JP2002207319A - Charge controlling agent, method for manufacturing the same and electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colorless or white charge controlling agent containing no heavy metals and showing a high electrifying effect, a method for manufacturing the charge controlling agent, and an electrostatic charge image developing toner containing the charge controlling agent. SOLUTION: The method for manufacturing the charge controlling agent is carried out by dropping a solution of aromatic hydroxycarboxylic acid onto a solution of a calcium compound as a metal imparting agent to react, and the charge controlling agent consists of the reaction product in which the aromatic hydroxycarboxylic acid and calcium form one or more kinds of coupling patterns of coordinate bond, covalent bond and ionic bond. The charge controlling agent produced by the above method shows <=250 average of the shape factor (SF-1) and <=200 average of the shape factor (SF-2). The electrostatic charge image developing toner contains the above charge controlling agent by >=2.00 mg/(1 g toner) present on the toner surface.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge control agent used in an image forming apparatus used for visualizing an electrostatic latent image in the fields of electrophotography, electrostatic recording material and the like, and a method for producing the charge control agent. And a developing method using the toner.

[0002]

2. Description of the Related Art In an electrophotographic image forming process, an electrostatic latent image is formed on a photoreceptor made of an inorganic or organic material, developed with toner, transferred to paper or a plastic film, and fixed to form a visible image. Get an image. The photoreceptor has a positive charge property and a negative charge property depending on its configuration, and when the printed portion is left as an electrostatic image by exposure, it is developed with a reverse-charging toner. On the other hand, in the case of performing reversal development by removing electricity from the printing portion, development is performed using the same sign charging toner. The toner is composed of a binder resin, a colorant, and other additives. A charge control agent is generally added to impart desirable frictional charging characteristics (charging speed, charging level, charging stability, etc.), stability over time, and environmental stability. The characteristics of the toner are greatly affected by the addition of the charge control agent.

In the case of a color toner expected to expand in the market in the future, a light-colored, preferably colorless, charge control agent which does not affect the hue is indispensable. Examples of conventional charge control agents include, for example, metal complex salts of salicylic acid derivatives (Japanese Patent Publication No. 55-42752, Japanese Patent Application Laid-Open No. Sho 61-6).
No. 9073, JP-A-61-221756, JP-A-9-124659, etc.), metal salts of aromatic dicarboxylic acid (JP-A-57-111541, etc.),
Metal complex salt compound of anthranilic acid derivative
94856, etc.), and organic boron compounds (US Pat. No. 4,767,688, JP-A-1-306686, etc.).

[0004]

However, these charge control agents are chromium compounds which are considered to be more important for environmental safety in the future, and have a colorless or pale color required for color toners. There are drawbacks such as insufficient compound, insufficient charging effect, reverse charging of the toner, and poor dispersibility and stability of the compound itself. JP-A-62-163061 discloses an electrophotographic toner containing a calcium salt of 3,5-di-tert-butylsalicylic acid. The charge control agent, which is a calcium salt of 3,5-di-tert-butylsalicylic acid disclosed in this publication, is pale white and does not contain heavy metals such as chromium, and thus can be applied to color toners. Although it is a charge control agent that also considers measures against heavy metals such as chromium, it has the disadvantage that the charge imparting effect required today is low and there is a disadvantage that image deterioration is likely to occur during long-term running, High charge control agents have been desired.

It is an object of the present invention to provide: 1. To provide a colorless or white charge control agent having a high charge-imparting effect that does not contain heavy metals. 2. To provide a method for producing the charge control agent; 3. To provide a toner for developing an electrostatic image having a high charge amount containing the charge control agent; An object of the present invention is to provide a developing method using the toner. More specifically, a charge control agent in which an aromatic hydroxycarboxylic acid having a high charge-imparting effect and calcium takes one or more of a coordination bond, a covalent bond, and an ionic bond, and a method for producing the same, An object of the present invention is to provide a toner containing an agent and a developing method using the toner.

[0006]

The present invention which can solve the above-mentioned problems includes the following inventions.

[0007] 1. A charge control agent which is a reaction product of an aromatic hydroxycarboxylic acid and a calcium compound, wherein the aromatic hydroxycarboxylic acid and the calcium compound take one or more of a coordination bond, a covalent bond, and an ionic bond. An average value of the shape factor (SF-1) calculated according to the following equation of the charge control agent is 250 or less. SF-1 = [(ML ² × π) / 4A] × 100 (where, ML represents the maximum length of a particle, and A represents the projected area of one particle.)

[0008] 2. 2. The charge control agent according to claim 1, wherein the charge control agent has an average value of shape factor (SF-2) calculated according to the following formula of 200 or less. SF-2 = (PM ² / 4Aπ) × 100 (where PM is the peripheral length of a particle, and A is the projected area of one particle.)

3. The charge control agent according to claim 1 or 2, wherein the aromatic hydroxycarboxylic acid is 3,5-di-tert-butylsalicylic acid.

[0010] 4. A solution of an aromatic hydroxycarboxylic acid is dropped into a solution of a calcium compound as a metal imparting agent,
A reaction product of an aromatic hydroxycarboxylic acid and a calcium compound, wherein the aromatic hydroxycarboxylic acid and calcium take one or more of a coordination bond, a covalent bond and an ionic bond. A method for producing a charge control agent comprising:

5. 5. The method for producing a charge control agent according to claim 4, wherein the average value of the shape factor (SF-1) calculated according to the following formula of the reaction product is 250 or less. SF-1 = [(ML ² × π) / 4A] × 100 (where, ML represents the maximum length of a particle, and A represents the projected area of one particle.)

6. 6. The method for producing a charge control agent according to claim 5, wherein the average value of the shape factor (SF-2) calculated according to the following formula of the reaction product is 200 or less. SF-2 = (PM ² / 4Aπ) × 100 (where PM is the peripheral length of a particle, and A is the projected area of one particle.)

7. 7. The method according to any one of items 4 to 6, wherein the solution of the aromatic hydroxycarboxylic acid is dropped into the solution of the calcium compound as the metal-providing agent, and the reaction temperature is 10 to 70 ° C. A method for producing a charge control agent.

8. The method for producing a charge control agent according to any one of claims 4 to 7, wherein the aromatic hydroxycarboxylic acid is 3,5-di-tert-butylsalicylic acid.

9. 9. The charge control agent according to any one of the above items 1 to 3 and at least one selected from the charge control agent produced by the method for producing a charge control agent according to any one of the above items 4 to 8. A toner for developing an electrostatic image, comprising a kind of charge control agent, a colorant and a binder resin.

10. 10. The electrostatic image developing toner according to claim 9, further comprising a wax and / or a magnetic material in addition to the charge control agent, the colorant, and the binder resin.

11. 11. The electrostatic image developing toner according to claim 9, wherein the toner content of the charge control agent is 2.0 mg / 1 g toner or more.

[12] 12. A one-component developing method, comprising using the electrostatic image developing toner according to any one of the above items 9 to 11.

13. 12. A two-component developing method using the electrostatic image developing toner according to any one of the above items 9 to 11.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION A charge control agent comprising a reaction product in which an aromatic hydroxycarboxylic acid of the present invention and calcium are bonded by one or more of a coordination bond, a covalent bond and an ionic bond. As a method for producing a compound, an aqueous solution of a calcium compound as a metal imparting agent such as calcium chloride is added to an aqueous solution of an aromatic hydroxycarboxylic acid such as 3,5-di-tert-butylsalicylic acid in advance to an alkali agent such as an aqueous sodium hydroxide solution. The dissolved solution is added dropwise,
The mixture can be reacted by stirring at 6.8 to 13.5 at a temperature of 10 to 70 ° C. for 1 to 2 hours, and the deposited precipitate can be obtained by filtration, washing with water, and drying.

The aromatic hydroxycarboxylic acid that can be used in the present invention will be described. Or (4), and these aromatic hydroxycarboxylic acids can be used alone or as a mixture of two or more.

