JPH10153880A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrostatic latent image developing toner which shows fast rising of charges, has excellent charge stability, resistance against spent and environmental resistance and uses a negative charge controlling agent containing no heavy metals by incorporating a specified bisphenol compd. SOLUTION: This electrostatic latent image developing toner contains at least one kind of bisphenol compd. expressed by the formula. The phenol deriv. compd. is effective as a charge controlling agent for a toner, and especially as a negative charge controlling agent. In the formula, R1 to R4 are hydrogen atoms, electron-withdrawing substituents, alkyl groups, alkoxy groups, or hydroxyl groups, and at least one of R1 to R4 is an electron-withdrawing substituent, R5 and R6 are hydrogen atoms, carbon atoms having electron-withdrawing groups, or carbon atoms or oxygen atoms bonded to aryl groups having electron- withdrawing groups, and R5 and R6 may be bonded to form a double bond or ring. However, it is not allowed that both of R5 and R6 are hydrogen atoms.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel toner for developing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like, and more particularly, to a toner containing a specific bisphenol compound.

[0002]

2. Description of the Related Art Conventionally, in electrophotography, electrostatic recording, electrostatic printing, and the like, an electrostatic latent image having a positive or negative charge formed on an image carrier such as a photosensitive member by various methods has been developed. ,
The toner is developed by electrostatically adsorbing the negatively or positively triboelectrically charged toner. Generally, a toner image obtained by development is transferred onto a transfer paper and then fixed to form a developed image.

[0003] Toner used for developing an electrostatic latent image is first required to have an appropriate charge amount in order to obtain a clear developed image without fog or the like. Further, it is required that the charge amount does not change with time and that the change in environment, for example, the change in humidity does not cause significant change in charge amount such as attenuation or solidification. This is because if the charge amount attenuates from the initially set value and becomes smaller, toner scattering increases, causing problems such as background fogging and toner contamination around the developing device.

[0004] In order to meet the above demand, a charge control agent is usually added at the time of toner production. In view of the recent progress in color development of developed images, such charge control agents are required to be white or pale yellow having excellent color reproducibility.

At present, colorless, white, and pale yellow negative charge control agents that impart a negative charge are commercially available. However, most of these are metal-containing compounds containing heavy metals, for example, complexes or salts containing chromium, and a metal-free negative charge control agent containing no heavy metals is demanded from the viewpoint of safety in particular.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a toner for developing an electrostatic latent image using a negative charge controlling agent containing no heavy metal.

Another object of the present invention is to provide a toner for developing an electrostatic latent image which has a fast charge rise, and is excellent in charge stability, spent resistance and environmental resistance.

Still another object of the present invention is to provide a toner for developing an electrostatic latent image which is excellent in color reproducibility and excellent in light transmission.

[0009]

That is, the present invention provides a compound represented by the following general formula [I]:

[0010]

Embedded image

[Wherein, R _{1 to} R ₄ represent a hydrogen atom, an electron-withdrawing substituent, an alkyl group, an alkoxy group, or a hydroxyl group, and at least one of R _{1 to} R ₄ represents an electron-withdrawing substituent. Group. R ₅ and R ₆ represent a hydrogen atom, a carbon atom having an electron-withdrawing group, a carbon atom to which an aryl group having an electron-withdrawing group is bonded, and an oxygen atom. R ₅ and R ₆ may combine to form a double bond or a ring. However, R ₅ , R ₆
Except that both are hydrogen atoms. And a toner for developing an electrostatic latent image, characterized by containing a bisphenol compound represented by the formula:

[0012]

Embodiments of the present invention will be described below.

The toner for developing an electrostatic latent image of the present invention contains at least a bisphenol compound represented by the above general formula [I]. Such a bisphenol compound is useful as a charge control agent for toner, and is particularly used as a negative charge control agent.

In the general formula [I], R _{1 to} R _{4 each} represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms,
5, an alkoxy group, a hydroxyl group, and a halogen atom, a halogenated alkyl group, a halogenated alkoxy group,
Preferred examples include electron-withdrawing substituents such as a nitro group and a cyano group. At least one of R _{1 to} R ₄ is an electron-withdrawing substituent.

R ₅ and R ₆ in the above general formula are a hydrogen atom, a halogen atom, a halogenated alkyl group,
Electron-withdrawing substituents such as halogenated alkoxy groups, nitro groups, and cyano groups; and carbon-containing atoms, halogen atoms, halogenated alkyl groups, halogenated alkoxy groups, nitro groups, and cyano groups. A carbon atom or an oxygen atom having an aryl group bonded thereto is preferred. R
₅ and R ₆ may combine to form a double bond or a ring. However, the case where both R ₅ and R ₆ are hydrogen is excluded.

Specific examples of the bisphenol compound represented by the above general formula [I] include the following.

[0017]

Embedded image

[0018]

Embedded image

[0019]

Embedded image

[0020]

Embedded image

[0021]

Embedded image

[0022]

Embedded image

[0023]

Embedded image

[0024]

Embedded image

[0025]

Embedded image

[0026]

Embedded image

[0027]

Embedded image

As the bisphenol compound, the compounds exemplified above may be used alone or in combination. Further, it may be used in combination with another charge control agent, for example, a metal salicylate complex or a metal benzylate complex.

The above-mentioned bisphenol compound is synthesized in high yield by, for example, halogenating or nitrating a phenolic compound as a raw material or reacting with a bisphenol compound having a corresponding substituent as a raw material.

The bisphenol compound represented by the general formula [I] can be used for a toner obtained by a conventionally known production method. For example, a pulverized toner obtained by heating and melting a binder resin, a colorant and other components as necessary, cooling, pulverizing, and classifying,
A core comprising a suspension-polymerized toner, a fixing resin, and a colorant obtained by dispersing at least one or more monomers and a polymerization initiator that is sparingly soluble in water and easily soluble in monomers in water and performs polymerization. Capsule toner in which a substance is coated with an outer shell layer, suspension-granulated toner in which a resin solution in which a binder resin is dissolved in an organic solvent is dispersed in a dispersion medium, and granulation is performed. A non-aqueous dispersion polymerized toner obtained by dispersing a polymerization initiator which is hardly soluble and easily soluble in a monomer in a dispersion medium comprising an organic solvent or a water / organic solvent mixture, and a matrix of a thermoplastic resin. Having a dispersed phase of a thermoplastic resin dispersed in the matrix and being phase-separated from the matrix, a toner in which substantially all of the colorant is filled in the dispersed phase, at least one obtained by suspension polymerization. Resin Toner obtained by crushing after heating and aggregating the particles comprising a colorant and a colorant, a spherical toner obtained by subjecting a toner obtained by subjecting a pulverized toner to a heat treatment, a spherical toner and an irregular toner Can be applied to a toner or the like in which is mixed. The bisphenol compound may be contained in the toner, or may be adhered and fixed to the toner surface.

