KR101200398B1 - The electrification control material for a toner containing polynuclear metallic complex and the producing method thereof - Google Patents

Abstract

One or more aqueous solutions selected from alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia water are mixed with the aqueous solution of the metal salts, stirred and matured in a heated state, and then the stirring is stopped and left to aged. After stirring or aging the aqueous solution of the metal salt in a warmed state, the stirring is stopped and static aging to produce an aqueous solution of the polynuclear metal complex salt, and the carboxyl group, the hydroxyl group, the amino group, the amido group, the liquor in the aqueous solution of the polynuclear metal complex salt thus formed. Complex salting an aromatic compound having any one or a plurality of functional groups selected from aeration to produce an aqueous aqua complex salt compound of an aromatic compound-metal complex salt, ammonia water in the aqueous solution of the aqua complex salt compound of the aromatic compound-metal complex salt compound, Ammonium salt, in amine Complete the charge control agent for the toner by filtering, washing, and drying the aqueous solution of the aromatic compound-metal-ammine complex compound formed by adding one or more selected ones and replacing the aqua complex of the aromatic compound-metal complex salt compound with an ammine complex. Charge control agent for a toner containing a multinuclear metal complex salt, characterized in that it is configured to a step and a manufacturing method.

Description

The electrification control material for a toner containing polynuclear metallic complex and the producing method

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge control agent for a toner for controlling charging of the toner, and more particularly, to a charge control agent for a toner, and more particularly, to any one or more selected from alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia water in an aqueous solution of a metal salt. After mixing the aqueous solution, the mixture is stirred and stirred in a warmed state, and then the stirring is stopped and static aging to produce an aqueous solution of the polynuclear metal complex salt, or the aqueous solution of the metal salt is stirred and aged in a heated state, and then the stirring is stopped and the static aging is carried out. Generating an aqueous solution of a metal complex salt, and complexing an aromatic compound having any one or a plurality of functional groups selected from a carboxyl group, a hydroxyl group, an amino group, an amido group, and a sulfo group in an aqueous solution of the polynuclear metal complex salt, thereby producing an aromatic compound-metal complex salt To generate an aqueous aqua complex salt compound of the compound In addition, any one or more selected from ammonia water, ammonium salt, and amine is added to the aqueous solution of the aqua complex salt compound of the aromatic compound-metal complex salt compound, and the aqua complex of the aromatic compound-metal complex compound is substituted with an ammonium complex to form an aromatic compound-metal. Generating an aqueous solution of an ammine complexing compound, and filtering, washing, and drying the aqueous solution of the produced aromatic compound-metal-ammine complexing compound to complete a charge control agent for the toner. It relates to a charge control agent for a toner and a manufacturing method thereof.

In the toner industry, there is a desire for a charge control agent for a toner of a clear image having a high charge amount, a resolution and an image density not lowering, and no contamination.

Conventional charge control agents for toners are prepared by mixing an aqueous solution of an organic compound having a carboxyl ion with an aqueous solution of a metal salt in which an aqueous solution of a metal salt and an aqueous solution of an alkali metal hydroxide are mixed, or a hydroxide in a monoazo compound solution. A method of producing by metallization by adding sodium, followed by addition of ferric chloride, or a method of dissolving a monoazo compound in ethylene glycol, followed by complexation by adding sodium hydroxide and ferric chloride there was.

When the charge control agent for a toner is prepared as described above, the organic metal having carboxyl ions during the conversion of the basic metal salt formed by the reaction of the metal salt and the hydroxide of the alkali metal to the polynuclear metal complex salt, i.e., before the polynuclear metal complex formation reaction is completed, It is complexed by reaction with the compound. Such a charge control agent for toner is a low molecule having a small number of metal atoms compared with the charge control agent for toner produced by the completion of the production reaction of the polynuclear metal complex salt and the organic compound having carboxyl ions.

When the number of metal atoms in the molecule is small, the charge amount is low, and when the number of organic compounds bonded is low, the commercial dispersion to the resin for toner is not easy enough, and the resolution and image concentration as toner are not sufficient, There is a problem that can not produce a clear image.

The present invention is to produce a multinuclear metal complex salt having a large number of metal atoms in order to solve the problems of the conventional method of manufacturing a charge control agent for toner, and then, the polynuclear metal complex salt has a large number of functional groups having electron donating properties. It is an object of the present invention to provide a charge control agent for a toner of a clear image having a high charge amount, no decrease in resolution and image density, and no contamination by producing a charge control agent for a toner reacted with the compound.

In order to achieve the above object, the present invention mixes any one or a plurality of aqueous solutions selected from alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia water with an aqueous solution of metal salts, stirs, stirs, stirs, stirs, stirs and stirs the mixture. After generating an aqueous solution of the polynuclear metal complex salt, or stirring and aging the aqueous solution of the metal salt in a warmed state, and then stopping the stirring and static aging to produce an aqueous solution of the polynuclear metal complex salt, and then a carboxyl group, a hydroxyl group, an amino group, an amido group, and a sulfo group Complex salting with an aromatic compound having a plurality of functional groups or a plurality of functional groups to form an aqueous solution of an aromatic compound-metal-aqua complex salt, and then any one selected from ammonia water, ammonium salt and amine in the aqueous solution of the aromatic compound-metal-aqua complex salt compound Or add more than one The present invention provides a charge control agent for a toner prepared by filtration, washing, and drying an aqueous solution of an aromatic compound-metal-ammine complex compound formed by substituting an aqua complex with an ammine complex.

The present invention produces a charge control agent for a toner in which a polynuclear metal complex salt is produced, and then reacts the polynuclear metal complex salt with an aromatic compound having a large number of functional groups with electron donating, thereby increasing the amount of charge and dispersing it into a resin for a toner. This makes it easy to obtain an image quality of a clear image without deterioration in resolution and image density.

In addition, since the charge control agent for toner of the present invention has a high charge amount, the toner having a high charge amount can be manufactured even by using 30 to 70% less than the conventional charge control agent for toner, thereby reducing the cost of manufacturing the toner. have.

The present invention mixes any one or a plurality of aqueous solutions selected from hydroxides of alkali metals, hydroxides of alkaline earth metals, and ammonia water to aqueous solutions of metal salts, and after stirring and aging in a heated state, the stirring is stopped and static aging to give an aqueous solution of polynuclear metal complex salts. Or by stirring and aging the aqueous solution of the metal salt in a warm state, and then stopping the stirring and aging to produce an aqueous solution of the polynuclear metal complex salt. The carboxyl group, the hydroxy group, the amino group, and the amino acid in the aqueous solution of the polynuclear metal complex salt thus formed. Complex salting an aromatic compound having any one or a plurality of functional groups selected from pottery and sulfo groups to produce an aqueous aqua complex salt compound of an aromatic compound-metal complex salt, an aqueous aqua complex salt solution of the aromatic compound-metal complex salt compound Ammonia water, ammonium salt, Adding any one or more selected from Min to replace the aqua complex of the aromatic compound-metal complex salt with an ammine complex to produce an aqueous solution of the aromatic compound-metal-ammine complex salt, wherein the produced aromatic compound-metal- It is to prepare a charge control agent for a toner of the formula (1) through the step of filtration, washing, and drying an aqueous solution of an ammine complex salt compound.