[0022]

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[In the above general formula (1), R is an alkyl group,
Aryl group, aralkyl group, cycloalkyl group, alkenyl group, alkoxy group, aryloxy group, hydroxyl group, alkoxycarbonyl group, aryloxycarbonyl group,
Represents an acyl group, an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, a substituted amide group, a carbamoyl group, or a substituted carbamoyl group; p represents an integer of 0 to 4; In the case of ~ 4, R
May be the same or different. Also, R
May be bonded to each other to form an aliphatic ring or a heterocyclic ring, and the formed ring may further have one or more of the above substituents R, When there are two or more, they may be the same or different. ]

[0024]

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[0025]

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[0026]

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[The above general formulas (2), (3) and (4)
Wherein R is an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carboxyl group, a halogen, Represents a nitro group, a cyano group, an amino group, an amide group, a substituted amide group, a carbamoyl group, or a substituted carbamoyl group; q represents an integer of 0 to 6;
Is 2 to 6, R may be the same or different. R may be mutually bonded to form an aliphatic ring or a heterocyclic ring, and the formed ring may further have one or more of the above substituents R. And when they have two or more, they may be the same or different. ]

Examples of the aromatic hydroxycarboxylic acids represented by the above general formulas include salicylic acid having an alkyl group (preferably having 1 to 9 carbon atoms) and 3,5-dialkyl (preferably having 1 to 9 carbon atoms). Salicylic acid, 2-hydroxy-3-naphthoic acid, alkyl (C1-9) -2
-Hydroxynaphthoic acid, 5,6,7,8-tetrahalogen-2-hydroxy-3-naphthoic acid, etc., and the reaction product obtained from 3,5-di-tert-butylsalicylic acid and a calcium compound is Since the charge control agent has a high charge imparting effect, 3,5-di-tert-
Butylsalicylic acid is particularly preferred.

The calcium compound as a metal-imparting agent (hereinafter also referred to as a calcium-imparting agent) used in the present invention includes calcium nitrate, calcium nitrite, calcium carbonate, masonry, slaked lime, quicklime, calcium hypophosphite, and peroxide. Calcium, calcium powder, calcium chloride and the like can be mentioned, but calcium chloride is preferred.

The ratio of the aromatic hydroxycarboxylic acid to the calcium-imparting agent is preferably in the range of 1.0 to 2.0 based on the molar ratio of calcium in the calcium-imparting agent.
2 moles, more preferably 1.9 to
2.0 moles. When the amount of the aromatic hydroxycarboxylic acid is less than 1.0 mol with respect to the calcium-imparting agent, the amount of the calcium-imparting agent that does not participate in the reaction increases, and by-products such as calcium hydroxide tend to be generated and the purity tends to decrease, If the amount exceeds 2.2 mol, the amount of aromatic hydroxycarboxylic acid and Na salt of aromatic hydroxycarboxylic acid increases, and the filterability is remarkably deteriorated. At the same time, these impurities may adversely affect the charge control effect.

The temperature at which the calcium-imparting agent is dissolved in water or the like to form a calcium aqueous solution and the alkaline aqueous solution of aromatic hydroxycarboxylic acid is added dropwise is preferably from 10 to 70 ° C, more preferably from 20 to 40 ° C. The temperature is 1
If the temperature is lower than 0 ° C., the reaction rate decreases, so that unreacted raw materials are taken into the crystal, and it is difficult to obtain a charge control agent having the desired charging performance. If the temperature exceeds 70 ° C., the crystal particle shape tends to be columnar or acicular, that is, the shape factor (SF-1) tends to exceed 250, and similarly, it is difficult to obtain a charge control agent having the intended charging performance. Becomes

Examples of the alkaline agent for dissolving the aromatic hydroxycarboxylic acid include sodium hydroxide, potassium hydroxide, sodium methoxide, and sodium ethoxide.
As the alkali for dissolving di-tert-butylsalicylic acid, sodium hydroxide or potassium hydroxide is preferable.

The reaction product of an aromatic hydroxycarboxylic acid and a calcium compound, wherein the aromatic hydroxycarboxylic acid obtained by the production method of the present invention and calcium has at least one kind of bonding mode of coordination bond, covalent bond and ionic bond. The substance includes a calcium complex, a calcium complex salt, a calcium salt, or a mixture thereof. Specifically, when a calcium salt, a calcium complex, or a calcium complex salt is represented, a compound having a structure represented by the following general formulas (5), (6), and (7) and the like can be given.

[0034]

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[0035]

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In the above formulas (5) and (6), R represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group,
A hydroxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyl group, an acyloxy group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, a substituted amide group, a carbamoyl group, or a substituted carbamoyl group; Integer of 0 to 4, m represents an integer of 1 to 8, and n represents an integer of 1 to 4. When l is 2 to 4, R
May be the same or different. R may be mutually bonded to form an aliphatic ring, an aromatic ring, or a heterocyclic ring, and the formed ring further has one or more of the above substituents R. When m is 2 or more, the aromatic hydroxycarboxylic acids serving as ligands may be the same or different from each other, and m and / or n It may be a mixture of compounds having different numbers, the hydroxyl group on the aromatic ring may be coordinated with calcium metal to form a chelate compound, or the hydroxyl group may not participate in the bond. . Further, these compounds may have one or more molecules of coordinating water.

[0037]

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In the general formula (7), R represents an alkyl group, an aryl group, an aralkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, Represents an acyl group, a carboxyl group, a halogen, a nitro group, a cyano group, an amino group, an amide group, a substituted amide group, a carbamoyl group, or a substituted carbamoyl group; l is an integer of 0 to 4; Represent
n represents an integer of 1 to 4. When 1 is 2 to 4, R may be the same or different. R may be mutually bonded to form an aliphatic ring, an aromatic ring, or a heterocyclic ring, and the formed ring further has one or more of the above substituents R. You can. When m is 2 or more, these compounds may have the same or different aromatic hydroxycarboxylic acids as ligands. It may be a mixture and furthermore, these compounds may have one or more molecules of coordinating water. ,

The shape factor (S) of the charge control agent used in the present invention
F-1) is a number calculated from the following equation, and SF
-1 indicates the strain of the particle, and the closer the particle is to a sphere (image is a perfect circle), the closer to 100, and the longer the particle is, the larger the numerical value becomes. SF-1 = [(ML ² × π) / 4A] × 100 (where ML is the maximum length of a particle image, and A is the projected area of one particle.)

The shape factor (S) of the charge control agent used in the present invention
F-2) is a number calculated from the following equation. SF
-2 represents the degree of unevenness on the surface of the particle. The closer the particle is to a sphere (the projected image of the particle is a perfect circle), the closer to 100. SF-2 = (PM ² / 4Aπ) × 100 (where PM is the peripheral length of a particle, and A is the projected area of one particle.)

In the above-mentioned shape factor (SF-1) and shape factor (SF-2), the maximum length ML of the particle, the projected area A of the particle and the perimeter PM of the particle are determined by an optical microscope equipped with a CCD camera (for example, Using Olympus BH-2), a product particle group magnified 1000 times in 30
Sampling is performed so that the number of images becomes about one, and the obtained image is transferred to an image analyzer manufactured by Nireco (Luzex FS). It is the average value of the numerical values for each particle calculated according to the above formula based on the numerical value obtained by measuring the projected area A of the particle and the peripheral length of the image of one particle (perimeter PM of the particle). The above measurement operation was repeated for one product until the number of particles reached about 3,000, and the average value of the numerical values of all the particles was used as the shape factor SF-1 of each charge control agent.
And SF-2.

The shape factor of the charge controlling agent of the present invention (SF-
1) is in the range of 250 or less. When a toner is manufactured using the charge control agent having a shape factor (SF-1) of 250 or less according to the present invention, a toner having a high charge amount can be obtained. When a toner is manufactured using a charge control agent having a shape factor (SF-1) of more than 250, the charge control effect is poor, and image formation such as fog and resolution degradation occurs in image formation by long-term running. Further, the shape factor (SF-2) is preferably 200 or less. As the shape factor (SF-2) increases beyond 200, the charge control effect is poor, and image formation such as fogging and resolution degradation becomes noticeable in image formation by long-term running.

In the method for producing the charge control agent of the present invention, an alkaline aqueous solution of an aromatic hydroxycarboxylic acid is dropped into an aqueous solution of a calcium-imparting agent such as calcium chloride, and
Preferably, PH 6.8-13.5, temperature 10-70 ° C
The reaction is carried out in the range of By adopting such a reaction method, the shape factor (SF-1) becomes 250
The following, that is, a compound having a nearly spherical crystal shape can be obtained. Conversely, in the method disclosed in JP-A-62-163061, in which an aqueous solution of calcium chloride as a calcium-imparting agent is dropped into an alkaline aqueous solution of an aromatic hydroxycarboxylic acid, the shape factor (SF-1) is reduced. 250
Above, ie a product of rod-like or needle-like crystals is obtained, such that the shape factor (SF-1) is 25
The effect of imparting charge to the reaction product of the calcium compound, which is a crystal exceeding 0, is low, and a satisfactory charge control agent cannot be obtained.

