 48: 1 , CI Pigment Red 122, CI Pigment Red 57: 1, CI Pigment Red 184, CI
Pigment Yellow 97, CI Pigment Yellow 1
2, CI Pigment Yellow 17, CI Solvent Yellow 162, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Blue 15: 1,
CI Pigment Blue 15: 3. In the black toner, in addition to various carbon blacks, activated carbon, and titanium black, a part or all of the colorant can be replaced with a magnetic substance. Examples of such a magnetic material include ferrite, magnetite, iron, and the like.
Known magnetic fine particles can be used. The average particle size of the magnetic particles is preferably 1 μm or less, particularly preferably 0.5 μm or less, from the viewpoint of obtaining dispersibility during the production. In the case where it is added from the viewpoint of preventing scattering while imparting the properties as a non-magnetic toner, the amount of addition is 0.5 to 10 parts by weight, preferably 0.5 to 8 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the binder resin. Is 1 to 5 parts by weight. If the addition amount exceeds 10 parts by weight, the magnetic binding force of the developer carrying member (with a built-in magnet roller) to the toner becomes strong, and the developing property is reduced. In addition, when added to magnetic toner, 20 to 60 parts by weight
Parts by weight are preferred. If the addition amount is less than 20 parts by weight, toner scattering tends to increase, and if it exceeds 60 parts by weight, the toner charge amount cannot be stably ensured, and image quality deteriorates.

Further, the toner of the present invention may contain a wax in order to improve properties such as offset resistance. Examples of such waxes include polyethylene wax, polypropylene wax, carnauba wax, rice wax, sasol wax, montan ester wax, Fischer-Tropsch wax and the like. When the wax is contained in the toner as described above, the content is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the binder resin in order to obtain the effect of the addition without causing a problem such as filming. . In addition, from the viewpoint of improving the offset resistance, it is preferable to include a polypropylene wax, and the smearing property (when the paper is fed on a sheet having an image already formed on one side at the time of automatic document feeding or double-sided copying, the image is It is preferable to contain polyethylene wax from the viewpoint of improving the image quality (phenomenon of image quality deterioration such as bleeding and dirt due to rubbing). Particularly preferable polypropylene wax from the above viewpoint has a melt viscosity at 160 ° C. of 50 to 300 cps,
Polypropylene wax having a softening point of 130 to 160 ° C. and an acid value of 1 to 20 KOH mg / g, and a particularly preferred polyethylene wax has a melt viscosity at 160 ° C. of 1000 to 8
A polyethylene wax having a 000 cps and a softening point of 130 to 150 ° C. That is, the polypropylene wax having the above-mentioned melt viscosity, softening point and acid value is excellent in dispersibility in the above-mentioned binder resin, and can improve the offset resistance without causing a problem due to the free wax. In particular, when a polyester resin is used as a binder resin, it is preferable to use an oxidized wax.

In addition, various resins having a polar functional group having an effect on negative charging may be used in combination with the salicylic acid metal complex in the toner. The charge control resin (CCR) may be a polymer obtained by polymerizing a monomer having a polar functional group alone or in combination with each other. , (Meth) acrylic monomers or other monofunctional and / or polyfunctional monomers, and / or monofunctional and / or
Alternatively, a polymer blend of a polymer obtained by polymerizing a polyfunctional monomer and a polymer containing a monomer having a polar functional group may be used. In such a resin, a polymer having a monomer component having fluorine as described below is particularly preferable.

Fluorine atoms are effective for negative charge. The fluorine-containing monomer is not particularly limited.
2-trifluoroethyl acrylate, 2,2,3,3
-Tetrafluoropropyl acrylate, 2,2,3
Preferred examples include fluoroalkyl (meth) acrylates such as 3,4,4,5,5-octafluoroamyl acrylate, 1H, 1H, 2H, 2H-heptadecafluorodecyl acrylate. In addition, trifluorochloroethylene, vinylidene fluoride, ethylene trifluoride,
It is possible to use ethylene tetrafluoride, trifluoropropylene, hexafluoropropene, hexafluoropropylene and the like. When the charge control resin contains such a fluorine-containing monomer, the content is preferably 0.5 to 50% by weight, more preferably 1 to 30% by weight, based on all monomers.

The toner of the present invention containing at least the above binder resin, colorant and salicylic acid metal complex has a volume average particle size of 2 to 9 μm, preferably 2 to 9 μm.
It is preferable to adjust the thickness to 7 μm from the viewpoint of improving the image quality. Further, the content of the toner particles having a particle diameter twice or more the volume average particle diameter is 2% by weight or less, preferably 1% by weight or less, and the toner particles having a particle diameter of 1/3 or less of the volume average particle diameter. The content is 5% by number or less, preferably 4%.
It is effective to have a particle size distribution of not more than a few percent from the viewpoint of narrowing the toner charge amount distribution and preventing fog.

The toner particles according to the present invention preferably have a circularity (average circularity) of 0.950 to 1.000 and a standard deviation (SD) of the circularity of 0.045 or less. If the average circularity is less than 0.950, the adhesion and cohesion of the toner particles to the image carrier and the intermediate transfer member are increased, resulting in poor transfer (transfer efficiency, dropout).
Tends to occur. If the SD exceeds 0.045, the uniformity of the charging property is impaired due to the deterioration of the shape, and fog is likely to be caused.

The toner of the present invention is excellent in chargeability, that is, initial charge rising property, charge stability and charge environment stability, and has stable durability characteristics for a long period of time. Also,
The toner of the present invention has high demands in recent years, such as halftone dot reproducibility, line reproducibility, low consumption (color material high filling type), and developability (fog,
Scattering, followability), transferability (transfer efficiency, hollow-out performance)
Has excellent characteristics.

The toner of the present invention as described above can be obtained by any of a so-called wet granulation method and a kneading-pulverization method, but is preferably prepared by a wet granulation method. The above salicylic acid metal complex can be used effectively, and a small particle size (2 to 9) is used from the viewpoint of reduction in production cost and high image quality.
μm) and uniform spherical toner particles (average circularity 0.950)
As described above, the circularity SD value of 0.045 or less can be easily obtained.

