JP2000284542A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner capable of stably obtaining high image quality even in the case of using it in low and high humidities and preventing occurrence of image defects even if it is left as it is, and capable of continuing to form images faithful to latent images for a long period. SOLUTION: This toner comprises at least a binder resin and a colorant and 2 kinds of organic metal compounds (a) and (b), and the organic metal compound (a) is a zirconium organic metal compound produced by reaction of zirconium with an aromatic hydroxycarboxylic acid, and the organic metal compound (b) is an organic metal compound produced by reaction of a metal atom selected from Al, Zn, Ti, Sr, B, Si, Ni, Fe and Cr with an aromatic hydroxycarboxylic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art Toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner retain electric charge, it is possible to use the frictional charging property of a resin which is a component of the toner. However, in this method, the charging of the toner is not stable.
Density rises slowly and fog is easy. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

At present, as charge control agents known in the art, as triboelectric charge control agents, metal complex salts of monoazo dyes, metal complex salts such as hydroxycarboxylic acid, dicarboxylic acid and aromatic diol; Resins containing components are known. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known as positive friction charge control agents.

However, most of these charge control agents are colored and unsuitable for color toners. Many colorless, white or light-colored toners applicable to color toners have insufficient performance. They have drawbacks such as lack of uniformity of highlights and large fluctuations in image density in a durability test.

In addition, some charge control agents have the following disadvantages. It is difficult to balance image density and fog, it is difficult to obtain sufficient image density in a high humidity environment, poor dispersibility in resin, and adversely affects storage stability, fixability, and offset resistance. .

Conventionally, metal complexes and metal salts of aromatic carboxylic acids have been disclosed in JP-A-53-127726 and JP-A-57-127726.
JP-A-1111541, JP-A-57-124357, JP-A-57-104940, JP-A-61-6
JP-A-9073, JP-A-61-73963, JP-A-61-267058, JP-A-62-10515
No. 6, JP-A-62-145255, JP-A-62-145255
JP-A-2-163601, JP-A-63-208865, JP-A-3-276166, JP-A-4-84
Some proposals have been made, such as Japanese Patent Application Laid-Open No. 141 and JP-A-8-160668. However,
These publications are all excellent in terms of imparting triboelectric charging.However, with a simple developing device configuration, stable developability can be obtained regardless of environmental changes, aging, and use conditions. There are few things that can be done. In addition, there are few examples in which replenishment is repeated and stable developability is obtained even during long-term durability. Further, there are many cases in which there is an influence of other raw materials and restrictions on other raw materials occur. At present, none of the above items are satisfactory.

Japanese Patent Application Laid-Open Nos. 5-45924 and 5-72795 propose that a metal complex of an aromatic carboxylic acid, a metal salt and another organometallic compound are contained to achieve the above-mentioned object by a synergistic effect. No., JP-A-9-1277
No. 20, JP-A-9-179400 and the like. However, those proposed in these publications are all excellent to some extent from the viewpoint of providing triboelectric charging, but are stable in a simple developing device configuration regardless of environmental changes, aging, and use conditions. Developability is rarely obtained. In addition, there are few examples in which replenishment is repeated and stable developability is obtained even during long-term durability.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which has solved the above-mentioned problems.

It is an object of the present invention to provide a toner which can stably provide high image quality even when used under low humidity or under high humidity and does not cause image defects even when left unattended. .

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which can provide excellent developability even when it is used up or when a large amount of toner is replenished at a time in a replenishment type or single use cartridge type developing device (CRG). .

An object of the present invention is to provide a toner capable of continuously obtaining an image faithful to a latent image even in long-term durability.

[0013]

According to the present invention, there is provided a toner having at least a binder resin, a colorant and two kinds of organometallic compounds (a) and (b), wherein the organometallic compound (a) is , An organic zirconium compound produced by the reaction of zirconium with an aromatic hydroxycarboxylic acid, wherein the organometallic compound (b) comprises Al, Zn, Ti,
The present invention relates to a toner which is an organometallic compound produced by a reaction with an aromatic hydroxycarboxylic acid containing a metal selected from Sr, B, Si, Ni, Fe, and Cr.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors provide a toner having at least a binder resin, a colorant and two kinds of organometallic compounds (a) and (b), wherein the organometallic compound (a) is made of zirconium and An organozirconium compound produced by a reaction with an aromatic hydroxycarboxylic acid, wherein the organometallic compound (b) comprises Al, Zn, Ti, Sr, B, Si,
An organic metal compound produced by a reaction with an aromatic hydroxycarboxylic acid containing a metal selected from Ni, Fe, and Cr. Fluctuation, aging,
It has been found that, regardless of the use condition, stable developability is obtained, and stable developability is obtained even during long-term durability by repeated replenishment.

Further, the present inventors have found that the use of a reaction product of zirconium and an aromatic hydroxycarboxylic acid ensures good startup and good mixing stability, while maintaining a high level even in a high humidity environment. It has been found that a charge amount can be obtained and a toner free from excessive charging can be obtained even in a low humidity environment. Furthermore, the present inventors have conducted intensive studies and as a result, in addition to the organic zirconium compound (a) of the present invention, Al, Zn, Ti, Sr, B, Si, N
It has been found that the object of the present invention is highly achieved by using an organometallic compound (b) selected from i, Fe, and Cr in combination. This is because the presence of sites having different charging characteristics and environmental characteristics on the toner surface in addition to the good charging characteristics of the organic zirconium compound (a) allows the environmental characteristics to be further improved by the synergistic effect, although the reason is not clear. It seems that it was done.

The organic zirconium compound (a) of the present invention is preferable because it has excellent transparency and can provide a clear color image for a color toner. In this case, the organometallic compound used in combination is preferably Al or Zn.

Further, the ratio (a) / (b) of the organometallic compounds (a) and (b) in the toner is preferably 0.1 to 10.

The organozirconium compound (a) and organometallic compound (b) of the present invention may contain less than 20% by weight of aromatic hydroxycarboxylic acid based on the reaction product, and hafnium based on zirconium element. The element may be contained at less than 20 wt%.

The organic zirconium compound (a) of the present invention
Is composed of a plurality of types of compounds such as compounds having different coordination numbers and bond numbers of aromatic hydroxycarboxylic acids and compounds having different structures. The aromatic hydroxycarboxylic acid units are contained in an amount of 1.2 to 1 per mole of zirconium atom. It is characterized by containing 2.8 moles, whereby excellent development stability is obtained, transferability is also improved, and toner utilization efficiency is improved by improving toner utilization. In order to obtain better developability, the amount is preferably from 1.3 to 1.7 mol. If it is less than 1.2 mol, the rise of triboelectric charging tends to be slow, and the density change, density unevenness, and fog increase when the CRG is shaken immediately before the CRG is completely used up tend to occur. In the replenishment system, when a large amount of toner is replenished, when the toner remaining in the developing device and the replenishment toner are mixed, density reduction, density unevenness, fog increase, and the like are likely to occur. If it exceeds 1.8 moles, a decrease in image density, an increase in fog, and the like are observed when left for a long period of time.

It is preferred that the aromatic hydroxycarboxylic acid is a compound represented by the following formula (I) in order to obtain a good charge rise and to stabilize developability such as image density, fog and image quality.

[0021]

Embedded image [In the general formula (I), R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl group, carboxyl group, halogen,
Represents a nitro group, an amino group, or a carbamoyl group, and the substituents R may be linked to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. May have 1 to 8 substituents R,
Each may be the same or different. ]

Above all, the aromatic hydroxycarboxylic acid is a salicylic acid having an alkyl group as a substituent, so that a high charge amount can be obtained, and a high image density and a high image quality with a faithful latent image reproduction can be achieved.

The following are specific examples of the aromatic hydroxycarboxylic acid used in the present invention.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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As a method for incorporating the organic zirconium compound (a) of the present invention into a toner, there are a method of adding the compound to the inside of the toner and a method of externally adding the compound. When adding internally, a preferable addition amount is 0.1 to 100 parts by weight of the binder resin.
It is used in an amount of 10 parts by weight, more preferably 0.5 to 5 parts by weight. In the case of external addition, the amount is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, and it is particularly preferable to mechanochemically fix the toner to the toner surface.

Further, it has been found that excellent developability can be obtained by combining with a magnetic toner containing a magnetic substance or by applying the toner to a toner used in a one-component developing method. That is, the organic zirconium compound (a) of the present invention is suitable for a negative charge control satisfying these requirements for a magnetic toner or a toner for one-component development that requires a rapid rise of charging with a small frictional charging opportunity and a high charge amount. It becomes an agent. As described above, it is suitably used for the toner used in the one-component developing method, and is most suitable for the toner used in the non-magnetic one-component developing method.

Further, in the present invention, when used together with a binder resin having an acid value, the polarity of water molecules can be used to greatly increase the effect of enhancing charging. Also, by using two or more kinds of waxes having different melting points or different compositions, the dispersibility can be made very good, and the durability and charge uniformity can be improved.