(Formula 1, M is any one selected from magnesium, aluminum, silicon, titanium, chromium, manganese, gold, silver, iron, copper, zinc, zirconium, tin, cerium, nickel, cobalt, barium, calcium, molybdenum, tungsten Or R ₁ represents -1 valent anion of aromatic hydroxy acid, R ₂ represents -2 valent anion of monoazo compound, n is an integer from 0 to 3, and a, b, c are D, e, f are integers from 0 to 3, and a + b + c + d + e + f≥ 1. g, h, i are integers from 0 to 6, and g + h + i≥1, j is an integer from 0 to 11)

The metal of the metal salt is any one selected from magnesium, aluminum, silicon, titanium, chromium, manganese, gold, silver, iron, copper, zinc, zirconium, tin, cerium, nickel, cobalt, barium, calcium, molybdenum, tungsten or There are a plurality.

The salt of the metal salt is any one or more selected from those consisting of nitrates, sulfates, chlorides, formates, acetates, oxalates, perchlorates.

Examples of the hydroxide of the alkali metal include sodium hydroxide, potassium hydroxide, lithium hydroxide and the like. Examples of hydroxides of alkaline earth metals include barium hydroxide, magnesium hydroxide, calcium hydroxide and the like.

The stirred aging in the warmed state is stirred for 1 to 15 hours at a temperature of 70 ~ 100 ℃ to produce a multinuclear metal complex salt, after stirring aging in the warmed state as described above to stand for 1 to 14 days without stirring again to the multinuclear metal complex salt Creates.

In the case of stirring and aging in a heated state, polynuclear metal complex salt formation is insufficient at a temperature below 70 ° C., and the effect is not increased any more than 100 ° C. In the case of stirring and aging in a warm state, if the time is less than 1 hour, the formation of polynuclear metal complex salt is insufficient, and if the time exceeds 15 hours, the effect does not increase further. After stirring and aging in a warmed state, the mixture is allowed to stand for 1 to 14 days without stirring again to complete the reaction of incomplete polynuclear metal complex salt formation. In the case of stationary ripening, the mixture is left without stirring at room temperature or at room temperature to form a polynuclear metal complex salt. If the settling time is less than 1 day, the completion of the polynuclear metal complex salt formation reaction is insufficient, and if it exceeds 14 days, the effect is not increased further (see [Example 4] and [Comparative Example 4]).

An aromatic compound containing any one or a plurality of functional groups selected from the above carboxyl group, hydroxy group, amino group, amido group and sulfo group includes aromatic hydroxy acid and monoazo compound. Aromatic hydroxy acids are salicylic acid, 4-methyl salicylic acid, 3,5-di-tert-butyl salicylic acid, 2-hydroxy-3-naphthoic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 1-hydroxy-2 -Naphthoic acid, butyl-1-hydroxy-2-naphthoic acid, or 1,2,3,4-tetrahydro-2-naphthoic acid. The monoazo compound consists of a diazo component and a coupling component. The diazo component is 4-chloro-2-aminophenol, 4-nitro-2-aminophenol, 2-aminophenol-4-sulfonic acid, and 3-diethylaminophenol. , o-aminophenol, 3-chloro-2-aminophenol, 4-methyl-2-aminophenol, 4-acetyl-2-aminophenol, 4-nitro-2-aminophenol, 4-methoxy-2-amino Phenol, 4-chloro-5-nitro-2-aminophenol, 4-tert-amyl-6-nitro-2-aminophenol, any one or more selected from anthranilic acid, the coupling component is 1-naphthol, 2- Naphthol, naphthol AS, 2- (4-chlorophenyl) -5-methyl-3-pyrazolone, 6-tert-butyl-β-naphthol, 1-phenyl-3-methyl-5-pyrazolone, 3-hydroxy Or two or more selected from 2-naphanilide and 3-hydroxy-2-naphth-o-anizide.

The sum of the ion value of the metal ion generated from the metal salt and the ion value of the aromatic compound ion is greater than or equal to 0, and the weight ratio of the aromatic compound ion to the metal ion is greater than or equal to 2 A multinuclear charge control agent with good dispersion can be produced. When the sum of the ion value of the metal ion and the ion value of the aromatic compound ion is less than 0, the effect is reduced and a clear image cannot be obtained. (Refer to [Example 5] and [Comparative Example 5].) When the weight ratio of the aromatic compound ions is smaller than 2, the commercial dispersion to the resin for toner is poor and a clear image cannot be obtained. (See [Example 7] and [Comparative Example 7].)

Examples of the ammonium salts include ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium acetate, ammonium phosphate and ammonium bicarbonate.

The reaction of mixing any one or a plurality of aqueous solutions selected from hydroxides of alkali metals, hydroxides of alkaline earth metals and aqueous ammonia with an aqueous solution of metal salts is followed by aging to produce a multinuclear metal complex salt, for example, a reaction of generating a metal complex. If it is the same as the formula (2) ~ (5). However, the coordinating water molecules were omitted.

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As an example of the chemical formula of a possible aromatic compound-metal-aqua complex salt produced by reacting a polynuclear metal complex salt with an aromatic compound having any one or a plurality of functional groups selected from carboxyl group, hydroxyl group, amino group, amido group, and sulfo group Something like this:

A monoazo compound prepared by reacting 4-chloro-2-aminophenol as a diazo component with naphthol-AS as a coupling component and 3,5-di-tert-butylsalicylic acid are reacted with the general formula (5) of the polynuclear iron salt. To produce an aromatic compound-metal-aqua complex salt compound is represented by the formula (6). It is thought that aromatic compounds bind randomly to iron atoms.

Formula (7) shows that an aromatic compound-metal-aqua complex salt compound reacts with ammonia water or ammonium salt to produce an aromatic compound-metal-ammine complex salt compound.

Formula (7) is, for example, a polynuclear metal complex salt having three iron atoms in comparison with one iron atom, and an aromatic compound having a carboxyl group that donates electrons, an azo and an amino acid capable of donating electrons. Since a plurality of aromatic compounds with pottery, ammonia for donating electrons, and the like are bonded to each other, the amount of charge becomes high. That is, since a plurality of aromatic compounds such as 3,5-di-tret-butylsalicylic acid and a monoazo compound are combined with a plurality of ammonia in the iron atom, dispersion in the toner resin is good, and thus the resolution and image density of the toner There is no deterioration and there is no contamination and a clear image is obtained.

The toner containing the charge control agent according to the present invention is sufficiently mixed with the binder resin, the colorant, the wax, and the charge control agent according to the present invention in a mixer such as a ball mill or a hexyl mixer, followed by a roll kneader, an extruder, or the like. It is prepared by kneading with a kneader, cooling, solidifying, and then pulverizing, classifying and post-treatment (external addition). It is also obtained by a spray method, a polymerization method, or the like.

The binder resin is a polymer of styrene such as polystyrene, poly-p-chlorostyrene, and a substituent thereof, styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methacrylic acid ester Styrene-based copolymers such as copolymer, styrene-α-chloromethacrylic acid copolymer, styrene-acrylnitro copolymer, styrene-vinyl methyl ether copolymer, polyvinyl chloride, phenol resin, acrylic resin, methacrylic resin, polyacetic acid Vinyl resins, polyester resins, epoxy resins, polyvinyl butyl resins, petroleum resins and the like.