The charge controlling agent of the present invention is preferably used after adjusting the volume average particle diameter in the range of 0.1 to 20 μm, more preferably 1 to 10 μm. When the volume average particle diameter is smaller than 0.1 μm, the amount of the charge control agent appearing on the toner surface becomes extremely small, so that the intended charge control effect cannot be obtained. It is not preferable because it increases and adverse effects such as in-flight contamination occur. The charge control agent of the present invention is used in an amount of 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass, per 100 parts by mass of the binder resin.

The charge controlling agent of the present invention can be used for a toner used in a one-component developing system or a toner used in a two-component developing system. Further, it can be used for a capsule toner and a polymerization toner. Further, the toner may be a magnetic toner or a non-magnetic toner.

The toner for developing an electrostatic charge 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 and a necessary additive such as a colorant, a charge control agent and other waxes 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, classification is performed to a predetermined particle size using an air classifier, for example, an inertia classification type elbow jet utilizing the Coanda effect, a cyclone (centrifugal) classification type microplex, a DS separator, or the like. Further, when an external additive or the like is to be treated on the toner surface, the toner and the external additive are stirred and mixed by a high-speed stirrer such as a Henschel mixer or a super mixer.

Further, 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 control 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, for example, an aqueous phase, with a suitable stirrer and disperser, for example, a homomixer, a homogenizer, an atomizer, a microfluidizer, a one-liquid fluid nozzle, The toner particles are dispersed using a liquid fluid nozzle, an electric emulsifier, or the like, and simultaneously undergo a polymerization reaction, whereby toner particles having a desired particle size can be obtained. 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 that can be used in the present invention will be described. The toner for developing an electrostatic image of the present invention basically comprises a binder resin, a colorant (pigment, dye) and a charge control agent, and further comprises a releasing agent such as a wax and an external additive (cleaning improver). And a fluidity improver) and a magnetic substance. 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, Polycarbonate resin, polyol resin, phenol resin, silicone resin, polyurethane resin, polyamide resin, furan resin, epoxy resin, xylene resin, terpene resin, coumarone indene resin, petroleum resin, and the like can be used.

The following are examples of the vinyl monomer constituting the vinyl polymer unit. Styrene; o-methylstyrene, m-methylstyrene,
p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-
Hexylstyrene, pn-octylstyrene, pn
-Nonylstyrene, pn-decylstyrene, pn-
Styrene such as dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3.4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene and derivatives thereof;

Monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate and vinyl propionate , Vinyl esters such as vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
Dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate,
Α-methylene aliphatic monocarboxylic esters such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate;

Methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-acrylic acid Acrylates such as chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole; N-vinyl compounds such as N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid such as acrylonitrile, methacrylonitrile, acrylamide Le acid derivatives.

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 and methyl half mesaconic acid; 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 β-unsaturated acids and lower fatty acids, alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid,
Examples thereof include monomers having a carboxyl group such as acid anhydrides and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

In the toner for developing an electrostatic image of the present invention,
The vinyl polymer unit used as the binder resin may have a cross-linked structure cross-linked with a cross-linking agent having two or more vinyl groups, but the cross-linking agent used in this case is an aromatic divinyl compound. For example, divinylbenzene,
Divinylnaphthalene; diacrylate compounds linked by alkyl chains, such as 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 are exemplified.

Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate,
Polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and those obtained by replacing acrylates of the above compounds with methacrylates may be used.

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 the polyester type diacrylates, for example, trade name MAND
A (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 cross-linking agents may be used in combination with other monomer components 10
0.01 to 10 parts by mass (more preferably 0.03 to 5 parts by mass) can be used with respect to 0 parts by mass. 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.

The polymerization initiator used for producing the vinyl copolymer of the present invention includes, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylpareronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 , 4-Dimethyl-4-methoxyvaleronitrile, 2,2'-azobis (2-methyl-propane);

Ketone peroxides such as methyl ethyl ketone peroxide, acetylacetone peroxide, 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, sicumyl peroxide, α'-bis (t-butylperoxyisopropyl) benzene, isobutylperoxide Oxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-trioilepoxide, di-isopropylperoxydicarbonate, di-2 -Ethylhexylperoxydicarbonate, di-n-propylperoxydicarbonate, di-
2-ethoxyethyl peroxycarbonate, di-ethoxyisopropylperoxydicarbonate, di (3-
Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxy-2-ethylhexarate, t-butylperoxide Oxylaurate, t
-Butyl-oxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxyisophthalate, t-butylperoxyallyl carbonate, isoamylperoxy-2-ethylhexanoate, di-t-butylperoxy Hexahydroterephthalate, t-butyl peroxyazelate and the like can be mentioned.

The vinyl polymer has a glass transition temperature of 40
To 90 ° C. and a number average molecular weight (Mn) of 1500 to 5
0000, mass average molecular weight (Mw) of 10,000 to 50
00000 is preferred. More preferably, the glass transition temperature is 45 to 85 ° C., and Mn is 2,000 to 20.
000 and Mw of 15,000 to 3,000,000 are preferred. The OH value of these vinyl polymers is 50 mgK
OH / g or less, more preferably O
H value is 30 mgKOH / g or less.

The monomers constituting the polyester-based polymer include the following. 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, and ether compounds of bisphenol A and ethylene glycol or propylene glycol.

In order to crosslink the polyester resin, it is preferable to use a trivalent or higher alcohol in combination. 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 at least 3, trimetic 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, mass 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. The resin has an OH value of 50 mgKOH / g
Hereinafter, desirably, the OH value is 30 mgKOH / g or less.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, phthalic acid, maleic acid,
Unsaturated dicarboxylic acids such as 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.

A binder resin such as a polyester polymer or a vinyl polymer has an acid value of 0.1 to 50 mgKOH / g.
Is preferable, and more preferably, the acid value is 0.1.
It is a binder resin having 1 to 45 mgKOH / g. 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 mass or more is preferable.

As the colorant, in the case of a black toner, black or blue dye or pigment particles are generally used for two-component development and non-magnetic one-component development, and various magnetic substances are used for magnetic one-component development. . As black or blue pigments, carbon black, aniline black, acetylene black,
Examples include 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, the amount required to maintain the optical reflection density of the image after fixing is used, and the addition amount is preferably 0.1 to 20 parts by mass, and more preferably 2 to 12 parts by mass with respect to 100 parts by mass of the resin. .

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, calcium, 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 mass, preferably 0.2 to 5 parts by mass.

The following are examples of the charge control agent in this case. For example, examples of the negatively chargeable charge control agent include an organic metal complex, a chelate compound, and an organic metal salt. 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. Further, a positive charge control agent may be used in combination for the purpose of improving stability. Can be used.

When the toner of the present invention is used as a magnetic toner, the magnetic materials contained in the magnetic toner include iron oxides such as magnetite, hematite, and ferrite, and iron oxides containing other metal oxides; Metals such as Ni, or these metals and A1, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Alloys with metals such as d, Ca, Mn, Se, Ti, W, and V, and mixtures thereof, and the like.

Specifically, as the magnetic material,
Iron (Fe_ThreeO_Four), Iron sesquioxide (γ-Fe_TwoO_Three),iron oxide
Zinc (ZnFe_TwoO_Four), Yttrium iron oxide (Y_ThreeFe_Five
O₁₂), Cadmium iron oxide (CdFe_TwoO_Four), Iron oxide gas
Dolinium (Gd_ThreeFe_FiveO₁₂), Iron oxide copper (CuFe_Two
O_Four), Lead iron oxide (PbFe₁₂O), Nickel iron oxide
(NiFe_TwoO_Four), Iron neodymium oxide (NdFe_TwoO),
Barium oxide (BaFe)_{1 Two}O₁₉), Iron oxide magnesium
(MgFe_TwoO_Four), Iron manganese oxide (MnFe)
_TwoO _Four), Iron oxide lanthanum (LaFeO)_Three), Iron powder (F
e), cobalt powder (Co), nickel powder (Ni), etc.
The above-mentioned magnetic materials can be used alone or in combination of two or more.
Use in combination. A particularly preferred magnetic material is ferric oxide
Or a fine powder of γ-iron sesquioxide.