As described above, not only the amount of charge in a low-humidity and high-humidity environment becomes sufficient, but also a decrease in density during long-term durability can be suppressed.

The present invention is particularly suitable for magnetic toners containing magnetic iron oxides having various different elements. Oxides of different elements, hydroxides, iron oxides incorporating different elements, and iron oxides mixed with different elements adsorb water molecules,
It is possible to effectively enhance charging using the polarity of water molecules. When used together with a binder resin having an acid value, charge enhancement can be performed more effectively.

The organic zirconium compound (a) of the present invention
Since the zirconium atom easily takes eight coordinations and the oxygen such as a carboxyl group or a hydroxyl group is easily coordinated, the chance of the zirconium atom being coordinated or bonded with a carboxyl group or a hydroxyl group is increased. When used with a binder resin having an acid value, such as a styrene resin having a carboxyl group or a hydroxyl group as a functional group, or a polyester resin as a binder resin, the resin can be easily blended into the binder resin, has excellent dispersibility, and has excellent dispersibility. , And uniform charge and durable stability of charge can be obtained. Further, the influence on the transparency of the toner is reduced, which is preferable for expressing a vivid color for the color toner. Also, via coordination of the carboxyl group of the binder resin and the zirconium atom of the hydroxyl group,
Since the polymer chains can be crosslinked, the binder resin can be made to have a large rubber elasticity, excellent in releasability, and can effectively prevent the fixing member from being stained. In addition, kneading shear can be applied during melt-kneading during the production of the toner, the dispersion of the magnetic substance, the pigment and the dye can be improved, and a toner having high coloring power and clear color can be obtained.

The combined use of the organozirconium compound (a) of the present invention and the organometallic compound (b) of the present invention provides excellent triboelectric charging ability and a high charge amount. This is a suitable charge control agent for the toner. Furthermore, in addition to the good dispersibility of the organic zirconium compound (a) itself, when a binder resin having an acid value is used, the dispersibility of the magnetic material is improved, so that durability and uniformity of charging can be obtained. It becomes.

Further, the organic zirconium compound (a) of the present invention has some effect on the surface tension of the binder resin used in the toner, and it is found that the use of a plurality of kinds of waxes gives a very excellent releasability. Was. This makes it possible to obtain a toner that has excellent offset resistance and is effective in preventing contamination of the fixing member. Further, in combination with the organometallic compound (b) of the present invention, and together with a binder resin having an acid value,
This effect is particularly great when used.

Further, when the organic zirconium compound (a) of the present invention and the organometallic compound (b) of the present invention are used in combination, the decrease in the developing property of the toner due to standing is small. Even at the time of re-use after pausing, the decrease in image density can be reduced.

Further, when the organozirconium compound (a) of the present invention and the organometallic compound (b) of the present invention are used in combination, the occurrence of insufficiently charged or overcharged toner particles is reduced, and the amount of scattered toner is reduced. Deterioration of developing property due to mixing of toner is reduced.

For example, the toner scatters and adheres to the charging wire, causing abnormal discharge, disturbing the latent image, causing streak-like image abnormalities, and causing streak-like transfer failure, thereby easily causing image defects. However, the toner of the present invention can reduce these phenomena. This scattering of toner also causes fusing and back contamination in the case of a contact charging member, but the toner of the present invention can also reduce these phenomena. In addition, since the in-flight scattering itself is reduced, image stains and the like due to these can be reduced.

In addition, when the old and new toners are mixed, for example, a large amount of toner is replenished, or when the remaining amount of toner in the cartridge is reduced and the cartridge is shaken, uneven development may occur. These image degradations can be reduced. In addition, it is possible to reduce the density unevenness of halftone due to the generation of poorly charged particles.

The organic zirconium compound (a) of the present invention
Is a reaction product of zirconium and an aromatic hydroxycarboxylic acid, and is an organic zirconium compound in which an aromatic hydroxycarboxylic acid is coordinated or / and bound to a zirconium atom, and is a zirconium complex, a zirconium complex salt,
Zirconium salts or mixtures thereof.

The zirconium complex or zirconium complex salt includes a complex compound in which 1 to 4 aromatic hydroxycarboxylic acids are chelated and a complex compound in which 1 to 6 aromatic hydroxycarboxylic acid anions are coordinated. A mixture of different numbers and coordination numbers may be used. The zirconium salt may be a metal salt having 1 to 4 aromatic hydroxycarboxylic acid anions, and may be a mixture of those having different numbers of aromatic hydroxycarboxylic acid ions.

Further, the following general formula (II):
Examples include compounds selected from compounds having a structure represented by (III), (IV), (V), and the like.

[0046]

Embedded image In the general formula (II), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group. Group, carboxyl group, halogen,
A nitro group, an amino group or a carbamoyl group, which may be linked to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring; in this case, the ring may have a substituent R; It may have 1 to 8 groups R, which may be the same or different, and C ₁ represents a monovalent cation, hydrogen, an alkali metal, ammonium or alkylammonium; Represents an integer of 8,
n represents 2, 3 or 4, m represents 0, 2 or 4, and the aromatic hydroxycarboxylic acid serving as a ligand in each complex or complex salt may be the same or different; Also, a mixture of complex compounds having different numbers of n and / or m may be used. Also, a mixture of complex salts having different counter ions C ₁ may be used. From the viewpoint of improving the dispersibility of the complex or complex salt in the binder resin or improving the chargeability, the substituent R is preferably an alkyl group, an alkenyl group, a carboxyl group or a hydroxyl group, and C ₁ is hydrogen,
Sodium, potassium, ammonium or alkyl ammonium is preferred.

[0047]

Embedded image In the general formula (III), R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group. Group, carboxyl group, halogen, nitro group, amino group or carbamoyl group,
They may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. In this case, the ring may have a substituent R, and may have 1 to 8 substituents R. A may be the same or different, and A represents an anion, a halogen, a hydroxide ion, a carboxylate ion, a carbonate ion, a nitrate ion, a sulfate ion, a cyanide ion or a thiocyan ion; May have different ions, C ₁ represents a monovalent cation, hydrogen, a monovalent metal ion, ammonium or alkylammonium, n represents 1, 2, 3, or 4, and k represents 1, 2,
Represents 3, 4, 5, or 6, and m is 0, 1, 2, 3, or 4.
Represents The aromatic hydroxycarboxylic acids serving as ligands in each complex or each complex salt may be the same or different, and may be a mixture of complex compounds having different numbers of n and / or m. . It may be a mixture of two or more complex compounds having different cations C ₁ and / or anions A. When A is a divalent anion, the counter ion coefficient k is doubled.

[0048] From the viewpoint of the viewpoint or electrification enhancer to improve the dispersibility of the complex or complex salt of the binder resin, examples of the substituent R, an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group are preferred, the C ₁ is Hydrogen, sodium, potassium, ammonium and alkylammonium are preferred, and A is preferably a hydroxyl ion or a carboxylate ion.

The zirconium complex or complex salt used in the present invention is a hexacoordinate or octacoordinate complex compound. In the octacoordinate, a dinuclear complex compound in which a ligand is bridged becomes a hexanuclear complex compound. There are complex compounds that are coordinated, and there is also a dinuclear complex compound in which a ligand such as a hydroxyl group is crosslinked to polymerize the complex compound one after another.

Representative structures of such complex compounds are exemplified by the following general chemical formulas (a) to (x). The following structures include those having no ligand L. In the formula, X and Y represent -O- and -COO-;
Represents an anionic ligand, L represents a neutral ligand, and C represents a counter cation. (V) to (x) omit the counter cation.

[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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Further, a complex compound having a structure in which a hydroxyl group or a carboxyl group of an aromatic ring is coordinated to different zirconium may be used, for example, a compound represented by the formula (y) as a partial structure.

[0058]

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The specific structure is represented by the formula (z).

[0060]

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Here, p represents an integer of 1 or more, q represents an integer of 2 or more, and in the formula (z), an anion ligand;
The neutral ligand and counter cation are omitted.

[0062]

Embedded image In the general formulas (IV) and (V), R represents hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group,
Represents a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group, an amide group or a carbamoyl group, and is connected to an aliphatic ring, an aromatic ring or a heterocyclic group. A ring may be formed. In this case, the ring may have a substituent R, and the substituent R may have 1 to 8 substituents, which may be the same or different. , A1 represents a monovalent anion, a halogen ion, a hydroxyl ion, a nitrate ion or a carboxylate ion;
A2 represents a divalent anion, sulfate ion, hydrogen phosphate ion or carbonate ion, 1 represents an integer of 1 to 7,
Represents 1, 2, 3 or 4. In each metal salt, the anion A1, the anion A2, and the aromatic hydroxycarboxylic acid serving as the acid ion may be the same or different. Further, a mixture of salts having different numbers of n may be used. From the viewpoint of improving the dispersibility of the metal salt in the binder resin or improving the chargeability, the substituent is preferably an alkyl group, an alkenyl group, a carboxyl group, a hydroxyl group, or an acyloxy group, and excellent environmental stability is obtained. Also, it is excellent in dispersibility in a binder resin, and excellent durability can be obtained.

The organic zirconium compound of the present invention is prepared by dissolving a zirconium compound such as zirconium chloride, zirconium sulfate or zirconium organic acid in water, an alcohol or an aqueous alcohol solution, and adding an aromatic hydroxycarboxylic acid and an alkali metal salt thereof. Alternatively, it is synthesized by adding an aromatic hydroxycarboxylic acid and an alkali agent. The reaction product is obtained by filtering and washing with water, an alcohol, and an aqueous alcohol solution. These organic zirconium compounds may be recrystallized with an alcohol aqueous solution or the like and purified by washing with alcohol or water. You. In the case of a complex salt, a complex salt having various counter ions can be obtained by treating the product with a mineral acid, an alkali agent, or an amine agent. In the present invention, a zirconium complex salt having a plurality of counter ions such as hydrogen ions, alkali metal ions, and ammonium ions is also included.

In the present invention, as a means for adjusting the content of the aromatic hydroxycarboxylic acid unit contained in the organic zirconium compound, there is a method in which the content is controlled by a charging ratio of the zirconium compound to the aromatic hydroxycarboxylic acid or a reaction time. Can be Further, a method of controlling the dropping time and the reaction temperature when dropping the aromatic hydroxycarboxylic acids into the zirconium compound solution can also be used.

One example of a method for calculating the number of moles of aromatic hydroxycarboxylic acid per mole of zirconium atom contained in the organic zirconium compound of the present invention is shown below.
It is not particularly limited to this.

Method for quantifying zirconium atoms: About 100 mg of an organometallic compound is precisely weighed in a beaker, heated and decomposed with an acid such as hydrochloric acid or nitric acid, and the decomposition solution is made constant in diluted nitric acid and further diluted as necessary. .

The zirconium element concentration in the solution obtained by the above pretreatment was calculated by ICP emission spectroscopy. At the same time, the amount of hafnium element can be determined.

In the present invention, a sequential ICP emission spectrometer SPS1 manufactured by Seiko Instruments Inc.
After using 200 VR, the conventional method was followed. The measurement was performed in a parallel test with 3 repetitions (n = 3) from the pretreatment.

Method for quantifying aromatic hydroxycarboxylic acid:
An organometallic compound, about 100 mg is precisely weighed in a sample tube,
Heat decomposition with an acid such as hydrochloric acid or nitric acid dissociates zirconium and aromatic hydroxycarboxylic acid. 10 mg of n-tridecane (internal standard) and acetonitrile (10 ml) are added thereto and shaken vigorously to dissolve the dissociated aromatic hydroxycarboxylic acid. 1 ml of this solution was filtered through a 0.5 μm filter, and a silylating agent (0.5 ml) such as N, O-bistrimethylsilylacetamide was added to the filtrate, and the mixture was vigorously shaken to obtain an analysis sample. After standing for about 20 minutes, the sample was subjected to gas chromatography analysis, and thereafter, the amount of aromatic hydroxycarboxylic acid was quantified according to a standard method.

The number of moles of zirconium atoms was calculated from the determined content of the zirconium element and the atomic weight of zirconium, and the aromatic hydroxycarboxylic acid and the molecular weight of the aromatic hydroxycarboxylic acid were used to calculate the aromatic hydroxycarboxylic acid. Calculate the number of moles of carboxylic acid and determine the ratio.

The kind of the binder resin used in the present invention includes styrene resin, styrene copolymer resin, polyester resin, polyol resin, polyvinyl chloride resin, phenol resin, natural modified phenol resin, and natural resin modified male. Examples include acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, cumarone indene resin, and petroleum resin.

As comonomers for the styrene monomer of the styrene copolymer, styrene derivatives such as vinyltoluene; acrylic acid; methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-acrylic acid Acrylates such as ethylhexyl and phenyl acrylate; methacrylic acid; methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate and octyl methacrylate; maleic acid; butyl maleate, methyl maleate and dimethyl maleate Dicarboxylic acid ester having a double bond such as: acrylamide, acrylonitrile, methacrylonitrile, butadiene; vinyl chloride; vinyl esters such as vinyl acetate and vinyl benzoate; ethylene, propylene Emissions, such as ethylene-based olefin butylene; vinyl methyl ketone, such as vinyl vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl propionate ether. These vinyl monomers are used alone or in combination of two or more.

[0073] binder resin is a styrene - For acrylic resin, a molecular weight distribution by GPC of THF-soluble matter, at least one peak exists in a molecular weight region of 3,000 to 50,000, molecular weight ¹⁰⁵ or more Preferably, there is at least one peak in the region. Further, the THF-soluble component is preferably a binder resin in which a component having a molecular weight distribution of 10 ⁵ or less accounts for 50 to 90%.

More preferably, the molecular weight is 3,000-3.
In the region of 000, most preferably 5,000 to 2
It is preferable to have a main peak in the region of 0000. Further, it is preferable to have a subpeak in a region having a molecular weight of 10 ⁵ to 10 ⁸ (more preferably, a region having a molecular weight of 10 ⁵ to 10 ⁷ ).

When the binder resin is a polyester resin,
The molecular weight distribution of the THF-soluble component is 3,000 to 5
Preferably, there is at least one peak in the region of 0000. Further, the THF-soluble component is preferably a binder resin in which a component having a molecular weight of 10 ⁵ or less is 60 to 100%. More preferably, the molecular weight is 5,000 to 20,000.
It is preferable that at least one peak exists in the region of 0.

It is preferable that the THF-soluble portion of the toner has a main peak in the molecular weight distribution of GPC of 3,000 to 50,000 in the molecular weight distribution of GPC. Furthermore, at least one peak in the region of molecular weight of 3,000 to 30,000, preferably those having at least one peak in the ^{105 to 107} region.

In the toner having such peaks in the molecular weight distribution, the fixing property, the anti-offset property and the storability are well-balanced.

The toner containing the organic zirconium compound used in the present invention has a small variation in charging characteristics even under a high or low humidity environment, can maintain stable developing characteristics, and uses a binder resin having an acid value. In this case, the dispersibility is very good, and the organic zirconium compound is less missing from the toner, so that the durability is excellent.

Crosslinking of the polymer chain through the coordination of the carboxyl group and / or hydroxyl group in the binder resin to zirconium allows the binder resin component of the toner to exhibit rubber elasticity.

As a result, a toner having excellent releasability can be obtained, which not only has excellent anti-offset properties, but also prevents contamination of the fixing member, and causes clogging (jamming) of the transfer material due to poor separation at the fixing portion. ) Can be prevented.

Further, the toner particles can be made tough, and the development stability can be obtained. Further, crushing in the cleaning section can be prevented and the cleaning property can be stabilized. In addition, the fluidity of the toner is improved, and the change thereof is reduced, thereby contributing to the improvement of the stability of development and cleaning.

Further, the gloss of the fixed image can be suppressed, and the density fluctuation can be reduced. In addition, since the fixed image also becomes tough, the fixing stability is improved, and even when two-sided copying, multiple copying or a document feeder is used, each member is less stained, so that the occurrence of stains on the image is reduced. be able to. In the present invention, it is more effective if the cross-linking is such that THF-insoluble matter is generated.

Preferably, the THF-insoluble content is 1 to 70% by weight.
The above effect is sufficiently exhibited when the content is 5% to 60% by weight (based on the toner excluding the residual ash of the toner), more preferably 5 to 60% by weight (based on the toner excluding the residual ash of the toner). 70w
Attention must be paid to the case where the content exceeds t%, since the fixing property starts to decrease.

Further, the crosslinked structure of zirconium and a carboxyl group and / or a hydroxyl group is stronger than the crosslinked structure formed of other aluminum, chromium, iron or zinc because of the large zirconium atom and easy formation of a bond with an oxygen atom. However, it is very flexible. Here, by using an organometallic compound other than a zirconium compound in combination, crosslinking points having different degrees of crosslinking appear, and in particular, although the releasability and toughness are more excellent than used alone,
Fixability is not easily reduced. Even if the same amount of the cross-linking component and the THF-insoluble matter are contained, the effect of the addition is large and the balance is good.

The effect of zirconium cross-linking is greater even if the amount is small, and the adverse effects can be reduced even if the amount increases.

Further, it has been found that the toner of the present invention exhibits excellent charging ability in a frictional charging process with a developer carrying member. That is, regarding the toner containing the binder resin having an acid value and the organic zirconium compound, the charging ability with the developer carrier material shows that a large amount of charge can be generated even with a small contact with the developer carrier surface. all right.