When the bisphenol compound is contained in the toner, the bisphenol compound as a charge control agent is added in addition to the raw materials of the toner such as a resin component and additives such as a colorant, and then the conventional method is applied. Depending on the method, a pulverization method toner, a suspension polymerization toner, a capsule toner and the like may be prepared by an ordinary method. In the case of a capsule toner, it is desirable to prepare the outer shell layer so as to contain the charge control agent.

In the embodiment in which the charge control agent is attached to the surface portion of the outer shell layer, the charge control agent is attached to the surface of the toner particles by the action of van der Waals force, electrostatic force or the like, and then the mechanical impact force is applied. The treatment may be performed by a wet method or a dry method.

Examples of the dry method apparatus that can be suitably used for such a method for immobilizing the charge control agent include a hybridization system (manufactured by Nara Machinery Co., Ltd.) to which a high-speed air impact method is applied, and an ngmill (manufactured by Hosokawa Micron Corporation). ), Mechanomill (manufactured by Okada Seiko Co., Ltd.) and the like, but are not limited thereto, and various devices can be used.

The content of the bisphenol compound represented by the general formula [I] is appropriately selected depending on the type of the toner, the toner additive, the type of the binder resin, and the like, and the developing method (two-component or one-component) of the toner. Should be,
When the toner is contained in the toner by a pulverization method, a suspension method, or the like, 0.1 to 20 parts by weight,
Preferably, it is 1 to 10 parts by weight, more preferably 1 to 5 parts by weight. If the amount is less than 0.1 part by weight, a desired charge amount may not be obtained. If the amount is more than 20 parts by weight, the charge amount may be unstable or the fixability may be reduced.

When phenol is used by adhering and fixing to the toner surface, 0.1 part by weight of the phenol is used for 100 parts by weight of the toner particles.
001 to 10 parts by weight, preferably 0.05 to 2 parts by weight,
More preferably, it is desirable to use 0.1 to 1 part by weight. If the amount is less than 0.001 part by weight, the amount of the charge control agent present on the surface of the toner particles is small, so that the charge amount may be insufficient. If the amount is more than 10 parts by weight, the charge control agent may not adhere to the toner surface. When the toner is used, the charge control agent may be peeled off from the toner surface during use.
When the charge control agent is adhered and fixed on the toner surface, a stable charge amount can be imparted by using a very small amount as described above, and the bisphenol compound is white, so that the charging performance is improved. It is possible to provide a color toner capable of forming an excellent and clear color image.

When the bisphenol compound represented by the general formula [I] is contained in the toner, it is desirably used in a particle size of 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less. When used with a particle size larger than 5 μm, the dispersion state becomes non-uniform, and various characteristics of the charge amount may be non-uniform. When the bisphenol compound is to be adhered to the toner surface, it is desirable that the particle diameter be 1 μm or less, more preferably 0.5 μm or less. When used with a particle size larger than 1 μm, it is disadvantageous in that it is uniformly adhered and fixed to the toner surface.

The bisphenol compound may be used in combination with another negative charge control agent. Further, in order to stabilize the charging property, a very small amount of a positive charge control agent may be added. As described above, when the charge control agent of the present invention is used in combination with another charge control agent, it is desirable that the total amount is within the above-mentioned usage range.

As the negative charge control agent used together with the above bisphenol compound, for example, oil black (Co
lor Index 26150), Oil Black B
Y (manufactured by Orient Chemical Co., Ltd.), salicylic acid metal complex E
-81 (manufactured by Orient Chemical Industries), thioindigo pigment, sulfonylamine derivative of copper phthalocyanine, Spiron Black TRH (manufactured by Hodogaya Chemical Industries), Bontron S-34 (manufactured by Orient Chemical Industries), Nigrosine S
O (manufactured by Orient Chemical Industries), Celes Schwarz (R) G (manufactured by Farben Fabriken Bayer),
Chromogen Schwarz ETOO (CI No. 14
645), azo oil black (R) (manufactured by National Aniline Co.), various boron compounds, calcium compounds and the like.

Examples of the positive charge control agent used together with the above bisphenol compound include Nigrosine Base EX (manufactured by Orient Chemical Industries), quaternary ammonium salt P-51 (manufactured by Orient Chemical Industries), Nigrosine, Bontron N -01 (manufactured by Orient Chemical Industries),
Sudan Chief Schwarz BB (Solvent Black 3; Color Index 26150), Fettschwarz HBN (CI No. 26150), Brilliant Spirits Schwarz TN (Fanben, Fabriken Bayer), Zavon Schwarz X (Falberge Hoechst) Co., Ltd.), alkoxylated amines, alkylamides, molybdic acid chelate pigments, imidazole compounds and the like. A small amount of the above-mentioned bisphenol compound may be added to a positively chargeable toner using such a positively charge control agent in order to stabilize the chargeability.

As the binder resin constituting the toner,
It is not particularly limited as long as it is generally used as a binder in toners, and examples thereof include styrene resins, (meth) acrylic resins, olefin resins, amide resins, carbonate resins, and polyethers. ,
Thermoplastic resins such as polysulfone, polyester resin and epoxy resin, thermosetting resins such as urea resin, urethane resin and epoxy resin, and copolymers and polymer blends thereof are used. As the synthetic resin used in the toner for developing an electrostatic latent image of the present invention, not only those in a perfect polymer state as in a thermoplastic resin, but also oligomers or prepolymers as in a thermosetting resin In addition, those containing a prepolymer, a cross-linking agent and the like partially in the polymer can also be used.

Specific examples of the monomer constituting the binder resin of the toner include the following.
That is, examples of the vinyl monomer include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, and p-TerT-. Butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p-phenyl styrene, p-phenyl styrene Examples thereof include styrene such as chlorostyrene and 3,4-dichlorostyrene and derivatives thereof, among which styrene is most preferable.

Other vinyl monomers include, for example, ethylenically unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl chlorides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride, and acetic acid. Vinyl esters such as vinyl, vinyl propionate, vinyl benzoate, and vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, n-butyl methacrylate Butyl, propyl methacrylate,
Α such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.
-Methylene fatty acid monocarboxylic acid esters, (meth) acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl methyl ketone, vinyl hexyl ketone And vinyl ketones such as methyl isopropenyl ketone; N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole and N-vinyl pyrrolidone; and vinyl naphthalenes.

Caprolactam is used as a monomer to obtain an amide resin, and terephthalic acid, isophthalic acid, adipic acid, maleic acid, succinic acid, sebacic acid, thioglycolic acid and the like are mentioned as dibasic acids. Classes include ethylenediamine, diaminoethyl ether, 1,4-diaminobenzene, 1,4
-Diaminobutane and the like.