The coloring agent is magnetic material such as magnetite, γ-iron oxide or ferrite, carbon black, lamp black, ultramarine blue, aniline blue, phthalocyanine blue, gtarrol cyanine green, kanji yellow-G, rhodamine 6G, carucoyru blue, chromium-based Yellow, kinacridone, benzine yellow, rose ben powder, a triaryl methane type compound, a mono azo dye, a diazo dye, etc. are mentioned.

The wax may include low molecular weight polypropylene, low molecular weight polyethylene, microcrystalline wax, caruna wax, paraffin wax or aliphatic solid alcohol.

Particulates, such as a fluidizing agent, a charging aid, or an abrasive, can be added to the toner as needed. Particulates such as silica, titanium oxide and alumina, or fine particles obtained by hydrophobization treatment with a silicone oil, a silicone wax, a silane coupling agent, or the like, And metal oxides such as potassium titanate, inorganic fine particles such as metal carbides and metal nitrides, organic fine particles such as polystyrene, organic metal compound fine particles such as zinc stearate and calcium stearate.

[Example]

EXAMPLES Hereinafter, the present invention will be described in detail by way of examples, which do not limit the present invention.

Example 1

Synthesis Example 1 of Multinuclear Charge Control Agent

20 g of ferric sulfate (0.05 mol, Fe ³⁺ : 0.1 mol) was dissolved in 250 g of water. Meanwhile, 5.6 g (0.14 mol) of sodium hydroxide was dissolved in 50 g of water. An aqueous solution of sodium hydroxide was added to the ferric sulfate aqueous solution, the mixture was stirred at a temperature of 80 ° C. for 1 hour, and then the stirring was stopped. The mixture was cooled, left to mature at room temperature for 10 days, and 325.6 g of a multinuclear ferric salt aqueous solution was prepared.

49.5 g (0.1 mol) of monoazo compound and sodium hydroxide synthesized by conventional diazotization and coupling reaction using 2-aminophenol-4-sulfonic acid and 3-hydroxy-2-naphth-o-anizide 10 g (0.25 mol) was dissolved in 400 g of ethylene glycol and stirred at 110 ° C. for 3 hours to prepare a monoazo compound solution.

To 459.4 g of this monoazo compound solution, 325.6 g of the aforementioned multinuclear iron complex salt aqueous solution was added dropwise. The mixture was heated and stirred at a temperature of 95 ° C. for 5 hours to produce an aqueous aromatic compound-iron-aqua complex salt compound. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 160 g of this cake was dispersed in 500 g of water. 250 g (2 mol) of 28% aqueous ammonia was added dropwise to the dispersion, the temperature was raised, and the mixture was stirred at 80 DEG C for 10 hours to produce an aqueous solution of aromatic compound-iron-ammine complex salt. After stirring and cooling to 35 DEG C, filtration, washing and drying in a conventional manner yielded 57 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein the trinuclear nucleus is represented by the following formula (8).

In Formula 8, R ₂ is a monoazo compound synthesized by conventional diazotization and coupling reaction using 2-aminophenol-4-sulfonic acid and 3-hydroxy-2-naphth-o-anizide. -2 represents an anion.)

<Manufacture of Toner, Example 1 of Performance Check>

Toner was prepared by the following formulation.

Styrene-acrylic acid ester copolymer 88 parts by weight

4 parts by weight of low molecular weight polypropylene NP-505

Carbon black MA-100 (3 parts by weight)

1 part by weight of the charge control agent of Example 1

The materials were dry mixed with a mixer (hensil mixer), and then kneaded with a twin screw kneader fixed at 130 캜. The kneaded product obtained as described above was cooled, coarsely pulverized to about 2 mm or less with a hammer mill, and then pulverized by a jet mill having a pulverization and classification function. The obtained fine powder was classified by the airflow classifier, and the fresh toner of average particle diameter of 8.5 micrometers was obtained. 0.4 parts by weight of hydrophobic colloidal silica and 1.0 parts by weight of titanium oxide were added to 100 parts by weight of the fresh toner, mixed with a mixer (hensil mixer), and then agglomerated bodies were removed to obtain a toner.

The charge amount of the toner was measured by a blow-off powder charge amount measuring device (trade name: TB-200, manufactured by Toyo Chemical). A continuous printing test of 5,000 sheets was conducted with a developing printer of a modified nonmagnetic one-component toner commercially available using this toner. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

In each Example and the comparative example, the result of evaluation about each item of the print image at the start of a continuous printing test, and the print image at the end is shown in <Table 1>. The test chart used an electroradiography test chart NO.1-R. Image density was measured by the Macbeth densitometer (trade name: RD-918, manufactured by Sadada Ink Co., Ltd.). The resolution was evaluated by visually observing a printed image using a loupe and counting the number of independent thin lines. Contamination is a value obtained by measuring the density of the non-image part of a printed image with a Macbeth densitometer and subtracting the density (0.05) of general paper before printing from this value. The sharpness of the image was evaluated by visually observing the printed image.

Comparative Example 1

18.9 g (0.05 mol) of monoazo compound synthesized by conventional diazotization and coupling reaction using 4-tert-amyl-6-nitro-2-aminophenol and 2-naphthol was synthesized with N, N-dimethylformamide. In 500 ml (DMF). 3.2 g (0.03 mol) of sodium carbonate was added to the solution, and heated to 70 ° C., and then 8.3 g (0.03 mol) of ferrous sulfate heptahydrate was added and reacted for 5 hours. The precipitate obtained by diluting the reaction solution with 5 times water was filtered, washed and dried in a conventional manner to obtain 19 g of a powder charge control agent.

Toner was manufactured in the same manner as in Performance Confirmation Example 1 except that the charge control agent of [Comparative Example 1] was used instead of the charge control agent of [Example 1] in <Manufacture of Toner, Performance Confirmation Example 1>. In the same manner as in 1, the charge amount measurement and the continuous printing test of the toner were performed. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

[Example 1] is the weight ratio of monoazo compound ions (Azo ^2- ) to iron ions (Fe ³⁺ ) is 8.8, and [Comparative Example 1] is monoazo compound ions (Fe ²⁺ ) to iron ions (Fe ²⁺ ) The weight ratio of Azo ^2- ) was 11.3, all greater than 2.

However, in Example 1, the molar ratio is iron ions (Fe ³⁺ ): monoazo compound ions (Azo ^2- ) = 1: 1 and the sum of ionic values is +1, which is larger than 0, but [Comparative Example 1] is The molar ratio of iron ions (Fe ²⁺ ): monoazo compound ions (Azo ^2- ) = 1: 1.67 and the sum of ionic values was -1.34, which was less than zero. In Example 1, warm stirring and maturation were carried out for 1 hour for 10 days for multinucleation, but in Comparative Example 1, there was no multinucleation process.

[Example 2]

Synthesis Example 2 of Multinuclear Charge Control Agent

13.6 g (0.1 mol) of zinc chloride were dissolved in 250 g of water. Meanwhile, 75.1 g (0.6 mol) of 28% ammonia water was diluted with 50 g of water. Aqueous ammonia solution was added to the zinc chloride aqueous solution, the mixture was stirred at a temperature of 75 ° C. for 2 hours, and then the stirring was stopped.

18.8 g (0.1 mole) of 2-hydroxy-3-naphthoic acid and 5 g (0.125 mole) of sodium hydroxide were dissolved in 250 g of isopropyl alcohol and stirred at 65 ° C. for 3 hours to prepare a 2-hydroxy-3-naphthoic acid solution. Ready.

388.7 g of an aqueous polynuclear zinc complex salt was added dropwise to 273.8 g of a 2-hydroxy-3-naphthoic acid solution, and then the temperature was adjusted to 75 ° C. and stirred for 10 hours to produce an aqueous aromatic compound-zinc-aqua complex salt compound. Thereafter, the mixture was cooled to 35 ° C, filtered and washed in a conventional manner to form a paste cake, and 80 g of the filter cake was dispersed in 500 g of water. 300 g (1 mol) of 45% ammonium sulfate aqueous solution was added dropwise to this dispersion, and stirred at 80 ° C for 10 hours to produce an aqueous aromatic compound-zinc-ammine complex salt compound. After cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 27 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, and the nucleus is represented by the following formula (9).

(In Formula 9, R ₁ represents a -monovalent anion of 2-hydroxy-3-naphthoic acid.)

<Production of Toner, Performance Confirmation Example 2>

Toner was prepared by the following formulation.

52 parts by weight of styrene-acrylic acid ester copolymer

45 parts by weight of magnetite

2 parts by weight of low molecular weight polypropylene NP-505

1 part by weight of the charge control agent of Example 2

Toner was prepared in the same manner as in [Example 1].

The charge amount of the toner was measured in the same manner as in [Example 1]. The continuous printing test of 10,000 sheets was carried out with the developing printer of the modified magnetic one-component toner marketed using this toner. As shown in Table 1, the charge amount was high, the resolution and the image density were not lowered, and the image was clear and free of contamination.

Comparative Example 2

4 g (0.1 mol) of sodium hydroxide was dissolved in 475 g of water, and 18.8 g (0.1 mol) of 2-hydroxy-3-naphthoic acid was added and stirred. This was reacted at 80 ° C. for 1 hour to prepare 497.8 g of 2-hydroxy-3-naphthoic acid solution.

13.6 g (0.1 mol) of zinc chloride were dissolved in 600 g of water. Meanwhile, 4 g (0.1 mol) of sodium hydroxide was dissolved in 600 g of water. An aqueous sodium hydroxide solution was added to the aqueous zinc chloride solution, and then 497.8 g of the aforementioned 2-hydroxy-3-naphthoic acid solution was added at 90 ° C. with stirring, followed by reaction at 90 ° C. for 2 hours. The reaction solution was filtered, washed and dried in a conventional manner to obtain 25 g of a powder charge control agent.

Toner was manufactured in the same manner as in Example 2 except that the charge control agent of [Comparative Example 2] was used instead of the charge control agent of [Example 2] in <Manufacture of Toner, Performance Confirmation Example 2>. The charge amount measurement and the continuous printing test of the toner were carried out in the same manner as in Example 2. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

[Example 2] and [Comparative Example 2] are both molar ratios of zinc ions (Zn ²⁺ ): 2-hydroxy-3-naphthoic acid ions (HN ⁻ ) = 1: 1 and the sum of ionic values is +1 and 0. Larger, the weight ratio of 2-hydroxy-3-naphthoic acid ion (HN ⁻ ) to zinc ion (Zn ²⁺ ) was all 2.9, greater than 2.

However, in Example 2, warm stirring and maturation were performed for 5 hours and 2 hours for multinucleation, whereas Comparative Example 2 did not have a multinucleation process.

[Example 3]

Synthesis Example 3 of Multinuclear Charge Control Agent

16.2 g (0.1 mol) of ferric chloride was dissolved in 250 g of water. Meanwhile, 4.8 g (0.2 mol) of lithium hydroxide was dissolved in 50 g of water. An aqueous lithium hydroxide solution was added to the ferric chloride aqueous solution, the mixture was stirred at a temperature of 95 ° C. for 12 hours, and then the stirring was stopped.

41.9 g (0.1 mole) of monoazo compound and 10 g (0.25 mole) of sodium hydroxide synthesized by conventional diazotization and coupling reaction using 4-chloro-2-aminophenol and naphthol AS were dissolved in 400 g of ethylene glycol. 451.9 g of a monoazo compound solution was prepared by stirring at 110 ° C. for 3 hours.

To 451.9 g of this monoazo compound solution, 321 g of the aforementioned polynuclear ferric salt aqueous solution was added dropwise. The mixture was heated and stirred at a temperature of 95 ° C. for 5 hours to produce an aqueous aromatic compound-iron-aqua complex salt compound. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 130 g of the cake was dispersed in 500 g of water. 154 g (2 mol) of ammonium acetate was dissolved in 700 g of water and added dropwise to the dispersion, and the temperature was raised and stirred at 80 ° C for 10 hours to produce an aqueous solution of aromatic compound-iron-ammine complex salt. After stirring and cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 50 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein four nuclei are shown as the following formula (10).

(In Formula 10, R ₂ represents the -divalent anion of the monoazo compound synthesized by conventional diazotization and coupling reaction using 4-chloro-2-aminophenol and naphthol AS.)

<Production of Toner, Example 3 of Performance Check>

Toner was prepared by the following formulation.

87 parts by weight of polyester resin

5 parts by weight of low molecular weight polypropylene NP-505

Carbon black MA-100 (3 parts by weight)

1 part by weight of the charge control agent of Example 3

Toner was manufactured from the above material in the same manner as in [Example 1].

The charge amount of the toner was measured in the same manner as in [Example 1]. A continuous printing test of 5,000 sheets was conducted with a developing printer of a modified nonmagnetic one-component toner commercially available using this toner. As shown in Table 1, the charge amount was high, the resolution and the image density were not lowered, and the image was clear and free of contamination.

[Comparative Example 3]

41.9 g (0.1 mole) of monoazo compound synthesized by conventional diazotization and coupling reaction using 4-chloro-2-aminophenol and naphthol AS was dissolved in 150 g of ethylene glycol, and 5 g (0.125 mole) sodium hydroxide. And 8.5 g (0.05 mol) of ferric chloride were added and complexed at 115 ° C. for 2 hours. The reaction solution was diluted with 5 times water and the precipitated product was filtered and washed in a conventional manner.

110 g of this filter cake was dispersed in 400 g of water, and 13.4 g (0.25 mol) of ammonium chloride was added, followed by reaction for 1 hour. The reaction solution was filtrated, washed and dried in a conventional manner to obtain 43 g of a powdery charge control agent.

Toner was manufactured in the same manner as in Performance Confirmation Example 3 except that the charge control agent in [Comparative Example 3] was used instead of the charge control agent in [Example 3] in <Manufacture of Toner, Performance Confirmation Example 3>. The charge amount measurement and the continuous printing test of the toner were carried out in the same manner as in Example 3. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

[Example 3] are iron ions (Fe ³⁺⁾ monoazo compound ions at a weight ratio of 7.5 (Azo ^2-) and Comparative Example 3 is a monoazo iron compound ions to come (Fe ³⁺⁾ to (Azo The weight ratio of ^2- ) was 14.9, all greater than 2.