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 mass of a magnetic material, preferably 20 to 15 parts by mass, based on 100 parts by mass of the binder resin.
It is preferred to use 0 parts by mass.

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, the dye may be CI Direct Red 1,
C. 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.
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 and the like.

Examples of pigments include mineral fast yellow, naple yellow, naphthol yellow S, Hansaero-G, permanent yellow-NCG, tartrazine lake, molybdenum orange, permanent oresi GTR, pyrazolone orange, and benzidine orange G.
Cadmium Red, Permanent Red 4R, Watching Red Calcium 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, Inn Dunlan 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 non-magnetic toner for two-component full-color printing, 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 Piolet 1, C.I.
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 obtained by substituting 1 to 5 phthalimidomethyl groups in a phthalocyanine skeleton. 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% with respect to 100 parts by weight of the binder resin.
To 60 parts by mass, preferably 0.5 to 50 parts by mass.

As the release agent used for the purpose of improving fixing, conventionally known release agents are used, and examples thereof include low molecular weight polyalkylenes, terpene resins and derivatives thereof, and various waxes. . Examples of the wax include 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 wax and its derivatives, terpene resin and its derivatives (deleted), carnauba Derivatives include waxes and derivatives thereof, and include derivatives of oxides, block copolymers with vinyl monomers, and modified grafts. Various waxes are preferred as the release agent. 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.

The wax in this case is represented by the following general formula (8)
(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). A mass average molecular weight (Mw) by GPC (gel permeation chromatography). ) Is preferably 3000 or less.

[0084]

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, waxes containing a high molecular alcohol represented by (A) as a main component are particularly preferred because of their high effects. 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 resin 1
It is preferably used in an amount of 0.5 to 20 parts by mass with respect to 00 parts by mass.

Further, a fluidity improver may be added to the toner of the present invention. The fluidity improver can be added to the toner surface to increase the fluidity before and after the addition. For example, a fluorine-based resin powder such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder, Fine powdered silica such as wet-processed silica and dry-processed silica, finely powdered titanium oxide, finely powdered non-alumina, and treated silica, titanium oxide, and titanium oxide, surface-treated with silane coupling agent, titanium coupling agent, and silicone oil. There is alumina. Preferred fluidity improvers are fine powders produced by the vapor phase oxidation of silicon halide inclusions, 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 ₂ + 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 compound such as aluminum chloride or titanium chloride together with the silicon halide compound. They are also included. The particle diameter is, as an average primary particle diameter, preferably in the range of 0.001 to 2 μm, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used. .

Examples of commercially available fine silica powder produced by the vapor phase oxidation of a silicon halide compound include those commercially available under the following trade names, for example.

AER0SIL 130 (Nippon Aerosil Co., Ltd.), AER0SIL 200 (Nippon Aerosil Co., Ltd.), AER0SIL 300 (Nippon Aerosil Co., Ltd.), AER0SIL 380 (Nippon Aerosil Co., Ltd.), AER0SIL TT600 (Nippon Aerosil Co., Ltd.), AER0SIL MOX170 (Nippon Aerosil Co., Ltd.), AER0SIL MOX80 (Nippon Aerosil Co., Ltd.), AER0SIL COK84 (Nippon Aerosil Co., Ltd.), Ca-O-SiLM-5 (Cabot Co., Ltd.), Ca-O-SiL MS-7 (CABOT Co., Ltd.) Ca-O-SiL MS-75 (manufactured by CABOT), Ca-O-SiL HS-5 (manufactured by CABOT), Ca-O-SiLEH-5 (manufactured by CABOT), Wacker HDK N20V15 (WACK)
ER-CHEMIEGMBH), N20E (WAC)
KER-CHEMIEGMBH), T30 (WAC
KER-CHEMIEGMBH), T40 (WAC)
KER-CHEMIEGMBH), D-Cine
Si1ica (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 a methanol titration test shows 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. There is dimethylpolysiloxane containing a hydroxyl group bonded to individual 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 mass of the fluidity improver with respect to 00 parts by mass,
Preferably, 0.1 to 4 parts by mass is used.

In the toner for developing an electrostatic image of the present invention, other additives such as protection of a photoreceptor and a carrier, improvement of cleaning properties, adjustment of thermal characteristics, electric characteristics and physical characteristics,
Various metallic soaps, fluorine-based surfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. Inorganic fine powder such as aluminum oxide and alumina can be added as required. Further, these inorganic fine powders may be hydrophobized if necessary. 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; and white and black fine particles having a polarity opposite to that of toner particles Can be used in a small amount as a developability improver.

These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organosilicon compounds for the purpose of controlling the amount of charge. It is also preferable to treat with a treating agent such as a compound or various treating 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 uniformly externally added to the surface of the toner particles to obtain the intended toner for electrostatic charge development. it can.

The charge controlling 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 mass with respect to 100 parts by mass of the carrier, and more preferably in an amount of 2 to 50 parts by mass of the toner with respect to 100 parts by mass of the carrier. .

The toner of the present invention can be used in a one-component developing system 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 to 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. .

In the case where the one-component contact developing method is used in the toner of the present invention, the peripheral speed of the surface of the roller carrying the toner and 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, 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 system which can be used for the toner of the present invention, in the one-component developing system, when a rigid roller is used as a 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 desirable 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 the two-component developing method will be specifically described. What is the two-component development method?
This method uses a toner and a carrier (having a role as a charge imparting material and a toner conveying material), and uses a magnetic material or glass beads as the carrier. The developer (toner and carrier) is agitated by the developer agitating member to generate a predetermined amount of charge, and is conveyed to the developing site by the 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, and makes contact with the electrostatic latent image holding member or opposes it at a predetermined interval in a non-contact state, thereby developing and visualizing 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 photoreceptor 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 adhesiveness 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 thiopyrylium salt, a triphenylmethane dye, selenium,
It is formed by dispersing a charge generating substance such as an inorganic substance such as amorphous silicon or the like in a suitable binder and coating, or by vapor deposition or the like. Of these, phthalocyanine pigments are preferred. The amount of the binder is desirably 80% by mass or less, preferably 0 to 40% by mass 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. As the charge transport material, biphenylene, anthracene, pyrene, polycyclic aromatic compounds having a structure such as phenanthrene, indole, carbazole, oxadiazole, nitrogen-containing cyclic compounds such as pyrazoline, a hydrazone compound, Examples include styryl compounds, selenium, selenium-tellurium, amorphous silicon, and cadmium sulfide.

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 in combination 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 mass, more preferably from 5 to 80% by mass, based on the total mass 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 surface layer can be applied 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 a direct charging means, a method using a charging blade,
There is 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 , A rubber or sponge such as butyl rubber, a styrene-butadiene thermoplastic elastomer, a polyurethane-based thermoplastic elastomer, a polyester-based thermoplastic elastomer, an ethylene-vinyl acetate-based thermoplastic elastomer, and the like. the, the volume resistivity of 10 ⁷ Ω · cm
Below, it is desirably 10 ⁶ Ω · cm or less.

For example, a metal vapor-deposited film, a conductive particle-dispersed resin, a conductive resin, or the like is used. Specific examples include a vapor-deposited film of aluminum, indium, nickel, copper, iron, and the like, and a conductive particle-dispersed resin. Is carbon, aluminum, nickel, conductive particles such as titanium oxide, urethane, polyester, vinyl acetate-vinyl chloride copolymer,
Examples thereof include those dispersed in a resin such as polymethyl methacrylate. As the conductive resin, quaternary ammonium salt-containing polymethyl methacrylate, polyvinyl aniline,
Polyvinylpyrrole, polydiacetylene, polyethyleneimine and the like can be mentioned. The resistance layer is, for example, a layer having a volume resistivity of 10 ⁶ to 10 ¹² Ω · cm, and a 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 a 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 of the present invention to which the toner for electrostatic image development can be applied 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 in which the surface of a photoreceptor uses an organic compound. 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. Due to the excellent charge control effect, the toner (1) has very little transfer residue of the toner and is excellent in transfer efficiency.

Examples of the surface material of the photoreceptor used in the image forming apparatus applicable to the toner for developing electrostatic images of the present invention include silicone resin, vinylidene chloride, ethylene-vinyl chloride, styrene-acrylonitrile, styrene- Methyl methacrylate, styrene, polyethylene terephthalate and polycarbonate and the like,
The present invention is not limited to these, and other monomers or copolymers and blends of the above-mentioned binder resins can be used. The toner of the present invention has a diameter of 50.
It is also effectively used for an image forming apparatus having a photoconductor having a small diameter of not more than mm. A known intermediate transfer belt can be used as a means for achieving color superposition when forming a color image.

As the cleaning member used in the image forming apparatus applicable to the electrostatic image developing toner 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 adopted as a method of cleaning the electrostatic image holder. Although it can be applied to efficient blade cleaning, as a means for easily improving these cleaning defects by toner, appropriate control is performed without excessively increasing the charge of the toner remaining on the photoreceptor without being transferred. It 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 is provided with a releasability, and the contact angle of water on the surface of the photoreceptor 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 increasing the load on cleaning. When the toner of the present invention is used, the occurrence of defective cleaning can be more reliably prevented.

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 as a charge transport layer of a function-separated organic photoreceptor, a surface layer composed of a charge transport material and a resin is provided. In some cases, a protective layer as described above may be further 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, compounds containing a fluorine atom, such as introducing a fluorine-containing group, a silicone-containing group, etc. into the structure of the resin, adding a surfactant, etc., ie, polyfluoroethylene, polyvinylidene fluoride, The surface layer is made of carbon or the like. By these means, the contact angle of the surface of the photoreceptor with water can be made 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, and the like.
Phenol resins, silicone resins, epoxy resins, vinyl acetate resins, and the like. It is preferably 1 to 60% by mass, more preferably 2 to 50% by mass, based on the total mass of the charge generation layer and the surface layer. When the amount is less than 1% by mass, the residual transfer toner is not sufficiently reduced, the cleaning efficiency of the residual transfer toner is not sufficient, the ghost prevention effect is insufficient, and the amount is 60% by mass.
Exceeding the range is not preferred because the strength of the film is reduced and the amount of light incident on the photoreceptor is significantly reduced. The particle size of the powder is preferably 1 μm or less, more preferably 0.5 μm or less from the viewpoint of image quality. 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 an image forming apparatus applicable to the toner for developing an electrostatic image of the present invention, a conventionally known method can be employed. 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 including a pressing member that is in pressure contact with a heating body and that 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 fluorine-based resin, and the surface of the roller is further coated with silicone. It is extremely effective to supply an offset preventing liquid such as oil and cover the roller surface with a thin film of the liquid. 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 image of the present invention, in terms of image quality and productivity of the toner, in the measurement using a laser type particle size distribution analyzer such as 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.

Regarding 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.),
It is desirable that the particles having a particle size of 1 μm or less are in the range of 10 to 90% on a number basis, and the content of 12.7 μm or more is 0% on a volume basis.
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 a range of 1.2 to 5.0 m ² / g in a BET specific surface area measurement using nitrogen as a desorption 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 image of the present invention, the apparent specific gravity (bulk density) is measured by using, for example, a powder tester (manufactured by Hosokawa Micron Co., Ltd.) by using a container attached to the measuring device. The measurement was performed according to the instruction manual.
0.2 to 0.6 g / ml for non-magnetic toner and 0.2 to 0.6 g / ml for magnetic toner, depending on the type and content of magnetic powder.
Those having a range of 2.0 g / ml 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 / ml,
In the case of a magnetic toner, it is preferably in the range of 0.9 to 4.0 g / ml, 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,
Put it in a tableting machine of 0mmφ, and 196 × 10 ⁵ under vacuum
Compression molding is performed while applying a pressure of Pa (200 kgf / cm 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, as a flowing angle of repose and a static 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 indicating the shape factor of the toner are magnified 1000 times using, for example, an optical microscope equipped with a CCD camera (for example, BH-2 manufactured by Olympus Corporation). 30 product particles per field
Sampling is performed so that the number of images becomes about one, and the obtained image is transferred to an image analyzer (Luzex FS) manufactured by Nireco, and the maximum length (maximum length ML of a particle) in the image of one particle, the area of the image of one particle ( The numerical value of each toner particle is calculated according to the following equation based on the numerical value obtained by measuring the projected area A of the particle and the peripheral length of the image of one particle (perimeter PM of the particle),
This measurement operation is repeated until about 3000 particles are obtained for one product, and the average value of the numerical values of all the particles is used as the shape factor SF-1 and SF-2 of each toner.

SF-1 = [(ML ² × π) / 4A] × 100 (where ML is the maximum length of a particle and A is the projected area of one particle) SF-2 = (PM ² / 4Aπ) ) × 100 (where PM represents the perimeter of the particle, and A represents the projected area of one particle.)

SF-1 represents the strain of the particles. 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 (eg, SE-70 manufactured by Ando Electric Co., Ltd.).
339A) is defined as a value after one hour has passed when a DC voltage of 100 V is continuously applied.

The toner for developing an electrostatic image of the present invention has a dielectric loss tangent of 1.0 × 10 ⁻³ to 1.0 × 10 ^{−3 in} the case of a non-magnetic toner.
The range is preferably 15.0 × 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.
-3 to 30 × 10 ^-3 is desirable. In this case, the toner volume resistivity is determined by compressing the toner particles to obtain a diameter of 50%.
A disk-shaped test piece having a thickness of 2 mm and a thickness of 2 mm was prepared, set on a solid electrode, and measured with an LCR meter (4284A, manufactured by Hewlett-Packard Company) at a measurement frequency of 1 mm.
It is defined as a dielectric loss tangent value (Tan δ) obtained when measured at KHz and 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 charge image of the present invention has a toner melt index (MI value) of 10 to 150 g / 10.
The range of min is desirable. The melt index (MI value) of the toner in this case is defined by JIS K-7210 (A
Method). 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 compressing the toner particles to produce a cylindrical test piece having a diameter of 10 mm and a thickness of 20 mm, and using a heat-melting characteristic measuring apparatus such as a flow tester (CFT-500C manufactured by Shimadzu Corporation). It is defined as the value at which melting starts when the piston is set and measured at a load of 196 × 10 ⁴ Pa (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 a 4 mm drop temperature.

The toner for developing an electrostatic image of the present invention preferably has a glass transition temperature (Tg) of 45 to 80 ° C., more preferably 55 to 75 ° C. In this case, the glass transition temperature of the toner was measured using a differential thermal analyzer (D
SC), the temperature is raised at a constant temperature, then quenched, and then determined 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 deteriorate, and when the Tg exceeds 80 ° C., the fixing strength of the image decreases.

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 mass average molecular weight (Mw). At this time, Mw indicating the molecular weight distribution is used.
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 a toner,
First, a certain amount of toner particles is dissolved in an organic solvent such as THF. At this time, insolubles are filtered with a filter, and only the dissolved materials are measured using GPC (gel permeation chromatography). Defined as analysis value.

The toner for developing an electrostatic image of the present invention comprises tetrahydrofuran (TH) among 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 terms of mass average molecular weight (Mw). At this time, the range of Mw / Mn showing the molecular weight distribution is 3 to 500.
Is better. 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.
It is preferably 30% by mass.

The toner for developing an electrostatic image of the present invention has a melt viscosity of 100 to 500 Pa · s (1000 to 50 Pa · s).
000 poise), more preferably 15
0-3800Pa / s (1500-38000 poise)
Range. 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 same in a heat melting property measuring apparatus, for example, a flow tester (CFT-500C manufactured by Shimadzu Corporation). And
It is defined as a value measured at a load of 196 × 10 ⁴ Pa (20 kgf / cm ² ).

In the toner for developing an electrostatic image of the present invention, the amount of the calcium product of the present invention, which is a charge controlling agent, present on the toner surface is preferably at least 2.0 mg / g of the toner. Those that are present at 2.5 mg or more are particularly preferred. The amount of calcium product on the toner surface (surface abundance) is determined by using an organic solvent that is insoluble in the resin, colorant, and wax of the toner and dissolves only the calcium product, for example, methyl alcohol. The object is sufficiently washed, and the concentration of the washing solution is quantified by a colorimetric method using a fluorescence spectrophotometer or the like.

For example, the surface abundance of the calcium product of the present invention is measured as follows. First, a methanol solution of each of 2, 5, 10 and 20 ppm of the calcium product of the present invention is prepared. This solution is measured using a fluorescence spectrophotometer. A calibration curve is drawn from the solution concentration and the maximum fluorescence intensity at this time. Next, 0.2 g of the toner containing the calcium product in each Example and Comparative Example was precisely weighed in a beaker, 20 ml of methanol was poured, and the mixture was slightly blended with the toner. Extract the calcium product from the surface. Filter this extract with filter paper (5B)
Natural filtration using. All the toner remaining in the beaker is also washed with methanol (30 ml) and filtered together. The filtration residue is washed with methanol (50 ml), and all calcium compounds on the toner surface are extracted to the filtrate side. After the filtrate is made up to 100 ml with methanol, the maximum fluorescence intensity of the filtrate is measured, and the amount of calcium product present on the surface of 1 g of the toner is calculated from the methanol calibration curve.

The toner for developing an electrostatic image of the present invention preferably has a calcium-based product, which is a charge control agent of the present invention, present on the surface of the toner and has a volume-based average particle diameter of 0.05 μm to 3 μm.

The particle size of the calcium product present on the toner surface can be measured as follows. First, a certain amount of toner is heat-melted into a thin film, which is magnified to about 500 times using, for example, a polarizing microscope equipped with a CCD camera (Olympus BH-2). Make it identifiable. The obtained image is transferred to a Nireco image analyzer (Luzex FS), and the particle size distribution of calcium product particles is calculated by image analysis.

In the same manner, the toner obtained by extracting only the calcium product from the toner surface is formed into a thin film by heat melting, and the particle size distribution at this time is also measured. From the difference between the particle size distribution of the calcium product present in the entire toner thus obtained and the distribution of the calcium compound present only inside the toner, the particle size distribution of the calcium product present on the toner surface is estimated, The average particle size at this time is defined as the average particle size of the calcium product present on the toner surface.

The solvent-dissolved residue of the toner of the present invention is 0 to 30% by mass as a tetrahydrofuran (THF) -insoluble content.
It is preferable that the content is in the range of 0 to 40% by mass as the ethyl acetate insoluble content and 0 to 30% by mass 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. The toner is quantified, and the ratio of the insoluble matter in the organic solvent in the toner is calculated from this value.

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, a paint for electrostatic coating using this charge enhancer is excellent in environmental resistance, storage stability, especially thermal stability and durability, has a coating efficiency of 100%, and has a thick film free from coating defects. Can be formed.

[0151]

Hereinafter, the present invention will be described with reference to Examples.
They do not limit the invention in any way. (Hereinafter, all parts are parts by mass)

Production Example 1 21 parts of 3,5-di-tert-butylsalicylic acid and 25 parts of
14 parts of sodium hydroxide was added to 100 parts of water, and the temperature was increased to 70 ° C. to adjust the pH to about 7.5. 3,5-
After confirming that di-tert-butylsalicylic acid was completely dissolved, the solution temperature was lowered to 30 ° C., and 8 parts of calcium chloride dihydrate was dissolved in 70 parts of water. And the 3,5-di-t with sufficient stirring.
A sodium hydroxide solution of tert-butylsalicylic acid was added dropwise. After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the temperature at 30 ° C. to cause a reaction. The precipitated crystals were filtered, washed with water, and dried to obtain 22 parts of white crystals. The melting point of this product is 300 ° C
That was all.

The result of elemental analysis of this product was as follows.
6% and 8.0% hydrogen. As a result of analyzing coordination water by the Karl Fitzcher method, it was 6.27%.
When IR measurement was performed on this product, the chart shown in FIG. 1 was obtained. When a proton NMR measurement was performed on this product, a characteristic spectrum shown in FIG. 2 was obtained. In the measurement, heavy methanol was used as the solvent,
The measurement was performed at a temperature of 25.6 ° C. X for this product
When the measurement was performed by the line diffraction, the chart of FIG. 3 was obtained.

The obtained white crystalline calcium product was pulverized to about 5 μm using a pot mill, and the shape factor (SF-1) was measured by the following method. A white crystal crushed to about 5 μm is placed on a slide glass so as to be uniform. The magnification of the optical microscope was adjusted so that about 30 particles were observed in one field of view of the optical microscope, and about 3 particles were obtained using an image analyzer (Nileco: Luzex FS).
The shape factor (SF-1) was statistically calculated for 000 particles. At this time, the average value of about 3000 shape factors (SF-1) is 226, and the shape factor (SF-
The average value of 2) was 152. A scanning electron micrograph is shown in FIG.

Production Example 2 21 parts of 3,5-di-tert-butylsalicylic acid and 25 parts of
14 parts of sodium hydroxide was added to 100 parts of water, the temperature was raised to 70 ° C., and the pH was adjusted to about 7.5. After confirming that 3,5-di-tert-butylsalicylic acid was completely dissolved, the solution temperature was lowered to 10 ° C., and adjusted to 10 ° C. by dissolving 8 parts of calcium chloride dihydrate in 70 parts of water. In a warm solution, the 3,5-di-te
A sodium hydroxide solution of rt-butylsalicylic acid was added dropwise. After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the temperature at 10 ° C. to cause a reaction. The precipitated crystals are filtered, washed with water, dried and dried.
Three parts of white crystals were obtained. The average value of the shape factor (SF-1) calculated by the same method as in Production Example 1 was 243, and the average value of the shape factor (SF-2) was 175.

Production Example 3 21 parts of 3,5-di-tert-butylsalicylic acid and 25 parts
14 parts of sodium hydroxide was added to 100 parts of water, the temperature was raised to 70 ° C., and the pH was adjusted to about 7.5. After confirming that 3,5-di-tert-butylsalicylic acid was completely dissolved, the solution temperature was maintained at 70 ° C., and calcium chloride 2
In a solution of 8 parts of hydrate dissolved in 70 parts of water, the temperature of which was adjusted to 70 ° C., with sufficient stirring, the 3,5-di-tert
A solution of -butylsalicylic acid in sodium hydroxide was added dropwise. After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the temperature at 70 ° C. to cause a reaction. The precipitated crystals are filtered, washed with water, dried and dried.
Some white crystals were obtained. The average value of the shape factor (SF-1) calculated by the same method as in Production Example 1 was 249, and the average value of the shape factor (SF-2) was 190.

Comparative Production Example 1 21 parts of 3,5-di-tert-butylsalicylic acid and 25 parts
14 parts of sodium hydroxide was added to 100 parts of water, the temperature was raised to 70 ° C., and the pH was adjusted to about 7.5. After confirming that 3,5-di-tert-butylsalicylic acid was completely dissolved, the temperature of the solution was raised to 8 ° C., and calcium chloride 2
The above-mentioned sodium hydroxide solution of 3,5-di-tert-butylsalicylic acid was added dropwise to a solution adjusted to 80 ° C. in which 8 parts of hydrate was dissolved in 80 parts of water while stirring sufficiently. After completion of the dropwise addition, stirring was continued for 1 hour while maintaining the temperature at 80 ° C. to cause a reaction. The precipitated crystals were filtered, washed with water, and dried to obtain 22 parts of white crystals. The average value of the shape factor (SF-1) calculated by the same method as in Production Example 1 was 268, and the shape factor (SF
The average value of -2) was 206.

Comparative Production Example 2 3,5-Di-tert-butylsalicylic acid 21 parts and 25 parts
14 parts of sodium hydroxide was added to 100 parts of water, the temperature was raised to 70 ° C., and the pH was adjusted to about 7.5. After confirming that 3,5-di-tert-butylsalicylic acid was completely dissolved, the mixture was cooled to 30 ° C. A solution prepared by dissolving 8 parts of calcium chloride dihydrate in 70 parts of water and adjusting the temperature to 30 ° C. was dropped into the sodium hydroxide solution of 3,5-di-tert-butylsalicylic acid with stirring. The mixture was stirred and reacted at 30 ° C. for 1 hour. The precipitated crystals were filtered, washed with water, and dried to obtain 22 parts of white crystals. As in Production Example 1, the obtained white crystals were crushed to about 5 μm, placed evenly on a slide glass, and the magnification was adjusted so that about 30 particles were observed in one visual field of an optical microscope. Using an image analyzer,
The shape factors (SF-1) and (SF-2) were statistically calculated for about 3000 particles. The calculated shape factor (SF
The average value of -1) is 292, and the shape factor (SF-2)
Was 209. The scanning electron micrograph is shown in FIG.