Examples of the monomer for obtaining the urethane resin include diisocyanates such as p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate. Examples of the glycols include ethylene glycol, diethylene glycol, and propylene. Glycol and polyethylene glycol.

Examples of the monomer for obtaining the urea resin include di-isocyanates such as p-phenylene diisocyanate, p-xylene diisocyanate, and 1,4-tetramethylene diisocyanate. Examples of the diamines include ethylene diamine, diamino ethyl ether, and the like. Examples thereof include 1,4-diaminobenzene and 1,4-diaminobutane.

Further, as a monomer for obtaining an epoxy resin,
Examples of the amines include ethylamine, butylamine, ethylenediamine, 1,4-diaminobenzene, 1,4-diaminobutane, and monoethanolamine. Examples of the diepoxy include diglycidyl ether, ethylene glycol diglycidyl ether, Bisphenol A diglycidyl ether, hydroquinone diglycidyl ether and the like can be mentioned.

As the monomer for obtaining the polyester resin, the polyol component includes ethylene glycol, diethylene glycol, triethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neo Pentyl glycol, 2-ethyl-1,3-pentanediol, 2,
2,4-trimethyl-1,3-pentanediol, 1,
4-bis (2-hydroxymethyl) cyclohexane,
Examples thereof include 2,2-bis (4-hydroxypropoxyphenyl) propane, bisphenol A, hydrogenated bisphenol A, and polyoxyethylenated bisphenol A. The polybasic acid component includes maleic acid, fumaric acid,
Mesaconic acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5
-Unsaturated carboxylic acids such as benzenetricarboxylic acid,
Phthalic acid, terephthalic acid, isophthalic acid, succinic acid, adipic acid, malonic acid, sebacic acid, 1,2,4-cyclohexanetricarboxylic acid, 1,2,5-cyclohexanetricarboxylic acid, 1,2,4-butanetricarboxylic acid ,
Examples include saturated carboxylic acids such as 1,3-dicarboxy-2-methyl-2-methylcarboxypropane and tetra (methylcarboxy) methane, and their anhydrides and esters with lower alcohols. Specifically, for example, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, dimethyl terephthalate, and the like. Can be.

The polyester resin used in the present invention is not limited to one obtained by polymerizing a polyol component and another basic acid component one by one, but may be obtained by polymerizing a plurality of types. In particular, as the polybasic acid component, a combination of an unsaturated carboxylic acid and a saturated carboxylic acid, or a combination of a polycarboxylic acid and a polycarboxylic anhydride is often performed.

It is desirable to add a low molecular weight polyolefin wax to the thermoplastic resin, and the amount is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the thermoplastic resin. The bisphenol compound represented by the above general formula [I] for these compositions is
It shows good negative charge controllability, and can provide sufficient chargeability for practical use.

The resin constituting the toner includes PVC resistance,
Polyester resins have attracted attention from the viewpoint of translucency as a translucent color toner and adhesion to an OHP sheet.
These polyester resins have a glass transition temperature of 55 to 70 ° C. and a softening point of 8 when used for translucent toner.
It is desirable to use a linear polyester at 0 to 150 ° C. When used as an oilless fixing toner, the glass transition temperature is 55 to 80 ° C., and the softening point is 80 to 150.
It is desirable that the gelling component contains 5 to 20% by weight at a temperature of 5 ° C.

When used as a low-temperature fixing toner,
It is desirable to use a toner having a flow starter temperature of 100 ° C. or lower and a softening point of 110 ° C. or lower as a toner constituent resin.

The bisphenol compound is obtained by graft polymerization and / or block polymerization of a vinyl monomer component containing a vinyl monomer and an amino group-containing vinyl monomer onto an unsaturated polyester component comprising at least an aliphatic unsaturated dibasic acid and a polyhydric alcohol. It can also be used for a toner composed of a vinyl-modified polyester resin obtained by polymerization.

As the colorant contained in the toner, various kinds of organic or inorganic pigments and dyes as shown below can be used.

That is, as the black pigment, carbon black, copper oxide, manganese dioxide, aniline black,
Activated carbon and the like.

Examples of the yellow pigments include graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, banza yellow G, banza yellow 10G, benzidine yellow G, and benzidine. Yellow GR, Quinoline Yellow Lake, Permanent Yellow N
There are CG and tartrazine lake.

Examples of the orange pigment include red yellow lead, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indaslen brilliant orange RK, benzidine orange G, and indaslen brilliant orange GK.

Red pigments include red iron, cadmium red, lead red, mercury sulfide, cadmium, permanent red 4R, lithol red, pyrazolone red, watching red, calcium salt, lake red D, brilliant carmine 6B, oxi lake, rhodamine lake. B, Alizarin Lake, Brilliant Ant Carmine 3B and the like.

The purple pigment includes manganese purple, fast violet B, methyl violet lake and the like.

As blue pigments, navy blue, cobalt blue, alka blue lake, victoria blue lake,
Phthalocyanine blue, metal-free phthalocyanine blue,
Phthalocyanine blue partially chlorinated product, Fast Sky Blue, Indaslen Blue BC, and the like.

The green pigment includes chrome green, chromium oxide, pigment green B, malachite green lake, final yellow green G, and the like.

As white pigments, zinc white, titanium oxide,
Examples include antimony white and zinc sulfide.

The extender includes baryte powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.

Various dyes such as basic, acidic, disperse, and direct dyes include nigrosine, methylene blue, rose bengal, quinoline yellow, and ultramarine blue.

These colorants can be used alone or in combination of two or more. However, the colorants are used in an amount of 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin constituting the toner. Is desirable. If the amount is more than 20 parts by weight, the fixability of the toner may be reduced.
If the amount is less than 1 part by weight, a desired image density may not be obtained.

When used as a translucent color toner, pigments and dyes of various colors and colors as described below can be used as the colorant.

As the yellow pigment, C.I. I. 10316
(Naphthol yellow S), C.I. I. 11710 (Hanza Yellow 10G), C.I. I. 11660 (Hanza Yellow 5G), C.I. I. 11670 (Hanza Yellow 3
G), C.I. I. 11680 (Hanza Yellow G), C.I.
I. 11730 (Hanza Yellow GR), C.I. I. 11
735 (Hanza Yellow A), C.I. I. 11740 (Hanza Yellow RN), C.I. I. 12710 (Hanza Yellow R), C.I. I. 12720 (Pigment Yellow L), C.I. I. 21090 (benzidine yellow),
C. I. 21095 (benzidine yellow G), C.I.
I. 21100 (benzidine yellow GR), C.I. I.
20040 (Permanent Yellow NCG), C.I. I.
21220 (Vulcan Fast Yellow 5), C.I. I.
21135 (Vulcan Fast Yellow R).

Examples of red pigments include C.I. I. 12055
(Stalin I), C.I. I. 12075 (permanent orange), C.I. I. 12175 (Resole Fast Orange 3GL), C.I. I. 12305 (Permanent Orange GTR), C.I. I. 11725 (Hansa Yellow 3
R), C.I. I. 21165 (Vulcan Fast Orange GG), C.I. I. 21110 (benzidine orange G), C.I. I. 12120 (permanent red 4
R), C.I. I. 1270 (Para Red), C.I. I. 12
085 (Fire Red), C.I. I. 12315 (Brilliant Fast Scarlet), C.I. I. 1231
0 (permanent red FR2), C.I. I. 12335
(Permanent red F4R), C.I. I. 12440
(Permanent red FRL), C.I. I. 12460
(Permanent red FRLL), C.I. I. 12420
(Permanent mosquito F4RH), C.I. I. 12450 (Light Fast Red Toner B), C.I. I. 12490
(Permanent carmine FB), C.I. I. 15850
(Brilliant Carmine 6B).

Examples of blue pigments include C.I. I. 7410
0 (metal-free phthalocyanine blue), C.I. I. 7416
0 (phthalocyanine blue), C.I. I. 74180 (first sky blue).

These colorants can be used alone or in combination of two or more. However, 1 to 10 parts by weight, more preferably 2 to 5 parts by weight, is used per 100 parts by weight of the resin contained in the toner particles. It is desirable to do. That is, if the amount is more than 10 parts by weight, the fixing property and the light transmitting property of the toner may be reduced. If the amount is less than 1 part by weight, a desired image density may not be obtained.

When carbon black is used as the coloring agent, it is desirable to use carbon black having a pH of 7 or less. Carbon black having a pH of 7 or less has good dispersibility in a binder resin due to the influence of polar groups present on the surface thereof, and a remarkable effect is obtained particularly when applied to a small particle size toner having an average particle size of 2 to 9 μm. .

Further, with respect to the negatively charged toner, it also contributes to improvement of the toner chargeability such as improvement of the negative chargeability.

An offset preventing agent may be used in combination with the toner to improve the fixability. As the anti-offset agent, various waxes, particularly natural waxes such as polyolefin waxes such as low molecular weight polypropylene and polyethylene, or oxidized polypropylene and polyethylene, carnauba wax, rice wax and montan wax are preferably used. The amount of the offset preventing agent is preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight of the binder resin. Further, these waxes have a number average molecular weight (Mn) of 1,000 to 200.
The one having a softening point (Tm) of 80 to 150 ° C is preferable. When the number average molecular weight Mn is 1000 or less or the softening point Tm is 80 ° C or less, uniform dispersion with the synthetic resin component in the synthetic resin coating layer cannot be performed, and only the wax elutes on the toner surface, and the toner Not only can it cause undesired results during storage or development,
Photoconductor contamination such as filming may occur.
Further, when the number average molecular weight exceeds 20,000,
If m exceeds 150 ° C., not only does the compatibility with the resin deteriorate, but also there is a possibility that the effect of containing a wax such as high-temperature offset resistance may not be obtained. When used with a synthetic resin having a polar group from the viewpoint of compatibility, a wax having a polar group is desirable.

For improving the fluidity, a fluidizing agent may be added to and mixed with the toner. As the fluidizing agent, various metal oxides such as silica, aluminum oxide, titanium oxide, a mixture of silica and aluminum oxide, a mixture of silica and titanium oxide, and magnesium fluoride can be used. These substances may be added internally.

A cleaning aid may be used. Examples of the cleaning aid include the above-mentioned inorganic fine particles as a fluidizing agent, metal soaps such as stearate, fluorine-based, silicon-based, styrene- (meth) acryl-based, and the like. Various synthetic resin fine particles such as benzoguanamine, melamine, and epoxy are used. As the synthetic resin particles, emulsion polymerization, soap-free emulsion polymerization, wet polymerization such as non-aqueous dispersion polymerization,
Various organic fine particles such as styrene, (meth) acrylic, olefinic, fluorine-containing, nitrogen-containing (meth) acrylic, silicon, benzoguanamine, and melamine granulated by a vapor phase method or the like can be used. As these synthetic resin fine particles, 0.01 to 3 smaller than the average particle diameter of the toner are used.
A substantially spherical particle having an average particle diameter of from 0.1 to 10% by weight, preferably from 0.1 to 5% by weight, more preferably from 0.1 to 5% by weight, based on the toner. It is desirable to add 2% by weight.

The above toner may be used as a magnetic toner. In this case, known magnetic fine particles may be dispersed in a binder resin. As the magnetic material, for example, metals exhibiting ferromagnetism such as cobalt, iron and nickel, cobalt, iron, nickel, aluminum, lead, magnesium, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, Known magnetic materials such as alloys of metals such as tungsten and vanadium, mixtures of these metals, oxides, and fired bodies (ferrites) can be used. It is desirable to add these magnetic materials in an amount of 1 to 80 parts by weight, preferably 5 to 60 parts by weight, based on 100 parts by weight of the binder resin of the toner.

Further, the above toner can be applied to both a two-component developer and a one-component developer (magnetic and non-magnetic). When used as a two-component developer, carrier powder,
For example, known carriers such as a ferrite carrier, a coating carrier, an iron powder carrier, a binder-type carrier, and a carrier having a composite charged surface can be used.

In addition, the toner is frictionally charged by passing the toner through a gap between a toner regulating member composed of a blade, a roller and the like and a toner carrier to form a thin toner layer on the surface of the toner carrier. It is also suitably used for a developing method having the above. As the toner carrier, a developing roller may be used, or a toner supply roller for the developing roller may be used.

The above bisphenol compound may be used in a photoconductive toner.

The toner produced by the above method can be used for development for visualizing an electrostatic latent image in electrophotography, electrostatic recording, electrostatic printing, and the like by a conventionally known means.

[0080]

EXPERIMENTAL EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific experimental examples.

<Example 1> Ingredients: parts by weight ・ Styrene-n-butyl methacrylate 100 (softening point: 132 ° C., glass transition point: 60 ° C.) ・ Carbon black (manufactured by Mitsubishi Kasei; MA # 8, pH: 3) 8 After sufficiently mixing the above materials with a ball mill, they were kneaded on three rolls heated to 140 ° C. After cooling the kneaded material,
Coarse pulverization was performed using a feather mill.

The coarsely pulverized product was finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder i having an average particle size of 8 μm.

Further, 1 part by weight of bisphenol compound 1 as a charge control agent was put into a Henschel mixer with respect to 100 parts by weight of the fine powder obtained here, and 1500 rpm.
The mixture was stirred at a rotation speed of 2 minutes for 2 minutes to adhere the compound 4 to the surface of the colorant-containing resin particles by van der Waals force and electrostatically.

Next, the compound 4 was fixed on the surface of the fine particles i by performing a treatment at 6000 rpm for 3 minutes using Nara Machine Hybridization System NHS-1. Finally, 0.1% by weight of hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .; average particle size: 17 μm) is added as a post-treatment agent, and the mixture is mixed with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1000%
The toner 1-1 was obtained by processing at 1 minute at 1 rpm.

<Examples 2 to 4> Toner 1-2 was prepared in the same manner as in Example 1 except that bisphenol compounds 2, 4, and 6 were used instead of bisphenol compound 1 as a charge control agent. To obtain toner 1-3 and toner 1-4.

<Example 5> Ingredients: parts by weight Polyester resin (Tuffton NE1110; manufactured by Kao Corporation) 100 Carbon black (Mogal L; manufactured by Cabot Corporation) 8 Bisphenol compound 10 3 Desorbed fatty acid-type carnauba wax (melting point) 85 ° C, acid value 0.5) 1.5 Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.)
After mixing sufficiently, a twin-screw kneader (Ikegai Iron Works)
And kneaded. The kneaded material was left to cool, coarsely pulverized using a feather mill, and further finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

To 100 parts by weight of the obtained fine powder, hydrophobic silica H-2000 (manufactured by Wakka Kabushiki Kaisha; average particle size: 17 m)
μ), 0.2 parts by weight were added, and the mixture was treated at 1000 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) to obtain Toner 2-1.

<Examples 6 to 8> Toner 2-2 in the same manner as in Example 1 except that bisphenol compounds 12, 14, and 16 were used instead of bisphenol compound 10 as the charge control agent in Example 5. , And toner 2-3 and toner 2-4.

Comparative Example 1 A toner 1-A having an average particle diameter of 8 μm was obtained in the same manner as in Example 1 except that the bisphenol compound 1 was not added.

Comparative Example 2 A toner 1 having an average particle diameter of 8 μm was prepared in the same manner as in Example 1 except that di-tert-butylhydroxytoluene having the following structural formula was added in place of the bisphenol compound 1 in Example 1. B was obtained.

[0091]

Embedded image

<Comparative Example 3> A method similar to that of Example 3 was used, except that 3 parts by weight of a chromium complex dye (S-34; manufactured by Orient Chemical Industries) was used instead of bisphenol compound 1. Toner 1 having an average particle size of 8 μm
C was obtained.

Comparative Example 4 A toner 1-D having an average particle diameter of 8 μm was obtained in the same manner as in Example 1 except that 4,4′-dihydroxybenzophenone was added instead of bisphenol compound 1. .

Comparative Example 5 A toner 1-E having an average particle diameter of 8 μm was obtained in the same manner as in Example 1 except that a bisphenol compound having the following structural formula was added instead of bisphenol compound 1.

[0095]

Embedded image

Comparative Example 6 A toner 1-F having an average particle size of 8 μm was obtained in the same manner as in Example 1, except that a bisphenol compound having the following structural formula was added in place of the bisphenol compound 1.

[0097]

Embedded image

<Example 9> Ingredients by weight Component: styrene-n-butyl methacrylate 100 (softening point: 132 ° C, glass transition point: 60 ° C) Carbon black (manufactured by Mitsubishi Kasei; MA # 8, pH; 3) 8. Low molecular weight polypropylene (manufactured by Sanyo Chemical Industry Co., Ltd .; Biscol 550P) 5 Bisphenol compound 195 The above materials were sufficiently mixed by a ball mill, and then kneaded on three rolls heated to 140 ° C. After cooling the kneaded material,
Coarse pulverization was performed using a feather mill, and further finely pulverized using a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

10 parts by weight of the obtained fine powder was added to hydrophobic silica R-974 (manufactured by Nippon Aerosil Co., Ltd .; average particle size: 17).
m.mu.) of 0.1 parts by weight, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1000 rpm for 1 minute to obtain Toner 3.

<Example 10> Ingredients by weight Component polyester resin (Tuffton NE382; manufactured by Kao Corporation) 100 Brilliant carmine 6B (CI15850) 3 bisphenol compound 234 Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.)
After mixing sufficiently, a twin-screw kneader (Ikegai Iron Works)
And kneaded. The kneaded material was left to cool, coarsely pulverized using a feather mill, and further finely pulverized by a jet mill. The finely pulverized product was subjected to air classification to obtain a fine powder having an average particle size of 8 μm.

100 parts by weight of the obtained fine powder was mixed with hydrophobic silica H-2000 (manufactured by Wakka Kabushiki Kaisha; average particle size: 17 m).
μ) was added, and the mixture was treated with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1000 rpm for 1 minute to obtain Toner 4.

Example 11 Polyoxyethylene (2)
-2,2-bis (4-hydroxyphenyl) propane 6
8 parts by weight, 16 parts by weight of isophthalic acid, 16 parts of terephthalic acid
Parts by weight, 0.3 parts by weight of maleic anhydride and 0.1 parts by weight of dibutyltin oxide were charged into a flask and reacted at 230 ° C. for 24 hours under a nitrogen atmosphere. The reaction product was taken out to obtain a polyester resin containing an unsaturated polyester. The weight average molecular weight of the obtained polyester resin was 9,800.

50 parts by weight of the obtained polyester resin and 50 parts by weight of xylene were charged into a flask and dissolved. The temperature was increased until xylenes refluxed. Under refluxing xylene, a solution prepared by dissolving 0.6 parts by weight of azobisisobutyronitrile in 13 parts by weight of styrene and 2 parts by weight of methyl methacrylate was added dropwise in about 30 minutes under a nitrogen atmosphere. After dropping, the temperature was kept for 3 hours. Xylene was distilled under reduced pressure to remove the resin. Weight average molecular weight 11700, Mw / Mn 2.8, 100 ° C
A styrene-acryl-modified polyester resin having a melt viscosity of 5 × 10 ⁴ poise and a glass transition temperature of 60 ° C. was obtained.

Here, the melt viscosity is a value measured using a flow tester CFT-500 manufactured by Shimadzu Corporation under the conditions of a nozzle diameter of 1 mm, a nozzle length of 1 mm, a load of 30 kg, and a heating rate of 3 ° C./min.

• 100 parts by weight of the styrene-acryl-modified polyester resin obtained above • 2.5 parts by weight of organic pigment Lionol Telllow FG-1310 • 2 parts by weight of bisphenol compound 24 The above materials were sufficiently mixed with a Henschel mixer and biaxially mixed. After kneading with an extruder, the mixture was cooled. The kneaded material was roughly pulverized by a feather mill and further finely pulverized by a jet pulverizer. The finely pulverized product was subjected to air classification to obtain particles having an average particle size of 8 μm.

For 100 parts by weight of the obtained 8 μm particles, 0.3 parts by weight of hydrophobic silica H-2000 / 4 (manufactured by Wakka) and 0.5 parts of hydrophobic titanium oxide T-805 (manufactured by Degussa) are used.
The toner 5 was obtained by adding 1 part by weight and treating with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.) at 1500 rpm for 1 minute.

Example 12 Monodisperse spherical copolymer of styrene and n-butyl methacrylate obtained by a seed polymerization method (average particle size: 6 μm: glass transition temperature: 54 ° C .: softening point: 128 ° C., gelling component: 100 parts by weight of toluene-insoluble component (containing 15%) and 8 parts by weight of carbon black (manufactured by Mitsubishi Chemical Corporation: MA # 8) were placed in a Henschel mixer having a capacity of 10 liters, and mixed and stirred at a rotation speed of 1000 rpm for 2 minutes. Carbon black was attached to the surface. Next, a carbon black was immobilized on the surface of the polymer particles by performing a treatment at 6000 rpm for 3 minutes using Nara Machine Hybridization System NHS-1.

Further, 100 parts by weight of the polymer particles treated with carbon black and MMA / iBMA (1: 9)
Particles MP-4951 (manufactured by Soken Chemical Co., Ltd .: average particle size 0.2 μm)
m; glass transition temperature 85 ° C.) 10 parts by weight as the processing conditions of the hybridization system, the number of rotations 8000 r.
A resin coat layer was provided by the same treatment as above except that the time was set to 5 minutes at pm.

Further, the polymer particles 10 obtained here were
By subjecting 2 parts by weight of bisphenol compound 25 to 0 part by weight to the same treatment as above in which a carbon black layer was formed, compound 25 was fixed to the surface of toner particles, and fine particles having an average particle diameter of 6.5 μm were obtained. Obtained.

To 100 parts by weight of the obtained 6.5 μm particles, 0.5 parts by weight of hydrophobic silica H-2000 (manufactured by Wakka Kabushiki Kaisha) was added, and the mixture was treated with a Henschel mixer at 1500 rpm for 1 minute to obtain toner 6. Obtained.

<Example 13>2,2'-bis [P- (2
-Hydroxy) -phenyl] propane (60 parts by weight), isophthalic acid (20 parts by weight), and dibutyltin oxide (0.1 part by weight) were charged into a flask, and reacted at 230 ° C for 24 hours under a nitrogen atmosphere. The reaction product was taken out to obtain a polyester resin having a weight average molecular weight of 7,000.

After 50 parts by weight of the obtained polyester resin and 50 parts by weight of xylene were charged in a flask and dissolved, the temperature was raised until xylene was refluxed. A solution prepared by dissolving 0.4 parts by weight of azobisisobutyronitrile in 13 parts by weight of styrene and 0.3 parts by weight of diethylaminoethyl methacrylate was added dropwise under a nitrogen atmosphere for about 30 minutes while refluxing xylene.
After dropping, the temperature was kept for 3 hours. After xylene was distilled under reduced pressure, the resin was taken out.

The amino-modified polyester resin thus obtained is
The weight average molecular weight (Mw) is 11,000, and Mw / Mn is 3.
0, melt viscosity at 100 ° C. is 5 × 10 ⁴ poise, T
g was 61 ° C.

Component parts by weight Amino-modified polyester resin 100 Organic pigment Lionol Red 6B FG-4213 2.5 (manufactured by Toyo Ink Co., Ltd.) Bisphenol compound 33 2.0 Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.)
And kneaded with a twin-screw extruder. The kneaded material was roughly pulverized using a feather mill, and then finely pulverized using a jet mill. Next, the pulverized product was classified by an air classifier to obtain particles having an average particle size of 8 μm.

To 100 parts by weight of the obtained 8 μm particles, 0.5 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.) was added, and 1 part at 1500 rpm using a Henschel mixer.
After that, the toner 7 was obtained.

Example 14 160 g of styrene, 90 g of butyl methacrylate, and 30 g of isobutyl acrylate
g, α-methylstyrene dimer (Nofmer MSD; manufactured by NOF CORPORATION) 3 g, silane coupling agent (TSL83
11; Toshiba Corporation) 2 g, 2,2′-azobis (2,4-
6 g of dimethylvaleronitrile) was uniformly mixed and dispersed using a homojetter (manufactured by Tokushu Kika Kogyo Co., Ltd.).

Next, a 4% solution of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) as a dispersion stabilizer was prepared.
0 g, 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP-75; manufactured by Nikko Chemical Co., Ltd.), and 0.3 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries) in 650 g of ion-exchanged water. Was used to suspend the above homogeneous dispersion in water.

The suspension was transferred to a four-necked flask and purged with nitrogen. After polymerization at a temperature of 50 ° C. and a stirring speed of 100 rpm for 24 hours, filtration and washing were repeated, and further dried to obtain suspended polymer resin particles.

100 parts by weight of the above-mentioned suspension-polymerized particles 8 parts by weight of carbon black (MA # 8; manufactured by Mitsubishi Kasei Kogyo Co., Ltd., pH: 3) 4 parts by weight of low molecular weight polypropylene (660P; manufactured by Sanyo Kasei Kogyo Co., Ltd.) Bisphenol compound 40 2 parts by weight The above materials were sufficiently mixed with a Henschel mixer, kneaded with a twin screw extruder, and then cooled. The kneaded material was roughly pulverized by a feather mill, and then finely pulverized by a jet pulverizer. The finely pulverized product was subjected to air classification to obtain particles having an average particle size of 8 μm.

To 100 parts by weight of the obtained 8 μm particles, 0.5 parts of hydrophobic silica (T-500; manufactured by Tokyo Material Co., Ltd.) was added.
Parts by weight, and 1500 rpm with a Henschel mixer.
m for 1 minute to obtain toner 8. Glass transition point (Tg): 56 ° C., softening point (Tm): 87 ° C., outflow starting temperature at the time of temperature rise by Koka type flow tester: 78
° C. The softening point (Tm) was measured using a perfect oven.

<Example 15> Ingredients: parts by weight • glycidyl methacrylate 10 • styrene 60 • butyl methacrylate 30 • benzoyl peroxide 5 A reaction vessel equipped with a stirrer, an inert gas introduction pipe, a reflux condenser, and a thermometer. Into it together with deionized water containing 0.1% by weight of polyvinyl alcohol,
The mixture was sufficiently mixed and dispersed. Then, the dispersion was stirred at high speed to form a uniform suspension.

Next, the mixture was heated to 80 ° C. while blowing nitrogen gas, and the polymerization reaction was carried out by continuing stirring at this temperature for 5 hours. Thereafter, water was removed to obtain a polymer having an epoxy group as a reactive group.

100 parts by weight of the obtained polymer, 40 parts by weight of carbon black MA-100R (pH: 3.5; manufactured by Mitsubishi Kasei Kogyo), 5 parts by weight of low molecular weight polypropylene (Viscol 605P; manufactured by Sanyo Kasei Kogyo) After mixing
The mixture was kneaded and reacted under the condition of 160 ° C. using a pressure kneader. Then, the reaction product was cooled and pulverized to obtain a wax-containing carbon black graft polymer as a colorant.

Next, in the same reaction vessel as above, 80 parts by weight of styrene and 20 parts by weight of n-butyl acrylate previously prepared in deionized water containing 0.5% by weight of sodium dodecylbenzenesulfonate as an anionic surfactant. Was mixed with 50 parts by weight of the carbon black graft polymer, 3 parts by weight of azobisisobutyronitrile and 3 parts by weight of 2-2′azobis- (2,4-dimethylvaleronitrile). The mixture was charged. K. It was mixed and stirred with a homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to form a uniform suspension.

Next, the mixture was heated to 65 ° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a suspension polymerization reaction, and further heated to 75 ° C. to terminate the polymerization reaction.

Separately, hydrophobic silica H-2000
2 parts by weight (manufactured by Wacker), silane coupling agent (T
SL8311; Toshiba Silicone Co., Ltd.) A solution prepared by dispersing 2 parts by weight in methyl alcohol was added to the above suspension, mixed, and heated at 80 ° C. for 1 hour to obtain a block-like product in which particles were fused together. Was. The filtration / washing of the block was repeated. Wash the washed product with a hot air dryer at 60 ° C, 8
After leaving for 5 hours under the condition of 0RH%,
It was dried for 5 hours under the condition of 0 RH%.

With respect to 100 parts by weight of the obtained suspension polymerization aggregate, 1.0 part by weight of bisphenol compound 44, 0.3 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.),
And tin oxide fine particles T-1 (manufactured by Mitsubishi Materials Corporation)
0.5 parts by weight of Henschel mixer (Mitsui Miike Kakoki)
After mixing and stirring at 3,000 rpm, the mixture was crushed at 18,000 rpm using a Kryptron system (KTM-XL type, manufactured by Kawasaki Heavy Industries, Ltd.) at an inlet air temperature of 0 ° C. and an average particle size of 6 0.0 μm crushed particles were obtained. The temperature of the discharged air at this time was 28 ° C.

To 100 parts by weight of the obtained crushed particles, 0.2 parts by weight of hydrophobic silica H-2000 (manufactured by Wacker Inc.) was added, and a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) was added.
Process at 1500 rpm for 1 minute at
I got

<Example 16> 60 g of styrene 35 g of n-butyl methacrylate 5 g of methacrylic acid 0.5 g of 2,2-azobis- (2,4-dimethylvaleronitrile) 0.5 g of low molecular weight polypropylene (Biscol 605P; Sanyo Chemical Co., Ltd.) 3 g The above-mentioned materials were mixed with a sand stirrer to prepare a polymerization composition.

The polymerization composition was subjected to a polymerization reaction at a temperature of 60 ° C. for 6 hours in an aqueous solution of gum arabic having a concentration of 3% while stirring at 4,000 rpm using a stirrer TK Auto Homomimixer (manufactured by Tokushu Kika Kogyo). Spherical particles having an average particle size of 6 μm were obtained.

Separately, 10 g of a black disperse dye (Kayaron Preester Black S-CONC; manufactured by Nippon Kayaku Co., Ltd.) was dispersed in 100 ml of pure water, and this dispersion was added to the aqueous dispersion of the above-mentioned suspended polymer particles. The medium was heated to 75 ° C. at a rate of 2 ° C./min while vigorously stirring the mixed dispersion using an ultrasonic vibrator, and kept in this state for 1 hour.

Thereafter, the system was cooled, filtration / washing was repeated, and the particles were dried by a slurry drying device (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.). Particles were obtained.

For 100 parts by weight of the obtained colored particles,
After mixing 1.0 part by weight of bisphenol compound 49 and 0.5 part by weight of hydrophobic alumina (RFY-C; manufactured by Nippon Aerosil Co., Ltd.) and mixing and stirring well, a hybridization system (manufactured by Nara Machinery Co., Ltd .; NHS-O) ), And a fixing process was performed at a peripheral speed of 60 m / sec.

To 100 parts by weight of this treated product, hydrophobic silica R-974 (manufactured by Nippon Aerosil Co .; average particle size: 17)
μm), and treated with a Henschel mixer (manufactured by Mitsui Miike Koki Co., Ltd.) at 1000 rpm for 1 minute to obtain toner 10.

Example 17 A polyester resin (NE-
382; Kao Corporation) was dissolved in 400 g of a mixed solvent of methylene chloride / toluene (8/2), and 5 g of a phthalocyanine pigment was placed in a ball mill and mixed for 3 hours to be uniformly dispersed.

Next, as a dispersion stabilizer, a 4% solution of methylcellulose (Methocel K35LV; manufactured by Dow Chemical Company) was used.
TK auto homomixer (0 g) in an aqueous solution prepared by dissolving 5 g of a 1% solution of dioctyl sulfosuccinate soda (Nikkor OTP75; manufactured by Nikko Chemical Co., Ltd.) and 0.5 g of sodium hexametaphosphate (manufactured by Wako Pure Chemical Industries) in 1000 g of ion-exchanged water ( The number of revolutions of the uniform dispersion was adjusted to an average of 3 to 10 μm by using Tokushu Kika Kogyo Co., Ltd., and suspended in water.

Thereafter, filtration / washing was repeated, and the particles were dried by a slurry drying apparatus (Dispercoat; manufactured by Nisshin Engineering Co., Ltd.). The dried particles were further subjected to air classification to obtain colored particles having an average particle diameter of 6 μm. Obtained.

To 100 parts by weight of the obtained colored particles, 0.5 parts by weight of bisphenol compound 57 and 0.3 parts by weight of hydrophobic silica (H-2000 / 4: manufactured by Wacker Inc.) were added, and the mixture was 3,000 rpm using a Henschel mixer. After mixing for 2 minutes, using a hybridization system (manufactured by Nara Machinery Co., Ltd .; NHS-O type), at a peripheral speed of 60 m
The fixation process was performed at / sec.

0.3 parts by weight of hydrophobic silica (H-2000; manufactured by Wacker Inc.) based on 100 parts by weight of the obtained colored particles
Toner 11 was obtained by adding 0.5 parts by weight of hydrophobic titanium oxide (T-805: manufactured by Nippon Aerosil Co., Ltd.) and treating the mixture at 1500 rpm for 1 minute with a Henschel mixer (manufactured by Mitsui Miike Kakoki Co., Ltd.).

<Manufacture of Carrier> As the carrier to be mixed with the toner for developing an electrostatic latent image obtained in the above Examples and Comparative Examples, four types of carriers A to D manufactured as described below are used. I made it.

(1) Carrier A polyester resin (manufactured by Kao Corporation; NE-1110) 100
Parts by weight, inorganic magnetic powder (manufactured by TDK; MFP-2) 600
Parts by weight and carbon black (Mitsubishi Kasei; M
A # 8) 2 parts by weight were sufficiently mixed and ground using a Henschel mixer.

Next, the pulverized material was melt-kneaded using an extruder kneader set at a cylinder portion of 180 ° C. and a cylinder head portion of 170 ° C.

The obtained kneaded material was cooled and coarsely pulverized.
The mixture was finely pulverized with a jet mill and further classified using an air classifier to obtain a binder type carrier A having an average particle size of 55 μm.

(2) Carrier B Ferrite carrier core (F-3, manufactured by Powder Tech)
00) was coated with a thermosetting silicone resin using a tumbling fluidized tank (manufactured by Okada Seiko; Spiracoater) to obtain a carrier B having an average particle size of 50 μm.

(3) Carrier C Ferrite carrier core (F-3, manufactured by Powder Tech)
The surface of (00) was coated with polyethylene by a surface polymerization coating method to obtain a carrier C having an average particle size of 51 μm.

(4) Carrier D Using the same core material as Carrier B, coating was performed by dipping using a thermosetting acrylic-modified silicone resin to obtain Carrier D having an average particle size of 50 μm.

<Evaluation> (1) Measurement of Particle Size The particle size of the toner and the carrier was measured according to the following procedure.

(A) Toner Particle Size The average toner particle size was measured using a Coulter Counter TA-II.
Using a mold (manufactured by Coulter Counter Co., Ltd.), the relative weight distribution by particle size was measured with a 100 μm aperture tube.

(B) Carrier particle size The carrier particle size is SALD1100 (manufactured by Shimadzu Corporation).
The average particle size was determined by calculating the average particle size.

(2) Measurement of Charge Amount and Low Chargeable Toner Amount Prior to the measurement, a combination of a toner and a carrier described in Table 1 described below was mixed so that the toner concentration was 5% by weight. To prepare a developer. The amount of charge of the developer and the amount of low charge toner were measured using the apparatus having the configuration shown in FIG. The measurement was performed under the following conditions.

(A) Measurement of Charge Amount First, 1 g of a developer sample after stirring for 30 minutes in a loading platform was weighed with a precision balance, and placed uniformly on the entire surface of the conductive sleeve 2. Then, the rotation speed of the magnet roll 3 was set to 1000 rpm.

Next, a bias voltage of 3 kV was applied by the bias power supply 4 to the same polarity as the charged potential of the toner, and the magnet roll 3 was rotated for 30 seconds.
The capacitor potential Vm at the time of stopping is read. Then, the weight (Mi) of the separated toner attached to the cylindrical electrode 1
Is measured with a precision balance to determine the average toner charge amount of each developer.

After the developer was exposed to the environment at an ambient temperature of 23 ° C. and a relative humidity of 55% for 24 hours, the same measurement was performed by mixing and stirring for 30 minutes on a rotating base.

(B) Measurement of Low-Charge Toner Amount In the above-described measurement of the charge amount, the same measurement is performed by applying a bias voltage to the conductive sleeve 2 and dropping it to the ground. The amount of the toner charged to the cylindrical electrode 1 was measured to determine the amount of the low-charged toner. The total amount of toner in the developer was ranked as follows. ○ and △ were accepted.

〇: Low chargeable toner amount is 1 wt% or less Δ: Low chargeable toner amount is 2 wt% or less ×: Low chargeable toner amount exceeds 2 wt% (3) Environmental stability of charge amount (Q / M) First, a developer was prepared by mixing a toner and a carrier shown in Table 1 below so that the toner concentration was 5% by weight. However, in Example 14, the toner powder was used as a non-magnetic one-component developer without using a carrier.

[0156]

[Table 1]

The developer thus prepared was heated at an ambient temperature of 5 ° C.
Charge amount (Q _{L / L} ) after exposure for 24 hours under an environment of 15% relative humidity (L / L environment), ambient temperature 35 ° C., relative humidity 8
Charge amount (Q _{H / H} ) after exposure for 24 hours under 5% environment (H / H environment), and further, ambient temperature 23 ° C. and relative humidity 55
% (N / N environment), and the charge amount (Q _{N / N} ) after exposure for 24 hours was measured in the same manner as described above. Then, A and B were calculated according to the following formula, and ranked as follows. ○ and △ were accepted.

[0158]

(Equation 1)

：: Both A and B are 15% or less Δ: Either A or B is 15% or more ×: Both A and B are 15% or more (4) Evaluation of image quality Developer prepared in the same manner as described above Was set in a commercially available image forming apparatus, an image was output using a chart having a B / W ratio of 6%, and the image quality was visually evaluated for the presence or absence of fog on a white background portion of the output image. This evaluation was performed for both the initial image and the image after the 10,000-sheet printing test. The evaluation criteria are as follows.

：: No fog Δ: Slight fog is recognized but no problem in practical use ×: Fog is generated and not suitable for practical use Note that Examples 1 to 9, Example 16, and Comparative Examples 1 to 6
Is a copying machine EP-570Z (manufactured by Minolta), and
Examples 0 to 13 and Example 17 are digital full-color copying machines CF-80 (Minolta), Example 14 is a printer SP-101 (Minolta), and Example 15 is a printer SP-500 (Minolta). Was used. Copy machine CF
Reference numeral -80 denotes a type in which a releasing oil is applied to the surface of the fixing roller. The printer SP-101 has a fixing temperature of 130 ° C.

Table 2 shows the above results.

[0162]

[Table 2]

[0163]

According to the present invention, there is provided a negatively chargeable toner for developing an electrostatic latent image using a bisphenol compound which is a novel charge control agent containing no heavy metal. The toner of the present invention is excellent in charge rising, charge stability, spent resistance, and environmental resistance. Further, the toner of the present invention is a toner excellent in color reproducibility and light transmission.

[Brief description of the drawings]

FIG. 1 shows an apparatus for measuring the amount of charge and the amount of low-chargeable toner.

[Explanation of symbols]

 1: cylindrical electrode 2: conductive sleeve 3: magnet roll 4: bias power supply

Claims (1)

[Claims] 1. A compound represented by the following general formula [I]: Wherein, R ₁ to R ₄ is a hydrogen atom, an electron withdrawing group, alkyl group, alkoxy group, a hydroxyl group, R ₁
At least one of R ₄ is an electron-withdrawing substituent. R ₅ and R ₆ represent a hydrogen atom, a carbon atom having an electron-withdrawing group, a carbon atom to which an aryl group having an electron-withdrawing group is bonded, and an oxygen atom. R ₅ and R ₆ may combine to form a double bond or a ring. However, this excludes the case where both R ₅ and R ₆ are hydrogen atoms. ] A toner for developing an electrostatic latent image, comprising a bisphenol compound represented by the following formula: