JP3287752B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image suitable for heat fixing used in an image forming method such as electrophotography and electrostatic recording.

[0002]

2. Description of the Related Art An electrophotographic method is disclosed in U.S. Pat.
7, 691, JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electrostatic charge image on a photoreceptor by various means,
Next, the electrostatic image is developed using toner, and the toner image is transferred to a transfer material such as paper using direct or indirect means as necessary. And a copy or print is obtained. Then, the toner remaining on the photoconductor without being transferred is cleaned by various methods, and then the above steps are repeated.

Further, a method of forming a general full-color image will be described. The photosensitive drum is charged by a primary charger, image exposure is performed by a laser beam modulated by a magenta image signal of a document, an electrostatic charge image is formed on the photosensitive drum, and the image is formed by a magenta developing device having magenta toner. The electrostatic image is developed to form a magenta toner image. Next, the magenta toner image developed on the photosensitive drum by the transfer charger is transferred to the conveyed transfer material using direct or indirect means.

On the other hand, the photosensitive drum after the development of the electrostatic charge image is neutralized by a static eliminator, cleaned by cleaning means, charged again by a primary charger, and similarly charged in cyan. A toner image is formed and a cyan toner image is transferred to a transfer material on which the magenta toner image has been transferred.
Development and transfer are sequentially performed in the same manner as for the black color to form toner images of four colors on the transfer material. A full-color image is formed on the transfer material by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing roller.

Further, a magenta toner image is transferred from a photosensitive drum to an intermediate transfer member, and then, a cyan toner image, a yellow toner image, and a black toner image are sequentially transferred onto the intermediate transfer member. There is also a method in which a full-color image is formed on a transfer material by transferring the toner image to a transfer material and fixing the transfer material having four color toner images by the action of heat and pressure by a fixing roller.

In addition, reflecting the recent ecology boom,
The need for double-sided copying for forming images on both sides of the transfer paper for the purpose of reducing the consumption of the transfer paper is increasing day by day.

[0007] As the toner to be loaded on these full-color copying machines or full-color printers, the respective toners are sufficiently mixed in the heat and pressure fixing step without increasing the color reproducibility and losing the transparency of the overhead projector (OHP) image. It is necessary to. Compared with a general black toner for a black-and-white copying machine, the toner for full-color images is preferably a low-molecular-weight binder resin having sharp melt properties. However,
Usually, when a sharp-melting binder resin is used, when the toner is melted in the heat-press fixing step, a problem is likely to occur in the high-temperature offset resistance because the self-cohesive force of the binder resin is low. In general black toner for black-and-white copying machines, a relatively high-crystalline wax typified by polyethylene wax or polypropylene wax is used as a release agent to improve high-temperature offset resistance during fixing. For example, Japanese Patent Publication No. 52-3304
JP, JP-B-52-3305, JP-A-57-5-5
No. 2,574. However, in a full-color image toner, the release agent itself has a high crystallinity and a difference in refractive index from the material of the OHP sheet.
When transmitted through the HP, transparency is impaired, and the projected image has low saturation and lightness.

In order to solve this problem, a method of reducing the crystallinity of the wax by using a nucleating material in combination with the wax is disclosed in JP-A-4-149559 and JP-A-4-107.
No. 467. Further, a method using a wax having a low crystallinity is disclosed in JP-A-4-301853,
It is proposed in Japanese Patent Application Laid-Open No. 5-61238. As a wax having a relatively high transparency and a low melting point, there is a montan-based wax.
185660, JP-A-1-185661,
JP-A-1-185662, JP-A-1-185566
No. 3 and JP-A-1-238672. However, these waxes do not sufficiently satisfy all of the transparency in OHP, the low-temperature fixing property at the time of heat and pressure fixing, and the high-temperature offset resistance. For this reason, in a normal color toner, an oil such as silicone oil or fluorine oil is applied to a heat fixing roller without adding a release agent as much as possible, thereby improving high-temperature offset resistance and transparency in OHP. However, the fixed image thus obtained has extra oil adhered to the surface. Oil may adhere to the photoconductor and contaminate it, or the oil may swell the fixing roller, thereby shortening the life of the fixing roller. In order not to generate oil streaks on the fixed image, it is necessary to supply oil uniformly and quantitatively onto the surface of the fixing roller, and the size of the fixing device tends to increase.