Comparative Production Example 3 20 parts of 3,5-di-tert-butylsalicylic acid was added to 50 parts of
200% ethanol water was added, and the temperature was raised to 60 to 65 ° C to dissolve. Gradually add 4 parts of calcium carbonate and add
The crystals precipitated by stirring at 0 to 65 ° C for 2 hours are filtered, washed with water,
Drying yielded 9 parts of white crystals. The average value of the shape factor (SF-1) calculated by the same method as in Production Example 1 was 285, and the average value of the shape factor (SF-2) was 214.

Example 1 91 parts of styrene-acrylic copolymer resin (acid value 0.1) (trade name, CPR-100, manufactured by Mitsui Chemicals, Inc.) 1 part of the product obtained in Production Example 1 1 part of carbon black 5 Part (trade name, MA-100, manufactured by Mitsubishi Chemical Corporation) Low molecular weight polypropylene 3 parts (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) The above mixture is melt-mixed with a heating and mixing apparatus at 140 ° C., and the cooled mixture is hammered. It was coarsely ground in a mill. Further, after finely pulverized by a jet mill, the mixture was classified and the volume average particle size was 9
A black toner of ± 0.5 μm was obtained. This toner was mixed with a non-coated ferrite carrier (trade name, F-100, manufactured by Powder Tech) and a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech) at a ratio of 4 to 100 parts each. After the mixture was shaken to negatively charge the toner, the measurement was performed with a blow-off powder charge amount measuring device. The results are shown in Table 1.

For the above toner, methanol solutions were prepared at concentrations of 2, 5, 10 and 20 ppm of a calcium product as a charge controlling agent. This solution was measured using a fluorescence spectrophotometer, and a calibration curve was prepared from the solution concentration and the maximum fluorescence intensity. Next, 0.2 g of the toner of Example 1 containing this charge control agent was precisely weighed in a beaker, and 20 ml of methanol was poured into the beaker. From which the calcium product was extracted. This extract was subjected to natural filtration using paper (5B), and the toner remaining in the beaker was also removed from methanol (30 B).
ml) and filtered together. The residue was washed with methanol (50 ml), and the charge control agent on the toner surface was entirely extracted to the filtrate side. After the filtrate was made up to 100 ml with methanol, the maximum fluorescence intensity of the filtrate was measured, and the amount of calcium product present on the surface of 1 g of the toner was calculated from the methanol calibration curve. The amount of the charge control agent present on the surface of the toner (toner surface existing amount) was 2.92 (mg / 1 g).
Toner).

Examples 2-3 The "product obtained in Production Example 1" described in Example 1 was
The product obtained in Production Example 2 and the product obtained in Production Example 3 were changed, and the toner was produced in the same manner as in Example 1 except for the amounts added, except that they were changed to Examples 2 and 3, respectively. Adjust,
It was measured by a blow-off powder charge measuring device. Table 1 shows the results
It was shown to. The amount of the charge control agent present on the surface of the toner of Example 2 was 2.64 (mg / 1 g toner). The amount of the charge control agent present on the surface of the toner of Example 3 was 2.54 (mg / 1 g toner).

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 the product obtained in Comparative Production Example 1 1 part of carbon black 5 Part (trade name, MA-100, manufactured by Mitsubishi Chemical Corporation) Low molecular weight polypropylene 3 parts (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) The above mixture is melt-mixed with a heating and mixing apparatus at 140 ° C., and the cooled mixture is hammered. It was coarsely ground in a mill. Further, after finely pulverized by a jet mill, the mixture was classified and the volume average particle size was 9
A black toner of ± 0.5 μm was obtained. This toner was mixed with a non-coated ferrite carrier (trade name, F-100, manufactured by Powder Tech) and a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech) at a ratio of 4 to 100 parts each. After mixing and shaking to charge the toner negatively, the toner was measured with a blow-off powder charge measuring device. The results are shown in Table 1. The amount of the charge control agent present on the surface of the toner was 1.92 (mg / 1 g toner).

Comparative Examples 2 and 3 "Product obtained in Comparative Production Example 1" described in Comparative Example 1
Was changed to the product obtained in Comparative Production Example 2 and the product obtained in Comparative Production Example 3, and Comparative Examples 2 and 3 were respectively used. The toner was adjusted by the method described above, and measured by a blow-off powder charge amount measuring device. The results are shown in Table 1. The amount of the charge control agent present on the toner surface of Comparative Example 2 was 1.99 (mg / 1 g toner), and the amount of the charge control agent present on the toner surface of Comparative Example 3 was 1.99 (mg / 1 g toner). )Met.

[0165]

[Table 1]

Example 4 100 parts of styrene-acrylic copolymer resin (acid value 0.1) (trade name, CPR-100, manufactured by Mitsui Chemicals, Inc.) 2 parts of the product obtained in Production Example 1 Magnetic iron oxide 90 parts Low molecular weight polypropylene 3 parts (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) The above mixture was melt-mixed with a heating and mixing device at 140 ° C., and the cooled mixture was roughly pulverized with a hammer mill. Further, after finely pulverized by a jet mill, the mixture was classified and the volume average particle size was 9
A black toner of ± 0.5 μm was obtained. This toner was mixed with a non-coated ferrite carrier (trade name, F-100, manufactured by Powder Tech) and a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech) at a ratio of 4 to 100 parts each. After mixing and shaking to charge the toner negatively, the toner was measured with a blow-off powder charge measuring device. The results are shown in Table 2.

Examples 5 to 6 "Product obtained in Production Example 1" described in Example 4
The product obtained in Production Example 2 and the product obtained in Production Example 3 were changed, and the toner was prepared in the same manner as in Example 4 except for the amounts added, except that Examples 5 and 6 were used. Adjust,
It was measured by a blow-off powder charge measuring device. Table 2 shows the results
It was shown to.

Comparative Example 4 100 parts of styrene-acrylic copolymer resin (acid value 0.1) (trade name, CPR-100, manufactured by Mitsui Chemicals, Inc.) 2 parts of the product obtained in Comparative Production Example 1 Iron 90 parts Low molecular weight polypropylene 3 parts (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) The above mixture was melt-mixed with a heating and mixing device at 140 ° C., and the cooled mixture was roughly pulverized with a hammer mill. Further, after finely pulverized by a jet mill, the mixture was classified and the volume average particle size was 9
A black toner of ± 0.5 μm was obtained. This toner is coated with a non-coated ferrite carrier (trade name, F-100, manufactured by Powder Tech) and a silicon-coated ferrite carrier (trade name, F96-100, manufactured by Powder Tech)
The toner was charged negatively after mixing and shaking at a ratio of 4 to 100 parts, respectively, and then measured by a blow-off powder charge measuring device. The results are shown in Table 2.

Comparative Examples 5 and 6 "Product obtained in Comparative Production Example 1" described in Comparative Example 4
Was changed to the product obtained in Comparative Production Example 2 and the product obtained in Comparative Production Example 3, and the same as Comparative Example 4 including the added amount except that Comparative Examples 5 and 6 were used, respectively. The toner was adjusted by the above method, and measured by a blow-off powder charge amount measuring device. The results are shown in Table 2.

[0170]

[Table 2]

(Evaluation of Image Characteristics by Non-Magnetic Two-Component Development Method) A silicon-coated ferrite carrier (trade name, F96) was applied to the toners produced in Examples 1 to 3 and Comparative Examples 1 to 3.
-100, manufactured by Powder Tech Co., Ltd.), and image characteristics were evaluated by a non-magnetic two-component developing system using a developer mixed at a ratio of 4: 100 parts. The image forming apparatus used for the evaluation of image characteristics was modified from a commercially available non-magnetic two-component developing type copying machine.
The photosensitive member surface potential, the developing roller applied voltage, the transfer voltage, and the fixing temperature were arbitrarily controllable, and various conditions were set so that printing was best in the initial image. After printing the test chart for the tenth sheet (initial image) and continuous printing of 5,000 sheets, start printing the test chart while continuously supplying toner.
Images after continuous printing of 20,000 sheets were sampled, and image characteristics were evaluated.

The image density was determined by using a plain paper (75 g / m ² ) and sampling the image after printing a predetermined number of sheets.
The solid black portion was measured using a Macbeth reflection densitometer (RD-918, manufactured by Sakata Inx Co., Ltd.). The fog density was obtained by measuring the reflection density of an unprinted portion, and subtracting the reflection density (0.05) of plain paper before printing as a base value from this value. The fine line reproducibility was evaluated based on whether or not a 30 μm fine line of the test chart could be faithfully reproduced. The occurrence of memory was visually observed. The results are shown in Table 3. In Table 3, the fine line reproducibility is indicated by ○ for those that can be faithfully reproduced, and × for those that cannot be faithfully reproduced.

[0173]

[Table 3]

In Examples 1 to 3, the image density is in the range of 1.40 to 1.45, which is desirable for a copying machine, and is excellent. Further, in long-term continuous printing, there is almost no change in density and the printing is stable. The fog density value is also very low and does not increase even in continuous printing. Good fine line reproducibility,
stable. No signs of occurrence of memory, which is image deterioration due to repetition, were observed at all.

In Comparative Examples 1 and 2, satisfactory images were obtained as the initial images, but when 5,000 sheets of continuous printing were performed, the image density slightly decreased and the fog density increased. After the continuous printing of 20,000 sheets was further performed, these image deteriorations became more remarkable, and reached a problematic level. Fine line reproducibility was greatly degraded by long-term continuous printing.

In Comparative Example 3, a satisfactory image could not be obtained from the initial image, and further deterioration occurred in continuous printing. After 20,000 sheets, deterioration of fine line reproducibility and generation of memory due to poor cleaning were also confirmed.

(Evaluation of Image Characteristics by Magnetic One-Component Development Method) Using the toners produced in Examples 4 to 6 and Comparative Examples 4 to 6, image characteristics were evaluated by the magnetic one-component development method.
The image forming apparatus applied in this embodiment is a modification of a commercially available magnetic one-component developing system printer (resolution: 600 dpi).
The photosensitive member surface potential, the developing roller applied voltage, the transfer voltage, and the fixing temperature were arbitrarily controllable, and various conditions were set so that printing was best in the initial image.

For printing, a test chart was transferred from a personal computer while toner was continuously supplied. Sampling the initial image from the start of printing to 10 sheets, and the image after 5,000 sheets after continuous printing of 1000 sheets,
The image characteristics were evaluated. Image density is plain paper (75 g / m
² ) The image after printing a predetermined number of sheets was sampled, and the solid black portion was measured using a Macbeth reflection densitometer (RD-918, manufactured by Sakata Inx Co., Ltd.). Also,
The fog density is obtained by measuring the reflection density of an unprinted portion, and using this value as a base value, the reflection density of plain paper before printing (0.0%).
5) was subtracted. The dot reproducibility was an evaluation as to whether the dots in the test chart could be faithfully reproduced, and the dot reproduction was determined based on whether or not an isolated dot pattern of about 50 μm could be reproduced without loss. Out of about 50 dots, 10% or more of the defective dots were regarded as bad, and less than 10% were regarded as good. Regarding the state of memory generation, the presence or absence was checked by visual observation. The results are shown in Table 4.

[0179]

[Table 4]

In Examples 4 to 6, the image density is in the range of 1.45 to 1.55, which is desirable for a printer, and is good. Further, in long-term continuous printing, there is almost no change in density and the printing is stable. The fog density value is also extremely low and does not increase even in continuous printing. The dot reproducibility is also good and stable. No sign of occurrence of memory, which is image deterioration due to repetition, was observed.

In Comparative Examples 4 and 5, satisfactory images were obtained as the initial images, but the image density decreased and the fog density increased when 1,000 sheets were continuously printed. After further continuous printing of 5,000 sheets, these image deteriorations became even more remarkable and reached a problematic level. The dot reproducibility was greatly deteriorated by long-term continuous printing.

In Comparative Example 6, a satisfactory image was obtained as the initial image, but image deterioration rapidly advanced in continuous printing. 5
In the image after 1,000 sheets, deterioration of dot reproducibility and generation of memory due to defective cleaning were confirmed.

[0183]

The charge control agent of the present invention does not contain heavy metals such as chromium, is pale white and can be used for color toners, and has a high charge imparting effect. Further, the toner of the present invention containing the charge control agent can obtain an image excellent in evaluation of image characteristics such as image density and fog density in any one-component or two-component development system.

[Brief description of the drawings]

FIG. 1 is a chart showing a chart obtained by IR measurement of a product obtained in Production Example 1.

FIG. 2 is a characteristic spectrum diagram of the product obtained in Production Example 1 obtained by proton NMR measurement.

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

FIG. 4 is a view showing a scanning electron micrograph of a product obtained in Production Example 1.

FIG. 5 is a view showing a scanning electron micrograph of a product obtained in Comparative Production Example 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideyuki Otsuka 45, Miyukigaoka, Tsukuba, Ibaraki Pref.Hodogaya Chemical Industry Co., Ltd.Tsukuba Research Laboratories (72) Inventor Mitsutoshi Anzai 45, Miyukigaoka, Tsukuba, Ibaraki F-term in Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Laboratory (reference) 2H005 AA05 AA21 CA02 CA14 CA25 CA30 DA02 EA10 FA01 FA05

Claims (13)

[Claims] 1. A reaction product of an aromatic hydroxycarboxylic acid and a calcium compound, wherein the aromatic hydroxycarboxylic acid and the calcium compound take one or more of a coordination bond, a covalent bond and an ionic bond. A charge control agent, wherein the average value of the shape factor (SF-1) calculated according to the following formula of the charge control agent is 250 or less. SF-1 = [(ML ² × π) / 4A] × 100 (where, ML represents the maximum length of a particle, and A represents the projected area of one particle.) 2. The charge control agent according to claim 1, wherein the charge control agent has an average value of shape factor (SF-2) calculated according to the following formula of 200 or less. SF-2 = (PM ² / 4Aπ) × 100 (where PM is the peripheral length of a particle, and A is the projected area of one particle.) 3. The method according to claim 2, wherein the aromatic hydroxycarboxylic acid is 3,3.
The charge control agent according to claim 1, wherein the charge control agent is 5-di-tert-butylsalicylic acid. 4. An aromatic hydroxycarboxylic acid and calcium are coordinated, covalently bonded, and a solution of an aromatic hydroxycarboxylic acid is added dropwise to a solution of a calcium compound as a metal-imparting agent and reacted. A method for producing a charge control agent comprising a reaction product of an aromatic hydroxycarboxylic acid and a calcium compound that employs one or more types of ionic bonding. 5. The method for producing a charge control agent according to claim 4, wherein the average value of the shape factor (SF-1) calculated according to the following formula of the reaction product is 250 or less. SF-1 = [(ML ² × π) / 4A] × 100 (where, ML represents the maximum length of a particle, and A represents the projected area of one particle.) 6. The method according to claim 5, wherein the average value of the shape factor (SF-2) calculated according to the following formula of the reaction product is 200 or less. SF-2 = (PM ² / 4Aπ) × 100 (where PM is the peripheral length of a particle, and A is the projected area of one particle.) 7. The method according to claim 4, wherein the solution of the aromatic hydroxycarboxylic acid is added dropwise to the solution of the calcium compound as the metal-providing agent, and the reaction temperature is 10 to 70 ° C. 2. A method for producing the charge control agent according to item 1. 8. The method according to claim 8, wherein the aromatic hydroxycarboxylic acid is 3,3.
The method for producing a charge control agent according to any one of claims 4 to 7, wherein the method is 5-di-tert-butylsalicylic acid. 9. A charge control agent selected from the charge control agent according to any one of claims 1 to 3 and a charge control agent manufactured by the method for manufacturing a charge control agent according to any one of claims 4 to 8. A toner for developing an electrostatic image, comprising at least one kind of charge control agent, a colorant and a binder resin. 10. The electrostatic image developing toner according to claim 9, further comprising a wax and / or a magnetic material in addition to the charge control agent, the colorant and the binder resin. 11. The electrostatic image developing toner according to claim 9, wherein a toner surface abundance of the charge control agent is 2.0 mg / 1 g toner or more. 12. A one-component developing method using the toner for developing an electrostatic image according to any one of claims 9 to 11. 13. A two-component developing method, comprising using the toner for developing an electrostatic image according to claim 9. Description: