JP2002268286A - Method for producing electric charge controlling agent and electrostatic charge image developing toner containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an electric charge controlling agent having high electrostatic charge performance with a small amount of waste liquor by completing a reaction using one solvent other than water from the preparation of starting materials to the formation of the object without causing foaming or increasing viscosity. SOLUTION: In the production of the electric charge controlling agent which is a reaction product of an aromatic hydroxycarboxylic acid and a metal zirconium imparting agent having one or more bond forms selected from coordinate, covalent and ionic bonds, an alcohol is used as a reaction solvent and the total amount of water in the aromatic hydroxycarboxylic acid, the metal zirconium imparting agent and an alkali agent solution as starting materials in a reactive solution is controlled to a certain value or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to an alcohol having 1 to 5 carbon atoms which can be easily recovered for producing a reaction product of an aromatic hydroxycarboxylic acid useful as a charge control agent and a zirconium metal-imparting agent. Is used as a reaction solvent,
By controlling the amount of water in the reaction step to a certain amount or less and proceeding, the reaction can be completed with one kind of solvent (excluding water) from the raw material to the product, and the amount of waste liquid is small.
Also, the present invention relates to a method for producing a charge control agent having a high charge imparting effect.

[0002]

2. Description of the Related Art Conventionally, as a method for producing a charge control agent obtained from an aromatic hydroxycarboxylic acid and a zirconium metal-imparting agent, as described in International Publication No. WO99 / 12941, an aromatic hydroxycarboxylic acid and an oxy It can be obtained by reacting a zirconium metal imparting agent such as zirconium chloride with water or an organic solvent such as toluene, and filtering and washing the product. However,
In the production method using water as the main solvent for the reaction, since the reaction proceeds with the reaction between the alkali aqueous solution of the aromatic hydroxycarboxylic acid and the metal-imparting material such as zirconium oxychloride, the reaction solution becomes near neutral as the reaction proceeds. As a result, an aromatic hydroxycarboxylic acid is precipitated, and it is difficult to obtain a target product. Further, as the reaction proceeded, the reaction solution took a form of foaming, and in the pH range of about 4 to 7, the viscosity was remarkably increased, and the filterability was extremely poor, which hindered the production. It is possible to lower the viscosity by further increasing the pH of the reaction solution (slurry), and to improve the product by coagulating the product by adding one or more organic solvents such as toluene. It is difficult to increase the volume to not less than% by volume, and in the production method using water as a main solvent, the amount of waste liquid is increased and the productivity is low. In addition, since other organic solvents are required, a complicated solvent recovery step is required, and there is a need for environmental and economical improvement.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to prepare a reaction between an aromatic hydroxycarboxylic acid and a zirconium metal-imparting agent by charging an aromatic hydroxycarboxylic acid as a raw material and a zirconium metal-imparting agent such as zirconium oxychloride. It is completed with one kind of solvent (except water) that is easy to recover until the product is obtained. Prevents the deposition of raw materials during the reaction process. Accordingly, it is an object of the present invention to provide a method for producing a charge control agent having a small amount of waste liquid and a high charge imparting effect.

[0004]

SUMMARY OF THE INVENTION The present invention relates to a method for producing a charge control agent which is a reaction product of an aromatic hydroxycarboxylic acid and a zirconium metal imparting agent.
Wherein the weight ratio of the alcohol having 1 to 5 carbon atoms to water in the reaction step is from 80:20 to 100: 0 in the reaction step using an alcohol having the following formula:

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the production method of the present invention, a solution prepared by dissolving at least an aromatic hydroxycarboxylic acid in an alcohol having 1 to 5 carbon atoms necessary to dissolve the aromatic hydroxycarboxylic acid, A zirconium metal-imparting agent in a solution with an alcohol having 1 to 5 is mixed and reacted by controlling the solution temperature. Further, neutralization with an alkali agent and pH adjustment, which are essential requirements for carrying out the present invention, are performed, followed by filtration, washing, and drying to obtain a reaction product of the objective aromatic hydroxycarboxylic acid and the zirconium metal-imparting agent. be able to. By reacting an aromatic hydroxycarboxylic acid with a zirconium metal imparting agent using an alcohol having 1 to 5 carbon atoms as a solvent, and further neutralizing and adjusting the pH with an alkaline agent, from the start to the end of the reaction The reaction can be performed in a solution state or a slurry state including the intermediate. In the present invention, the reaction step refers to the steps from charging raw materials to neutralization with an alkaline agent and pH adjustment.

Aromatic hydroxycarboxylic acids and zirconium
The metal metal imparting agent according to the present invention can be reacted at any ratio.
The desired product can be obtained, but aromatic hydroxycarbo
Metal conversion of zirconium metal-imparting agent per mole of acid
The reaction yields 0.3 to 1.4 moles with
It is preferable in view of the performance of the charge control agent to be obtained.

In the production method of the present invention, the ratio of the alcohol having 1 to 5 carbon atoms to water in the reaction step is such that the weight ratio of the alcohol having 1 to 5 carbon atoms to water is 8%.
0: 20-100: 0, preferably 85:15
100: 0, most preferably 90:10 to 10
0: 0. By controlling the water content to 20 or less, the resulting product becomes a charge control agent having a high charge-providing effect. If the water content is controlled to 10 or less, a charge control agent having a higher charge-providing effect is obtained. In the present invention, the ratio of alcohol having 1 to 5 carbon atoms and water in the reaction step means the total amount of alcohol having 1 to 5 carbon atoms and the total amount of water from the preparation of raw materials to neutralization with an alkali agent and pH adjustment. For example, the total amount of water refers to an amount including water of crystallization in the raw material and water attached to the raw material.

In the production method of the present invention, a solution comprising an aromatic hydroxycarboxylic acid, a zirconium metal imparting agent, an alcohol solvent having 1 to 5 carbon atoms or a mixed solvent of an alcohol having 1 to 5 carbon atoms and water ( In the reaction precursor solution, the reaction between the aromatic hydroxycarboxylic acid and the zirconium metal-imparting agent proceeds under strong acidity, and as a result, a product which is a precursor of the target product is deposited.
There are two types of precipitation, a solid product and an oily or candy-state product. However, in consideration of industrial production, a solid product is preferable, and a precursor of a target product that can take two forms is preferred. The form of the product changes its form depending on the ratio of water and alcohol having 1 to 5 carbon atoms in the reaction precursor solution. 1-5 carbon atoms in the reaction precursor solution
The proportion of alcohol and water having a water content of 9% by weight or less
By controlling to [moisture / (alcohol having 1 to 5 carbon atoms + moisture)], it is possible to obtain a solid product which is a preferred form of the target precursor.

[0009] Generally, 3,5-di-ter
An aromatic hydroxycarboxylic acid such as t-butylsalicylic acid contains 10 to 20% by weight, and a zirconium metal imparting agent such as zirconium oxychloride contains 40 to 50% by weight of water. When dissolved in a solvent, the amount of water in the reaction solution increases, and the reaction product becomes oily or candy-like. As a method for preventing this, it is desirable to reduce the water content by drying an aromatic hydroxycarboxylic acid such as 3,5-di-tert-butylsalicylic acid and a zirconium metal imparting agent such as zirconium oxychloride. As a particularly easy method, it is effective to use an aromatic hydroxycarboxylic acid such as dried 3,5-di-tert-butylsalicylic acid. Commercially available 3,5-di-tert-
Considering the water contained in the aromatic hydroxycarboxylic acid such as butylsalicylic acid and the water contained in the zirconium metal-imparting agent such as zirconium oxychloride, the amount of water in the reaction solution is controlled to 9% by weight or less. To
The charged amount of the alcohol having 1 to 5 carbon atoms is preferably at least 5 times the weight of 1 mole of the aromatic hydroxycarboxylic acid.

From the viewpoint of the charging performance (high charging effect) of the charge control agent obtained as a product, the temperature during the reaction step is 1
The range is preferably 0 to 65 ° C, and more preferably 30 to 65 ° C in consideration of productivity.

The alcohol used in the present invention has 1 to 1 carbon atoms.
This is an alcohol having 5 and having 1 to 5 carbon atoms may be linear or branched. For example, methanol, ethanol, propanol, butanol, pentanol and the like can be mentioned. Most preferred is methanol. When methanol is used for production, the yield of the reaction product is excellent, and when the reaction product is used as a charge control agent, excellent charge characteristics are exhibited. In the neutralization with an alkali agent and the adjustment of pH, the alkali agent to be added is not particularly limited. Examples include sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, and the like. The pH to be adjusted varies depending on the reaction conditions, but is generally adjusted within a range from neutral to weak alkali (pH 7 to 10). Is preferred. In addition, when the reaction product of the obtained aromatic hydroxycarboxylic acid and the zirconium metal-imparting agent is used as a charge control agent, excellent charge characteristics are exhibited. The alkali agent is added alone, dispersed and dissolved in an alcohol having 1 to 5 carbon atoms, or added in an aqueous solution of an alkali agent, or a mixture of an alcohol having 1 to 5 carbon atoms and an aqueous solution of an alkali agent. It may be added.

After neutralization with an alkali agent and pH adjustment, the precipitated reaction product is collected by filtration. Since the filtered reaction product contains a water-soluble inorganic substance such as sodium chloride generated in the reaction step, it is necessary to wash the reaction product with water or hot water. The reaction product obtained by filtration has a gel-like appearance when blended with water, and the completely dried product has a property of exhibiting strong water repellency and being difficult to disperse. As a preferred washing method, efficient dispersion washing can be performed by drying the wet product obtained by filtration until the liquid content becomes 10 to 40% by weight, preferably 20 to 30% by weight. Of water-soluble inorganic substances can be removed. According to the above method, the reaction product of the target aromatic hydroxycarboxylic acid and the zirconium metal-imparting agent can be obtained by dispersing, washing, filtering and drying.

The aromatic hydroxycarboxylic acids usable in the present invention include, for example, salicylic acid, alkyl (1-9 carbon atoms) salicylic acid, 3,5-dialkyl (1 carbon atoms).
~ 9) salicylic acid, 2-hydroxy-3-naphthoic acid,
Alkyl (C1-9) -2-hydroxy-3-naphthoic acid and the like. Further, derivatives of aromatic hydroxycarboxylic acids such as alkyl ethers and alkyl esters thereof are also included. Preferably, salicylic acid derivatives such as salicylic acid, alkyl (C1-9) salicylic acid, and 3,5-dialkyl (C4-9) salicylic acid are preferred, and 3,5-di-tert-butylsalicylic acid is more preferred. .

As an example of the zirconium metal-imparting agent usable in the present invention, in the case of a tetravalent cation, ZrCl4, Zr
Examples include zirconium halide compounds such as F4, ZrBr4, and ZrI4, inorganic zirconium compounds such as Zr (OR) 4 (R represents an alkyl group, an alkenyl group, and the like), and Zr (SO4) 2. In the case of a divalent cation of an oxo compound, ZrOCl2, ZrO (NO3) 2, ZrO (ClO4)
2, H2ZrO (SO4) 2, ZrO (SO4) ・ Na2SO4, ZrO
(HPO4) 2 and other inorganic acid zirconium compounds, ZrO (CO
3), (NH4) 2ZrO (CO3) 2, (NH4) 2ZrO (C
Organic acid zirconium compounds such as 2H3O2) 3 and ZrO (C18H35O2) 2. A preferable zirconium metal imparting agent is ZrOCI2, which is usually supplied in a form in which eight molecules of crystallization water are coordinated.