For this reason, the use of oil for preventing high-temperature offset or the use of a reduced amount of oil in the heating and pressurizing fixing means is a toner in which the occurrence of offset is suppressed. There is a long-awaited demand for toners having excellent transparency.

[0010] Further, since the first copy image is subjected to the heating and pressurizing and fixing step twice when making a double-sided copy, a toner having a high-temperature offset resistance more excellent than the toner used for making a single-sided copy. Is long-awaited.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image which solves the above-mentioned problems.

An object of the present invention is to provide a toner for developing an electrostatic image having a high coloring power.

An object of the present invention is to provide a toner for developing an electrostatic image, which is excellent in offset resistance, especially in high-speed fixing.

It is a further object of the present invention to provide a toner for developing an electrostatic charge image which can fix a toner image to a transfer material well without applying a small amount of oil to a fixing roller or without applying any oil. It is in.

It is a further object of the present invention to provide a toner for developing an electrostatic image having excellent blocking resistance.

An object of the present invention is to provide a color toner for developing an electrostatic charge image having a large coloring power.

An object of the present invention is to provide a color toner for developing an electrostatic image, which is excellent in offset resistance, especially in high-speed fixing.

It is a further object of the present invention to provide a color toner for developing an electrostatic charge image which can fix a toner image to a transfer material without applying a small amount of oil to a fixing roller or without applying any oil. Is to do.

It is a further object of the present invention to provide a color toner for developing an electrostatic image having excellent offset resistance and excellent blocking resistance.

An object of the present invention is to provide a color toner for developing an electrostatic charge image, which has good transparency in OHP and excellent high-temperature offset resistance.

An object of the present invention is to provide a color toner for developing an electrostatic image having excellent low-temperature fixability.

An object of the present invention is to provide a color toner for developing an electrostatic image which does not cause image defects even in double-sided fixing.

[0023]

SUMMARY OF THE INVENTION The present invention provides a binder resin, a colorant, a polar resin, and a solid wax represented by the following formula (A) or (B) formed of a styrene polymer or styrene copolymer. The present invention relates to a toner for developing an electrostatic image, comprising toner particles containing:

[0024]

[Outside 4] [Wherein R ₁ and R ₃ are straight-chain alkyl groups having 6 to 32 carbon atoms.
Indicates alkyl group, R ₁ and R ₃ may be different even if the same thing, R ₂ is a straight chain having 4 to 20 carbon atoms
Shows an alkylene group. ]

[0025]

[Outside 5] [In the formula, when R ₅ is the following group (1) or (2),
₄ and R ₆ represent a straight-chain alkyl group having 6 to 32 carbon atoms, R ₄ and R ₆ may be the same or different, and when R ₅ is the following group (3), ₄ and R ₆ represent a linear alkyl group having 10 to 25 carbon atoms;
₄ and R ₆ may be the same or different.

—CH ₂ CH ₂ OC ₆ H ₄ OCH ₂ CH ₂ — (1)

[0027]

[Outside 6]

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the following formula (A) or (B) is used in order to improve the low-temperature fixability and offset resistance of a toner and to obtain good transparency of a fixed color image on an OHP film.

[0029]

[Outside 6] [Wherein R ₁ and R ₃ are straight-chain alkyl groups having 6 to 32 carbon atoms.
Indicates alkyl group, R ₁ and R ₃ may be different even if the same thing, R ₂ is a straight chain having 4 to 20 carbon atoms
Shows an alkylene group. ]

[0030]

[Outside 7] [In the formula, when R ₅ is the following group (1) or (2),
₄ and R ₆ represent a straight-chain alkyl group having 6 to 32 carbon atoms, R ₄ and R ₆ may be the same or different, and when R ₅ is the following group (3), ₄ and R ₆ represent a linear alkyl group having 10 to 25 carbon atoms;
₄ and R ₆ may be the same or different.

—CH ₂ CH ₂ OC ₆ H ₄ OCH ₂ CH ₂ — (1)

[0032]

[Outside 9] The toner contains a solid ester wax represented by the following formula.

The solid ester wax is ASTM D34
The temperature of the main maximum peak (main peak) value in the endothermic curve measured according to 18-8 (hereinafter referred to as “melting point”) is 40 to 90 ° C. (more preferably 55 to 90 ° C.).
85 ° C.) from the viewpoint of low-temperature fixability and offset resistance of the toner.

For the measurement according to ASTM D3418-8, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a sample, an empty pan was set as a control, and the temperature was raised at a rate of 10 ° C / min. At a temperature in the range of 20 to 200 ° C.

The solid ester wax preferably has a solubility parameter (SP) value of 7.5 to 10.5.

The solubility parameter (SP) value is determined by the method of Fedors using the additive property of atomic groups [Polym.
Eng. Sci. , 14 (2) 147 (1974)].

The solid ester wax has an SP value of 7.5.
When the average particle size is from 10.5 to 10.5, the solid ester wax contained in the toner particles hardly adheres to the surface of the carrier particles or the developing sleeve, stabilizes the amount of triboelectric charge of the toner, hardly causes fogging, and changes in the image density when replenishing the toner. Is also suppressed.
Further, even when the toner is stored for a long period of time, the occurrence of blocking of the toner is suppressed, and the ester wax forms the release layer on the fixing surface at the time of heat and pressure fixing. Can be prevented.

The solid ester wax preferably has a melt viscosity at 130 ° C. of 1 to 300 cPs.
More preferably, an ester wax compound having 3 to 50 cPs is particularly preferable. When the melt viscosity is lower than 1 cPs, when the toner layer is thinly coated on the sleeve by the application blade in the non-magnetic one-component developing method, the sleeve is easily contaminated by mechanical shearing force. Also in the two-component developing method, when a toner is developed using a carrier, the toner tends to be damaged due to a shear force between the toner and the carrier, and the external additive is easily buried or the toner is crushed. When having a melt viscosity of more than 300 cPs,
When producing toner particles using a polymerization method, the viscosity of the polymerizable monomer composition increases, and it is not easy to obtain toner particles having a small particle size having a uniform particle size, and a toner having a wide particle size distribution. It is easy to be.

The melt viscosity of the ester wax is HAAK
A cone plate type rotor (P
K-1) at 130 ° C.

The solid ester wax has a hardness of 0.3 to
The range of 5.0 is preferable, and the Vickers hardness of 0.5 to 3.0 is more preferable.

A toner containing a solid ester wax having a Vickers hardness lower than 0.3 tends to be crushed at the cleaning portion of a copying machine when many sheets are used, and the toner is liable to fuse on the drum surface, resulting in an image on the image. Black streaks are likely to occur. Further, when multiple fixed image samples are stored in a stacked state, the toner is easily transferred to the other sample surface. A toner containing a solid ester wax having a Vickers hardness of more than 5.0 requires a high pressing force at the time of heat and pressure fixing.

The hardness of the solid ester wax can be measured by, for example, a measuring method using a Shimadzu Dynamic Ultra Micro Hardness Tester (DUH-200). The measurement conditions were as follows. After displacing 10 μm at a load speed of 9.67 mg / sec under a load of 0.5 g using a Vickers indenter, holding for 15 seconds, and analyzing the dents on the sample, the Vickers hardness was determined. . As a sample, a sample melted in advance using a mold having a diameter of 20 mm is formed into a column having a thickness of 5 mm.

The amount of the solid ester wax added is 5 to 40 parts by weight (more preferably 10 to 30 parts by weight) per 100 parts by weight of the binder resin in consideration of obtaining a double-sided fixed image.
It is good to use. The double-sided fixing method is a method in which a fixed image is once formed on the front surface of a transfer sheet, and then an image is further formed on the back surface of the transfer sheet. At this time, since the surface-fixed image once fixed passes through the fixing device again, it is necessary to sufficiently consider the high-temperature offset resistance of the toner. Therefore, in the present invention, it is preferable to add a relatively large amount of solid ester wax. When added in an amount of less than 5 parts by weight, the high-temperature offset resistance and the low-temperature fixability are reduced, and the image on the back surface tends to show an offset phenomenon when a double-sided image is fixed. If the amount is more than 40 parts by weight, fusing in the apparatus is likely to occur in the production by the pulverization method during the production of the toner, and the coalescence of the toner particles tends to occur during the granulation in the production by the polymerization method. In general, a toner having a wide particle size distribution is easily generated. Further, when the amount exceeds 40 parts by weight, the durability of the toner tends to decrease.

In order to enclose a large amount of the solid ester wax in the toner particles, it is preferable to polymerize particles of the polymerizable monomer composition containing the solid ester wax in an aqueous medium to form toner particles.

In this case, as shown in FIG. 1, a capsule structure in which a solid ester wax forms a nucleus and an outer shell is formed of a binder resin by a method of measuring a tomographic plane of a toner using a transmission electron microscope (TEM). Toner particles can be efficiently generated. The form of the toner particles is fixability at a low temperature,
It is preferable to satisfy the blocking characteristics and durability of the toner. In the case where the ester wax is not included, the toner cannot be sufficiently pulverized unless a special freeze pulverization is used in the pulverization process, resulting in a broad particle size distribution, and in some cases, the fusion of the toner to the device. appear. In freezing and pulverization, the device becomes complicated to prevent dew condensation on the device, and if the toner absorbs moisture, it causes a decrease in workability in the production of the toner, and sometimes it is necessary to add a drying process. Is a problem.

As a specific method for measuring the tomographic plane of the toner particles, the toner particles are sufficiently dried in a cold-setting epoxy resin, and then cured in an atmosphere at a temperature of 40 ° C. for 2 days. Is stained with ruthenium tetroxide and, if necessary, osmium tetroxide, and then sliced using a microtome with diamond teeth. The morphology of the toner particles is measured using a transmission electron microscope (TEM). I do. It is preferable to use a ruthenium tetroxide dyeing method in order to give a contrast between materials by utilizing a difference in crystallinity between the ester wax used and the resin constituting the outer shell.

In the solid ester wax (A),
R ₁ and R ₃ have 10 to 25 carbon atoms, R ₂ has 6 to 18 carbon atoms, and the total carbon number is 28 or more. Good in terms of sex. R ₁ and R ₃ are preferably an alkyl group, and R ₂ is preferably an alkylene group.

Specific examples of the solid ester wax (A) are shown below.

[0049]

[Outside 10] Table 1 shows the physical properties of the solid ester waxes A-1 to A-6.

[0050]

[Table 1]

In the fixed ester wax (B), R
₄ and R ₆ have 10 to 25 carbon atoms, and the total carbon number is preferably 28 or more in terms of low-temperature fixability and high-temperature offset resistance of the toner. R ₅

[0052]

[Outside 11] In this case, n is preferably from 6 to 18 in terms of low-temperature fixability and high-temperature offset resistance of the toner. Specific examples of the solid ester wax (B) are shown below. The solid ester wax B-10 is a reference example.

[0053]

[Outside 12]

[0054]

[Outside 13]

The method for producing the solid ester wax used in the present invention includes a synthesis method by an oxidation reaction, a synthesis from a carboxylic acid and a derivative thereof, an ester group introduction reaction represented by a Michael addition reaction, a carboxylic acid compound and an alcohol compound. It is produced by a method utilizing a dehydration condensation reaction from phenol, a reaction between an acid halide and an alcohol compound, and a transesterification reaction. As the catalyst, general acidic or alkaline catalysts used for the esterification reaction, for example, zinc acetate and titanium compounds are preferable. At the time of the reaction, the reaction is carried out in the same molar ratio or by adding one component in a large excess. After that, it may be highly purified by a recrystallization method, an evaporation method, or the like.