However, in Example 3, the molar ratio is iron ions (Fe ³⁺ ): monoazo compound ions (Azo ^2- ) = 1: 1 and the sum of ionic values is +1, which is larger than 0, but [Comparative Example 3] is The molar ratio was iron ions (Fe ³⁺ ): monoazo compound ions (Azo ^2- ) = 1: 2 and the sum of ionic values was -1, which was less than zero. In Example 3, warm stirring and maturation were carried out for 10 hours and 12 hours for multinucleation, but in Comparative Example 3, there was no multinucleation process.

Example 4

Synthesis Example 4 of Multinuclear Charge Control Agent

14.2 g (0.1 mol) of magnesium acetate was dissolved in 250 g of water. Meanwhile, 75.1 g (0.6 mol) of 28% ammonia water was diluted with 50 g of water. An aqueous ammonia solution was added to the aqueous magnesium acetate solution, the mixture was stirred at a temperature of 70 ° C. for 10 hours, the stirring was stopped, the mixture was cooled, left to stand at room temperature for 12 days, and 389.3 g of a multinuclear magnesium complex aqueous solution was prepared.

18.8 g (0.1 mole) of 3-hydroxy-2-naphthalenecarboxylic acid and 5 g (0.125 mole) of sodium hydroxide were dissolved in 250 g of isopropyl alcohol and stirred at 65 ° C. for 3 hours to 3-hydroxy-2-naphthalenecar 273.8 g of acid solution were prepared.

389.3 g of an aqueous polynuclear magnesium complex salt was added dropwise to 273.8 g of a 3-hydroxy-2-naphthalene carboxylic acid solution, and then the temperature was adjusted to 75 ° C. and stirred for 10 hours to give an aqueous aromatic compound-magnesium-aqua complex salt solution. Produced. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 70 g of the cake was dispersed in 500 g of water. 80 g (1 mol) of ammonium nitrate was dissolved in 400 g of water, and the mixture was added dropwise and stirred at 80 ° C. for 10 hours to produce an aqueous solution of aromatic compound-magnesium-ammine complex salt. After cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 25 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, and the nucleus is represented by the following formula (11).

(In Formula 11, R ₁ represents the -valent monoanion of 3-hydroxy-2-naphthalenecarboxylic acid.)

<Production of Toner, Example 4 of Performance Confirmation>

Toner was prepared in the same manner as in Performance Check Example 1 except that the charge control agent in [Example 4] was used instead of the charge control agent in [Example 1], and the charge amount of the toner was measured and measured in the same manner as in Performance Check Example 1. Continuous printing test was done. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

[Comparative Example 4]

Prepared in the same manner as in [Example 4], but after adding an aqueous ammonia solution to the magnesium acetate aqueous solution, instead of `` Stop stirring at a temperature of 70 ℃ for 10 hours, stop the stirring to cool at room temperature for 12 days '', instead of `` A charge control agent was prepared in the same manner as in [Example 4], except that the mixture was stirred at 60 ° C. for 30 minutes.

Toner was manufactured in the same manner as in Performance Confirmation Example 4 except that the charge control agent in [Comparative Example 4] was used instead of the charge control agent in [Example 4] in <Manufacture of Toner, Performance Confirmation Example 4>. The charge amount measurement and the continuous printing test of the toner were carried out in the same manner as in Example 4. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

In Example 4 and Comparative Example 4, the weight ratio of 3-hydroxy-2-naphthalenecarboxylion (HN ⁻ ) to magnesium ion (Mg ²⁺ ) is both 7.7 and greater than 2, and the molar ratio is magnesium ion. (Mg ²⁺ ): 3-hydroxy-2-naphthalenecarboxylic acid ion (HN ⁻ ) = 1: 1 and the sum of all ions was +1, which was greater than zero.

However, in Example 4, warm stirring and maturation were carried out for 10 hours for 12 days for multinucleation, but in Comparative Example 4, the heating temperature was low at 60 ° C. and the heating time was also short at only 30 minutes, so that the multinucleation proceeded sufficiently. It wasn't.

[Example 5]

Synthesis Example 5 of Multinuclear Charge Control Agent

21.3 g (0.1 mol) of aluminum nitrate was dissolved in 250 g of water. Meanwhile, 2.8 g (0.05 mol) of potassium hydroxide was dissolved in 50 g of water. An aqueous potassium hydroxide solution was added to an aqueous solution of aluminum nitrate, the mixture was stirred at a temperature of 90 ° C. for 3 hours, and then the stirring was stopped.

32.1 g (0.1 mole) of monoazo compound and 10 g (0.25 mole) of sodium hydroxide synthesized by conventional diazotization and coupling reaction using 3-diethylaminophenol and 1-naphthol were dissolved in 400 g of ethylene glycol and 110 The monoazo compound solution was prepared by stirring at 3 ° C. for 3 hours.

To 442.1 g of this monoazo compound solution, 324.1 g of the aforementioned polynuclear aluminum complex aqueous solution was added dropwise. The mixture was heated and stirred at a temperature of 95 ° C. for 5 hours to produce an aqueous solution of aromatic compound-aluminum-aqua complex salt. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 100 g of the cake was dispersed in 500 g of water. 53 g (1 mol) of ammonium chloride was dissolved in 300 g of water and added dropwise to the dispersion, and the temperature was raised and stirred at 80 ° C. for 10 hours to produce an aqueous solution of aromatic compound-aluminum-ammine complex salt. After stirring and cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 38 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein the nucleus is shown as the following formula (12).

(In Formula 12, R ₂ represents -divalent anion of a monoazo compound synthesized by conventional diazotization and coupling reaction using 3-diethylaminophenol and 1-naphthol.)

<Production of Toner, Performance Confirmation Example 5>

Toner was prepared in the same manner as in Example 2 except that the charge control agent of [Example 5] was used instead of the charge control agent of [Example 2]. Continuous printing test was done. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

[Comparative Example 5]

Prepared in the same manner as in [Example 5], except for using 884.2 g of monoazo compound (0.2 mol) solution, which was doubled in amount, instead of `` 442.1 g of monoazo compound solution ''. 5] was prepared in the same manner as the charge control agent.

Toner was manufactured in the same manner as in Performance Confirmation Example 5 except that the charge control agent in [Comparative Example 5] was used instead of the charge control agent in [Example 5] in <Production of Toner, Performance Confirmation Example 5>. In the same manner as in Example 5, the charge amount measurement and the continuous printing test of the toner were performed. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

Example 5 is the weight ratio of the monoazo compound ions (Azo ^2-) to aluminum ion (Al ³⁺⁾ 11.8, [Comparative Example 5] A monoazo compound ions to aluminum ions (Al ³⁺⁾ ( The weight ratio of Azo ^2- ) was 23.7, all greater than 2. [Example 5] and [Comparative Example 5] were both warm stirring and political ripening for 3 hours and 3 hours for multinucleation.

[Example 5], however, the molar ratio of aluminum ions (Al ³⁺ ): monoazo compound ions (Azo ^2- ) = 1: 1 and the sum of ionic values is +1, which is larger than 0, but [Comparative Example 5] is The molar ratio was aluminum ion (Al ³⁺ ): monoazo compound ion (Azo ²⁻ ) = 1: 1 and the sum of ionic values was −1, which was less than zero.