The binder resin used in the present invention has an acid value of 1
mgKOH / g to 100 mgKOH / g, preferably 1 mgKOH / g to 70 mgKOH / g, and more preferably 1 mgKOH / g to 50 mgKOH / g.
mgKOH / g is good, especially 2 mgKOH / g to 4 mgKOH / g.
It is preferably 0 mgKOH / g. When the acid value of the binder resin is less than 1 mgKOH / g, the development stability and the durability stabilization effect due to the interaction with the organic zirconium compound and other organic metal compounds cannot be sufficiently exhibited,
The cross-linking effect is unlikely to appear. On the other hand, if it exceeds 100 mgKOH / g, the binder resin has a high hygroscopicity, the image density tends to decrease, and the fog tends to increase.

The acid value measured from the toner is 0.5 m
When the gKOH / g is in the range of 100 mgKOH / g, the above effect is sufficiently exhibited. Furthermore, 0.5mgKOH
/ G to 50 mgKOH / g, especially 2.0
It is preferably in the range of mgKOH / g to 30 mgKOH / g.

In the present invention, the acid values of the toner and the binder resin component are determined by the following method.

<Measurement of Acid Value> The basic operation is JIS K-0.
070. 1) 0.5 to 2.0 (g) of the crushed sample is precisely weighed, and the weight is defined as W (g). 2) The sample is placed in a 300 (ml) beaker, and 150 (ml) of a mixed solution of toluene / ethanol (4/1) is added and dissolved. 3) Using an ethanol solution of 0.1 mol / l KOH, titrate with a potentiometric titrator (for example, a potentiometric titrator AT-400 manufactured by Kyoto Electronics Co., Ltd. (win)
workstation) and automatic titration using an ABP-410 motorized burette is available). 4) The amount of the KOH solution used at this time is defined as S (ml), a blank is measured at the same time, and the amount of the KOH solution used at this time is defined as B (ml). 5) Calculate the acid value by the following equation. f is a factor of KOH.

Acid value (mgKOH / g) = ｛(S−B) ×
f × 5.61｝ / W

In the present invention, the binder resin or toner T
The molecular weight distribution by GPC using HF (tetrahydrofuran) as a solvent is measured under the following conditions.

The column was stabilized in a heat chamber at 40 ° C., and TH was used as a solvent at this temperature.
F at a flow rate of 1 ml / min.
Measure by injecting 0 μl. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value of a calibration curve prepared from several types of monodisperse polystyrene standard samples and the count value. As a standard polystyrene sample for preparing a calibration curve, for example, one having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK, and it is appropriate to use a standard polystyrene sample having at least about 10 points. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, showex GPC KF-801, 80 manufactured by Showa Denko KK
2, 803, 804, 805, 806, 807, 800
P combination or Tosoh TSKgel G10
00H (H _XL ), G2000H (H _XL ), G3000H
(H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ) and the combination of TSKguard column.

The sample is prepared as follows.

The sample is put in THF, left for several hours, shaken sufficiently, mixed well with THF (until the sample is no longer united), and left still for 12 hours or more. Then TH
The time of leaving in F is set to 24 hours or more. After that, sample processing filter (pore size 0.2 ~
0.5 μm, for example, Mysholi Disc H-25-2
(Manufactured by Tosoh Corporation) can be used. ) Is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the present invention, the THF-insoluble content of the binder resin itself or the toner is measured as follows.

A sample of 0.5 to 1.0 g was weighed (W ₁
g) and a cylindrical filter paper (for example, No. 86R manufactured by Toyo Roshi Kaisha, Ltd.) was put into a Soxhlet extractor, and THF2 was used as a solvent.
After extracting with a solvent for 10 hours and evaporating the soluble component solution extracted with the solvent, vacuum drying was performed at 100 ° C. for several hours, and the amount of the THF soluble component was weighed (W
₂ g). Calculate the weight of residual ash in the toner (W
₃ g).

The residual ash from combustion is determined by the following procedure. About 2.0 g of a sample is placed in a 30 ml magnetic crucible that has been precisely weighed in advance, and precisely weighed, and the weight (Wa) of the sample is precisely weighed. The crucible is placed in an electric furnace, heated at about 900 ° C. for 3 hours, allowed to cool in an electric furnace, allowed to cool in a desiccator at room temperature for 1 hour or more, and then accurately weighed. From this, the residual combustion ash (Wb) g is determined.

(Wb / wa) × 100 = residual ash content (wt%) From this content, the weight of the residual ash in the sample is determined.

The THF insoluble content is determined by the following equation.

[0101]

(Equation 1)

In the case of a binder resin, the THF-insoluble matter may be determined from the following equation.

[0103]

(Equation 2)

Examples of the monomer for adjusting the acid value of the binder resin include acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinyl acetic acid, isocrotonic acid, and angelic acid; Or β-alkyl derivatives; fumaric acid, maleic acid, citraconic acid, alkenyl succinic acid, itaconic acid, mesaconic acid,
Examples include unsaturated dicarboxylic acids such as dimethylmaleic acid and dimethylfumaric acid, and monoester derivatives or anhydrides thereof. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired binder resin. Among them, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid for controlling the acid value.

For example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate, monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc. Monoesters of α, β-unsaturated dicarboxylic acids such as monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate and monobutyl n-butenyladipate Monoesters of alkenyl dicarboxylic acid and the like can be mentioned.

The above-mentioned carboxyl group-containing monomer may be added in an amount of 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, based on 100 parts by weight of all the monomers constituting the binder resin.

The reason that the monoester monomer of dicarboxylic acid is selected as described above is that it has a low solubility in an aqueous suspension, while an ester having a high solubility in an organic solvent or another monomer. It is because it is preferable to use.

The binder resin of the toner and the composition containing the binder resin have a glass transition temperature (T
g) is 45-75 ° C, preferably 50-70 ° C.
If the Tg is lower than 45 ° C., the toner tends to deteriorate in a high-temperature atmosphere, and offset tends to occur during fixing.
On the other hand, when Tg exceeds 75 ° C., the fixability tends to decrease.

As a polymerization method that can be used in the present invention as a method for synthesizing the binder resin of the present invention, there are a solution polymerization method, an emulsion polymerization method and a suspension polymerization method.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, the reaction heat can be easily adjusted, and the phase in which the polymerization is performed (oil phase composed of a polymer and a monomer)
And the aqueous phase are separate, so that the termination reaction rate is low, resulting in a high polymerization rate and a high degree of polymerization. Further, due to the relatively simple polymerization process and the fact that the polymerization product is fine particles, in the production of toner,
There is an advantage as a method for producing a binder resin for a toner because it is easy to mix with a colorant, a charge control agent and other additives.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to take out the polymer. To avoid this inconvenience, suspension polymerization is convenient.

In the suspension polymerization, 100 parts by weight or less of the monomer (preferably 1 part by weight) is added to 100 parts by weight of the aqueous solvent.
(0 to 90 parts by weight). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like, and generally 0.05 to 1 part by weight based on 100 parts by weight of the aqueous solvent. The polymerization temperature is suitably from 50 to 95 ° C, but is appropriately selected depending on the polymerization initiator used and the polymer to be produced.

The binder resin used in the present invention is preferably formed by using a polyfunctional polymerization initiator alone or in combination with a monofunctional polymerization initiator as exemplified below.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane and 2,2-t
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as -butylperoxyoctane; and diallyl peroxydicarbonate, t-butyl peroxymaleic acid , T
In one molecule such as -butyl peroxyallyl carbonate and t-butyl peroxyisopropyl fumarate;
A polyfunctional polymerization initiator having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group is exemplified.

Among these, more preferred are 1,1
-Di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-tert-butylperoxycyclohexane, di-tert-butylperoxyhexahydroterephthalate, di-tert-butylperoxyase And 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder resin for a toner.
In particular, it is preferable to use the polyfunctional polymerization initiator together with a polymerization initiator having a half life of 10 hours lower than the decomposition temperature for obtaining a half life of 10 hours.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α, α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Organic peroxides such as -butyl peroxide; azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator. However, in order to maintain the efficiency of the polyfunctional polymerization initiator properly,
It is preferable to add the compound after the half-life of the polyfunctional polymerization initiator has passed in the polymerization step.

These initiators are preferably used in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the monomer from the viewpoint of efficiency.

The binder resin is preferably crosslinked with a crosslinking monomer.

As the crosslinkable monomer, a monomer having two or more polymerizable double bonds is mainly used. Specific examples include aromatic divinyl compounds (eg, divinylbenzene, divinylnaphthalene, etc.); diacrylate compounds linked by an alkyl chain (eg, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4 -Butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6
Hexanediol diacrylate, neopentyl glycol diacrylate, and methacrylates instead of the above compounds; diacrylate compounds linked by an alkyl chain containing an ether bond (for example, diethylene glycol diacrylate, triethylene glycol) Diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate); Diacrylate compounds linked by a chain containing, for example, polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propanediacryle DOO, polyoxyethylene (4) -
2,2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate; and polyester type diacrylate compounds (for example, trade name MANDA (Nippon Kayaku)). Can be As multifunctional crosslinking agents, pentaerythritol acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate, and acrylates of the above compounds to methacrylate Alternatives: triallyl cyanurate and triallyl trimellitate.

These crosslinking agents can be used in combination with other monomer components 10
It is preferably used in the range of 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight with respect to 0 part by weight.

Among these crosslinkable monomers, those which are preferably used from the viewpoint of toner fixing properties and anti-offset properties, include aromatic divinyl compounds (especially divinylbenzene), and a chain containing an aromatic group and an ether bond. Diacrylate compounds.

As other synthesis methods, a bulk polymerization method and a solution polymerization method can be used. However, in the bulk polymerization method, any polymer can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control. In this regard, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature, It is preferable to obtain a low molecular weight compound in the resin composition used in the present invention. In particular, a solution polymerization method under a pressurized condition is also preferable from the viewpoint of minimizing the amount of the initiator used and minimizing the influence of the residual initiator.

Examples of the monomer for obtaining the binder resin of the present invention include the following.

Styrene: o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,
4-dichlorostyrene, p-ethylstyrene, 2,4-
Dimethylstyrene, pn-butylstyrene, p-te
rt-butylstyrene, pn-hexylstyrene, p
-N-octylstyrene, pn-nonylstyrene, p
Styrene derivatives such as -n-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene,
Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyls such as vinyl acetate, vinyl propionate and vinyl benzoate Esters: methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid (2-ethylhexyl), stearyl methacrylate, phenyl methacrylate, Α such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate
-Methyl aliphatic monocarboxylic acid ester; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n acrylate
Acrylates such as octyl, dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; vinyl naphthalene; acrylonitrile, methacryloyl Acrylic acid derivatives such as nitrile and acrylamide or methacrylic acid derivatives are mentioned. These vinyl monomers are used alone or as a mixture of two or more monomers.

Among these, a combination of monomers that results in a styrene-based copolymer and a styrene-acrylic copolymer is preferred.

As a method for producing a binder resin, a high-molecular-weight polymer and a low-molecular-weight polymer are separately synthesized by a solution polymerization method, then mixed in a solution state, and then the solvent is removed. A low-molecular-weight polymer obtained by a solution blending method or the like, which is melt-kneaded by a mixer or the like, is dissolved in a monomer constituting a high-molecular-weight polymer in which a low-molecular-weight polymer is dissolved, suspension polymerization is performed, and water washing and drying are performed. And a two-stage polymerization method for obtaining a product. However, the dry blending method has problems in terms of uniform dispersion and compatibility, and the two-stage polymerization method has many advantages in uniform dispersibility, but increases the amount of low molecular weight components to higher molecular weight components. In the presence of a low molecular weight polymer component, it is difficult to synthesize a high molecular weight polymer having a large molecular weight, and there is a problem that an unnecessary low molecular weight polymer is produced as a by-product. Therefore, the solution blending method is most preferable. Further, as a method for introducing a predetermined acid value into the low molecular weight polymer component, a solution polymerization in which the acid value can be easily set as compared with an aqueous polymerization method is preferable.

It is preferable to use a polyester resin as the binder resin, and the composition of the polyester resin will be described below.

The dihydric alcohol component includes ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. , 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, and bisphenol represented by the formula (A) and derivatives thereof can be mentioned.

[0131]

Embedded image (Wherein R is an ethylene or propylene group, x,
y is an integer of 0 or more, and the average value of x + y is 0 to 10. ).

Furthermore, a diol represented by the formula (B) as a dihydric alcohol component

[0133]

Embedded image Where x 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

Examples of the divalent acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof, and lower alkyl esters; succinic acid, adipic acid, sebacic acid and azelaic acid. Alkyl dicarboxylic acid or anhydride or lower alkyl ester thereof; alkenyl succinic acid or alkyl succinic acid such as n-dodecenyl succinic acid or n-dodecyl succinic acid, or anhydride or lower alkyl ester thereof; fumaric acid, maleic acid, citracone Examples include unsaturated dicarboxylic acids such as acids and itaconic acids, and dicarboxylic acids such as anhydrides and lower alkyl esters thereof and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The polyhydric alcohol component having a valency of 3 or more includes
Sorbitol, 1,2,3,6-hexanetetrol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,2
4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2
-Methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene and the like.

The trivalent or higher polycarboxylic acid component includes trimellitic acid, pyromellitic acid, 1,2,4-
Benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, 1,2,4-
Butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid , Empole trimer acid, and anhydrides and lower alkyl esters thereof;

[0138]

Embedded image (Wherein X is an alkylene group or alkenylene group having 1 to 30 carbon atoms having at least one side chain having 1 or more carbon atoms), such as tetracarboxylic acids and their anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

The alcohol component is 40 to 60 mol
%, Preferably 45 to 55 mol%, and 6% as the acid component.
It is preferably 0 to 40 mol%, preferably 55 to 45 mol%.

It is also preferable that the content of the trivalent or higher polyvalent component is 1 to 60 mol% of all the components.

The polyester resin can also be obtained by generally known condensation polymerization.

The magnetic material used in the present invention includes iron oxides such as magnetite, maghemite, and ferrite;
Metals such as cobalt and nickel or these metals and aluminum, cobalt, copper, lead, magnesium, tin,
Alloys of metals such as zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium and mixtures thereof are used, and those containing a non-ferrous element on the surface or inside the magnetic material are preferable.

As the magnetic material used in the present invention, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements and mixtures thereof are preferably used.

In particular, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, sulfur,
Germanium, titanium, zirconium, tin, lead, zinc,
Calcium, barium, scandium, vanadium, chromium, manganese, cobalt, copper, nickel, gallium,
Magnetic iron oxide containing at least one element selected from indium, silver, palladium, gold, platinum, tungsten, molybdenum, niobium, osmium, strontium, yttrium, technetium, ruthenium, rhodium and bismuth is preferable. Especially lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium,
Tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper,
Zinc and gallium are preferred. Most preferably, it is a magnetic iron oxide containing an element selected from the group consisting of magnesium, aluminum, silicon, phosphorus and sulfur as a different element. These elements may be taken into the iron oxide crystal lattice, may be taken into the iron oxide as an oxide, or may exist as oxides or hydroxides on the surface. It is a preferred embodiment that it is contained as an oxide.

These elements can be incorporated into the particles by mixing the salts of the respective elements during the production of the magnetic material and adjusting the pH. In addition, precipitation can be performed on the particle surface by adjusting the pH after the formation of the magnetic particles or adjusting the pH by adding a salt of each element.

The magnetic material containing these elements is well compatible with the binder resin and has very good dispersibility. Further, this good dispersibility can improve the dispersibility of the organic zirconium compound used in the present invention, and the effect of the organic zirconium compound of the present invention can be sufficiently exhibited.
The magnetic material functions as a dispersion medium, and the dispersion of the organic zirconium compound is assisted by the good dispersibility of the magnetic material, and the dispersibility of the organic zirconium compound is improved. In addition, these magnetic substances adsorb water molecules, and the organic zirconium compound is
It has the effect of making it easier to emphasize the electrification by water molecules. This effect can be exhibited more effectively when used together with a binder resin having an acid value.

Further, these magnetic materials have a uniform particle size distribution,
In combination with the dispersibility in the binder resin, the chargeability of the toner can be stabilized. Further, in recent years, the toner particle diameter has been reduced, and the weight average particle diameter is 2.5 to 10%.
Even in the case of μm, the uniformity of charging is promoted, the cohesion of the toner is reduced, and the developability such as improvement of image density and improvement of fog is improved. In particular, the weight average particle size is 2.5 to 6.0.
With a μm toner, the effect is remarkable, and an extremely high-definition image can be obtained. It is preferable that the weight average particle size is 2.5 μm or more, since sufficient image density can be obtained. On the other hand, as the particle size of the toner progresses, release of the zirconium compound also easily occurs.However, the toner of the present invention is excellent in charge uniformity, so that the toner is less susceptible to sleeve contamination even if some zirconium compound is present. Become. The magnetic toner preferably has a weight average particle size of 2.5 to 10 μm (more preferably, 2.5 to 6.0 μm). Even in the case of a non-magnetic toner, the weight average particle size is preferably from 2.5 to 10 μm, more preferably from 2.5 to 6.0 μm.

The weight average particle size and the particle size distribution of the toner are measured by using a Coulter counter method. The electrolyte is 1% N using 1st grade sodium chloride.
An aqueous aCl solution is prepared. For example, ISOTON R-I
I (manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic aqueous solution 100 to
In 150 ml, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) is added as a dispersant, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the measurement apparatus used an aperture of 100 μm.
The volume distribution and the number distribution are calculated by measuring the volume and the number of the toner particles of 2.00 μm or more using the aperture. Then, the weight-based weight average particle diameter (D ₄ ) obtained from the volume distribution according to the present invention is calculated.

As the channels, 2.00 to 2.52
less than 2.5 μm; less than 2.52 to 3.17 μm;
4. less than 4.00 μm; 4.00 to less than 5.04 μm;
04 to less than 6.35 μm; 6.35 to less than 8.00 μm; 8.00 to less than 10.08 μm; 10.08 to 1
2.70 μm or less; 12.70 to less than 16.00 μm;
16.00 to less than 20.20 μm; 20.20 to 25.
Less than 40 μm; 25.40 to less than 32.00 μm; 3
13 channels of 2.00 to less than 40.30 μm are used.

The content of these different elements is preferably 0.05 to 10% by weight based on the iron element of the magnetic iron oxide. More preferably 0.1 to 7% by weight,
Particularly preferably, it is 0.2 to 5% by weight, more preferably 0.3 to 4% by weight. If it is less than 0.05% by weight, the effect of containing these elements cannot be obtained, and good dispersibility and uniform charging cannot be obtained. When the content is more than 10% by weight, the discharge of electric charge is increased to cause insufficient charging, which may lower the image density or increase fog.

In the content distribution of these different elements, it is preferable that the one which is present more in the vicinity of the surface of the magnetic material. For example, when the dissolution rate of the iron element in the iron oxide is 20%, the dissolution rate of the different element is 20% of the total amount of the different element.
% To 100% is preferred. Further, it is preferably from 25% to 100%, particularly preferably from 30% to 100%. By increasing the surface abundance, the dispersion effect and the electric diffusion effect can be further improved.

These magnetic materials have a number average particle size of 0.05.
To 1.0 μm, more preferably 0.1 to 0.5 μm
Are preferred. The magnetic material has a BET specific surface area of 2 to 40.
m ² / g (more preferably, 4~20m ² / g) it is preferably used for. The shape is not particularly limited, and an arbitrary shape is used. As magnetic properties, the magnetic field 79
Saturation magnetization is 10 to 200 Am ² / k under 5.8 kA / m
g (more preferably, 70 to 100 Am ² / kg), and the residual magnetization is 1 to 100 Am ² / kg (more preferably, 2 to 100 Am ² / kg).
To ²⁰ Am2 / kg) and those having a coercive force of 1 to 30 kA / m (more preferably, 2 to 15 kA / m) are preferably used. These magnetic materials are used in an amount of 20 to 200 parts by weight based on 100 parts by weight of the binder resin. Preferably, it is used in an amount of 40 to 150 parts by weight.

The amount of elements in the magnetic iron oxide is measured by X-ray fluorescence analysis using a fluorescent X-ray analyzer SYSTEM3080 (manufactured by Rigaku Denki Kogyo KK) in accordance with JIS K0119 General rules for X-ray fluorescence analysis. can do. Regarding element distribution, the amount of elements dissolved in hydrochloric acid or hydrofluoric acid is measured and quantified by plasma emission spectroscopy (ICP), and the dissolution rate is determined from the concentration of each element in each dissolution with respect to the concentration of each element in total dissolution. Is obtained by

The number average diameter can be determined by measuring a photograph enlarged and taken with a transmission electron microscope with a digitizer or the like. The magnetic properties of the magnetic material are values measured using an “oscillating sample magnetometer VSM-3S-15” (manufactured by Toei Kogyo Co., Ltd.) under an external magnetic field of 795.8 kA / m. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device Autosoap 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

The waxes used in the present invention include the following. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax and sasol wax; oxides of aliphatic hydrocarbon wax such as polyethylene oxide wax Or a block copolymer thereof; candelilla wax, carnauba wax,
Plant waxes such as wood wax and jojoba wax;
Animal waxes such as lanolin and whale wax; mineral waxes such as ozokerite, ceresin and petrolatum; waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax; fatty acid esters such as deoxidized carnauba wax. A partially or wholly deoxidized product may be used. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinaric acid; stearyl alcohol Saturated alcohols such as eicosyl alcohol, behenyl alcohol, carnaubyl alcohol, seryl alcohol, merylsyl alcohol, or long-chain alkyl alcohols having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linoleic acid amide, oleic acid Fatty acid amides such as amides and lauric amides; saturated fatty acid bisamides such as methylenebisstearic acid amide, ethylenebiscapramide, ethylenebislauricamide, hexamethylenebisstearic acid amide; Ren acid amide, hexamethylene bis-oleic acid amide, N, N'-dioleyl adipic acid amide, N, N '
-Unsaturated fatty acid amides such as dioleyl sebacamide; m-xylene bisstearic acid amide, N, N '
-Aromatic bisamides such as distearyl isophthalamide; fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (commonly referred to as metal soaps); aliphatic hydrocarbon waxes and styrene Wax grafted with a vinyl monomer such as acrylic acid or acrylic acid; partially esterified product of fatty acid and polyhydric alcohol such as behenic acid monoglyceride; methyl ester compound having hydroxyl group obtained by hydrogenating vegetable oil or fat Is mentioned.

The waxes preferably used include polyolefins obtained by radical polymerization of olefins under high pressure;
Polyolefin obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefin; polyolefin polymerized under low pressure using a catalyst such as Ziegler catalyst or metallocene catalyst; polyolefin polymerized using radiation, electromagnetic wave or light; Low molecular weight polyolefin obtained by pyrolyzing polyolefin; paraffin wax,
Microcrystalline wax, Fischer-Tropsch wax; Synthetic hydrocarbon wax synthesized by the Zintall method, the Hydrochol method, the Age method, etc .; Synthetic wax using a compound having 1 carbon atom as a monomer, having a functional group such as a hydroxyl group or a carboxyl group. Hydrocarbon wax; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group; a wax obtained by graft-modifying these waxes with a vinyl monomer such as styrene, maleic ester, acrylate, methacrylate, or maleic anhydride. Is mentioned.

[0157] These waxes may be obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, or a low molecular weight solid fatty acid. Also, those from which low-molecular-weight solid alcohols, low-molecular-weight solid compounds, and other impurities have been removed are preferably used.

The wax used in the present invention has a melting point of 70 to 150 in order to balance the fixing property and the offset resistance.
° C, more preferably 70 to 130 ° C. Particularly, 70 to 120 ° C. is preferable. 7
If the temperature is lower than 0 ° C., the anti-blocking property is reduced.

In the toner of the present invention, the total content of these waxes is 0.2 to 100 parts by weight of the binder resin.
It is effective to use at 20 to 20 parts by weight, preferably 0.5 to 10 parts by weight.

In the present invention, the melting point of the wax is determined by DSC
The temperature at the peak top of the maximum endothermic peak of the wax measured in the above is defined as the melting point of the wax.

In the present invention, in the DSC measurement of the wax or the toner by the differential scanning calorimeter, it is preferable to measure the wax or the toner with a high-precision internal heating type input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by raising and lowering the temperature once, taking a pre-history, and then setting the temperature rate to 10 ° C./m.
In, a DSC curve measured when the temperature is raised is used.

When the organic zirconium compound used in the present invention is used with two or more different waxes, more excellent effects can be obtained. The wax exerts a plasticizing action and a releasing action on the toner, and when used at the same time, one of the actions is emphasized. The presence of the organic zirconium compound makes these effects stand out, and their effects work more effectively than when each wax is used alone. When plasticized by the wax, the dispersion of the organic zirconium compound is improved, and accordingly, the releasability of another wax becomes more apparent. At this time, it is even more effective when used together with a binder resin having an acid value.

As a condition for selecting two kinds of waxes, in the case of waxes having the same structure, a wax having a relatively low melting point exhibits a plasticizing effect, and a wax having a relatively high melting point exhibits a releasing effect. At this time, the difference in melting point is 10 ° C to 100 ° C.
In this case, the function separation is effectively exhibited. When the temperature is lower than 10 ° C., the function separation effect is hardly exhibited, and when the temperature is higher than 100 ° C., the function is hardly emphasized by the interaction.

In this case, the melting point of at least one of the waxes is preferably 70 to 120 ° C. (more preferably 70 to 120 ° C.).
To 100 ° C.), since the function separation effect is easily exhibited.

In addition, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exert a plasticizing action, and those having a more linear structure and A non-polar or unmodified straight product having no functional group exhibits a releasing effect. Preferred combinations include a combination of a polyethylene homopolymer or copolymer having ethylene as a main component and a polyolefin homopolymer or copolymer having an olefin other than ethylene as a main component; a combination of a polyolefin and a graft-modified polyolefin; an alcohol wax, a fatty acid wax or an ester wax. A combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystalline wax; a combination of Fischer-Tropsch wax and polyolefin wax; a combination of paraffin wax and microcrystalline wax; carnauba wax, candelilla wax, Rice wax or montan wax and hydrocarbon wax The combination of the scan and the like.

In each case, the endothermic peak observed in the DSC measurement of the toner was 70 to 120.
It is preferable that there is a peak top temperature of the maximum peak in the region of ° C, and it is more preferable that the peak peak temperature be in the region of 70 to 110 ° C. This makes it easier to balance the storability and fixability of the toner.

As the colorant that can be used in the toner of the present invention, any suitable pigment or dye can be used. For example, as pigments, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, bengara,
Examples include phthalocyanine blue and indanthrene blue. These are used in an amount necessary to maintain the optical density of the fixed image, and are used in an amount of 0.1 to 100 parts by weight of the binder resin.
An addition amount of 20 parts by weight, preferably 0.2 to 10 parts by weight is good. A dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight, per 100 parts by weight of the binder resin is good. .

In the present invention, it is preferable that an inorganic oxide such as silica, alumina and titanium oxide, and an inorganic fine powder having a small particle size such as carbon black and carbon fluoride are externally added to the toner particles.

The fine silica powder, fine alumina powder or fine titanium oxide powder is preferably formed into fine particles when dispersed on the surface of the toner particles, since the fluidity-imparting property becomes higher.
The number average particle size is preferably from 5 to 100 nm, more preferably from 5 to 50 nm. Preferably as maternal fine powder in the range of 30 m ² / g or more in specific surface area according to the measured nitrogen adsorption (especially 60~400m ² / g) by the BET method, the surface-treated fine powder, 2
0 m ² / g or more (especially 40 to 300 m ² / g) in the range are preferred.

The application amount of these fine powders is as follows.
An appropriate surface coverage is obtained when 0.03 to 5 parts by weight is added to 00 parts by weight.

The hydrophobicity of the inorganic fine powder used in the present invention is preferably 30% or more in methanol wettability, more preferably 50% or more. As the hydrophobizing agent, a silane compound which is a silicon-containing surface treating agent and silicone oil are preferable.

For example, alkylalkoxysilanes such as dimethyldimethoxysilane, trimethylethoxysilane and butyltrimethoxysilane; dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethyl A silane coupling agent and a silane compound such as chlorosilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, and dimethylvinylchlorosilane can be used.

The toner of the present invention may be mixed with a carrier and used as a two-component developer. The resistance value of the carrier is preferably adjusted to 10 ⁶ to 10 ¹⁰ Ω · cm by adjusting the degree of unevenness of the carrier surface and the amount of resin to be coated.

As the resin for coating the carrier surface, styrene-acrylate copolymer, styrene-methacrylate copolymer, acrylate copolymer, methacrylate copolymer, silicone resin,
Fluorine-containing resin, polyamide resin, ionomer resin,
Polyphenylene sulfide resin or a mixture thereof can be used.

As the magnetic material of the carrier core, oxides such as ferrite, iron-rich ferrite, magnetite and γ-iron oxide, metals such as iron, cobalt and nickel, or alloys thereof can be used. The elements contained in these magnetic materials include iron, cobalt, nickel, aluminum, copper, lead, magnesium, tin,
Examples include zinc, antimony, beryllium, bismuth, calcium, manganese, selenium, titanium, tungsten, and vanadium.

As the additives for imparting various properties used in the present invention, for example, the following are used.

(1) Abrasives: metal oxides (such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide), nitrides (such as silicon nitride) and carbides (such as silicon carbide), and metal salts (such as sulfuric acid) Calcium, barium sulfate, calcium carbonate).

(2) Lubricants: fluororesin powder (polyvinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.) and the like.

(3) Charge controllable particles: metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide), carbon black, and resin fine particles.

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

In the case of a magnetic toner, it is preferable to use fine powders of two or more kinds of inorganic oxides or metal oxides in order to obtain the durability stability of development and the development stability after standing. In the case of a non-magnetic one-component developing method, it is preferable to use titanium oxide or alumina in order to improve fluidity and obtain image uniformity.

The method for producing the toner of the present invention includes the following.
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is kneaded well using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a predetermined material is mixed with a monomer to constitute a binder resin to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if desired, the desired additive and toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention.

For example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo Co., Ltd.). Kneading machines include KRC kneader (manufactured by Kurimoto Tekkosho); bus co-kneader bussman); Extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); (Mitsui Mining Co., Ltd.); MS type pressure kneader, Nidder Ruder (Moriyama Seisakusho Co., Ltd.); ). Examples of the pulverizer, a counter jet mill, micron jet, Inomizer (manufactured by Hosokawa Micron); IDS type mill, PJ
M jet crusher (manufactured by Nippon Pneumatic Industries); cross jet mill (manufactured by Kurimoto Iron Works); ulmax (manufactured by Nisso Engineering); SK Jet O.
Mills (manufactured by Seishin Enterprises); Kryptron (manufactured by Kawasaki Heavy Industries); Turbo Mills (manufactured by Turbo Kogyo). Classifiers include Crasheal, Micron Classifier, and Spedd Classifier (manufactured by Seishin Company). Turbo Classifier (Nisshin Engineering); Micron Separator, Turboplex (ATP), TSP Separator (Hosokawa Micron); Elbow Jet (Nisshin Mining), Dispersion Separator (Nihon Pneumatic) ; Y
M microcut (manufactured by Yasukawa Shoji Co., Ltd.) is mentioned. As a sieving device used for sifting coarse particles, etc.,
Ultrasonic (made by Koei Sangyo Co., Ltd.); resonator sieve, gyro shifter (made by Tokuju Kogyo Co., Ltd.); Vibrasonic system (made by Dalton); Sonic Clean (made by Shinto Kogyo); turbo screener (made by Turbo Kogyo); Micro shifter (manufactured by Makino Sangyo Co., Ltd.); circular vibrating sieve and the like.

[0185]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Table 1 shows the resins used in the examples, Table 2 shows the waxes, Table 3 shows the magnetic substances, and Table 4 shows the organic zirconium compounds.

The styrene-based resin was synthesized by solution-blending a suspension-polymerized resin and a solution-polymerized resin, and the polyester resin was synthesized by a dehydration condensation method.

The magnetic material produced magnetite particles while adjusting the presence or absence and the pH of the salt of the element present inside when magnetite was produced, to obtain a magnetic iron oxide.

The organic zirconium compound is prepared by dissolving a corresponding aromatic hydroxycarboxylic acid or a sodium salt of an aromatic hydroxycarboxylic acid in water, an aqueous alcohol solution or an alcohol, and reacting with an aqueous solution of zirconium chloride to form an aromatic hydroxycarboxylic acid and zirconium oxide. Is obtained by filtering and washing with water. At this time, the charge ratio of aromatic hydroxycarboxylic acid and zirconium chloride,
Various organic zirconium compounds were prepared by adjusting the solvent, the order of addition, the rate of addition, the reaction temperature, and the reaction time. Table 4 shows the analytical values of the molar ratio to Zr.

[0190]

[Table 1]

[0191]

[Table 2]

[0192]

[Table 3]

[0193]

[Table 4]

Example 1 100 parts by weight of binder resin B 100 parts by weight of magnetic substance β 3 parts by weight of wax b 2 parts by weight of organic zirconium compound 2 0.5 parts by weight of aluminum salicylate compound After pre-mixing with a mixer, 130
The mixture was melt-kneaded by a twin-screw kneading extruder set at a temperature of ° C.
The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified using a multi-part classifier utilizing Coanda effect. A classified product (toner particles) having a volume average particle size of 6.1 μm was obtained. 15% by weight of hexamethyldisilazane and 15% by weight of dimethyl silicone
Toner 1 was obtained by externally adding and mixing 1.5 parts by weight of silica having a BET of 120 m ² / g hydrophobized by wt%. Table 5 shows the formulation of the toner and Table 6 shows the physical properties of the toner.

Using a commercially available laser beam printer LBP-930 (Canon Inc.), this toner 1 was placed in an environment of 10 ° C. and 15% RH, followed by 32.5%.
The environment was repeatedly changed in an environment of a temperature of 85 ° C. and a relative humidity of 85% each day, and an image output test of 2000 sheets / day, that is, 12000 sheets in total was performed. Thereafter, the sample was allowed to stand for 1 week in an environment of 32.5 ° C. and 85% RH, and an image output test of 2,000 sheets was performed. As a result, a high-definition image with high image density and no fog was obtained in both environments. The details are shown in Table 7.

Here, the image density was measured using a Macbeth densitometer (manufactured by Macbeth) using an SPI filter to measure the reflection density, and an image of 5 mm square was measured. Fog is a reflection densitometer (Reflectometer Model TC-6DS
The fog is evaluated using Ds as the worst value of the reflection density of the white portion after image formation, Dr as the average reflection density of the transfer material before image formation, and Fs as Ds-Dr. Was. The smaller the value, the better the fog suppression. The image quality was evaluated by forming an image of 100 isolated dots,
The evaluation was based on the number of dots that could be represented. The higher the number of reproduced dots, the higher the image quality.

These evaluations were carried out at the initial stage of heat cycle (L / L → (H / H → L / L) × 2 → H / H) durability 12
The test was carried out at the time of 000 sheets and one week after the end of the durability.

The contamination of the pressure roller of the fixing device due to durability was evaluated according to the following criteria. A: No dirt B: Slight dirt C: Dirt is present but does not affect the image D: Dirt is transferred to the image

These evaluations were carried out at the initial stage, at the end of each environmental durability test, and after one week from the end of the endurance. Table 7 shows the results.
It writes in.

<Examples 2 to 6> Toners 2 to 6 were prepared in the same manner as in Example 1 using the formulations shown in Table 5, and the physical properties of the toners were measured.
Table 7 shows the results of the same test.

<Comparative Example 1> Toner 7 was prepared in the same manner as in Example 1 except that only the organic zirconium compound 5 was used without using the aluminum salicylate compound.
Table 7 shows the results of the evaluation.

<Comparative Example 2> Toner 8 was prepared in the same manner as in Example 1 except that an organic zirconium compound was not used and only a chromium salicylate compound was used instead of an aluminum salicylate compound. Are shown in Table 7.

Example 7 100 parts by weight of binder resin C 4 parts by weight of copper phthalocyanine 3 parts by weight of organic zirconium compound 2 0.5 parts by weight of aluminum salicylate compound 2 parts by weight of wax b After pre-mixing with 115
The mixture was kneaded with a twin-screw kneading extruder set to ° C. The obtained kneaded material is cooled and coarsely pulverized by a cutter mill, finely pulverized using a pulverizer using a jet stream, and classified using a multi-segment classifier utilizing the Coanda effect to obtain a volume average diameter of 6. 7
A classified product (toner particles) of μm was obtained. To 100 parts by weight of the obtained toner particles, isobutyltrimethoxysilane 10w was added to anatase-type titania fine powder produced by a sulfuric acid method.
hydrophobic titania treated with t% and dimethyl silicone 10 wt% (methanol wettability 65%, BET
1.8 parts by weight (specific surface area: 75 m ² / g) were externally added and mixed to obtain Toner 9.

The following evaluation tests were performed on the obtained toner 9.

<Image Evaluation Test> An oil application roller was mounted on a fixing device using a commercially available color printer LBP-2040 (manufactured by Canon Inc.), followed by an environment of 10 ° C. and 15% RH, followed by an environment of 30 ° C. and 80% RH. , The environment was changed every day, and an image output test was performed on a total of 4000 images, that is, 1000 images / day. Then, at 30 ° C and 80% RH,
The sample was allowed to stand for a week, and an image output test of 2,000 sheets was performed. As a result, a high-definition image with high image density and no fog was obtained in both environments.

The image density was measured using a “Macbeth reflection densitometer” (manufactured by Macbeth). The fog is measured using a "reflection densitometer" (manufactured by Tokyo Denshoku Technology Center) to measure the reflection density of the transfer paper and the reflection density of the transfer paper after copying solid white, and the difference is used as the fog value The smaller the value, the better the fog suppression. The fog is measured by measuring the reflection density of a transfer material before image formation and a white background after image formation using a reflection densitometer (reflectometer model TC-6DS manufactured by Tokyo Denshoku Co., Ltd.), and calculating an average value. . The difference between the reflection densities before and after image formation is evaluated as fog.

The image quality is evaluated by forming 100 images of isolated dots and expressing how many of the 100 dots can be represented. The higher the number of reproduced dots, the higher the image quality.

Table 6 summarizes the physical properties of the toner, and Table 7 summarizes the evaluation results of the image evaluation test.

[0209] These evaluations were carried out at the initial stage, when the heat cycle (L / L → H / H → L / L → H / H) durability was 4,000 sheets, and after one week after the end of the durability, image formation was performed.

[0210]

[Table 5]

[0211]

[Table 6]

[0212]

[Table 7]

[0213]

According to the present invention, a toner having excellent developability can be obtained irrespective of a use form such as a replenishment type or a single use cartridge type. Further, the present invention is a toner for suppressing generation of image stains from a fixing member. Further, the present invention is a toner that can obtain high image quality regardless of the use environment, and does not change even when left, replenished, or shaken the cartridge.
This is a toner from which an image faithful to a latent image can be obtained for a long time.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Yoshihiro Ogawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Hirohide Tanigawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Non-corporation (72) Inventor Yuki Karaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA02 AA06 CA14 CA25 CB03 CB04 DA02 EA03 EA05 EA06 EA07 EA10

Claims (24)

[Claims] 1. A toner comprising at least a binder resin, a colorant and two kinds of organometallic compounds (a) and (b), wherein the organometallic compound (a) is composed of zirconium and an aromatic hydroxycarboxylic acid. And an organozirconium compound produced by the reaction with
A toner characterized by being an organometallic compound produced by a reaction with an aromatic hydroxycarboxylic acid containing a metal selected from 1, Zn, Ti, Sr, B, Si, Ni, Fe, and Cr. 2. The toner according to claim 1, wherein said organometallic compound (a) contains 1.2 to 1.8 mol of an aromatic hydroxycarboxylic acid unit. 3. The toner according to claim 1, wherein the organometallic compound (a) contains 1.3 to 1.7 mol of an aromatic hydroxycarboxylic acid unit. 4. The toner according to claim 1, wherein the aromatic hydroxycarboxylic acid of the organometallic compound (a) is a compound represented by the following formula (I). Embedded image [In the general formula (I), R is hydrogen, an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Acyl group, carboxyl group, halogen,
Represents a nitro group, an amino group, or a carbamoyl group, and the substituents R may be linked to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring. May have 1 to 8 substituents R,
Each may be the same or different. ] 5. The toner according to claim 1, wherein the aromatic hydroxycarboxylic acid of the organometallic compound (a) is salicylic acid having an alkyl group as a substituent. 6. The organic metal compound (a) (organic zirconium compound) is used in an amount of 0.1 to 1 based on 100 parts by weight of the binder resin.
6. The toner according to claim 1, wherein the toner is added in an amount of 0 part by weight. 7. The organic metal compound (a) (organic zirconium compound) is used in an amount of 0.01 to 100 parts by weight of the binder resin.
7. The toner according to claim 1, wherein the toner is externally added to 5 parts by weight of toner particles. 8. The toner according to claim 1, wherein the ratio (a) / (b) of the organometallic compounds (a) and (b) in the toner is 0.1 to 10. The toner according to 1. 9. The method according to claim 9, wherein the organometallic compound (b) is Al, Zn
The toner according to any one of claims 1 to 8, wherein the toner is an organometallic compound generated by a reaction with an aromatic hydroxycarboxylic acid containing a metal selected from the group consisting of: 10. The toner having an acid value of 0.5 to 100 mg.
10. The toner according to claim 1, wherein KOH / g is used. 11. The toner having an acid value of 5 to 30 mg KOH.
The toner according to any one of claims 1 to 9, wherein the ratio is / g. 12. The toner according to claim 1, wherein the colorant is magnetic iron oxide, and is contained in an amount of 20 to 200 parts by weight based on 100 parts by weight of the binder resin. 13. The toner according to claim 12, wherein said magnetic iron oxide is magnetic iron oxide fine particles containing 0.05 to 10% by weight of a different element based on the iron element. 14. The toner according to claim 13, wherein the different element is an element selected from the group consisting of magnesium, aluminum, silicon, phosphorus, and sulfur. 15. The toner comprises a binder resin 10 and a wax.
15. The toner according to claim 1, wherein the toner is contained in an amount of 0.2 to 20 parts by weight based on 0 part by weight. 16. The wax contains at least wax A and wax B, and wax A and wax B
The toner according to claim 15, wherein the melting point is different from that of the toner. 17. The wax contains at least a wax C and a wax D, and the wax C and the wax D
2. The composition component is different from the above.
5. The toner according to 5. 18. The toner according to claim 15, wherein the wax has a melting point of 70 to 150 ° C. 19. The toner according to claim 1, wherein a content of a tetrahydrofuran (THF) -insoluble content excluding residual ash of the toner is 1 to 70 wt%. 20. The THF-soluble component of the toner has a molecular weight distribution of 3,000 to 3,000 as measured by GPC.
20. The toner according to claim 1, having a main peak in an area of 50,000. 21. A molecular weight distribution of the THF-soluble component of the toner measured by GPC of 3,000 to 3,000.
2. The compound according to claim 1, wherein the compound has at least one peak in a region of 30,000 and has at least one peak in a region of molecular weight of 100,000 to 10,000,000.
20. The toner according to any one of items 1 to 19 above. 22. The toner according to claim 15, which has a maximum endothermic peak in a temperature range of 70 to 120 ° C. in an endothermic curve measured by DSC of the toner. 23. The method according to claim 1, wherein the colorant is a nonmagnetic colorant, and is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the binder resin. toner. 24. The toner has a weight average particle diameter of 2.5 to 10.
The toner according to any one of claims 1 to 23, wherein the particle diameter is μm.