The reaction product obtained by the above-mentioned production method is an aromatic hydroxycarboxylic acid in which an aromatic hydroxycarboxylic acid and a zirconium atom take one or more bonding modes of a coordination bond, a covalent bond, and an ionic bond. It is a reaction product with a zirconium metal imparting agent, and is represented by the following formulas (1) to (3) as general formulas of typical products. The fact that the aromatic hydroxycarboxylic acid and the zirconium atom take one or more bonding modes of a coordination bond, a covalent bond, and an ionic bond means that the aromatic hydroxycarboxylic acid and the zirconium atom are directly bonded by the above bonding mode. It means that you are.

[0016]

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[0017]

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[0018]

Embedded image In the general formulas (1) to (3), R represents hydrogen, an alkyl group, an aryl group, an arylalkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, or an aryl group. Represents an oxycarbonyl group, an acyl group, a carboxyl group, a halogen, a nitro group, an amino group or a carbamoyl group, and may be connected to each other to form an aliphatic ring, an aromatic ring, or a heterocyclic ring; Substituent R
And may have 1 to 8 substituents R, which may be the same or different.
l represents an integer of 1 to 4, in which case R may be the same or different, m is an integer of 1 to 20, n is 0
Or an integer of 1 to 20, s is 0 or an integer of 1 to 20,
p represents an integer of 1 to 20. The aromatic hydroxycarboxylic acid serving as a ligand in each complex or salt may be the same or different, and p, l, m,
n and s may be a mixture of different compounds. As the substituent R, an alkyl group is preferable, and a 3,5-di-tert-butyl group is particularly preferable. The above general formulas (1) to
In the product represented by (3), it does not necessarily mean that one zirconium atom is bonded to one aromatic hydroxycarboxylic acid, and when exemplified by the above general formula (2), Two zirconium atoms are bonded to one aromatic hydroxycarboxylic acid, and one zirconium atom is coordinated, and the other zirconium is ionic or covalent. Includes the case of binding. In the above general formulas (1) to (3), the whole formula may have a negative charge, and in this case, the counter ion is a hydrogen ion and / or an alkali metal ion. Further, counter ion exchange is performed by a conventionally known method, and the counter ion is an ammonium ion, an ammonium ion having a substituent,
It may be replaced with an alkaline earth metal. Further, a charge controlling agent having a mixture of different counter ions may be contained in the toner of the present invention. Further, the product obtained by the production method of the present invention may have coordination water.

The charge controlling agent of the present invention uses an alcohol having 1 to 5 carbon atoms as a reaction solvent and adjusts the ratio of the alcohol in the solvent in the reaction step to a specific range to provide an aromatic hydroxycarboxylic acid and a zirconium metal. It is a reaction product obtained by reacting with an agent, and may be a mixture of compounds produced by different raw materials and reaction (other than solvent) conditions. The charge control agent of the present invention may contain a raw material of an aromatic hydroxycarboxylic acid such as salicylic acid. The charge control agent of the present invention has a volume average particle size of 0.1.
It is preferable to adjust and use in the range of 1 to 20 μm,
More preferably, it is 1 to 10 μm. When the volume average particle size is larger than 0.1 μm, the charge control agent appearing on the toner surface increases, and a charge imparting effect is easily obtained,
When the thickness is 20 μm or less, the amount of the charge control agent missing from the toner is reduced, and contamination in the apparatus can be prevented. The charge control agent of the present invention is added in an amount of 0.1 to 100 parts by weight of the binder resin.
It is desirable to use 10 parts by weight, preferably 0.2 to 5 parts by weight.

The toner for developing an electrostatic image of the present invention is basically composed of a binder resin, a colorant (pigment, dye) and a charge control agent. (A fluidity improver or a fluidity improver) and a magnetic substance. The charge control agent of the present invention can be used for a one-component toner or a two-component toner. Further, it can be used for a capsule toner and a polymerization toner. Further, it can be used for both magnetic and non-magnetic toners.

The toner for developing an electrostatic image of the present invention can be manufactured by a conventionally known manufacturing method. As an example of the production method, a method in which a mixture of a binder resin, a charge control agent, a colorant, and the like is melted, kneaded, and pulverized by a heating and mixing device, and then classified (pulverization method). And atomized by spraying,
There are a method of drying and classification, a method of a polymerization method in which a colorant and a charge control agent are dispersed in suspended monomer particles, and the like.

The production method by the pulverization method will be described in more detail. First, a binder resin, a colorant, a charge control agent, a wax if necessary, and other necessary additives are uniformly mixed. The mixing can be performed using a known stirrer, for example, a Henschel mixer, a super mixer, a ball mill, or the like. The obtained mixture is hot-melt kneaded using a closed kneader or a single-screw or twin-screw extruder.
After cooling the kneaded material, it is roughly pulverized using a crusher or a hammer mill, and finely pulverized using a pulverizer such as a jet mill or a high-speed rotor rotary mill. Furthermore, an air classifier, for example, an elbow jet of an inertial classification method utilizing the Coanda effect, a microplex of a cyclone (centrifugal) classification method,
Classification is performed to a predetermined particle size using a DS separator or the like. Further, when an external additive or the like is applied to the surface of the toner, the toner and the external additive are stirred and mixed by a high-speed stirrer, such as a Henschel mixer or a super mixer.

The toner of the present invention can also be produced by a suspension polymerization method. In the suspension polymerization method, a monomer composition is prepared by uniformly dissolving or dispersing a polymerizable monomer, a colorant and a polymerization initiator, a charge controlling agent, and, if necessary, a crosslinking agent and other additives. After that, the monomer composition is dispersed in a continuous phase containing a dispersion stabilizer, such as an aqueous phase, with a suitable stirrer and disperser, such as a homomixer, a homogenizer, an atomizer, a microfluidizer, a one-fluid nozzle, a gas-liquid The toner particles are dispersed by using a fluid nozzle, an electric emulsifier, or the like, and simultaneously undergo a polymerization reaction, so that toner particles having a desired particle diameter can be obtained at a stretch. The method described above can be used for the external addition treatment after the preparation of the particles.

The toner of the present invention can also be produced by an emulsion polymerization method. In general, although the uniformity is superior to the particles obtained by the above-mentioned suspension polymerization method, the average particle diameter is extremely small, such as 0.1 to 1.0 μm. It is also possible to employ a method in which a polymerizable monomer is added later to grow particles, so-called seed polymerization, or a method in which emulsified particles are united and fused to an appropriate average particle size. Since production by these polymerization methods does not go through a pulverizing step, it is not necessary to impart brittleness to toner particles, and furthermore, it is possible to use a large amount of a low softening point substance which has been difficult to use in a conventional pulverization method. Because it is possible, the range of material selection can be expanded. The release agent and the colorant, which are hydrophobic materials, are less likely to be exposed on the surface of the toner particles, so that contamination of the toner carrying member, the photoconductor, the transfer roller and the fixing device can be reduced. By producing the toner of the present invention by a polymerization method, image fidelity,
Characteristics such as releasability and color reproducibility can be further improved, and the particle size of the toner is reduced in order to respond to minute dots, and it is relatively easy to obtain a toner with a sharp particle size distribution and a fine particle size. Can be.

Next, specific constituent materials of the electrostatic image developing toner which can be used in the present invention will be described. Any known binder resin can be used. Styrene-based monomers, acrylic-based monomers, polymers having vinyl-based polymer units such as methacrylic monomers, and copolymers of two or more of these monomers, such as polyester-based polymers, Polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin,
Epoxy resins, xylene resins, terpene resins, chromaindene resins, polycarbonate resins, petroleum resins and the like can be used.

The vinyl monomers constituting the vinyl polymer unit include the following. Styrene; o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-acetylstyrene, p-tert-butylstyrene, pn
-Hexylstyrene, pn-octylstyrene, p-
n-nonylstyrene, pn-decylstyrene, pn
Styrenes such as dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof; ethylene, propylene, butylene, isobutylene Unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate, vinyl propionate and vinyl benzoate Vinyl esters such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, Methacrylic Α-methylene aliphatic monocarboxylic esters such as phenyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid Acrylic esters such as n-octyl, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl Vinyl ketones such as methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone; N such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone -Vinyl compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Further, unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid and mesaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride Unsaturated dibasic acid anhydrides, such as: methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, methyl itaconate Half esters of unsaturated dibasic acids such as half ester, methyl alkenyl succinate half ester, methyl half fumarate ester and methyl half ester of mesaconate; unsaturated dibasic acid esters such as dimethyl maleic acid and dimethyl fumaric acid; Le acid, methacrylic acid, crotonic acid,
Α, β-unsaturated acids such as cinnamic acid; crotonic anhydride, α, β-unsaturated acid anhydrides such as cinnamic anhydride, anhydrides of the α, β-unsaturated acids with lower fatty acids, alkenyl Examples thereof include monomers having a carboxyl group such as malonic acid, alkenyl glutaric acid, alkenyl adipic acid, anhydrides thereof, and monoesters thereof. Furthermore, 2-
Acrylic acid or methacrylic acid esters such as hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4
-(1-hydroxy-1-methylbutyl) styrene, 4
And monomers having a hydroxy group such as-(1-hydroxy-1-methylhexyl) styrene.

In the toner for developing an electrostatic image of the present invention,
The vinyl polymer unit of the binder resin may have a cross-linked structure cross-linked with a cross-linking agent having two or more vinyl groups. , Divinylbenzene, divinylnaphthalene; diacrylate compounds linked by an alkyl chain, for example, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-
Pentanediol diacrylate, 1,6 hexanediol diacrylate, neopentyl glycol diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate. As diacrylate compounds linked by an alkyl chain containing an ether bond,
For example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 40
0 acrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing the acrylate of the above compound with methacrylate. As diacrylate compounds linked by a chain containing an aromatic group and an ether bond, for example, polyoxyethylene (2) -2, 2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2 , 2-bis (4-hydroxyphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate. As polyester type diacrylates, for example,
Trade name: MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing the acrylate of the above compound with methacrylate; Triallyl cyanurate and triallyl trimellitate; These crosslinking agents are based on 100 parts by weight of the other monomer components.
0.01 to 10 parts by weight (more preferably 0.03 to 5 parts by weight)
Parts by weight). Among these crosslinkable monomers, those which are preferably used in terms of fixability and offset resistance to a toner resin include an aromatic divinyl compound (particularly divinylbenzene), a chain containing one aromatic group and one ether bond. Tied diacrylate compounds.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2'-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (2,4-dimethylpareronitrile),
2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1,1′-
Azobis (1-cyclohexanecarbonitrile), 2-
(Carpamoylazo) -isobutyronitrile, 2,2 '
-Azobis (2,4,4-trimethylpentane), 2-
Ketone peroxides such as phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide, acetylacetone peroxide and cyclohexanone peroxide; 2,2-bis (t-
Butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide, 1,1,
3,3-tetramethylbutyl hydroperoxide,
Di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α'-bis (t
-Butylperoxyisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide,
3,5,5-trimethylhexanoyl peroxide,
Benzoyl peroxide, m-trioile peroxide, diisopropyl peroxydicarbonate, di-
2-ethylhexyl peroxydicarbonate, di-n
-Propylperoxydicarbonate, di-2-ethoxyethylperoxycarbonate, diethoxyisopropylperoxydicarbonate, di (3-methyl-3-
Methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexarate,
t-butyl peroxy laurate, t-butyl oxybenzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t
-Butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxyazelate and the like.

The vinyl polymer has a glass transition point of 40 to
90 ° C. and a number average molecular weight (Mn) of 1500 to 50
000, weight average molecular weight (Mw) of 10,000 to 500
0000 is good. More preferably, the glass transition point is 45 to 85 ° C, and Mn is 2000 to 2000.
0 and Mw of 15,000 to 3,000,000 are preferred. The OH value of these vinyl polymers is 50 mg KOH / g
The following are preferred, and more preferably the OH value is 3
0 mgKOH / g or less.

The following are examples of the monomer constituting the polyester polymer. Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol,
Triethylene glycol, 1,5-pentanediol,
1,6-hexanediol, neopentyl glycol,
Examples thereof include 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, or an ether compound of bisphenol A and ethylene glycol or propylene glycol.

It is preferable to use a trihydric or higher alcohol in combination to crosslink the polyester resin. Sorbitol, 1,2,2
3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol,
1,2,5-pentatriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxybenzene and the like. .

Examples of the acid component include benzenedicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid, and anhydrides and lower alkyl esters thereof, succinic acid, adipic acid, sebacic acid; alkyldicarboxylic acids such as azelaic acid and the like. Anhydride, maleic acid, citraconic acid,
Unsaturated dibasic acids such as itaconic acid, alkenyl succinic acid, fumaric acid, and mesaconic acid; unsaturated dibasic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride; Is raised. Also, 3
As the polyvalent carboxylic acid component having a valency of 3 or more, trimet acid,
Pyrometic 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, empol trimer acid,
And their anhydrides and lower alkyl esters.

The polyester resin obtained after the polymerization has a glass transition point of 40 to 90 ° C. and a number average molecular weight (M
n) is 1500 to 50,000, weight average molecular weight (Mw)
Is preferably 10,000 to 5,000,000.
More preferably, the glass transition point is 45-85 ° C., and Mn
Is 2000-20,000 and Mw is 15000-3000
000. Further, it is preferable that the OH value of the resin is 50 mgKOH / g or less, preferably, the OH value is 30 mgKOH / g or less.

In the present invention, the vinyl copolymer component and / or
Alternatively, the polyester resin component preferably contains a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those which can react with the vinyl copolymer include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid and itaconic acid, and anhydrides thereof. Examples of the monomer constituting the vinyl copolymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters. Binder resins such as polyester polymers or vinyl polymers have an acid value of 0.1.
A binder resin having an acid value of 0.1 to 45 mgKOH / g is more preferable, and a binder resin having an acid value of 0.1 to 45 mgKOH / g is more preferable. Further, two or more different binder resins may be used, and in that case, a resin having an acid value of 0.1 to 50 mgKOH / g and having 60% by weight or more is preferable.

In the case of a black toner as a coloring agent, black or blue dye or pigment particles for two-component development are generally used.
Various magnetic materials are used for one-component development. Examples of black or blue pigments include carbon black, aniline black, acetylene black, phthalocyanine blue, and indanthrene blue. Examples of the black or blue dye include an azo dye, an anthraquinone dye, a xanthene dye, and a methine dye. In each case, an amount necessary to maintain the optical reflection density of the image after fixing is used, and an addition amount of 0.1 to 20 parts by weight, preferably 2 to 12 parts by weight based on 100 parts by weight of the resin is desirable. .

Materials used as the magnetic substance for coloring purposes include fine powders of metals such as iron, nickel, and cobalt;
Alloys of metals such as lead, magnesium, antimony, beryllium, bismuth, cadmium, zirconium, manganese, selenium, titanium, tungsten, vanadium, cobalt, copper, aluminum, nickel, zinc, and metals such as aluminum oxide, iron oxide, and titanium oxide Oxides, ferrites such as iron, manganese, nickel, cobalt and zinc, nitrides such as vanadium nitride and chromium nitride, carbides such as tungsten carbide and silicon carbide, and mixtures thereof can be used. As the magnetic material, iron oxide such as magnetite, hematite, and ferrite is preferable. These magnetic materials greatly affect the chargeability of the toner, but the charge control agent of the present invention gives good charging performance regardless of the magnetic materials. The toner of the present invention may be used in combination with another type of charge control agent, if necessary, in order to further stabilize its chargeability. It is desirable to use 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight. Examples of the charge control agent in this case include the following. For example, examples of the negatively chargeable charge control agent include organic metal complexes, chelate compounds, and organic metal salts. Specific examples include a metal complex or metal salt of a monoazo metal complex, an aromatic hydroxycarboxylic acid, or an aromatic dicarboxylic acid compound. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their anhydrides, esters thereof, and phenol derivatives of bisphenol. A positive charge control agent may be used in combination for the purpose of improving stability. In this case, a nigrosine dye, an azine dye, a triphenylmethane dye, a quaternary ammonium salt, or a quaternary ammonium salt is added to the side chain. Can be used.

Use of the toner of the present invention as a magnetic toner
In this case, the magnetic material contained in the magnetic toner
Iron oxides such as tight, hematite, ferrite, and others
Oxides containing metal oxides such as Fe, Co, Ni
Metals, or these metals and A1, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
with metals such as d, Ca, Mn, Se, Ti, W, V
Alloys, and mixtures thereof. Specifically
Indicates that as a magnetic material, ferric oxide (Fe_ThreeO_Four), 32
Iron oxide (γ-Fe_TwoO_Three), Zinc iron oxide (ZnFe
_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_FiveO₁₂),iron oxide
Cadmium (CdFe_TwoO_Four), Iron gadolinium oxide (G
d_ThreeFe_FiveO₁₂), Iron oxide copper (CuFe_TwoO_Four), Lead iron oxide
(PbFe₁₂O), nickel iron oxide (NiFe_TwoO_Four),
Neodymium oxide (NdFe_TwoO), barium iron oxide (B
aFe_{1 Two}O₁₉), Magnesium iron oxide (MgFe
_TwoO_Four), Iron manganese oxide (MnFe)_TwoO _Four), Iron oxide orchid
Tan (LaFeO)_Three), Iron powder (Fe), cobalt powder (C
o), nickel powder (Ni) and the like.
The conductive materials are used alone or in combination of two or more. Special
Preferred magnetic materials are triiron tetroxide or γ-iron sesquioxide.
It is a fine powder.

These ferromagnetic materials have an average particle size of 0.1 to 2
μm (more preferably 0.1-0.5 μm) and 10K
The magnetic properties upon application of Oersted are coercive force of 20 to 150 Oersted, saturation magnetization of 50 to 200 emu / g (preferably 50 to 100 emu / g), and residual magnetization of 2 to 20 em.
u / g is preferred. 10 to 200 parts by weight, preferably 20 to 15 parts by weight of the magnetic material, based on 100 parts by weight of the binder resin
It is better to use 0 parts by weight.

In addition to the magnetic material, carbon black, titanium white, and other pigments and / or dyes can be used as the colorant used in the magnetic toner. For example, when the toner of the present invention is used as a magnetic color toner, CI direct red 1, C.I. I. Direct Red 4, C.I. I. Acid Red 1, C.I. I. Basic Red 1, C.I. I. Modant Red 30, C.I. I. Direct Blue 1, C.I.
I. Direct Blue 2, C.I. I. Acid blue 9,
C. I. Acid Blue 15, C.I. I. Basic Blue 3, C.I. I. Basic Blue 5, C.I. I. Modant Blue 7, C.I. I. Direct Green 6, C.I. I.
Basic Green 4, C.I. I. Basic Green 6
Etc. As pigments, mineral fast yellow,
Naple Yellow, Naphthol Yellow S, Hansaero-G, Permanent Yellow-NCG, Tartrazine Lake, Molybdenum Orange, Permanent Oresi GT
R, pyrazolone orange, benzidine orange G, cadmium red, permanent red 4R, watching red zirconium salt, eosin lake, brilliant carmine 3B, manganese purple, fast violet B,
Methyl Violet Lake, Cobalt Blue, Alkaline Blue Lake, Victoria Blue Lake, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue BC, Pigment Green B, Malachite Green Lake, Final Yellow Green G and the like.

When the toner of the present invention is used as a two-component non-magnetic full color toner, the following colorants may be used. As the color pigment for magenta,
C. I. Pigment Red 1, 2, 3, 4, 5, 6,
7, 8, 9, 10, 11, 12, 13, 14, 15, 1
6, 17, 18, 19, 21, 22, 23, 30, 3
1,32,37,38,39,40,41,48,4
9, 50, 51, 52, 53, 54, 55, 57, 5
8,60,63,64,68,81,83,87,8
8, 89, 90, 112, 114, 122, 123, 1
63, 202, 206, 207, 209, C.I. I. Pigment Violet 19, C.I. I. Bat Red 1,
2, 10, 13, 15, 23, 29, 35 and the like. Although the above pigments may be used alone, it is more preferable to improve the sharpness by using them together with the dye and the pigment from the viewpoint of the image quality of a full-color image.

Examples of magenta dyes include C.I. I. Solvent Red 1,3,8,23,24,25,27,3
0, 49, 81, 82, 83, 84, 100, 109,
121, C.I. I, Displacer thread 9, C.I. I. Solvent Violet 8, 13, 14, 21, 27, C.I.
I. Oil-soluble dyes such as Disperse Violet 1;
I. Basic Red 1,2,9,12,13,14,
15, 17, 18, 22, 23, 24, 27, 29, 3
2, 34, 35, 36, 37, 38, 39, 40, C.I.
I. Basic violet 1,3,7,10,14,
And basic dyes such as 15, 21, 25, 26, 27, and 28.

Examples of the coloring pigment for cyan include C.I. I. Pigment Blue 2, 3, 15, 16, 17, C.I. I. Bat Blue 6, C.I. I. Acid Blue 45 or a copper phthalocyanine pigment having a phthalocyanine skeleton substituted with 1 to 5 phthalimidomethyl groups. Coloring pigments for yellow include C.I. I. Pigment Yellow 1, 2, 3, 4,
5, 6, 7, 10, 11, 12, 13, 14, 15, 1
6, 17, 23, 65, 73, 83, C.I. I. Bat Yellow 1, 3, 20 and the like. The amount of the colorant used in the non-magnetic toner is 0.1% based on 100 parts by weight of the binder resin.
To 60 parts by weight, preferably 0.5 to 50 parts by weight.

Examples of the releasing agent used for the purpose of improving fixing include low-molecular-weight polyalkylene, low-molecular-weight polypropylene, low-molecular-weight polyethylene, paraffin wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives,
Polyolefin waxes and derivatives thereof, terpene resins and derivatives thereof, carnauba waxes and derivatives thereof, and the derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Further, a toner containing two or more kinds of waxes can be used in order to exhibit the effect of adding the wax more from the low temperature region to the high temperature region.

In this case, the wax used has two or more endothermic peaks measured by differential thermal analysis (DSC), and the peak having the largest endothermic amount is on the lower temperature side than the next largest peak. Is good. As such a wax, two or more kinds of waxes having different endothermic peaks may be used in combination, or a mixture having two or more DSC peaks may be used as the wax. The wax preferably has two endothermic peaks measured by DSC, and more preferably, the two peaks have a temperature difference of 5 to 15 ° C. If the temperature difference is less than 5 ° C., it is difficult to sufficiently obtain the above-mentioned effects. Because. If the temperature difference between the two endothermic peaks is too large, the dispersibility and liberation of the two components in the toner are different from each other. , Which may have an adverse effect on the charging performance.

In this case, the wax is represented by the following general formula (4)
(Wherein, R represents a hydrocarbon group, Y represents a hydroxyl group, a carboxyl group, an alkyl ether group, an ester group, or a sulfonyl group). ) Is 3000 or less.

[0048]

Embedded image

Specific examples of the compound include: (A) CH ₃ (CH ₂ ) _n CH ₂ OH (n = about 20 to about 30)
0) (B) CH ₃ (CH ₂ ) _n CH ₂ COOH (n = about 20 to about 300) (C) CH ₃ (CH ₂ ) _n CH ₂ OCH ₂ (CH ₂ ) _m CH
₃ (n = about 20 to about 200, m = 0 to about 100) and the like. The compounds (B) and (C) are derivatives of the compound (A), and the main chain is a linear saturated hydrocarbon. As long as it is a compound derived from the compound (A), those other than those shown in the above examples can be used.

Of the above compounds, a wax containing a high molecular alcohol represented by (A) as a main component is particularly preferred because of its high effect. The above wax has good slipperiness, and is particularly excellent in offset resistance. When the particle size of the toner is reduced, it becomes more important to uniformly disperse the wax. However, the wax has an interaction with a binder resin component of the toner, and further has a crystallinity of the wax itself. Is not so high, it can be more uniformly dispersed in the toner. These waxes are used as binder resins 10
It is preferably used in an amount of 0.5 part by weight or more and 20 parts by weight or less based on 0 part by weight.

Further, a fluidity improver may be added to the toner of the present invention. By adding the fluidity improver to the toner surface, the fluidity can be increased before and after the addition. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, wet-process silica, fine-powder silica such as dry-process silica, fine-powder non-oxidized titanium, fine-powder non-alumina, silane coupling agent, There are treated silica, treated titanium oxide, and treated alumina which have been surface-treated with a titanium coupling agent and silicone oil. Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halide compounds, and are so-called dry silica or fumed silica. For example, it utilizes the thermal decomposition oxidation reaction of silicon tetrachloride gas in an oxyhydrogen flame, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl

In this production process, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride or titanium chloride together with the silicon halide. They are also included. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Commercially available silica fine powder produced by vapor phase oxidation of a silicon halide compound includes, for example, those commercially available under the following trade names. AER0SI
L130 (manufactured by Nippon Aerosil Co., Ltd.), AER0SIL
200 (manufactured by Nippon Aerosil Co., Ltd.), AER0SIL 30
0 (manufactured by Nippon Aerosil Co., Ltd.), AER0SIL 380
(Nippon Aerosil Co., Ltd.), AER0SIL TT600
(Nippon Aerosil Co., Ltd.), AER0SIL MOX17
0 (manufactured by Nippon Aerosil Co., Ltd.), AER0SIL MOX8
0 (manufactured by Nippon Aerosil Co., Ltd.), AER0SIL COK8
4 (manufactured by Nippon Aerosil Co., Ltd.), Ca-O-SiL M-5
(Manufactured by CABOT), Ca-O-SiL MS-7 (C
ABOT), Ca-O-SiL MS-75 (CA
BOT), Ca-O-SiL HS-5 (CABO
T), Ca-O-SiLEH-5 (manufactured by CABOT), Wacker HDK N20 V15 (WAC)
KER-CHEMIEGMBH), N20E (WA
CKER-CHEMIEGMBH), T30 (WA
CKER-CHEMIEGMBH), T40 (WA
CKER-CHEMIEGMBH), D-CFin
eSi1ica (Dow Corning), Franco1
(Fransi 1) and the like are commercially available.

Further, a treated silica fine powder obtained by subjecting a silica fine powder produced by vapor-phase oxidation of the silicon halide compound to a hydrophobic treatment is more preferable. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by an alcohol titration test having 1 to 5 carbon atoms has a value in the range of 30 to 80. Hydrophobicity is imparted by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halide is treated with an organosilicon compound.

Examples of the organosilicon compound include hexamethyldisilane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, Bromomethyldimethylchlorosilane,
α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate vinyldimethylacetoxysilane, dimethylethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule.
And dimethylpolysiloxane containing a hydroxyl group bonded to each Si. Further, a silicone oil such as dimethyl silicone oil may be used. These are used alone or as a mixture of two or more.

The fluidity improver has a specific surface area by nitrogen adsorption measured by the BET method of 30 m ² / g or more, preferably 5 m ² / g or more.
Those with 0 m ² / g or more give good results. Toner 1
0.01 to 8 parts by weight of a fluidity improver based on 00 parts by weight,
Preferably, 0.1 to 4 parts by weight is used. In the electrostatic image developing toner of the present invention, as other additives,
Various metal soaps, fluorine-based surfactants, phthalic acid, for the purpose of protecting photoreceptors and carriers, improving cleaning properties, adjusting thermal, electrical, and physical properties, adjusting resistance, adjusting softening point, and improving fixing rate Dioctyl, tin oxide, zinc oxide, carbon black, antimony oxide, and the like, and an inorganic fine powder such as titanium oxide, aluminum oxide, and alumina can be added as necessary. Further, these inorganic fine powders may be made hydrophobic as required. Also, lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride; abrasives such as cesium oxide, silicon carbide, and strontium titanate; anti-caking agents; Can be used in a small amount as a developability improver. These additives include silicone varnish, various modified silicone varnish,
It is also preferable to treat with a silicone oil, various modified silicone oils, a silane coupling agent, a silane coupling agent having a functional group, a treatment agent such as another organosilicon compound, or various treatment agents. The above-mentioned additives are sufficiently mixed and stirred together with the toner by a mixer such as a Henschel mixer or a ball mill, and externally uniformly applied to the surface of the toner particles to obtain a desired toner for developing an electrostatic image. Can be.

The charge control agent of the present invention is thermally stable, does not undergo a thermal change during the electrophotographic process, can maintain stable charging characteristics, and can be used in any manner. Because it has the characteristic that the charge distribution of the fresh toner is very uniform because it is evenly dispersed in the resin,
In the untransferred toner and the recovered toner (waste toner), little change is observed in the saturated triboelectric charge amount and the charge distribution as compared with the fresh toner. When the toner is reused, a polyester resin containing an aliphatic diol is selected as a binder resin, or a metal-crosslinked styrene-acryl copolymer is used as a binder resin, and a large amount of polyolefin is added to this. By manufacturing the toner, the difference between the fresh toner and the waste toner can be further reduced.

When the toner of the present invention is used as a two-component developer, fine glass beads, iron powder,
Binder type carrier of resin particles in which ferrite powder, nickel powder and magnetic particles are dispersed, and resin coated carrier whose surface is coated with polyester resin, fluorine resin, vinyl resin, acrylic resin, silicon resin, etc. are used. Can be The carrier may have a particle size in the range of 4 to 200 μm, preferably 10 to 150 μm, more preferably 20 to 100 μm. In a two-component developer, the toner is preferably used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the carrier, and more preferably in an amount of 2 to 50 parts by weight of the toner based on 100 parts by weight of the carrier. .

The toner of the present invention can be used in a one-component developing method which is one of the image forming methods. The one-component developing method refers to a developing unit in which toner is applied to the surface of a toner carrier called a developing roller and developed with or without contact with the surface of the photoreceptor. At this time, the toner may be magnetic or non-magnetic. The material of the developing roller is controlled in resistance to a medium resistance region to prevent conduction with the surface of the photoreceptor and maintain an electric field, or a method of providing a thin dielectric layer on the surface layer of the conductive roller can be used.
Furthermore, the present invention can also be applied to a developing method in which a conductive resin sleeve in which the side facing the photoconductor surface is coated with an insulating material on a conductive roller, or a conductive layer provided on the side not facing the photoconductor with an insulating sleeve. .

When the toner of the present invention uses the one-component contact developing method, the peripheral speed of the surface of the roller carrying the toner and the peripheral speed of the photosensitive member may be rotated in the same direction or in the opposite direction. Often, the higher the peripheral speed ratio (the peripheral speed of the roller / the peripheral speed of the photoreceptor), the greater the amount of toner supplied to the development site, and the more frequently the toner is attached to and detached from the latent image.
An unnecessary portion is repeatedly scraped off and applied to a necessary portion, so that an image faithful to the latent image can be obtained. Therefore, it is desirable that the peripheral speed ratio is also high in the method applied to the toner of the present invention.

The toner of the present invention can be used when the toner carrier and the electrostatic latent image carrier are not in contact with each other, and whether the toner is magnetic or non-magnetic. Normally, when developing in a non-contact state, since a toner is developed by flying in a space at a fixed interval, it is necessary to generate an electric field between the developer and the latent image holding member. In general, the method can be applied to a method in which alternating current is superimposed in order to develop a sharper image having excellent developability of an edge portion and a solid image.

In the developing method which can be used for the toner of the present invention, in the one-component developing method, when a rigid roller is used as the toner carrier, a photosensitive member having a flexible structure such as a belt can be used. The use of rollers is also possible. When a conductive material is used as the toner carrier as the developing roller, the resistivity of the developing roller is preferably in a range of 10 ¹ to 10 ¹² Ω · cm, more preferably in a range of 10 ² to 10 ⁹ Ω · cm. is there. Further, in developing the toner in the present invention, it is preferable to coat the surface of the toner carrier with a resin layer in which conductive fine particles and / or a lubricant are dispersed from the viewpoint of controlling the total charge amount of the toner.

The case where the toner of the present invention is applied to a two-component developing method will be specifically described. The two-component developing method is a method using a toner and a carrier (having a role as a charge-imparting material and a toner conveying material), and a magnetic material is generally used for the carrier. The developer (toner and carrier) is agitated by a developer agitating member to generate a predetermined amount of electric charge, and is conveyed to a development site by a magnet roller. The developer is held on the roller surface by the magnetic force on the magnet roller,
A magnetic brush whose layer is regulated to an appropriate height by a developer regulating plate or the like is formed. The developer moves on the roller with the rotation of the developing roller, contacts the electrostatic latent image holding member or opposes it at a predetermined interval in a non-contact state, and develops and visualizes the latent image. In the case of development in a non-contact state, a driving force for causing the toner to fly in a space at a fixed interval can be obtained by generating a DC electric field between the developer and the latent image holding member. In order to develop an image, the present invention can be applied to a method of superimposing an alternating current.

One preferred embodiment of the photosensitive member used in the image forming apparatus applied to the toner for developing an electrostatic image of the present invention is described below. Examples of the conductive substrate include metals such as aluminum and stainless steel, plastics having a coating layer of an aluminum alloy, indium oxide-tin oxide alloy, etc., paper and plastic impregnated with conductive particles, and plastics having a conductive polymer. Cylindrical cylinders and films are used.

On these conductive substrates, the adhesion of the photosensitive layer is improved, the coating property is improved, the substrate is protected, the defects existing on the substrate are covered, the charge injection property from the black body is improved, and the electrical conductivity of the photosensitive layer is improved. An undercoat layer may be provided for the purpose of protection against breakage and the like. The undercoat layer is polyvinyl alcohol, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenolic resin, casein, polyamide, copolymerized nylon, glue, gelatin, It is formed of a material such as polyurethane or aluminum oxide. The film thickness is usually 0.1
10 to 10 μm, preferably about 0.1 to 3 μm.

The charge generation layer is made of an azo pigment, a phthalocyanine pigment, an indigo pigment, a perylene pigment, a polycyclic quinone pigment, a squarylium dye, a pyrylium salt, a thiapyrylium salt, a triphenylmethane dye, selenium, or an amorphous pigment. It is formed by dispersing a charge-generating substance such as an inorganic substance such as porous silicon in a suitable binder, applying the dispersion, or by vapor deposition. Of these, phthalocyanine pigments are preferred. The amount of the binder is desirably 80% by weight or less, preferably 0 to 40% by weight in the charge generation layer. Further, the thickness of the charge generation layer is preferably 5 μm or less, particularly preferably 0.05 to 2 μm. The charge transport layer has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting them. The charge transporting layer is formed by dissolving a charge transporting substance in a solvent together with a binder resin if necessary, and applying the solution. The film thickness is generally 5 to 40 μm. As the charge transport substance, biphenylene, anthracene, pyrene, a polycyclic aromatic compound having a structure such as phenanthrene, a nitrogen-containing cyclic compound such as indole, carbazole, oxadiazole, or pyrazoline, a hydrazone compound, Examples include styryl compounds, selenium, selenium-tellurium, amorphous silicon, cadmium sulfide, and the like.

Examples of the binder resin for dispersing these charge transporting substances and the like include resins such as polycarbonate resin, polyester resin, polymethacrylate, polystyrene resin, acrylic resin and polyamide resin, poly-N-vinylcarbazole, polyvinylanthracene and the like. Organic photoconductive polymer and the like.

Further, a protective layer may be provided as a surface layer. As the resin of the protective layer, polyester, polycarbonate, acrylic resin, epoxy resin, phenol resin, or a curing agent of these resins alone or
It is used in combination of more than one species. Further, conductive fine particles may be dispersed in the resin of the protective layer. Examples of the conductive fine particles include metals, metal oxides and the like, preferably, zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, There are ultrafine particles such as antimony-coated tin oxide and zirconium oxide. These may be used alone or as a mixture of two or more. Generally, when particles are dispersed in the protective layer, it is necessary that the particle size of the particles is smaller than the wavelength of the incident light in order to prevent scattering of the incident light due to the dispersed particles. The particle size of the insulating particles is preferably 0.5 μm or less. The content in the protective layer is preferably from 2 to 90% by weight, more preferably from 5 to 80% by weight, based on the total weight of the protective layer. The thickness of the protective layer is 0.1 to 10 μm
m is preferable, and 1 to 7 μm is more preferable. The coating of the surface layer can be performed by spray coating, beam coating or permeation (dipping) coating of the resin dispersion. As a method for charging these photoreceptors, a known corona charging method called corotron or scorotron is used, and a method using a pin electrode or the like can also be used. Further, the following direct charging method can be similarly used. As direct charging means,
There are a method using a charging blade and a method using a conductive brush. These contact charging means have the effects of eliminating the need for high voltage and reducing the generation of ozone.

In the case of a roller or a blade as the photosensitive member direct charging member, a metal such as iron, copper, stainless steel, a carbon dispersed resin, a metal or a metal oxide dispersed resin is used as a conductive substrate. Rod-shaped, plate-shaped or the like can be used. For example, as the configuration of the elastic roller, a structure in which an elastic layer, a conductive layer, and a resistance layer are provided on a conductive substrate is used. As the roller elastic layer, chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber And a rubber or sponge such as butyl rubber, or a thermoplastic plastic elastomer such as a styrene-butadiene thermoplastic elastomer, a polyurethane thermoplastic elastomer, a polyester thermoplastic elastomer, or an ethylene-vinyl acetate thermoplastic elastomer. the, the volume resistivity of 10 ⁷ Omega
Cm or less, preferably 10 ⁶ Ω · cm or less. For example, a metal vapor-deposited film, a conductive particle-dispersed resin, a conductive resin, and the like are used.Specific examples include a vapor-deposited film of aluminum, indium, nickel, copper, iron, and the like.Examples of the conductive particle-dispersed resin include carbon. , Conductive particles such as aluminum, nickel, titanium oxide, urethane, polyester,
Examples thereof include those dispersed in a resin such as a vinyl acetate-vinyl chloride copolymer and polymethyl methacrylate. Examples of the conductive resin include quaternary ammonium salt-containing polymethyl methacrylate, polyvinylaniline, polyvinylpyrrole, polyacetylene, and polyethyleneimine. The resistance layer has, for example, a volume resistivity of 10 ⁶ to 10 ^12.
It is a layer of Ω · cm, and semiconductive resin, conductive particle dispersed insulating resin, or the like can be used. As the semiconductive resin, resins such as ethyl cellulose, nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin, and casein are used. Examples of the conductive particle dispersion resin include a small amount of conductive particles such as carbon, aluminum, indium oxide, and titanium oxide in an insulating resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer, and polymethyl methacrylate. Dispersed materials are exemplified.

As the brush as the charging member, a brush whose resistance is adjusted by dispersing a conductive material in a generally used fabric is used. As the fiber, generally known fibers can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, and polyester.
Further, as the conductive material, a generally known conductive material can also be used, such as copper, nickel, iron, aluminum,
Metals such as gold and silver or iron oxide, zinc oxide, tin oxide,
Examples include metal oxides such as antimony oxide and titanium oxide, and conductive powders such as carbon black. In addition, these conductive powders may be subjected to a surface treatment for the purpose of hydrophobization and resistance adjustment as required. At the time of use, it is selected and used in consideration of dispersibility with fibers and productivity. As for the shape of the brush, the fiber thickness is 1 to 20 denier (weave diameter 10 to 10)
The length of the weave of the brush is 1-15m
m, brush density is 10,000 to 300,000 brushes per square inch (1.5 × 100 to 4.5 × 100 per square meter)
) Are preferably used.

The transfer step applicable in the image forming method applicable to the electrostatic image developing toner of the present invention will be specifically described. The transfer is to electrostatically transfer a developed image to a transfer material via a photoreceptor and a transfer material, and is performed in a contact or non-contact manner. As a non-contact transfer method, transfer by a known corona charging method called corotron or scorotron is used. As a transfer unit in the contact transfer, an apparatus having a transfer roller or a transfer belt is used. The transfer roller is composed of at least a core metal and a conductive elastic layer. The conductive elastic layer is an elastic material having a volume resistivity of 10 ¹ to ^{10 10} Ω · cm, such as urethane or EPDM in which a conductive material such as carbon is dispersed. The body is used.

The toner for developing an electrostatic image of the present invention is particularly effective in an image forming apparatus using an organic compound on the surface of a photoreceptor. In general, when an organic compound forms a surface layer of a photoreceptor, since the adhesiveness to toner particles is better than other photoreceptors using an inorganic material, the transferability tends to decrease. With the toner (1), transfer residue of the toner is extremely small due to the excellent charge control effect, and the transfer efficiency is excellent.

Examples of the surface material of the photoconductor used in the image forming apparatus applicable to the toner for developing an electrostatic image of the present invention include silicone resin, vinylidene chloride, ethylene-vinyl chloride, styrene-acrylonitrile, styrene- Examples include, but are not limited to, methyl methacrylate, styrene, polyethylene terephthalate, polycarbonate, and the like, and other monomers or copolymers and blends between the aforementioned binder resins can also be used. . Further, the toner of the present invention can be effectively used for an image forming apparatus having a photoconductor having a small diameter of 50 mm or less. A known intermediate transfer belt can be used as a means for achieving color superposition when forming a color image.

As a cleaning member used in an image forming apparatus applicable to the toner for developing an electrostatic image of the present invention, a blade, a roller, a fur brush, a magnetic brush or the like can be used. Further, two or more of these cleaning members may be used in combination.

In the image forming apparatus applicable to the toner for developing an electrostatic image of the present invention, various methods can be employed for cleaning the electrostatic image holder. Although it can be applied to efficient blade cleaning, as a means to easily improve these cleaning defects by toner, appropriate control without excessively increasing the charge of the toner remaining on the photoreceptor without transfer is provided. Is mentioned.

It is also preferred that the surface of the photoreceptor used in the image forming apparatus applicable to the toner for developing an electrostatic image of the present invention has a releasability, and the contact angle of the surface of the photoreceptor with water is 85 ° or more. Is preferred. More preferably, the contact angle of water on the surface of the photoreceptor is 90 degrees or more. Having a high contact angle on the photoreceptor surface means that the photoreceptor surface has high releasability, and this effect can significantly reduce the amount of toner remaining on the transfer, greatly reducing the load on cleaning. By using the toner of the present invention, it is possible to more reliably prevent the occurrence of cleaning failure.

The image forming apparatus applicable to the electrostatic image developing toner of the present invention is also effective when the surface of the photoreceptor is mainly composed of a polymer binder resin. For example, when a protective film mainly composed of resin is provided on an inorganic photoreceptor such as selenium or amorphous silicon, or when a charge transport layer of a function-separated organic photoreceptor has a surface layer made of a charge transport material and a resin, Further, there is a case where the above-mentioned protective layer is provided thereon. As a means for imparting release properties to such a surface layer, a resin having a low surface energy is used for the resin itself constituting the film, or water repellency, an additive that imparts lipophilicity is added, And dispersing a material having releasability. Specifically, a fluorine-containing compound, such as introducing a fluorine-containing group, a silicone-containing group, or the like into a resin structure, adding a surfactant, or the like, that is, a compound containing a fluorine atom, that is, polyfluoroethylene, polyvinylidene fluoride, or carbon fluoride. Constituting a surface layer. By these means, the contact angle of the photoreceptor surface with water is 85
Degrees or more. If it is less than 85 degrees, the toner and the toner carrier are likely to deteriorate due to durability. Among them, polyfluoroethylene is particularly preferred, and dispersion of a releasable powder such as a fluororesin in the outermost surface layer is particularly preferred. In order to include these powders on the surface, a layer in which the powders are dispersed in a binder resin is provided on the outermost surface of the photoreceptor, or an organic photoreceptor originally composed mainly of resin is used. If so, the powder may be dispersed in the uppermost layer without providing a new surface layer. The amount of the powder to be added to the surface layer is preferable for adjusting the sensitivity so as to conform to the invention.

Examples of the binder resin include polycarbonate resin, polyester resin, polyvinyl butyral resin, polystyrene resin, acrylic resin, methacrylic resin, phenol resin, silicone resin, epoxy resin,
And vinyl acetate resin. It is preferably 1 to 60% by weight, more preferably 2 to 50% by weight, based on the total weight of the charge generation layer and the surface layer. When the amount is less than 1% by weight, the residual toner of the transfer is not sufficiently reduced, the cleaning efficiency of the residual toner is not sufficient, and the ghost prevention effect is insufficient. This is not preferable because the amount of light incident on the photosensitive member is significantly reduced. The particle size of the powder is 1 μm or less from the viewpoint of image quality.
Preferably, it is 0.5 μm or less. If it is larger than 1 μm, the line is poorly cut due to scattering of incident light, which is not practical. On the other hand, a technique called cleaning at the same time as development or cleanerless is disclosed in JP-A-5-2287, but the toner of the present invention can also be used in such a method.

As the image forming apparatus applicable to the toner for developing an electrostatic image of the present invention, a conventionally known method can be adopted. For example, a compression heating method using a heat roller or a method for high-speed fixing is used. Fixing by flash can be mentioned. In the pressure heating method using a heating roller, the fixing is performed by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heat roller, which is formed of a material having releasability from the toner, while contacting the toner image surface under pressure. It is. In this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. And is very effective in high speed electrophotographic copiers. Instead of the pressure heating method using a heat roller, a fixing method comprising a pressing member which is brought into pressure contact with a heating body and which makes a recording material adhere to the heating body via a film can be used. For the purpose of improving the offset, for example, in order to prevent the toner from adhering to the surface of the fixing roller, the roller surface is formed of a material having excellent releasability with respect to the toner such as a fluororesin, and the surface of the roller is further formed of silicone oil or the like. It is extremely effective to supply the offset preventing liquid and cover the roller surface with a liquid thin film. When a toner that is soft against heat is used to improve the fixing performance, the toner tends to adhere to the developing roller electrostatic image holding member, the contact charging member, and the like. A molecular weight component may be contained.

In the case of the toner for developing an electrostatic charge image of the present invention, in terms of image quality and productivity of the toner, for example, in the measurement using a laser type particle size distribution analyzer such as a micron sizer (manufactured by Seishin Enterprise Co., Ltd.), Is preferably in the range of 2 to 15 μm in terms of volume-based average particle size. More preferably, it is in the range of 3 to 12 μm. If the average particle size exceeds 15 μm, problems occur in resolution and sharpness.
When the average particle size is less than μm, the resolution is good, but there is a tendency for problems such as high cost due to a decrease in the yield at the time of toner production, toner scattering inside the machine, and skin penetration such as skin penetration.

With respect to the particle size distribution of the toner, in the case of the toner for developing an electrostatic image of the present invention, for example, by measuring the particle size with a Coulter counter (TA-II manufactured by Coulter Co., Ltd.), 2
It is desirable that the particles having a particle size of 1 μm or less are in the range of 10 to 90% based on the number, and the content of 12.7 μm or more is 0% by weight.
It is desirable that the ratio is up to 30%.

In the case of the toner for developing an electrostatic image of the present invention, the specific surface area of the toner is preferably in the range of 1.2 to 5.0 m ² / g in BET specific surface area measurement using nitrogen as the desorbed gas. More preferably, it is 1.5 to 3.0 m ² / g. For the measurement, for example, using a BET specific surface area measuring device (FlowSorb II 2300, manufactured by Shimadzu Corporation), the adsorption gas on the toner surface is desorbed at 50 ° C. for 30 minutes, quenched by liquid nitrogen to re-adsorb the nitrogen gas, and then re-adsorbed. The temperature was raised to ° C. and defined as the value obtained from the degassing amount at this time.

In the case of the toner for developing an electrostatic charge image of the present invention, the apparent specific gravity (bulk density) is measured by using a container attached to the measuring device by using, for example, a powder tester (manufactured by Hosokawa Micron Corporation). The measurement was performed according to the instruction manual.
0.2 to 0.6 g / cc for non-magnetic toner, and 0.2 to 0.6 g / cc for magnetic toner, depending on the type and content of magnetic powder.
Those having a range of 2.0 g / cc are desirable.

In the case of the toner for developing an electrostatic image of the present invention, the true specific gravity of the non-magnetic toner is 0.9 to 1.2 g / cc.
In the case of a magnetic toner, it preferably ranges from 0.9 to 4.0 g / cc, depending on the type and content of the magnetic powder. The true specific gravity of the toner was determined by precisely weighing 1.000 g of toner,
200mmf / c under vacuum in a 0mmφ tablet press
compression molding while applying a pressure of m ^2. The height of the columnar molded product is measured with a micrometer, and the true specific gravity is calculated from this.

The fluidity of the toner is defined, for example, by a flowing angle of repose and a stationary angle of repose by a Tsutsui-type repose angle measuring device (manufactured by Tsutsui Rika Co., Ltd.). The flow angle of repose is desirably 5 to 45 degrees in the case of the toner for developing an electrostatic image using the charge control agent of the present invention. The rest angle of repose is preferably in the range of 10 to 50 degrees.

The toner for developing an electrostatic image of the present invention has a shape factor (SF-1) of 120 to 400 in the case of a pulverized toner.
Is preferable, and the shape factor 2 (SF-2) is 110 to 110
A range of 350 is preferred. In the present invention, SF-1 and SF-2, which indicate the shape factor of the toner, refer to a group of zirconium compound particles that have been magnified 1000 times using, for example, an optical microscope (BH-2 manufactured by Olympus Corporation) equipped with a CCD camera. Sampling was performed so that the number of images was about 30 in the field of view, and the obtained image was analyzed by an image analysis device (Luzex F.
S), and the same work was performed for about 3000 compounds.
The process was repeated until the number of pieces was reached, and the shape factor was calculated. The shape factor (SF-1) and the shape factor 2 (SF-2) are calculated by the following equations. SF-1 = ((ML ² × π) / 4A) × 100 (where ML represents the maximum length of a particle, and A represents the projected cross-sectional area of one particle.) SF-2 = PM ² / 4Aπ × 100 ( In the formula, PM indicates the perimeter of the particle, and A indicates the projected cross-sectional area of one particle.)

SF-1 represents the strain of a particle. The closer the particle is to a sphere, the closer to 100, and the longer the particle is, the larger the numerical value becomes. SF-2 represents the irregularities of the particles. The closer the particle is to a sphere, the closer to 100, and the more complicated the shape of the particle, the larger the numerical value.

The toner for developing an electrostatic image of the present invention has a volume resistivity of 1 × 10 ¹² to 1 in the case of a non-magnetic toner.
A range of × 10 ¹⁶ Ω · cm is desirable. In the case of a magnetic toner, although it depends on the type and content of the magnetic powder, 1 × 10 ⁸ to
It is desirable that the thickness be in the range of 1 × 10 ¹⁶ Ω · cm. In this case, the toner volume resistivity is determined by compressing the toner particles to obtain a toner having a diameter of 5 mm.
A disk-shaped test piece having a thickness of 0 mm and a thickness of 2 mm was prepared, and set on a solid electrode (for example, SE-70 manufactured by Ando Electric Co., Ltd.).
39A), it is defined as a value after one hour has passed when a DC voltage of 100 V is continuously applied.

The toner for developing electrostatic images of the present invention has a dielectric loss tangent of 1.0 × 10 ^-3 to 1 when the toner has a non-magnetic tangent.
The range is preferably 5.0 × 10 ⁻³ , and in the case of a magnetic toner, it depends on the type and content of the magnetic powder, but 2 × 10 ^−3.
It is preferably in the range of ３０30 × 10 ⁻³ . In this case, the toner volume resistivity is determined by compressing and molding the toner particles to a diameter of 50 m.
A disc-shaped test piece having a thickness of 2 m and a thickness of 2 mm was prepared, and set on a solid electrode.
z is defined as a dielectric loss tangent value (Tan δ) obtained when measured at a peak-to-peak voltage of 0.1 KV.

The electrostatic image developing toner of the present invention preferably has an Izod impact value of the toner in the range of 0.1 to 30 kg · cm / cm. The Izod impact value of the toner in this case is measured by melting a toner particle to prepare a plate-shaped test piece, and measuring the plate in accordance with JIS K-7110 (hard plastic impact test method).

The toner for developing an electrostatic image of the present invention has a melt index (MI value) of 10 to 150 g / 1.
A range of 0 min is desirable. The melt index (MI value) of the toner in this case is based on JIS K-7210.
It is measured according to (Method A). In this case, the measurement temperature is 125 ° C., and the load is 10 kg.

The toner for developing an electrostatic image of the present invention preferably has a melting start temperature of 80 to 180 ° C.
It is desirable that the mm drop temperature is in the range of 90 to 220 ° C. In this case, the toner melting start temperature is determined by compression molding of toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, which is then transferred to a heat melting property measuring apparatus, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). It is defined as the value at which melting starts when the load is measured at a load of 20 kgf / cm ² and the piston starts to descend. In a similar measurement,
The temperature at which the piston has dropped 4 mm is defined as the 4 mm drop temperature.

The toner for developing an electrostatic image of the present invention preferably has a glass transition point (Tg) of 45 to 80 ° C., more preferably 55 to 75 ° C. The glass transition point of the toner in this case is determined by a differential thermal analyzer (DS
C) is measured, the temperature is raised at a constant temperature, then quenched, and the temperature is defined as the value obtained from the peak value of the phase change that appears when the temperature is raised again. When the Tg of the toner is lower than 45 ° C., the offset resistance and the storage stability are deteriorated. When the Tg is higher than 80 ° C., the fixing strength of the image is lowered.

The toner for developing an electrostatic image of the present invention preferably has a molecular weight of 50,000 to 3,000,000 in terms of weight average molecular weight (Mw). At this time, Mw /
It is preferable that the range of Mn is 3 to 500. At this time, the molecular weight distribution may have a single peak or two or more peaks. To measure the molecular weight of the toner, first, a certain amount of toner particles is dissolved in an organic solvent such as THF, and at this time, insolubles are filtered with a filter.
Only the dissolved substance is defined as an analysis value when measured using GPC (gel permeation chromatography).

The toner for developing an electrostatic image of the present invention comprises tetrahydrofuran (TH) among the resin components constituting the toner.
The molecular weight of the gel component insoluble in F) is preferably in the range of 500,000 to 6,000,000 in weight average molecular weight (Mw). At this time, the range of Mw / Mn showing the molecular weight distribution is 3 to 500.
What is good. At this time, the molecular weight distribution may have a single peak or two or more peaks. In addition, this gel-like component is used for the resin constituting the toner.
Preferably, it is 30% by weight.

The toner for developing an electrostatic image of the present invention preferably has a melt viscosity of 1,000 to 50,000 poise, more preferably 1500 to 38,000 poise. In this case, the melt viscosity of the toner is determined by compression molding toner particles to prepare a cylindrical test piece having a diameter of 10 mm and a thickness of 2 cm, and setting the test piece in a heat melting property measuring apparatus, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). And defined as a value measured at a load of 20 kgf / cm ² .

The toner for developing an electrostatic image of the present invention preferably contains at least 3 mg of the present zirconium compound, which is a charge controlling agent, present on the toner surface per 1 g of the toner. The amount of the zirconium compound on the toner surface is determined by using an organic solvent in which the resin, colorant, and wax of the toner are insoluble and only the zirconium compound is dissolved,
For example, the zirconium compound on the toner surface is sufficiently washed with methyl alcohol, and the concentration of the washing solution is quantified by a colorimetric method using a fluorescence spectrophotometer or the like.

In the toner for developing an electrostatic image of the present invention, the zirconium compound present on the toner surface preferably has a volume-based average particle diameter of 0.05 μm to 3 μm.

The particle size of the zirconium compound present on the toner surface was measured by thinning a fixed amount of the toner by thermal melting and using a polarizing microscope (Olympus BH-2) equipped with a CCD camera, for example, at a magnification of about 500 times. Then, only the zirconium compound particles in the toner can be identified. The obtained image is transferred to an image analyzer (Luzex FS) manufactured by Nireco, and the particle size distribution of the zirconium compound particles is calculated by image analysis. Further, a toner obtained by extracting only the zirconium compound from the surface of the toner was formed into a thin film by heat melting in the same manner, and the particle size distribution at this time was also measured. From the difference between the particle size distribution of the zirconium compound present in the entire toner thus obtained and the distribution of the zirconium compound present only inside the toner, the particle size distribution of the zirconium compound present on the toner surface was estimated. Was defined as the average particle size of the zirconium compound present on the toner surface.

The solvent-dissolved residue of the toner of the present invention is 0 to 30% by weight as a tetrahydrofuran (THF) insoluble content,
It is preferable that the content is in the range of 0 to 40% by weight as the ethyl acetate insoluble content and 0 to 30% by weight as the chloroform insoluble content. The solvent-dissolved residue is obtained by uniformly dissolving / dispersing 1 g of the toner in 100 ml of each solvent of tetrahydrofuran (THF), ethyl acetate and chloroform, filtering the solution / dispersion under pressure, and drying the filtrate. Quantify,
From this value, the ratio of the insoluble matter in the organic solvent in the toner is calculated.

Further, the charge control agent of the present invention is also suitable as a charge enhancer in a paint for electrostatic powder coating. That is, the paint for electrostatic powder coating using this charge enhancer has excellent environmental resistance, storage stability, particularly excellent thermal stability and durability, has a coating efficiency of 100%, and has no coating film defects. A thick film can be formed.

[0103]

The present invention will be described in more detail with reference to the following examples.
(The following parts are by weight.) (Production Example 1) In a 500 ml kolben equipped with a stirrer, 30.0 g (0.1198 mol) of dried 3,5-di-tert-butylsalicylic acid was added. Next, 240 g of methanol was added and dissolved. To this solution, 23.0 g of zirconium oxychloride (octahydrate, 0.0685 mol, 4% by weight of water) was added as powder, and the temperature was raised to 50 ° C. The mixture was stirred and reacted at 50 ° C. for 2.5 hours (water: methanol = 4.1: 95.9). 27.68 g (0.1938 mol) of a 28.0% by weight aqueous sodium hydroxide solution and 35.9 g of methanol were mixed, and the mixture was added dropwise at 50 ° C. over 30 minutes. After stirring for 1 hour, The mixture was cooled to room temperature and collected by filtration (water: methanol = 10.0: 90.
0). The product obtained by filtration was dried until the liquid content became 25% by weight, and this product was dispersed and washed with 140 g of water, filtered, and dried to obtain 27.5 g of a white product.
The slurry concentration in this production example was about 6.5% by weight / volume. However, the slurry concentration indicates the slurry concentration after neutralizing the reaction solution and adjusting the pH (the same applies to the slurry concentration hereinafter). During the course of the reaction, no foaming of the reaction solution and no remarkable increase in viscosity were observed.

The product obtained in Production Example 1 was subjected to IR measurement. The chart is shown in FIG. 3,5-di-te
rt- butyl absorption peak of the carbonyl stretching vibration of the carboxyl group of the salicylic acid disappeared in but this product is about 1650 cm ^-1, a new absorption peak at about 1610 cm ^-1 is a short number (long wavelength) band instead confirmed. This was determined to be the result of a shift in the absorption peak due to the binding of the carboxyl group of 3,5-di-tert-butylsalicylic acid to the zirconium atom. An X-ray diffraction measurement was performed on the product obtained in Production Example 1. The chart is shown in FIG. The diffraction peak of the zirconium product of 3,5-di-tert-butylsalicylic acid did not show a sharp peak, and was a halo type indicating that it was an amorphous body. Measurement conditions X-ray Cu / 50kV / 200mA Goniometer RINT2000 Vertical type kiniometer Divergence slit 1 ° Divergence vertical restriction slit 10mm Scattering slit 1.16mm Light receiving slit 0.15mm Scan mode FT Count time 0.5sec Step width 0.050 ° Scan axis 2θ / Θ Scanning range 3.000-80.000 ° θ offset 0.000 ° The product of Production Example 1 was measured for molecular weight by the ESI-MS method, and the mass spectrum diagram shown in FIG. 4 was obtained.
(The horizontal axis indicates M / Z [mass / charge], and the vertical axis indicates tiveabundance [existence ratio]). The obtained mass spectrum confirmed that the compound was the compound of the present invention containing the zirconium element from the pattern. Measurement conditions The sample was dissolved in ethyl acetate, further diluted with acetonitrile to adjust the concentration to 50 ppm, and 40 μl was introduced for measurement. Apparatus: MS700 manufactured by JEOL Acceleration voltage: 4 KV Mobile phase: acetonitrile Flow rate: 100 μl / min For the product of Production Example 1, Zr and 3,5-di-ter
The molar ratio of t-butylsalicylic acid was determined by the following method. Quantification of 3,5-di-tert-butylsalicylic acid is performed using HPLC. This compound 30 was precisely weighed in 45 ml of acetonitrile to which 4 to 5 drops of 6 mol / l hydrochloric acid was added.
Add mg and sonicate to completely dissolve. This solution is made up to 50 ml with acetonitrile, 10 ml of this solution is measured and taken up to 25 ml with acetonitrile to obtain a measurement solution. This was measured under the following LC conditions. (HPLC conditions) Column: Inertosyl ODS-2 4.6φ × 150 [mm × mm] Carrier: (CH ₃ CN) / (0.1 vol% H ₃ PO)
₄ aqueous solution) = 75/25 [V / V] RATE: 1.0 [ml / min] Temperature: 40 [° C.] 1 g of this compound from a calibration curve previously prepared with 3,5-di-tert-butylsalicylic acid 3,5-
The amount of di-tert-butylsalicylic acid is calculated. next,
A method for quantifying Zr using plasma emission spectrometry (ICP) will be described. First, the compound is completely decomposed by a strong acid, and the solution is diluted to a specified concentration. The content of Zr contained in 1 g of the present compound is measured using ICP. From the aforementioned quantitative value of 3,5-di-tert-butylsalicylic acid and the quantitative value of Zr, Zr and 3,5-di-tert were determined.
When the molar ratio of -butylsalicylic acid was determined, 1.0 mol of 3,5-di-tert-butylsalicylic acid was contained per 1 mol of zirconium atom.

(Production Example 2) 500 m equipped with a stirrer
30.0 g (0.1198 mol) of dried 3,5-di-tert-butylsalicylic acid was added to 1 kolben, and 240 g of methanol was added and dissolved. 23.0 g of zirconium oxychloride (0.06
(85 mol) was added as a powder, and the temperature was raised to 50 ° C. 50 ℃
The mixture was reacted under stirring for 2.5 hours (water: methanol =
4.1: 95.9). At 50 ° C., 16.3 g (0.1956 mol) of a 48.0% by weight aqueous sodium hydroxide solution was added dropwise over 30 minutes, stirred for 1 hour, and cooled to room temperature (water: methanol = 7.4: 92.6). The product obtained by filtration was dried to a liquid content of 25% by weight. This product was dispersed and washed with 140 g of water, collected by filtration and dried to obtain 27.5 g of a white product. This product was subjected to IR measurement, X-ray diffraction measurement, and ESI-MS in the same manner as in Production Example 1.
The measurement was performed to confirm that the product was a zirconium product of 3,5-di-tert-butylsalicylic acid. Also book
The slurry concentration of the production example was about 7.5% w / v,
During the course of the reaction, no foaming of the reaction solution and no remarkable increase in viscosity were observed.

(Production Example 3) 500 m equipped with a stirrer
30.0 g (0.1198 mol) of dried 3,5-di-tert-butylsalicylic acid was placed in 1 kolben,
Next, 240 g of methanol was added and dissolved. 30.0 g (0.0894 g) of zirconium oxychloride was added to this solution.
Mol) was added as a powder and the temperature was raised to 50 ° C. The mixture was stirred and reacted at 50 ° C. for 2.5 hours (water: methanol = 5.
3: 94.7). At 50 ° C., 17.9 g (0.2148 mol) of a 48.0% by weight aqueous sodium hydroxide solution was added to 30
The mixture was added dropwise over 1 minute, stirred for 1 hour, and cooled to room temperature (water: methanol = 8.9: 91.1). The product obtained by filtration was dried until the liquid content was 25% by weight. This product was dispersed and washed with 190 g of water, collected by filtration, and dried to obtain 37.4 g of a white product. This product was subjected to IR measurement, X-ray diffraction measurement, and ESI-MS measurement in the same manner as in Production Example 1, and was confirmed to be a zirconium product of 3,5-di-tert-butylsalicylic acid. Further, the slurry concentration of this production example was about 10.0% by weight / volume, and no foaming of the reaction solution and a remarkable increase in the viscosity were observed in the course of the reaction.

(Production Example 4) 500 m equipped with a stirrer
30.0 g (0.1198 mol) of dried 3,5-di-tert-butylsalicylic acid was placed in 1 kolben,
Next, 205 g of methanol was added and dissolved. 30.0 g (0.0894 g) of zirconium oxychloride was added to this solution.
Mol) was added as a powder and the temperature was raised to 50 ° C. The mixture was stirred and reacted at 50 ° C. for 2.5 hours (methanol: water = 6.
4: 93.6). 16.7 g (0.2148 mol) of a 50.0% by weight aqueous sodium hydroxide solution was added dropwise over 30 minutes. After stirring for 1 hour, the mixture was cooled to room temperature and collected by filtration (water: methanol = 9.9: 90.1). The product obtained by filtration was dried until the liquid content became 25% by weight, and this product was dispersed and washed with 190 g of water, filtered, and dried to obtain 37.4 g of a white product. This product was subjected to IR measurement, X-ray diffraction measurement, and ESI-MS measurement in the same manner as in Production Example 1, and was confirmed to be a zirconium product of 3,5-di-tert-butylsalicylic acid. The slurry concentration in this production example was about 11.3% by weight / volume. During the course of the reaction, no foaming of the reaction solution and no remarkable increase in viscosity were observed.

(Production Example 5) 500 m equipped with a stirrer
3,5-di-tert-butyl butter
30.0 g (0.1198 mol) of lusalicylic acid was added,
Next, 240 g of methanol was added and dissolved. This solution
23.0 g of zirconium oxychloride (octahydrate, 0.
(0.685 mol) as a powder and heated to 50 ° C. 5
The mixture was stirred and reacted at 0 ° C. or lower for 2.5 hours (water: methanol)
= 4.1: 95.9). 48.0% by weight of sodium hydroxide
14.6 g (0.1754 mol) of an aqueous solution of lithium was added at 50 ° C.
The mixture is added dropwise over 30 minutes and stirred for 1 hour.
The mixture was cooled and collected by filtration (water: methanol = 7.6: 92.
4). The product obtained by filtration has a liquid content of 25% by weight.
After drying, the product is dispersed and washed with 150 g of water.
After filtering, filtering and drying, 30.2 g of a white product was obtained.
This product was subjected to IR measurement and X-ray diffraction measurement in the same manner as in Production Example 1.
And ESI-MS measurement to determine 3,5-di-tert-
Butyl salicylic acid
I accepted. The slurry concentration in this production example was about 10 wt /
% Of the reaction solution during the course of the reaction.
No significant foaming and viscosity increase was observed. Manufacturing example
3,5-di-tert-butylsalicylic acid
From the quantity value, this Zr quantitative value and each molecular weight, Zr
The molar ratio of 3,5-di-tert-butylsalicylic acid is
As a result, 3,5-diamine was added to 1 mole of zirconium atom.
Containing 1.25 mol of tert-butylsalicylic acid
Was.

(Production Example 6) 500 m equipped with a stirrer
30.0 g (0.1198 mol) of dried 3,5-di-tert-butylsalicylic acid was placed in 1 kolben,
Next, 240 g of methanol was added and dissolved. 23.0 g of zirconium oxychloride (0.0685) was added to this solution.
Mol) was added as a powder and the temperature was raised to 50 ° C. The mixture was stirred and reacted at 50 ° C. or lower for 2.5 hours (water: methanol = 4.
1: 95.9). 13.0 g (0.1560 mol) of a 48.0% by weight aqueous sodium hydroxide solution was added at 50 ° C for 30 minutes.
The mixture was added dropwise over 1 minute, stirred for 1 hour, cooled to room temperature, and collected by filtration (water: methanol = 7.3: 92.7). The product obtained by filtration was dried until the liquid content became 25% by weight, and the product was dispersed and washed with 170 g of water, filtered, and dried to obtain 33.2 g of a white product. This product was subjected to IR measurement, X-ray diffraction measurement, ESI-M
An S measurement was performed to confirm that the product was a zirconium product of 3,5-di-tert-butylsalicylic acid. Further, the slurry concentration in this production example was about 11% by weight / volume, and no foaming of the reaction solution and a remarkable increase in viscosity were observed in the course of the reaction. As in Production Example 1,
Quantitative value of 5-di-tert-butylsalicylic acid and this Zr
From the quantitative values and the respective molecular weights, Zr and 3,5-di-te
When the molar ratio of rt-butylsalicylic acid was determined, 1.5 moles of 3,5-di-tert-butylsalicylic acid was contained per mole of zirconium atoms.

(Production Comparative Example 1) 50 equipped with a stirrer
3,5-di-tert- dried in 0 ml Kolben
Add 18.4 g (0.0647) of butylsalicylic acid,
Then, a 25.0% by weight aqueous sodium hydroxide solution11.
0 g (0.0687) and 197 g of water were added, and the temperature was raised to 50 ° C., followed by stirring and dissolving. Thereafter, 64.9 g of a solution of 10.9 g (0.0325 mol) of zirconium oxychloride dissolved in 54 g of water was dropped at 50 ° C. over 30 minutes, stirred for 1 hour, and then cooled to room temperature. 3.8 g (0.0238 mol) of a 25.0% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7.5 to 8.0, and while stirring, 4.63 g (0.050 mol) of toluene and methanol were added. 137 g of the mixture was added. The product is filtered and water 34
g of methanol and 26.9 g of methanol, dispersed in 60.9 g, washed, filtered and dried to give a white product 14.5.
g was obtained. This product was subjected to IR measurement, X-ray diffraction measurement and ESI-MS measurement in the same manner as in Production Example 1 to give 3,5-di-te
It was confirmed to be a zirconium product of rt-butylsalicylic acid. The slurry concentration of this comparative example was about 3.3.
In the course of carrying out the above reaction, the reaction solution gradually exhibited a foaming mode by dropping the aqueous zirconium solution, and the viscosity increased remarkably in a pH range of about 4 to 7. In this production example, since the filterability of the reaction solution was extremely poor, a mixed solvent of toluene and methanol was added to coagulate the product to perform the treatment. FIG. 2 shows an IR measurement chart of the obtained product.

(Production Comparative Example 2) 50 equipped with a stirrer
3,5-di-tert- dried in 0 ml Kolben
30.0 g (0.1198 mol) of butylsalicylic acid was added, and then 205 g of methanol was added and dissolved. 30.0 g of zirconium oxychloride (0.08
94 mol) as a powder and the temperature was raised to 50 ° C. 50 ℃
The mixture was reacted under stirring for 2.5 hours (water: methanol =
6.4: 93.6). 85.9 g (0.2148 mol) of a 10.0% by weight aqueous sodium hydroxide solution was added dropwise over 30 minutes, and after stirring for 1 hour, cooled to room temperature and collected by filtration (water: methanol = 30.8: 69.2). The product obtained by filtration was dried until the liquid content became 25% by weight, and this product was dispersed and washed with 190 g of water, filtered, and dried to obtain 37.4 g of a white product. This product was subjected to IR measurement, X-ray diffraction measurement, and ESI-MS measurement in the same manner as in Production Example 1, and was confirmed to be a zirconium product of 3,5-di-tert-butylsalicylic acid. The slurry concentration in this production example was about 9% by weight / volume. During the course of the reaction, no foaming of the reaction solution and no remarkable increase in viscosity were observed. Production Examples 1 to 6, Production Comparative Examples 1 and 2
Table 1 shows the results. In Production Examples 1 to 6 in which the reaction solvent is methanol, there is no foaming of the solution and no significant increase in viscosity in the reaction process, as compared with Production Comparative Example 1 in which the reaction solvent is water. Thus, the slurry concentration can be greatly increased, and the productivity is good. Further Production Examples 1
6, the waste liquids of Production Comparative Examples 1 and 2 are subjected to normal pressure and tower top temperature 61 to 64 using an Oldershaw rectification column (actual number of stages: 10).
As a result of recovering methanol under the conditions of a temperature of 1 ° C. and a reflux ratio of 1, the waste liquid other than Comparative Example 1 was able to recover methanol having a water content of 0.3% by weight and a purity of 99.7% by weight by Karl Fischer. Since the waste liquid of Production Comparative Example 1 had a methanol concentration of about 50% and further contained toluene, reusable methanol could not be recovered by the above method. The ratio of the amount of the secondary waste liquid to the zirconium product after the solvent recovery was about 8.2 times and 7.5 for the zirconium product in the order of Production Examples 1 to 6.
Times, 7 times, 6.8 times, 7.2 times, 7.1 times (g / g). Production Comparative Example 1 could not be recovered by the above-mentioned method. Compared to the waste liquid ratio of 34 times, the production method of the present invention has a significantly smaller amount of waste liquid after methanol recovery and higher productivity than the production method of Production Comparative Example 1. As a result of producing the recovered methanol under the same conditions as in Production Example 1, no foaming of the solution and a significant increase in viscosity were observed in the reaction process, and the obtained zirconium product was the same as that in Production Example 1. Obtained
The product was used to produce and evaluate a toner in the same manner as in Example 1. As a result, a toner having the same charge amount as in Example 1 was obtained. Further, in the production methods of Production Examples 1 to 6, since the methanol concentration of the filtrate was 80% or more, methanol could be easily recovered with high purity and high yield, and the waste liquid after recovery was greatly reduced. In the production method of Production Comparative Example 1, it is not easy to recover methanol with high purity and high yield, and the entire amount becomes waste liquid, which is economically and environmentally undesirable.

[0112]

[Table 1]

[Example 1] 91 parts of styrene-acrylic copolymer resin (0.1 oxidation) (trade name, CPR-100, manufactured by Mitsui Chemicals, Inc.) 1 part of zirconium product obtained in Production Example 1 carbon Black 5 parts (trade name, MA-100, manufactured by Mitsubishi Chemical Corporation) Low molecular weight polypropylene 3 parts (trade name, Viscol 550P, manufactured by Sanyo Kasei Co.) Was coarsely pulverized with a hammer mill. Furthermore, after finely pulverizing with a jet mill, it is classified and 10 to 12 μm
Was obtained. This toner was mixed with a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech) at a ratio of 4 to 100 parts and shaken to charge the toner negatively, followed by blow-off powder charging. It was measured with a volume measuring device. Further, the charge amount of the toner on the 50,000th running sheet was also measured by a blow-off powder charge amount measuring apparatus, and the results are shown in Table 2.

[Examples 2 to 6] The "zirconium product obtained in Production Example 1" described in Example 1 was replaced with the zirconium product obtained in Production Example 2 and the zirconium product obtained in Production Example 3. Product, zirconium product obtained in Production Example 4, zirconium product obtained in Production Example 5, Production Example 6
Example 1 except that the products obtained in the above were respectively changed.
(Including the amount of addition), and each was performed in Example 2,
Example 3, Example 4, Example 5, and Example 6 were set. The results are shown in Table 2.

Comparative Example 1 91 parts of styrene-acrylic copolymer resin (0.1 oxidation) (trade name, CPR-100, manufactured by Mitsui Chemicals, Inc.) 1 part of zirconium product obtained in Production Comparative Example 1 Carbon black 5 parts (trade name, MA-100, manufactured by Mitsubishi Chemical Corporation) Low molecular weight polypropylene 3 parts (trade name, Biscol 550P, manufactured by Sanyo Chemical Co., Ltd.) The above mixture was melted and mixed by a heating and mixing apparatus at 140 ° C., and cooled. The mixture was coarsely pulverized with a hammer mill. Furthermore, after finely pulverizing with a jet mill, it is classified and 10 to 12 μm
Was obtained. This toner was mixed with a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech) at a ratio of 4 to 100 parts and shaken to charge the toner negatively, followed by blow-off powder charging. It was measured with a volume measuring device. Further, the charge amount of the toner on the 50,000th running sheet was also measured by a blow-off powder charge amount measuring apparatus, and the results are shown in Table 2.

Comparative Example 2 The zirconium product obtained in Comparative Example 1 described in Comparative Example 1 was prepared in Comparative Example 2.
Comparative Example 2 was performed in the same manner as in Comparative Example 1 (including the amount added), except that the zirconium product obtained in was changed. The results are shown in Table 2.

[0117]

[Table 2]

[0118]

As is clear from Table 1, when an organic zirconium product is produced by using the production method of the present invention, it is necessary to dissolve the aromatic hydroxycarboxylic acid as a raw material and a zirconium metal imparting agent such as zirconium oxychloride. Until the reaction product is obtained, the reaction can be completed with one kind of solvent such as methanol, and the productivity (slurry concentration) is improved as compared with the conventional production method using water as a solvent. It can be seen that there is no increase, the solvent can be easily recovered, and the production method has little waste liquid. Moreover, as is clear from Table 2, the reaction between the methanol and water in the reaction solution at a specific ratio is controlled, and the reaction between the aromatic hydroxycarboxylic acid as a colorless amorphous body and the zirconium metal-imparting agent is performed. When the reaction product was contained in the toner as a charge control agent, good results were shown in both the initial blow-off charge and the running charge.

[Brief description of the drawings]

FIG. 1 is an IR chart of a product obtained in Production Example 1.

FIG. 2 is an IR chart of a product obtained in Production Comparative Example 1.

FIG. 3 is an X-ray diffraction chart of a product obtained in Production Example 1.

FIG. 4 is an ESI-MS chart of the product obtained in Production Example 1.

Continuing from the front page (72) Inventor Kosuke Murai 4-5 Tanijimacho, Koriyama-shi, Fukushima Tohoku Hodogaya Inside the Koriyama Office (72) Inventor Iku Kasahara 4-5 Tanijimacho, Koriyama-shi, Fukushima Tohoku Hodogaya Co., Ltd. Koriyama Office F-term (reference) 2H005 AA02 AA06 AB02 CA14 CA25 CB03 DA02 4H049 VN06 VP01 VQ32 VQ92 VR43 VS32 VU25 VV05 VV20 VW02 VW11

Claims (13)

[Claims] In producing a charge control agent which is a reaction product of an aromatic hydroxycarboxylic acid and a zirconium metal-providing agent, an alcohol having 1 to 5 carbon atoms is used as a reaction solvent, and a carbon atom having 1 carbon atom in the reaction step is used. The weight ratio of alcohol to water having a weight of 5 to 80 is from 80:20 to 100: 0.
A method for producing a charge control agent, characterized in that: 2. The weight ratio of alcohol having 1 to 5 carbon atoms to water in the reaction step is 85:15 to 100:
The method for producing a charge control agent according to claim 1, wherein the charge control agent is 0. 3. The weight ratio of alcohol having 1 to 5 carbon atoms to water in the reaction step is 90:10 to 100:
The method for producing a charge control agent according to claim 1, wherein the charge control agent is 0. 4. The method for producing a charge control agent according to claim 1, wherein the alcohol having 1 to 5 carbon atoms is methanol. 5. The method according to claim 1, wherein the aromatic hydroxycarboxylic acid is 3,5-
The method for producing a charge control agent according to claim 1, wherein the method is di-tert-butylsalicylic acid. 6. The method according to claim 1, wherein the aromatic hydroxycarboxylic acid is 3,5-
The method for producing a charge control agent according to any one of claims 1 to 4, wherein the method is di-tert-butylsalicylic acid, and the zirconium metal imparting agent is zirconium oxychloride. 7. The reaction of an aromatic hydroxycarboxylic acid with a zirconium metal-providing agent in the presence of an alcohol having 1 to 5 carbon atoms, wherein the aromatic hydroxycarboxylic acid 1
The amount of the zirconium metal-imparting agent is 0.1 mol in terms of metal per mol.
A method for producing a charge control agent, wherein the reaction is carried out at 3 to 1.4 mol. 8. When reacting an aromatic hydroxycarboxylic acid with a zirconium metal-imparting agent in the presence of methanol, the zirconium metal-imparting agent is used in an amount of 0.3 to 1.4 in terms of metal per mole of the aromatic hydroxycarboxylic acid. A method for producing a charge controlling agent, characterized in that the reaction is carried out in moles. 9. The method according to claim 9, wherein the aromatic hydroxycarboxylic acid is 3,5-
9. The method for producing a charge control agent according to claim 7, wherein the charge control agent is di-tert-butylsalicylic acid. 10. The method according to claim 10, wherein said aromatic hydroxycarboxylic acid is 3,5.
9. The method for producing a charge control agent according to claim 7, wherein the charge control agent is -di-tert-butylsalicylic acid, and the zirconium metal imparting agent is zirconium oxychloride. 11. A toner for developing an electrostatic image, comprising a charge control agent, a colorant and a binder resin obtained by the production method according to claim 1. Description: 12. The toner according to claim 11, further comprising a wax. 13. The electrostatic image developing toner according to claim 11, further comprising a magnetic material.