[Example 6]

Synthesis Example 6 of Multinuclear Charge Control Agent

15.8 g (0.1 mol) of chromium chloride was dissolved in 250 g of water. After stirring for 7 hours at a temperature of 100 ° C., the stirring was stopped and left to mature at room temperature for 14 days to prepare 265.8 g of an aqueous polynuclear chromium salt solution.

33.5 g (0.1 mole) of monoazo compound and 10 g (0.25 mole) of sodium hydroxide synthesized by conventional diazotization and coupling reaction using 4-methyl-2-aminophenol and 6-tert-butyl-β-naphthol Was dissolved in 400 g of ethylene glycol and stirred at 110 ° C. for 3 hours to prepare a monoazo compound solution.

To 443.5 g of this monoazo compound solution, 265.8 g of the aforementioned multinuclear chromium complex aqueous solution was added dropwise. The mixture was heated and stirred at a temperature of 95 ° C. for 5 hours to produce an aqueous aromatic compound-chromium-aqua complex salt compound. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 110 g of the filter cake was dispersed in 500 g of water. 92 g (0.7 mol) of ammonium diphosphate was dissolved in 400 g of water, and the mixture was added dropwise and stirred at 80 ° C. for 10 hours to produce an aqueous solution of aromatic compound-chromium-ammine complex salt. After cooling to 35 DEG C, filtration, washing and drying in a conventional manner yielded 41 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein trinuclear bodies are shown as an example in the following formula (13).

In Formula 13, R ₂ is a 2- _divalent anion of a monoazo compound synthesized by conventional diazotization and coupling reaction using 4-methyl-2-aminophenol and 6-tert-butyl-β-naphthol. Indicates.)

<Manufacture of Toner, Example 6 of Performance Confirmation>

Toner was prepared in the same manner as in Example 2 except that the charge control agent of [Example 6] was used instead of the charge control agent of [Example 2]. Continuous printing test was done. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

[Comparative Example 6]

4 g (0.1 mol) of sodium hydroxide was dissolved in 475 g of water, and 25 g (0.1 mol) of 3,5-di-tert-butylsalicylic acid was added thereto and stirred. This was reacted at 80 ° C. for 1 hour to prepare 504 g of 3,5-di-tert-butylsalicylic acid solution.

39.2 g of Zychrome sulfate (0.1 mol, Cr ³⁺ : 0.2 mol) was dissolved in 600 g of water. Meanwhile, 4 g (0.1 mol) of sodium hydroxide was dissolved in 600 g of water. An aqueous sodium hydroxide solution was added to the aqueous solution of chromium chromium sulfate, followed by addition of 504 g of the aforementioned 3,5-di-tert-butylsalicylic acid solution at 90 ° C. with stirring, followed by reaction at 90 ° C. for 2 hours. The reaction solution was filtered, washed and dried in a conventional manner to obtain 26 g of a powder charge control agent.

Toner was manufactured in the same manner as in Performance Confirmation Example 6 except that the charge control agent in [Comparative Example 6] was used instead of the charge control agent in [Example 6] in <Manufacture of Toner, Performance Confirmation Example 6>. In the same manner as in 6, the charge amount measurement and the continuous printing test of the toner were performed. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

Example 6 is the weight ratio of the monoazo compound ions (Azo ^2-) to chromium ions (Cr ³⁺⁾ 6.4, [Comparative Example 6] is 3,5 to chromium ions (Cr ³⁺⁾ di The weight ratio of -tert-butylsalicylic acid ion (SA ⁻ ) was 2.4, which was greater than 2 in all. [Example 6] has a molar ratio of chromium ion (Cr ³⁺ ): monoazo compound ion (Azo ^2- ) = 1: 1 and the sum of ionic values is +1, which is greater than 0, and in [Comparative Example 6], the molar ratio is chromium Ion (Cr ³⁺ ): 3,5-di-tert-butylsalicylic acid ion (SA ⁻ ) = 2: 1 and the sum of ionic values was +5, which was greater than zero.

However, in Example 6, the mixture was heated and aged for 7 hours for 14 days for multinucleation, but in Comparative Example 6, there was no multinucleation process.

[Example 7]

Synthesis Example 7 of Multinuclear Charge Control Agent

11.1 g (0.1 mol) of calcium chloride was dissolved in 250 g of water. Meanwhile, 75.1 g (0.6 mol) of 28% ammonia water was diluted with 50 g of water. Aqueous ammonia solution was added to the aqueous calcium chloride solution. After stirring at this temperature for 15 hours at 95 ° C, the stirring was stopped, and the mixture was left to mature at 95 ° C for 1 day to prepare 386.2 g of a multinuclear calcium complex salt aqueous solution.

17.6 g (0.1 mol) of 1,2,3,4-tetrahydro-2-naphthoic acid and 5 g (0.125 mol) of sodium hydroxide were dissolved in 250 g of isopropyl alcohol and stirred at 65 ° C. for 3 hours to produce 1,2,3 272.6 g of, 4-tetrahydro-2-naphthoic acid solution were prepared.

386.2 g of an aqueous polynuclear calcium complex salt was added dropwise to 272.6 g of 1,2,3,4-tetrahydro-2-naphthoic acid solution, and then the temperature was adjusted to 75 ° C. and stirred for 10 hours to produce an aromatic compound-calcium- An aqueous aqua complex salt compound was produced. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 65 g of the cake was dispersed in 500 g of water. 80 g (1 mol) of ammonium bicarbonate was dissolved in 400 g of water and added dropwise to the dispersion. The temperature was raised to 10 hours and stirred at 80 ° C. to produce an aqueous solution of aromatic compound-calcium-ammine complex salt. After stirring and cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 24 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein the nucleus is represented by the following formula (14).

(In Formula 14, R ₁ represents the monovalent anion of 1,2,3,4-tetrahydro-2-naphthoic acid.)

<Manufacturer of Toner, Example 7 of Performance Confirmation>

Toner was prepared in the same manner as in Performance Check Example 3 except that the charge control agent in [Example 7] was used instead of the charge control agent in [Example 3]. Continuous printing test was done. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

[Comparative Example 7]

Manufactured in the same manner as in [Example 7], except that "1,2,3,4-tetrahydro-2-naphthoic acid solution 272.6 g" was reduced to 0.4 times the amount of "1,2,3,4" A charge control agent was prepared in the same manner as in [Example 7], except that 109.0 g of tetrahydro-2-naphthoic acid solution was used.

Toner was manufactured in the same manner as in Performance Confirmation Example 7 except that the charge control agent in [Comparative Example 7] was used instead of the charge control agent in [Example 7] in <Production of Toner, Performance Confirmation Example 7>. In the same manner as in 7, the charge amount measurement and the continuous printing test of the toner were carried out. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

Example 7 is a molar ratio of calcium ion (Ca ²⁺ ): 1,2,3,4-tetrahydro-2-naphthoic acid ion (HN ⁻ ) = 1: 1 and the sum of ions is +1, which is greater than 0. , [Comparative Example 7] has a molar ratio of calcium ion (Ca ²⁺ ): 1,2,3,4-tetrahydro-2-naphthoic acid ion (HN ⁻ ) = 1: 0.4 and the sum of ions is +1.6, which is greater than zero. It was great. [Example 7 and] [Comparative Example 7] All were subjected to warm stirring and political ripening for 15 hours a day for multinucleation.

[Example 7] However, the weight ratio of 1,2,3,4-tetrahydro-2-naphthoic acid ion (HN ⁻ ) to calcium ion (Ca ²⁺ ) is 4.4, which is larger than 2, 7] has a weight ratio of 1,2,3,4-tetrahydro-2-naphthoic acid ion (HN ⁻ ) to calcium ion (Ca ²⁺ ) of 1.7, which is less than 2.

[Example 8]

Synthesis Example 8 of Multinuclear Charge Control Agent

23.3 g (0.1 mol) of zirconium tetrachloride were dissolved in 250 g of water. Meanwhile, 6.8 g (0.17 mol) of sodium hydroxide was dissolved in 50 g of water. An aqueous solution of sodium hydroxide was added to the aqueous solution of zirconium tetrachloride, the mixture was stirred at a temperature of 85 ° C. for 5 hours, and then the stirring was stopped. After stirring at 85 ° C. for 7 days, 330.1 g of a polynuclear zirconium complex salt solution was prepared.

42.5 g (0.1 mole) of monoazo compound and 10 g (0.25) of sodium hydroxide synthesized by conventional diazotization and coupling reaction using 4-acetyl-2-aminophenol and 3-hydroxy-2-naphthanilide Mole) was dissolved in 400 g of ethylene glycol and stirred at 110 ° C. for 3 hours to prepare 452.5 g of monoazo compound solution.

Meanwhile, 50 g (0.2 mole) of 3,5-di-tert-butyl salicylic acid and 10 g (0.25 mole) of sodium hydroxide were dissolved in 500 g of isopropyl alcohol, and stirred at 65 ° C. for 3 hours to produce 3,5-di-tert-butyl salicylic acid. 560 g of solution was prepared.

330.1 g of the above-mentioned multinuclear zirconium complex salt aqueous solution was added dropwise to 1,012.5 g of the mixed solution of these two solutions. The mixture was heated and stirred at a temperature of 80 ° C. for 8 hours to produce an aqueous aromatic compound-zirconium-aqua complex salt compound. Thereafter, the mixture was cooled to 35 DEG C, filtered and washed in a conventional manner to form a paste cake, and 260 g of this cake was dispersed in 500 g of water. 250 g (2 mol) of 28% ammonia water was added dropwise to this dispersion, the temperature was raised, and the mixture was stirred at 80 DEG C for 10 hours to produce an aqueous solution of aromatic compound-zirconium-ammine complex salt. After stirring and cooling to 35 ° C., filtration, washing and drying in a conventional manner yielded 102 g of a powder charge control agent.

The charge control agent prepared as described above is a mixture containing 2 to 5 nuclei as a main component, wherein the nucleus is represented by the following formula (15).

In Formula 15, R ₂ is -2 of a monoazo compound synthesized by conventional diazotization and coupling reaction using 4-acetyl-2-aminophenol and 3-hydroxy-2-naphthanilide. An anion, and R ₁ represents a -1 -valent anion of 3,5-di-tert-butylsalicylic acid.)

<Production of Toner, Example 8 of Performance Confirmation>

Toner was prepared in the same manner as in Performance Check Example 3 except that the charge control agent in [Example 8] was used instead of the charge control agent in [Example 3]. Continuous printing test was done. As shown in Table 1, the charge amount was high, the resolution and the image density did not decrease, and the image was free from contamination and clear.

[Comparative Example 8]

33 g (0.132 mol) of 3,5-di-tert-butyl salicylic acid and 19 g (0.12 mol) of 25% caustic soda were dissolved in 350 g of water and heated to 50 ° C with stirring. While stirring this aqueous solution, the aqueous solution which dissolved 19 g (0.107 mol) of zirconium oxychlorides in 90 g of water was dripped. After stirring at the same temperature for 1 hour, the mixture was cooled to room temperature and adjusted to pH 7.7 by adding 6 g of 25% caustic soda. Precipitated crystals were filtered, washed and dried in a conventional manner to obtain 25 g of white crystals.

Toner was manufactured in the same manner as in Performance Confirmation Example 8 except that the charge control agent in [Comparative Example 8] was used instead of the charge control agent in [Example 8] in <Manufacture of Toner, Performance Confirmation Example 8>. In the same manner as in 8, the charge amount measurement of the toner and the continuous printing test were performed. As shown in Table 1, the charge amount was low, the resolution and image density were lowered, and the image was contaminated and was not clear.

[Example 8] has a molar ratio of zirconium ions (Zr ^4+): A monoazo compound ions (Azo ^{2-): -} an ionic valency of 2: 3,5-di -tert- butyl salicylate ion (SA) = 1: 1 the sum is 0, Comparative example 8] is a molar ratio of zirconium ions (Zr ^4+): 3,5- di -tert- butyl salicylate ion (SA ^-) = 1: 1.23 and the total ionic valency of greater than zero to +2.77 It was great. Example 8 is a weight ratio of zirconium ions (Zr ⁴⁺ ) to monoazo compound ions (Azo ^2- ) and 3,5-di-tert-butylsalicylic acid ions (SA ⁻ ) to 10.1, which is greater than 2, [ In Comparative Example 8, the weight ratio of 3,5-di-tert-butylsalicylic acid ion (SA ⁻ ) to zirconium ion (Zr ⁴⁺ ) was 3.4, which was larger than 2.

However, in [Example 8], warm stirring and maturation were performed for 7 hours and 5 hours for multinucleation, but in [Comparative Example 8], there was no multinucleation process.

Toner charge measurement and continuous print test results evaluation
Item Charge Burn density resolution pollution burn
(Quality)
On start At the end On start At the end On start At the end On start At the end Example 1 18.0 16.8 1.45 1.42 5.0 4.0 0.01 0.02 sharpness Comparative Example 1 14.2 11.2 1.30 1.15 4.0 3.2 0.03 0.05 Invisibility Example 2 15.8 15.1 1.43 1.43 5.0 4.0 0.00 0.02 sharpness Comparative Example 2 9.5 6.6 1.34 1.34 3.2 2.5 0.04 0.07 Invisibility Example 3 17.7 16.7 1.44 1.44 5.0 4.0 0.01 0.03 sharpness Comparative Example 3 11.0 8.7 1.38 1.38 4.0 3.2 0.04 0.06 Invisibility Example 4 15.6 15.3 1.44 1.42 5.0 4.0 0.01 0.02 sharpness Comparative Example 4 10.2 9.3 1.32 1.21 3.8 3.0 0.04 0.05 Invisibility Example 5 16.2 15.1 1.44 1.43 5.0 4.0 0.01 0.03 sharpness Comparative Example 5 9.9 7.2 1.32 1.30 3.6 2.7 0.04 0.05 Invisibility Example 6 18.0 16.7 1.45 1.44 5.0 4.0 0.00 0.02 sharpness Comparative Example 6 13.9 11.3 1.38 1.37 4.0 3.3 0.03 0.05 Invisibility Example 7 16.1 15.7 1.42 1.42 4.8 4.0 0.01 0.03 sharpness Comparative Example 7 9.6 6.8 1.30 1.26 3.4 2.7 0.04 0.06 Invisibility Example 8 18.1 16.7 1.45 1.44 5.0 4.0 0.00 0.02 sharpness Comparative Example 8 14.2 11.0 1.38 1.37 4.0 3.3 0.03 0.04 Invisibility

* At start: When printing started * At end: When printing finished

Claims (9)

One or more aqueous solutions selected from alkali metal hydroxides, alkaline earth metal hydroxides, and ammonia water are mixed with the aqueous solution of the metal salts, stirred and matured in a heated state, and then the stirring is stopped and left to aged. After stirring or aging the aqueous solution of the metal salt in a warmed state, the stirring is stopped and static aging to produce an aqueous solution of the polynuclear metal complex salt, and the carboxyl group, the hydroxyl group, the amino group, the amido group, the liquor in the aqueous solution of the polynuclear metal complex salt thus formed. Complex salting an aromatic compound having any one or a plurality of functional groups selected from aeration to produce an aqueous aqua complex salt compound of an aromatic compound-metal complex salt, ammonia water in the aqueous solution of the aqua complex salt compound of the aromatic compound-metal complex salt compound, Ammonium salt, in amine Adding one or more selected to replace the aqua complex of the aromatic compound-metal complex salt compound with an ammine complex to produce an aqueous solution of the aromatic compound-metal-ammine complex compound, wherein the generated aromatic compound-metal-ammine complex salt A method for producing a charge control agent for a toner containing a polynuclear metal complex salt, comprising the steps of filtration, washing, and drying an aqueous solution of a compound to complete a charge control agent for a toner.
The metal salt of claim 1, wherein the metal of the metal salt is selected from among magnesium, aluminum, silicon, titanium, chromium, manganese, gold, silver, iron, copper, zinc, zirconium, tin, cerium, nickel, cobalt, barium, calcium, molybdenum and tungsten. A method for producing a charge control agent for a toner containing a multinuclear metal complex salt, characterized in that any one or a plurality of selected ones.
The charge control agent for a toner containing a polynuclear metal complex salt according to claim 1, wherein the salt of the metal salt is one or plural selected from nitrate, sulfate, chloride, formate, acetate, oxalate, and perchlorate. Way.
The method of claim 1, wherein the alkali metal hydroxide is any one or more selected from sodium hydroxide, potassium hydroxide, lithium hydroxide, and the alkaline earth metal hydroxide is any one or more selected from barium hydroxide, magnesium hydroxide, calcium hydroxide. A method for producing a charge control agent for a toner containing a polynuclear metal complex salt.
The method of claim 1, wherein the stirring aging in a heated state is stirred for 1 to 15 hours at a temperature of 70 to 100 ℃ to produce a multinuclear metal complex salt, the aging in a state in which the stirring is stopped again after stirring aging in a warm state 1 A process for producing a charge control agent for a toner containing a multinuclear metal complex salt, characterized in that the mixture is aged for 14 days without stirring to produce a multinuclear metal complex salt.
The aromatic compound according to claim 1, wherein the aromatic compound containing any one or a plurality of functional groups selected from a carboxyl group, a hydroxy group, an amino group, an amido group, and a sulfo group includes an aromatic hydroxy acid and a monoazo compound, and the aromatic hydroxy acid is salicylic acid, 4- Methyl salicylic acid, 3,5-di-tert-butylsalicylic acid, 2-hydroxy-3-naphthoic acid, 3-hydroxy-2-naphthalenecarboxylic acid, 1-hydroxy-2-naphthoic acid, butyl-1- One or more selected from hydroxy-2-naphthoic acid, 1,2,3,4-tetrahydro-2-naphthoic acid, and the monoazo compound consists of a diazo component and a coupling component. The diazo component is 4- Chloro-2-aminophenol, 4-nitro-2-aminophenol, 2-aminophenol-4-sulfonic acid, 3-diethylaminophenol, o-aminophenol, 3-chloro-2-aminophenol, 4-methyl- 2-aminophenol, 4-acetyl-2-aminophenol, 4-nitro-2-aminophenol, 4-methoxy-2- One or more selected from aminophenol, 4-chloro-5-nitro-2-aminophenol, 4-tert-amyl-6-nitro-2-aminophenol, and anthranilic acid, and the coupling component is 1-naphthol, 2 -Naphthol, naphthol AS, 2- (4-chlorophenyl) -5-methyl-3-pyrazolone, 6-tert-butyl-β-naphthol, 1-phenyl-3-methyl-5-pyrazolone, 3-hydrate A method for producing a charge control agent for a toner containing a polynuclear metal complex salt, characterized in that any one or plural selected from oxy-2-naph anide and 3-hydroxy-2-naphth-o-anidide.
The method of claim 1, wherein the sum of the ionic values of the metal ions generated from the metal salt and the ionic values of the aromatic compound ions is 0 to 6, and the weight ratio of the aromatic compound ions to the metal ions formed from the metal salt is 2 to 24. A method for producing a charge control agent for a toner containing a polynuclear metal complex salt.
A charge control agent for a toner containing a multinuclear metal complex salt represented by the following general formula (1).
[Formula 1]

In Formula 1, M is any one selected from magnesium, aluminum, silicon, titanium, chromium, manganese, gold, silver, iron, copper, zinc, zirconium, tin, cerium, nickel, cobalt, barium, calcium, molybdenum, tungsten or A plurality is shown. R ₁ represents -1 valent anion of aromatic hydroxy acid, and R ₂ represents -2 valent anion of monoazo compound. n is an integer of 0 to 3, a, b, c are integers of 0 to 6, and d, e, f are integers of 0 to 3, and a + b + c + d + e + f ≧ 1. g, h, i are integers from 0 to 6, where g + h + i ≧ 1. j is an integer of 0-11.
The method of claim 8, wherein the aromatic hydroxy acid is salicylic acid, 4-methyl salicylic acid, 3,5-di-tert-butyl salicylic acid, 2-hydroxy-3-naphthoic acid, 3-hydroxy-2-naphthalenecarboxylic acid, Any one or a plurality of 1-hydroxy-2-naphthoic acid, butyl-1-hydroxy-2-naphthoic acid, 1,2,3,4-tetrahydro-2-naphthoic acid, and monoazo compounds It consists of a component and a coupling component, and the diazo component is 4-chloro-2-aminophenol, 4-nitro-2-aminophenol, 2-aminophenol-4-sulfonic acid, 3-diethylaminophenol, o-aminophenol , 3-chloro-2-aminophenol, 4-methyl-2-aminophenol, 4-acetyl-2-aminophenol, 4-nitro-2-aminophenol, 4-methoxy-2-aminophenol, 4-chloro -5-nitro-2-aminophenol, 4-tert-amyl-6-nitro-2-aminophenol, any one or more selected from anthranilic acid, the coupling component is 1-naphthol, 2-naphthol, naphthol AS, 2- (4-clock Rophenyl) -5-methyl-3-pyrazolone, 6-tert-butyl-β-naphthol, 1-phenyl-3-methyl-5-pyrazolone, 3-hydroxy-2-naphthanilide, 3- A charge control agent for a toner containing a multinuclear metal complex salt, characterized in that any one or a plurality selected from hydroxy-2-naphth-o-anidide.