In the wet granulation method, toner particles are obtained by granulating a toner composition in water or a mixed medium of water and a water-soluble organic solvent, followed by drying. Examples of the wet granulation method include suspension polymerization, emulsion polymerization, soap-free emulsion polymerization, and non-aqueous dispersion polymerization in which a toner composition such as a colorant is dissolved / dispersed in a resin monomer and then granulated. In addition, capsule toner by in-situ polymerization method, interfacial polymerization method, etc., and further, a toner composition is dissolved / dispersed in a suitable solvent in advance and then dispersed / granulated to obtain a suspension method, an emulsion dispersion method. Granulation method and the like. According to these wet granulation methods, it is generally easy to obtain toner particles having a small particle size, so that it is possible to sufficiently cope with high image quality.

More specifically, for example, when producing the toner of the present invention by an emulsion dispersion granulation method, first, a toner component (for example, a binder resin, a colorant, a salicylic acid metal complex, or any other desired additive) is added to a water-insoluble organic solvent. ) Is dissolved or dispersed to prepare a colored resin solution, and then the colored resin solution is emulsified and dispersed in an aqueous medium to form an O / W emulsion. The solid content concentration in the colored resin solution is determined by heating an O / W emulsion obtained by emulsifying and dispersing the colored resin solution in water or a mixed medium of water and a water-soluble organic solvent (hereinafter, simply referred to as an aqueous medium). When the water-insoluble organic solvent is removed from the droplets, 5 to 50% by weight, preferably 10% by weight, so that the droplets can be easily solidified into fine particles.
It is preferably set to 40% by weight. In order to form an O / W emulsion, a method in which the above-mentioned colored resin solution is added to an aqueous medium and droplets of the colored resin solution are dispersed in the aqueous medium, or an aqueous medium is added to the colored resin solution A method of causing phase inversion and dispersing droplets of the colored resin solution in an aqueous medium can be adopted.

Examples of the aqueous medium used to form the O / W emulsion include water and water containing a water-soluble organic solvent that does not destroy the emulsion.
Water / methanol mixture (weight ratio 50 / 50-100 / 0), water / ethanol mixture (weight ratio 50 / 50-100 / 0), water / acetone mixture (50 / 50-100 / 0), water / methyl ethyl ketone mixture (Weight ratio 70 / 30-100 / 0) or the like can be used. It is preferable to add an appropriate known dispersion stabilizer and dispersion stabilizing aid to such an aqueous medium.

In the emulsification dispersion granulation method, the obtained O /
By heating the W-type emulsion while stirring to remove the water-insoluble organic solvent, a suspension in which colored resin particles having a predetermined particle size are dispersed in an aqueous medium is obtained. Thereafter, the aqueous medium is removed by filtration or the like to isolate the colored resin particles, washed and dried, and if necessary, classified to obtain toner particles. In addition, a method of spraying an O / W emulsion in a dry atmosphere, completely removing the water-insoluble organic solvent in the droplets to form colored resin fine particles, and evaporating and removing the aqueous medium is used. You may.

In producing the toner of the present invention by a suspension polymerization method, first, a polymer composition containing a resin monomer capable of forming a binder resin, a polymerization initiator, a colorant and other desired additives is used. The mixture is suspended in water or a mixed medium of water and a water-soluble organic solvent (aqueous medium) and polymerized to perform granulation. Thereafter, the medium is removed and dried to produce toner particles. As the aqueous medium, those similar to the aqueous medium used in the above emulsification-dispersion granulation method can be used. As the polymerization initiator when polymerizing the raw resin monomer, for example,
2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
Azo or diazo polymerization initiators such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile, benzoyl peroxide, methyl ethyl ketone peroxide, Peroxide polymerization initiators such as isopropyl peroxycarbonate and lauroyl peroxide are exemplified.

In producing the toner of the present invention by a kneading and pulverizing method, first, a binder resin, a colorant and other desired additives are mixed, and the mixture is melted and kneaded, and the kneaded material is cooled. Later, coarsely crushed, finely crushed,
Classification produces toner particles.

After the toner particles are produced by the above-described kneading and pulverizing method, the toner particles are subjected to a surface modification device, for example,
Hybridization system (Nara Machinery Co., Ltd.), Cosmos System (Kawasaki Heavy Industries, Ltd.), Inomizer System (Hosokawa Micron, Ltd.) and Turbo Mill (Turbo Kogyo), a dry mechanochemical method using the high-speed air impact method. Applied mechanofusion system (Hosokawa Micron) and mechanomill (Okada Seiko Co., Ltd.), surffusing system (Nippon Pneumatic Industrial Co., Ltd.) and heat treatment equipment (Hosokawa Micron) using hot air reforming method, and wet type It is preferable to perform a surface modification treatment with a disper coat (manufactured by Nisshin Engineering Co., Ltd.) or a coatmizer (manufactured by Freund Corporation) to which a coating method is applied. By performing such a surface modification treatment, the average circularity and the circularity standard deviation of the toner of the present invention can be easily controlled.

Incidentally, such a surface modification treatment may be performed on the toner particles obtained by the above-mentioned wet granulation method.
As a result, a spherical toner having a more uniform shape can be stably obtained, and the dot reproducibility and the line reproducibility are excellent.
Further, it is possible to easily obtain a toner which has low image noise and excellent image performance and achieves stable image performance over a long period of time.

To the toner of the present invention obtained as described above, it is preferable to add various organic / inorganic fine particles as a fluidity adjusting agent after adjusting the toner particles. Examples of inorganic fine particles include various carbides such as silicon carbide, boron carbide, titanium carbide, zirconium carbide, hafnium carbide, vanadium carbide, tantalum carbide, niobium carbide, tungsten carbide, chromium carbide, molybdenum carbide, calcium carbide, and diamond carbon lactam. , Various nitrides such as boron nitride, titanium nitride, zirconium nitride, borides such as zirconium boride, oxides, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, aluminum oxide, silica, colloidal silica, etc. Various oxides, various titanate compounds such as calcium titanate, magnesium titanate, strontium titanate, sulfides such as molybdenum disulfide, fluorides such as magnesium fluoride and carbon fluoride, aluminum stearate, calcium stearate Zinc stearate, various metal soaps such as magnesium stearate, talc, various non-magnetic inorganic fine particles of bentonite can be used alone or in combination. In particular, silica, titanium oxide, alumina, inorganic fine particles such as zinc oxide, silane coupling agent, titanate coupling agent, silicone oil,
Conventionally used hydrophobizing agents such as silicone varnish, furthermore, fluorine-based silane coupling agents, or fluorine-based silicone oils, and coupling agents having amino groups or quaternary ammonium bases, modified silicone oils, etc. It is preferable that the surface is treated with a treatment agent by a known method. Further, styrene, (meth) acrylic, benzoguanamine, granulated by a wet polymerization method such as an emulsion polymerization method, a soap-free emulsion polymerization method, a non-aqueous dispersion polymerization method, a gas phase method, etc. Various organic fine particles such as melamine, Teflon, silicon, polyethylene, and polypropylene can also be used. The relatively large-diameter inorganic fine particles such as metal titanate and various organic fine particles may or may not be subjected to a hydrophobic treatment. The addition amount of these fluidizing agents is 0.1 to 100 parts by weight of the toner particles.
5 parts by weight, preferably 0.5 to 3 parts by weight are added.

The toner of the present invention obtained as described above can be used in either a one-component developer without using a carrier or a two-component developer used with a carrier. As the carrier used with the toner of the present invention, a known carrier can be used.
Iron powder, a carrier composed of magnetic particles such as ferrite, a coated carrier in which the surface of the magnetic particles is coated with a coating material such as a resin,
Alternatively, any of a dispersion type carrier obtained by dispersing a magnetic substance fine powder in a binder resin can be used. As such a carrier, those having a volume average particle size of 15 to 100 μm, preferably 20 to 80 μm are suitable.

An example of a full-color image forming apparatus which can effectively use the toner of the present invention will be described with reference to FIG. In the following full-color image forming apparatus, a photosensitive member is used as an image carrier, an endless intermediate transfer belt is used as an intermediate transfer member, and a sheet-like recording paper is used as a recording member.

Referring to FIG. 4, a full-color image forming apparatus generally includes a photosensitive drum 10 driven to rotate in the direction of arrow a.
Laser scanning optical system 20, full-color developing device 30,
Endless intermediate transfer belt 40 that is driven to rotate in the direction of arrow b.
And a paper feed unit 60. Around the photoconductor drum 10, a charging brush 11 for charging the surface of the photoconductor drum 10 to a predetermined potential, and a cleaner 12 having a cleaner blade 12a for removing toner remaining on the photoconductor drum 10 are provided. is set up.

The laser scanning optical system 20 is a laser diode,
It is a well-known device with a built-in polygon mirror and fθ optical element, and its control unit includes C (cyan), M (magenta), Y
(Yellow) and Bk (black) print data are transferred from the host computer. Laser scanning optical system 20
Outputs print data for each color sequentially as a laser beam, and scans and exposes the photosensitive drum 10. As a result, an electrostatic latent image for each color is sequentially formed on the photosensitive drum 10.

The full-color developing device 30 includes Y, M, C, and Bk.
The four color developing devices 31Y, 31M, 31C, and 31Bk containing one-component toner composed of the non-magnetic toner described above are integrated, and can be rotated clockwise about the support shaft 81 as a fulcrum. Each developing device includes a developing sleeve 32 and a toner regulating blade. The toner conveyed by the rotation of the developing sleeve 32 is charged by passing through the pressure contact portion (gap) between the blade 34 and the developing sleeve 32.

The installation positions of the developing devices for accommodating the yellow toner, magenta toner, cyan toner, and black toner are determined by whether the full-color image forming apparatus is for copying a line diagram image such as a character or a photograph. It depends on whether the purpose is to copy a shaded image of each color such as a picture, etc. For example, when the purpose is to copy a line diagram image such as a character, gloss (gloss) is used as a black toner. When using something that does not have
When the black toner layer is formed on the top of the full-color copy image, a sense of incongruity occurs. Therefore, it is preferable to load the black toner into the developing device so that the black toner layer is not formed on the top of the full-color copy image. In this case, it is most preferable that the black toner layer is formed on the intermediate transfer body at the time of primary transfer so that the black toner layer is formed on the lowermost position on the copy image. Will be loaded. At this time, the yellow toner, the magenta toner, and the cyan toner (color toner) may be arbitrarily loaded into the developing device so that the order of formation of the respective layers in the primary transfer is one of the first to third.

On the other hand, when the full-color image forming apparatus is intended to copy an image having various shades of each color such as a photographic image, a black toner having a gloss (glossiness) is used. Even if the black toner layer is formed on the top of the copied image, it does not cause a sense of incompatibility with other color toner layers.

The intermediate transfer belt 40 is endlessly stretched over the support rollers 41 and 42 and the tension rollers 43 and 44, and is rotated in the direction of arrow b in synchronization with the photosensitive drum 10. A projection (not shown) is provided on a side portion of the intermediate transfer belt 40. By detecting the projection by the microswitch 45, image forming processes such as exposure, development, and transfer are controlled. The intermediate transfer belt 40 is pressed by a rotatable primary transfer roller 46 and is in contact with the photosensitive drum 10. This contact portion is the primary transfer portion T
_Is one. The intermediate transfer belt 40 is in contact with a rotatable secondary transfer roller 47 at a portion supported by the support roller. The contact portion is a secondary transfer portion T _2.

Further, the developing device 30 and the intermediate transfer belt
The cleaner 50 is installed in the space between the 40.
The cleaner 50 has a blade 51 for removing residual toner on the intermediate transfer belt 40. The blade 51 and the secondary transfer roller 47 can contact and separate from the intermediate transfer belt 40.

The paper feed section 60 is composed of a paper feed tray 61 that can be opened to the front side of the image forming apparatus main body 1, a paper feed roller 62, and a timing roller 63. The recording sheets S are stacked on a paper feed tray 61, fed one by one to the right in the drawing by the rotation of a paper feed roller 62, and synchronized with an image formed on the intermediate transfer belt 40 by a timing roller 63. To the secondary transfer section. The horizontal conveyance path 65 for the recording sheet is constituted by an air suction belt 66 and the like including the paper feed section, and a vertical conveyance path 71 provided with conveyance rollers 72, 73, 74 from the fixing device 70 is provided. The recording sheet S is discharged from the vertical conveyance path 71 to the upper surface of the main body 1 of the image forming apparatus.

Here, the printing operation of the full-color image forming apparatus will be described. When the printing operation is started, the photosensitive drum 10 and the intermediate transfer belt 40 are driven to rotate at the same peripheral speed, and the photosensitive drum 10 is charged to a predetermined potential by the charging brush 11.

Subsequently, exposure of the yellow image is performed by the laser scanning optical system 20, and an electrostatic latent image of the yellow image is formed on the photosensitive drum 10. This electrostatic latent image is immediately developed by the developing device 31Y, and the toner image is transferred onto the intermediate transfer belt 40 in the primary transfer section. Immediately after the end of the primary transfer, the developing device 31M is switched to the developing section D, and then exposure, development, and primary transfer of the magenta image are performed. further,
Switching to developing device 31C, exposure and development of cyan image, 1
Next transfer is performed. Further, switching to the developing device 31Bk, exposure of black image, development, and primary transfer are performed.
The toner image is superimposed on the intermediate transfer belt 40 for each next transfer.

When the final primary transfer is completed, the recording sheet S is sent to the secondary transfer section, and the full-color toner image formed on the intermediate transfer belt 40 is transferred onto the recording sheet S. When the secondary transfer is completed, the recording sheet S is conveyed to the belt-type contact heating and fixing device 70, and the full-color toner image is fixed on the recording sheet S and discharged to the upper surface of the printer body 1.

The toner of the present invention is more effectively used in a full-color image forming apparatus having a brush cleaning device for removing residual toner on the surface of an image carrier. Hereinafter, description will be made with reference to FIG. 5 showing an example of a flash cleaning device. The conductive brush 2 is used as a brush member 211 for rubbing the surface of the image carrier (photosensitive drum) 201.
11a is provided, the brush member 211 is rotated in the opposite direction to the image carrier 201, and the surface of the image carrier 201 is rubbed by the brush 211a provided on the brush member 211, A bias voltage for toner recovery having a polarity opposite to the charging polarity of the toner 202 is applied from the power supply 212 to the brush member 211, and the toner 202 remaining on the surface of the image carrier 201 is removed by the brush of the brush member 211. 211a.

Therefore, even if the toner 202 remaining on the surface of the image carrier 201 has a small particle size, the brush member 2
11 ensures that the toner 202 is removed from the surface of the image carrier 201. After the toner 202 is collected by the brush member 211, the brush 211a of the rotating brush member 211 is applied to the hitting rod 213 as described above, and the toner 202 collected by the brush 211a is removed by the brush 211a.
Strike out from inside 211a.

Further, the toner 202 thus collected
After the toner 202 has been beaten out of the brush 211a, the toner 202 attached to the brush 211a is further removed by a collection roller 214.
To be collected. Here, when the toner 202 attached to the brush 211a is collected by the collection roller 214, the brush 211a of the rotating brush member 211 is brought into contact with the peripheral surface of the rotating collection roller 214, as in the related art. A bias voltage for toner collection higher than the bias voltage applied to the brush member 211 is applied from the power supply 215 to the collection roller 214, and the remaining toner 202 that has not been beaten from the brush 211a is applied to the collection roller 214.
14 to be collected on the peripheral surface.

Next, the scraping member 216 is pressed against the peripheral surface of the collection roller 214 from which the toner 202 has been collected in this manner by a biasing means 217 such as a spring.
The toner 202 collected on the peripheral surface of the
Thus, the toner 202 scraped off from the peripheral surface of the collection roller 214 is conveyed by the toner conveying coil 218. Then, in this cleaning device, when the toner 202 attached to the brush 211a is collected by the collection roller 214 as described above,
The cleaning agent 221 is supplied to the peripheral surface of the collection roller 214 by a cleaning agent supply unit (a regulating blade) 222.

Here, when supplying the cleaning agent 221 to the peripheral surface of the collection roller 214, the scraping member 21 is provided on the opposite side of the brush member 211 of the collection roller 214.
6, the cleaning agent 221 is housed so that the cleaning agent 221 is in contact with the peripheral surface of the collection roller 214, and a rubber regulating blade 222 is pressed against the peripheral surface of the collection roller 214 so that the regulating blade 222 Cleaning agent 2 supplied to the peripheral surface of the collection roller 214 by
The amount of 21 is adjusted and the cleaning agent 221 is supplied thinly and uniformly to the peripheral surface of the collection roller 214. By supplying the cleaning agent 221 to the peripheral surface of the collecting roller 214 in this manner, the toner 202 collected by the collecting roller 214 can be easily scraped off from the peripheral surface of the collecting roller 214 by the scraping member 216. Thus, the accumulation of the toner 202 on the peripheral surface of the collection roller 214 can be prevented.

As a result, the toner 202 adhered to the brush 211a as described above can be stably collected by the collecting roller 214 for a long period of time.
The toner 202 adhered to the surface of the image carrier 201 is not accumulated because the toner 202 gradually accumulates in the brush 211a, and the removing power of the toner 202 by the brush member 211 does not decrease. Will be performed.

In this apparatus, the collecting roller
In supplying the cleaning agent 221 to the peripheral surface of the recovery roller 214, a rubber regulating blade 222 is pressed against the peripheral surface of the collection roller 214 to adjust the amount of the cleaning agent 221 supplied to the peripheral surface of the collection roller 214. In place of the rubber regulating blade 222 described above, a metallic regulating blade is used, or a regulating member formed of a sponge or the like is pressed against the peripheral surface of the collecting roller 214 to collect the collecting roller. It is also possible to adjust the amount of the cleaning agent 221 supplied to the peripheral surface of the 214.

[0063]

EXAMPLES (Production Example of Polyester Resin A) 4.0 mol of polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as "PO"),
Polyoxyethylene (2,0) -2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as "EO") 6.
0 mol, 9.0 mol of terephthalic acid (hereinafter referred to as “TPA”) and dibutyltin oxide as a catalyst are placed in a glass four-necked flask, and a thermometer, a stainless steel stirring rod, a falling condenser, and a nitrogen inlet tube are attached. While stirring and heating under a nitrogen stream in a mantle heater,
It was allowed to react. The progress of the reaction was followed by measuring the acid value. When the acid value reached a predetermined value, the reaction was terminated and cooled to room temperature to obtain a polyester resin A. Each obtained polyester resin 1
Those crushed to a size of not more than mm were used in the production of the following toner.
The physical properties of the polyester resin obtained here were as follows: number average molecular weight (Mn): 3300, weight average molecular weight (Mw) / number average molecular weight (Mn): 4.2, glass transition temperature (Tg): 6
8.5 ° C, softening point (Tm): 110.3 ° C, acid value: 3.3, hydroxyl value: 28.1.

Production Example 1 of Charge Control Agent 50 g of 3,5-di-tert-butylsalicylic acid was dissolved in 450 g of methanol, and a 40% aqueous solution of dichromic sulfate was added thereto.
Add 51g. Add about 50 g of 25% caustic soda aqueous solution,
Adjust to pH 4-5. The liquid obtained here is heated at about 70 ° C for 3 hours.
Reflux for hours. The solution containing the precipitate obtained here is heated to about 50 ° C.
Filter while preserving the temperature and collect the precipitate. Next, the obtained cake was washed with 1% diluted sulfuric acid, and further washed with purified warm water at 60 ° C. until pH 7 and filtered repeatedly. Thereafter, after drying at 50 ° C. for 24 hours,
Compound A was obtained by vacuum drying at 120 ° C. for 5 hours.
(The general formula (i)) was obtained. The weight loss at 200 ° C. of the metal salicylate complex obtained here was 4 wt%.

Production Example 2 of Charge Control Agent The cake obtained in Production Example 1 was washed with 1% diluted sulfuric acid, and then repeatedly washed with purified hot water at 60 ° C. until pH 7 and filtered. Thereafter, the resultant was dried at 50 ° C. for 24 hours to obtain Compound B. The heat loss at 200 ° C. of the obtained metal salicylate complex was 8% by weight.

Preparation Example 3 of Charge Control Agent After the cake obtained in Preparation Example 1 was washed with 1% diluted sulfuric acid, the washing was completed at pH 6, and then dried at 50 ° C. for 24 hours. Thereby, compound C was obtained. The heat loss at 200 ° C of the obtained metal salicylate complex was 1
It was 3 wt%.

Preparation Example 4 of Charge Control Agent 50 g of 3,5-di-tert-butylsalicylic acid was dissolved in 450 g of ethanol, and a solution prepared by dissolving 16 g of caustic soda in 400 g of water was added to completely dissolve the solution. The temperature was raised to 70 ° C. Next, 13.6 g of zinc chloride was dissolved in 60 g of water and added dropwise for 30 minutes. 70
After maintaining at ~ 80 ° C for 2 hours, the pH was adjusted to 7.0 ± 0.5, and the reaction was completed. Next, the obtained cake was washed with purified warm water of 60 ° C. and filtered 5 times. After this, 50
After drying at 24 ° C. for 24 hours, and further performing vacuum drying at 120 ° C. for 5 hours, compound D (the above-mentioned general formula (i)
i)) got. 200 of the salicylic acid metal complex obtained here
The loss on heating at 7 ° C. was 7% by weight.

Preparation Example 5 of Charge Control Agent The cake obtained in Preparation Example 4 was washed twice with purified water at 10 ° C., and then dried at 50 ° C. for 24 hours to obtain a compound E. Was. The heat loss at 200 ° C. of the metal salicylate complex obtained here was 14 wt%.

Example 1: Production Example A of Toner 60 parts by weight of styrene, 35 parts by weight of n-butyl methacrylate, 5 parts by weight of methacrylic acid, 2,2'-azobis (2,2
4-dimethylvaleronitrile) 0.5 part by weight, low molecular weight polypropylene (Viscol 660P; manufactured by Sanyo Chemical Industries) 3
Parts by weight, carbon black (MA # 8; manufactured by Mitsubishi Chemical Corporation)
8 parts by weight and 1 part by weight of a salicylic acid metal complex: compound A were mixed with a sand stirrer to prepare a polymerization composition. This polymerization composition was subjected to a polymerization reaction at 60 ° C. for 6 hours in a 3% by weight aqueous solution of gum arabic at 60 ° C. while stirring at 4300 rpm using a stirrer TK Auto Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.). Spherical particles having a particle diameter of 6.0 μm were obtained. After repeating the filtration of spherical particles / washing with 50 ° C warm water 5 times,
The filtrate was air-dried in an environment of 35 ° C. and 30% RH to obtain toner particles A.

Example 2: Production Example B of Toner Metal salicylic acid complex: Toner particles B were obtained in the same manner as in Production Example A of toner except that Compound B was used instead of Compound A.

Comparative Example 1 Toner Production Example C Toner Particle C was obtained in the same manner as in Toner Production Example A, except that Compound C was used in place of Compound A.

0.5% by weight of hydrophobic silica fine particles (R-972; manufactured by Nippon Aerosil Co., Ltd.) and strontium titanate fine particles (particle size: 350 nm, BET specific surface area) having a BET specific surface area of 140 m ² / g : 9 m ² / g) 0.5 wt% was added and mixed at a peripheral speed of 40 m / sec for 3 minutes using a Henschel mixer, and then sieved with a sieve having an opening of 106 μm to prepare toners A to C for evaluation.

Production of Pigment Masterbatch The pigments used in the production of full-color toners are thermoplastic resin and CI Pigment Yell used in Examples, respectively.
ow180, CIigment Blue15-3, or CIigment Red
184 was charged into a pressure kneader at a weight ratio of 7: 3 and kneaded at 120 ° C. for 1 hour. After cooling, the mixture was roughly pulverized with a hammer mill to obtain a pigment master batch having a pigment content of 30% by weight.

Example 3 Production Example D of Toner 15 parts by weight of a pigment masterbatch (yellow), 1 part by weight of a metal complex of salicylic acid: 1 part by weight of compound D and 400 parts by weight of toluene were added to 100 parts by weight of a polyester resin A, using an ultrasonic homogenizer (output). (400 μA) for 30 minutes to dissolve and disperse to prepare a colored resin solution. On the other hand, an aqueous dispersion was prepared by dissolving 0.1 part by weight of sodium lauryl sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) in 1,000 parts by weight of an aqueous solution containing 4% by weight of calcium hydroxide phosphate as a dispersion stabilizer. 100 parts by weight of the above aqueous dispersion
42 K automatic homomixer (manufactured by Tokushu Kika Kogyo)
While stirring at 00 rpm, 50 parts by weight of the above colored resin solution was dropped, and the droplets of the colored resin solution were suspended in the aqueous dispersion. The suspension was allowed to stand at 60 ° C. and 100 mmHg for 5 hours to remove toluene from the droplets and precipitate colored resin particles. Then, after dissolving calcium hydroxide phosphate with concentrated sulfuric acid, filtration and washing with water were repeated. Thereafter, the colorant particles were dried at 80 ° C. using a slurry drying device (Dispercoat: manufactured by Nisshin Engineering Co., Ltd.) to obtain yellow toner particles D.

Examples 4 and 5: Toner Production Examples E and F Toner production examples D, except that the pigment masterbatch was changed from yellow to cyan and magenta, respectively.
In the same manner as in the above, toner particles E and F were obtained.

BET was applied to each of these toner particles DF.
Hydrophobic silica fine particles having a specific surface area of ^{140m 2 / g (R-972} ; manufactured by Nippon Aerosil Co., Ltd.) 0.5 wt% and strontium titanate fine particles (particle size: 350 nm, BET specific surface area: adding 9m ² /g)0.5 wt% Peripheral speed 40m / sec using Henschel mixer
, And then sieved with a sieve having an opening of 106 µm to prepare toners D to F used for evaluation.

Example 6: Production Example G of Toner (Production Example of Polyester Resin H (L Form)) A glass four-necked flask equipped with a thermometer, a stirrer, a falling condenser and a nitrogen inlet tube was charged with polystyrene. Oxypropylene (2,2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxyethylene (2,2) -2,2-bis (4-hydroxyphenyl) propane, indodecenyl succinic anhydride, terephthalic acid and fumaric acid in a weight ratio
The mixture was adjusted to 82: 77: 16: 32: 30 and added together with dibutyltin oxide as a polymerization initiator. This was reacted in a mantle heater under a nitrogen atmosphere at 220 ° C. with stirring. The softening point of the obtained polyester resin H is 110 ° C.
The glass transition point was 60 ° C, and the acid value was 17.5 KOHmg / g.

(Production Example of Polyester Resin I (H Form)) Styrene and 2-ethylhexyl acrylate were adjusted to a weight ratio of 17: 3.2, and added to a dropping funnel together with digmyl peroxide as a polymerization initiator. On the other hand, polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene were placed in a glass four-necked flask equipped with a thermometer, a stirrer, a falling condenser, and a nitrogen inlet tube. Ethylene (2,2) -2,2
-Bis (4-hydroxyphenyl) propane, isododecenyl succinic anhydride, terephthalic acid, 1,2,4-anhydride
Benzene tricarboxylic acid and acrylic acid in a weight ratio of 42:
The mixture was adjusted to 11: 11: 11: 8: 1 and added together with dibutyltin oxide as a polymerization initiator. This was stirred in a mantle heater under a nitrogen atmosphere at 135 ° C. while styrene and the like were dropped from a dropping funnel, and then heated to 230 ° C. for reaction. The softening point of the obtained polyester resin I is 15
The temperature was 0 ° C, the glass transition point was 62 ° C, and the acid value was 24.5 KOHmg / g.

40 parts by weight of polyester resin H (L form), 60 parts by weight of polyester resin I (H form), polyethylene wax (800P; manufactured by Mitsui Petrochemical Industries, Ltd .; 160 ° C.)
Melt viscosity at 5400 cps; softening point 140 ° C) 2 parts by weight, polypropylene wax (TS-200; manufactured by Mitsui Chemicals, Inc .; 16
Melt viscosity at 0 ° C 120cps; Softening point 145 ° C; Acid value 3.5KOH
mg / g) 2 parts by weight, acidic carbon black (Mogal L;
8 parts by weight of Cabot Corporation; pH 2.5; average primary particle size of 24 nm) and 2 parts by weight of a metal complex of salicylic acid: compound D are sufficiently mixed with a Henschel mixer, melt-kneaded with a twin-screw extruder, cooled, and then cooled. After coarse grinding with a hammer mill,
Medium pulverization using a pulverizer (KTM: manufactured by Kawasaki Heavy Industries, Ltd.)
Jet crusher (AFG: manufactured by Hosokawa Micron)
And pulverized. Thereafter, toner particles G having a volume average particle diameter of 7.5 μm were obtained by air classification (ATP: manufactured by Hosokawa Micron Corporation).

Comparative Examples 2, 3, and 4: Production Example H of Toner
I, J Salicylic acid metal complex: Toner particles H, I, and J were obtained in the same manner as in Production Examples DF of the toner, except that Compound E was used instead of Compound D. Comparative Example 5 Toner Production Example K Metallic Salicylate: Toner particles K were prepared in the same manner as in Production Example A of toner except that a commercially available chromium salicylate complex E-81 (manufactured by Orient Chemical Industries) was used instead of compound A. Obtained. The chromium salicylate complex E-81 used here was
The loss on heating at 200 ° C. was 13% by weight. Comparative Example 6: Toner Production Example L Metal salicylate complex: Toner particles L were prepared in the same manner as in Production Example A of toner except that a commercially available zinc salicylate complex E-84 (manufactured by Orient Chemical Industry Co., Ltd.) was used instead of Compound A. Obtained. The zinc salicylate complex E-84 used here
The loss on heating at 0 ° C. was 15% by weight.

0.5% by weight of hydrophobic silica fine particles (R-972; manufactured by Nippon Aerosil Co., Ltd.) and strontium titanate fine particles (particle size: 350 nm, BET specific surface area) having a BET specific surface area of 140 m ² / g : 9 m ² / g) 0.5 wt% was added and mixed for 3 minutes at a peripheral speed of 40 m / sec using a Henschel mixer, and then sieved with a sieve having openings of 106 μm to prepare toners GL for evaluation.

The following physical properties of the toners obtained in the above Examples and Comparative Examples were measured as follows. -The volume average particle size (D50) of the toner is measured using a Coulter Multisizer II (manufactured by Coulter Counter) with an aperture tube of 50 µm, and the particle size is twice or more the volume average particle size (> 2D). And the proportion (number%) of particles having a particle diameter (<１D) of / or less of the volume average particle diameter were simultaneously determined. The average circularity is (perimeter of a circle equal to the projected area of the particle /
Perimeter of a projected particle image) and was measured in an aqueous dispersion using a flow type particle image analyzer (FPIA-2000: manufactured by Toa Medical Electronics Co., Ltd.). In addition, the standard deviation of circularity (roundness SD)
Was also analyzed.

Table 1 summarizes the results obtained.

[Table 1]

(Two-component developer) 2 g of each toner obtained in the examples and comparative examples and 28 g of a carrier described below were put in a 50 cc plastic bottle, placed on a rotating base, and rotated at 1200 rpm for 3, 10, and 30 minutes (mixing). ) To prepare a developer. The charge amount of the developer thus obtained was measured, and the sharpness of the charge amount distribution was ranked based on Mp described later.

The method of measuring the charge amount and Mp will be described below with reference to FIG. The rotation speed of the magnet roll (3)
The developer was set at 100 rpm, and the developer (6) was used after stirring as described above. 3 g of the developer (6) is weighed with a precision balance, and is placed on the entire surface of the conductive sleeve (2) so as to be uniform. Next, from the bias power supply (4),
A bias voltage is sequentially applied from 0 to 10 kV, the sleeve (2) is rotated for 5 seconds, and the potential Vm when the sleeve (2) is stopped is read. At that time, the weight Mi of the separated toner (7) attached to the cylindrical electrode (1) is measured by a precision balance, and the average toner charge amount is obtained. The weight% of the mass of the toner thus obtained is plotted on the vertical axis, and the charge amount Q / M is logarithmically plotted on the horizontal axis. In this graph, the horizontal axis (Q / M) of ^100-
One scale that divides the range of 10 ² into 20 equals one channel,
The cumulative weight% (Mp) of the three channels is determined in order from the one with the largest weight% in this Q / M 1 channel.

The ranking of the sharpness of the charge amount distribution was as follows.

Further, the obtained developer at the time of mixing for 10 minutes was mixed with HH (35 ° C./80% RH) and LL (10 ° C./15% R).
After being left for 24 hours in the environment of H), the charge amount was measured by the above-described method using the charge amount measuring device shown in FIG.
The environmental stability was evaluated according to the following ranking. ：: [(LL charge amount) − (HH charge amount)] / HH charge amount × 100:
(%) Was less than 20%, which was no problem. Δ: The above value was 20% or more and less than 30%, which was practically acceptable. X: The above value was 30% or more, and there was a problem in practical use.

Table 2 summarizes the obtained results.

[Table 2]

Manufacture of carrier 100 parts by weight of polyester resin (manufactured by Kao Corporation: NE-1110)
Magnetic particles (magnetite; EPT-1000: manufactured by Toda Kogyo) 70
0 parts by weight and 2 parts by weight of carbon black (Mogal L; manufactured by Cabot) were sufficiently mixed with a Henschel mixer, and the mixture was melt-kneaded at 180 ° C. in the cylinder section and 170 ° C. in the cylinder head section using a twin-screw extruder. The kneaded product was cooled, then coarsely pulverized by a hammer mill, finely pulverized by a jet pulverizer, and classified to obtain carrier particles. At this time, by changing the pulverization and classification conditions, the volume average particle size 40μ
m binder type carrier was obtained.

(One-Component Developer) The full-color toners selected in the above Examples and Comparative Examples were evaluated for the following items. The initial evaluation was performed in an H / H environment (30 ° C /
85% RH) and predetermined print patterns (Y, M, C, Bk total 6%) under L / L environment (10 ° C / 15% RH)
Was performed in accordance with the following evaluation method. After the initial evaluation, the above print pattern was used under N / N environment (25 ° C / 50% RH).
Evaluation was performed after continuous copying of 000 sheets. The evaluation method after continuous copying of 3000 sheets is the same as the following evaluation method except that the evaluation was performed in an N / N environment and the evaluation was performed after copying 3000 sheets. The used copying machine is a modified type in which a full-color image forming apparatus (manufactured by Minolta) having the configuration shown in FIG. 4 is provided with a brush cleaning device shown in FIG.

[0091] The fog color toner, was loaded into the modified full-color image forming apparatus (manufactured by Minolta Co.), B by 4 color superimposition ne printing /
Copy images obtained by copying 10 character pattern images having a W ratio of 30% were visually observed and evaluated according to the following ranking. The four types of toner are applied to the four developing devices in order of layer formation on the intermediate transfer belt from the bottom in the order of Y, M, C, and Bk.
It is loaded to be. ：: Fog was hardly observed; Δ: Fog was slightly observed, but there was no practical problem; ×: Fog was present over the entire surface, and there was a practical problem.

[0092] The hollowing color toner, was loaded into the modified full-color image forming apparatus (manufactured by Minolta Co.), copies the full-color image (General pattern) by 4 color superimposition ne printing, a full-color copy image after 10 sheets copying, Evaluation was made according to the following ranking. Note that the four types of toners are applied to four developing devices in order of layer formation on the intermediate transfer belt from the bottom, Y,
M, C, and Bk are loaded. ：: no hollowing occurred on the copied image; Δ: slight hollowing occurred on the copied image, but no practical problem; ×: many hollowing occurred on the copied image. There was a practical problem.

The scattered full-color toner is loaded into the above-mentioned modified full-color image forming apparatus (manufactured by Minolta), and a full-color line image (general pattern) is copied by four-color overprinting.
The full-color copy image after one sheet copy was visually observed and evaluated according to the following ranking. The four types of toners are loaded in the four developing devices such that the layers are formed in the order of Y, M, C, and Bk from the bottom on the intermediate transfer belt. ：: no toner scattering was observed around the line copied image; Δ: toner scattering was found around the line copied image, but there was no practical problem; ×: toner was splashed around the line copied image. Were often recognized and recognized as bleeding, and had a practical problem.

The transferable full-color toner is loaded into the above-mentioned modified full-color image forming apparatus (manufactured by Minolta), and yellow, magenta, cyan, red, green, and blue (hereinafter, Y, M, C,
R, G, and B) and six types (six colors) of solid patterns are copied and evaluated according to the following ranking based on the ratio of the amount of toner adhered on the photosensitive drum to the amount of toner adhered on the photosensitive drum in the tenth copy process. did. ：: The above ratios for the six types of patterns were all 80% or more; Δ: The minimum value among the above ratios for the six types of patterns was 70% or more and less than 80%; The minimum value of the above ratios for the pattern was less than 70%.

[0095] 10 sheets of conformability B / W ratio of 30%, after the sheet passing, and print out the images of B / W100% to evaluate its density unevenness. ：: No density unevenness, Δ: Slight density unevenness was generated, but no practical problem was observed. X: Density unevenness was generated, and there was a practical problem.

An image of a 2-dot half-tone dot is reproduced at a dot reproducibility of 600 dpi, and a loupe (50
Observing the dots at ×), the dots are reproduced one by one, and the variation in the dot size is small ○, the dot and the dot are separated and there is no loss, but the variation in the dot size is A large number of samples was evaluated as Δ, and a dot which was missing or stuck to each of the two dots and was not sufficiently reproduced was evaluated as ×.

Line image reproducibility A 2-dot line image is formed at 600 dpi, and a loupe (50
Observe the line image at ×), and if the line has a small rattling and the line width is small, o is acceptable, although there is some variation in the line rattling and line width, but it is acceptable for practical use (by visual observation). The evaluation was evaluated as “Poor” when there was a defect in the line image or the line was loose and the line width was so large that it was unacceptable for practical use (by visual observation).

Tables 3 and 4 summarize the evaluation results.
Shown in

[Table 3]

[0099]

[Table 4]

The measuring method is described below.・ Method for measuring TG of salicylic acid and salicylic acid metal complex The TG was measured using TG / DTA-200 (manufactured by Seiko Denshi), using alumina (Pt pan) as a reference and heating a sample of about 10 mg at a heating rate of 10 ° C. The measurement was performed at 28/500 ° C under the condition of / min. The measurement was performed while purging nitrogen gas. TG data of salicylic acid and salicylic acid metal complex; Compound B are shown in FIGS. 2 and 1, respectively.

Method for measuring glass transition point Tg of resin Using a differential scanning calorimeter (DSC-200: manufactured by Seiko Instruments Inc.), alumina was used as a reference, and a 10 mg sample was heated at a rate of 10 ° C./min. The temperature was measured between 20 and 120 ° C., and the shoulder value of the main endothermic peak was defined as the glass transition point.・ Measurement method of softening point Tm of resin Using a flow tester (CFT-500: manufactured by Shimadzu Corporation)
Pores of a die (diameter 1 mm, length 1 mm), pressure 20 kg / cm ^2, the flow ending point from the flow starting point for a sample of 1 cm ² were melted runoff under the conditions of heating rate 6 ° C. / min The temperature corresponding to 1/2 of the height was defined as the softening point. The molecular weight was determined by gel permeation chromatography (Type 807-IT; manufactured by JASCO Corporation) using tetrahydrofuran as a carrier solvent and calculating the molecular weight in terms of polystyrene.

The particle size of the carrier was measured using a Coulter Multisizer II (manufactured by Coulter Counter) with an aperture tube of 150 μm.・ Acid value is 0.1% by dissolving 10mg sample in 50ml toluene
This is a value calculated from the consumption of the N / 10 potassium hydroxide / alcohol solution by titration with a previously standardized N / 10 potassium hydroxide / alcohol solution using a mixed indicator of bromthymol blue and phenol red. -The hydroxyl value was expressed in mg of potassium hydroxide required to treat a weighed sample with acetic anhydride, hydrolyze the obtained acetyl compound, and neutralize liberated acetic acid.

[0103]

The toner of the present invention has excellent chargeability, that is, excellent charge rising property, charge stability and charge environment stability, and can be obtained by any of a wet granulation method and a kneading and pulverizing method. Further, the toner of the present invention has a small particle size, a high average circularity, a small variation in shape, and excellent chargeability. Further, the toner of the present invention is excellent in chargeability and image quality.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of a TG curve of a salicylic acid metal complex used in a toner of the present invention.

FIG. 2 is a graph showing a TG curve of salicylic acid.

FIG. 3 shows a schematic configuration diagram of a charge amount distribution measuring device used for measuring a charge amount distribution.

FIG. 4 is a schematic configuration diagram of a full-color image forming apparatus.

FIG. 5 shows a schematic configuration diagram of an example of a brush cleaning device.

[Explanation of symbols]

1: cylindrical electrode, 2: conductive sleeve, 3: magnetic roll,
4: bias power supply, 5: measuring capacitor, 6: developer, 7: separated toner, 10: photosensitive drum, 11: charging brush, 12: cleaner, 20: laser scanning optical system, 30: full color developing device, 31C , 31M, 31Y, 31Bk: developing device, 32: developing sleeve (sleeve), 34: toner regulating blade (blade), 40: intermediate transfer belt, 41: support roller, 42: support roller, 43: tension roller, 44: Tension roller, 46: primary transfer roller, 47: secondary transfer roller, 60: paper feed unit, 61: paper feed tray, 62: paper feed roller,
63: Timing roller, 66: Air suction belt,
70: fixing device, 71: vertical conveyance path, 201: image carrier, 202: toner, 211: brush member, 211a: brush, 212: power supply, 2
13: Flap stick, 214: Collection roller, 215: Power supply, 216, 2
17: scraping member, 218: toner transport coil, 221: cleaning agent, 222: cleaning agent supply means (regulating blade).

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 6, 2000 (200.7.6)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

Claims (2)

[Claims] 1. A toner for developing an electrostatic image, comprising at least a binder resin, a colorant and a metal salicylate complex, wherein the weight loss at 200 ° C. of the metal salicylate complex is 12% by weight or less. . 2. The method according to claim 1, which is obtained by a wet granulation method using at least a binder resin or a resin monomer, a coloring agent, and a metal salicylate complex, and wherein the weight loss of the metal salicylate complex at 200 ° C. is 12% by weight or less. Toner for developing an electrostatic image.