As the binder resin used in the present invention, generally used styrene- (meth) acryl copolymers, polyester resins, epoxy resins, and styrene-butadiene copolymers can be used. In the method of obtaining toner particles by a direct polymerization method, a vinyl monomer is preferably used. Specifically, styrene, o (m
-, P-)-methylstyrene, styrene-based monomers such as m (p-)-ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acryl Butyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate,
(Meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene,
Ene monomers such as (meth) acrylonitrile and acrylamide are preferably used. These can be used alone or in the published Polymer Handbook, 2nd edition III-P139.
192 (manufactured by John Wiley & Sons), and the monomers are appropriately mixed and used so that the theoretical glass temperature (Tg) of 40 to 75 ° C is indicated. When the theoretical glass transition temperature is lower than 40 ° C., the storage stability of the toner and the durability stability of the toner are apt to decrease, while when it exceeds 75 ° C., the fixing temperature becomes high. In particular, in the case of a full-color toner, the color mixing property of each color toner is reduced, the color reproducibility is reduced, and the transparency of the OHP film image is further reduced.

The molecular weight of the binder resin is measured by gel permeation chromatography (GPC). As a specific GPC measurement method, the toner is previously extracted with toluene using a Soxhlet extractor for 20 hours, and then toluene is distilled off from the extract using a rotary evaporator. Further, the ester wax is dissolved but the binder resin is dissolved. After adding an insoluble organic solvent (eg, chloroform) and washing well, tetrahydrofuran (TH
A sample obtained by filtering the solution dissolved in F) through a solvent-resistant membrane filter having a pore diameter of 0.3 μm was used, and the column configuration was A-80 manufactured by Showa Denko, using 150C manufactured by Waters.
1, 802, 803, 804, 805, 806, 807
And measuring the molecular weight distribution using a calibration curve of a standard polystyrene resin. The obtained THF-soluble resin component has a number average molecular weight (Mn) of 5,000 to 1,0.
It is preferable that the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 2 to 100.

In the present invention, it is particularly preferable to encapsulate the solid ester wax with a binder resin. To this end, it is effective to add a polar resin to the toner particles. As the polar resin used in the present invention, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with the binder resin or monomer in the molecule. In the case of including a polar resin having an unsaturated group,
Excessive monomer cross-linking reaction to form the binder resin is not preferable because color mixing property is reduced.

As the black colorant used in the present invention, carbon black, a magnetic substance, and those toned to black using the following yellow / magenta / cyan colorants are used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

As the magenta coloring agent, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds are used. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8; 2, 48; 3, 48; 4, 57; 1, 81; 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Specifically, C.I. I.
Pigment Blue 1, 7, 15, 15: 1, 15: 2,
15: 3, 15: 4, 60, 62, 66, etc. can be particularly preferably used.

These colorants can be used alone or as a mixture or in the form of a solid solution. Colorants include hue angle, saturation, lightness, weather resistance, transparency on OHP film,
It is selected from the viewpoint of transparency on a film and dispersibility in toner particles. The amount of the colorant to be added is generally 1 to 20 parts by weight per 100 parts by weight of the binder resin.

When a magnetic material is used as a black colorant, unlike other colorants, 40 to 40 parts by weight of resin are used.
150 parts by weight are commonly used.

As the charge control agent used to stabilize the triboelectric charging characteristics of the toner, a charge control agent which is colorless, has a high toner charging speed and can stably maintain a constant charge amount is preferable. Further, when a direct polymerization method is used in the present invention, a charge control agent having no polymerization inhibition and having no solubilized substance in an aqueous medium is particularly preferable. Specific compounds include salicylic acid as a negative control agent, alkyl salicylic acid, dialkyl salicylic acid, naphthoic acid, a metal compound of dicarboxylic acid, sulfonic acid, a polymer compound having a carboxylic acid in a side chain, a boron compound, a urea compound, Silicon compounds, curryxarene and the like can be used. A quaternary ammonium salt as a positive control agent, a polymer compound having the quaternary ammonium salt in a side chain, a guanidine compound,
Imidazole compounds and the like are preferably used. The charge control agent is preferably used in an amount of 0.5 to 10 parts by weight based on 100 parts by weight of the resin. However, in the present invention, the addition of a charge control agent is not essential, and when a two-component developing method is used, a carrier and frictional charging are used, and even when a non-magnetic one-component blade coating developing method is used, a blade member is used. It is not always necessary to include a charge control agent in toner particles by actively utilizing frictional charging with the sleeve member.

When toner particles are produced by a direct polymerization method, for example, 2,2'-azobis-
(2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2, Azo or diazo polymerization initiators such as 4-dimethylvaleronitrile and azobisisobutyronitrile; peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide An oxide polymerization initiator is used. The amount of the polymerization initiator varies depending on the desired degree of polymerization, but is generally used in an amount of 0.5 to 20% by weight based on the monomer. The type of the polymerization initiator varies depending on the polymerization method, but is used alone or in combination with reference to the 10-hour half-life temperature.

In order to control the degree of polymerization, a crosslinking agent, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

As a method for producing the toner particles of the present invention, a binder resin, a solid ester wax, a colorant, a charge control agent and the like are uniformly dispersed using a pressure kneader, an extruder or a media disperser. Other than a method for producing a toner by a so-called pulverization method in which a target is pulverized to a desired toner particle size by mechanical pulverization or collision with a target under a jet stream, and then a classification process is performed to sharpen the particle size distribution to form a toner. Japanese Patent Publication No. 56-13945 discloses a method of atomizing a molten mixture into air using a disk or a multi-fluid nozzle to obtain a spherical toner.
No. 10231, JP-A-59-53856 and JP-A-59-61842, in which a toner is directly produced using a suspension polymerization method, or a method in which a toner is soluble in a monomer. Either a dispersion polymerization method of directly producing a toner using an aqueous organic solvent in which the resulting polymer is insoluble, or an emulsion polymerization method typified by a soap-free polymerization method of producing a toner by directly polymerizing in the presence of a water-soluble polar polymerization initiator. It is possible to produce a toner.

In the method of producing toner particles using the pulverization method, it is extremely difficult to control the shape of the toner. In the melt spray production method, a product having a wide particle size distribution is easily produced. In some cases, excessive energy is consumed particularly in the melting step, which is not preferable from the viewpoint of energy use efficiency.

In the dispersion polymerization method, the obtained toner has an extremely sharp particle size distribution, but the selection range of materials to be used is narrow, and the waste solvent generated due to the use of an organic solvent and the organic solvent used in the production process are not used. In view of the flammability of the solvent, there is a problem that the manufacturing apparatus is complicated and easily complicated. Emulsion polymerization methods typified by soap-free polymerization are effective because the particle size distribution of the toner is relatively uniform, but when the used emulsifier and initiator terminals are present on the surface of the toner particles, the environmental characteristics are likely to deteriorate.

The method for producing the toner is a suspension polymerization method capable of relatively uniformly controlling the shape of the toner, easily obtaining a sharp particle size distribution, and easily obtaining a fine particle toner having a small particle size of 3 to 8 μm. Is particularly preferred. Further, a sheet polymerization method in which a monomer is further adsorbed on the polymer particles once obtained and then polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed. When suspension polymerization is used as the toner production method of the present invention, toner particles can be directly produced by the following production method. Ester wax, colorant, charge control agent, polymerization initiator, and other additives are added to the monomer, and the monomer composition uniformly dissolved or dispersed by a homogenizer, an ultrasonic disperser, or the like is dispersed and stabilized. It is dispersed in an aqueous medium containing the agent using a conventional stirrer, homomixer, homogenizer or the like. Preferably, the stirring speed and time are adjusted so that the droplets of the monomer composition have a desired size of the toner particles, and the granulation is performed. After that, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization is performed at a polymerization temperature of 40 ° C. or higher, generally 50 to 90 ° C. The temperature may be increased in the latter half of the polymerization reaction, and further, in order to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner, the second half of the reaction, or a part after the completion of the reaction. The aqueous medium may be distilled off. After the reaction, the generated toner particles are collected by washing and filtration, and dried.

In the suspension polymerization method, it is usually preferable to use 300 to 3000 parts by weight of water as a dispersion medium with respect to 100 parts by weight of the monomer composition. Examples of the dispersant used include inorganic oxides such as tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide,
Examples include magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica, and alumina. As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used. These dispersants are used in an amount of 0.2 to 2.0 based on 100 parts by weight of the polymerizable monomer.
It is preferred to use parts by weight.

As these dispersants, commercially available ones may be used as they are, but in order to obtain fine and uniform dispersed particles, the inorganic compound may be formed under high-speed stirring in a dispersion medium. I can do it. For example, in the case of tricalcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring. In order to make these dispersants finer, a surfactant of 0.001 to 0.1% by weight may be used in combination. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate,
Sodium oleate, sodium laurate, potassium stearate, calcium oleate and the like are preferably used.

The toner of the present invention has a shape factor SF-
The value of 1 is 100 to 160, particularly preferably 100 to 15
At 0, toner is preferred.

In the present invention, SF-1 indicating the shape factor is used.
Means, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd.
, 100 toner images enlarged at a magnification of 500 times are sampled at random, and the image information is transmitted via an interface to, for example, an image analyzer (Luzex I, manufactured by Nicole).
Introduced in II) and analyzed, the value calculated by the following equation is defined as shape factor SF-1.

[0076]

[Outside 14] [Wherein, MXLNG indicates the absolute maximum length of the toner particles,
AREA indicates the projected area of the toner particles. ]

The shape factor SF-1 indicates the degree of roundness of the toner particles.

A toner having a toner shape factor SF-1 larger than 160 gradually changes from a spherical shape to an irregular shape, and a decrease in transfer efficiency is observed as the shape factor SF-1 decreases. When an intermediate transfer member is used to cope with various types of transfer materials, the transfer step is performed substantially twice, so that a decrease in transfer efficiency causes a decrease in toner use efficiency. Further, in recent digital full-color copying machines and digital full-color printers, a color image original is subjected to color separation using a B (blue), G (green), and R (red) filter in advance, and then 20 to
A 70 μm dot latent image is formed and a multicolor color image that is faithful to the original or color information by utilizing the subtractive color mixing action using Y (yellow), M (magenta), C (cyan), and B (black) toners. Need to be reproduced. At this time, since a large amount of Y, M, C, and B toners are applied on the photoreceptor or the intermediate transfer member in accordance with the color information of the document or the CRT, each color toner used in the present invention is extremely High transferability is required. Therefore, the ester wax is preferable in order to maintain good transferability of the toner, and a toner having a shape factor SF-1 of 100 to 160 is more preferable.

In the present invention, the toner has a shape factor SF-2, which indicates the degree of unevenness on the surface of the toner particles, of 100 to 13;
A value of 0 is preferable for improving the transferability of the toner. As with SF-1, SF-2 randomly samples 100 toner images magnified 500 times using, for example, FE-SEM (S-800) manufactured by Hitachi, Ltd. It is introduced into an image analyzer (Luzex III) manufactured by Nicolet and analyzed, and the value calculated by the following equation is defined as a shape factor SF-2.

[0080]

[Outside 15] [Where PERIME represents the perimeter of the toner particle, and AREA represents the projected area of the particle. ]

In order to faithfully develop minute latent image dots for higher image quality, the weight average diameter measured by a Coulter counter is 3 μm to 8 μm and the number variation coefficient is 3 μm.
5% or less toner is preferred. A toner having a weight average diameter of less than 3 μm has a low transfer efficiency, generates a large amount of untransferred toner on a photoreceptor or an intermediate transfer member, and is likely to cause non-uniform unevenness of an image due to fog or poor transfer. When the weight average diameter of the toner exceeds 8 μm, the resolution and dot reproducibility are reduced, and fusion to each member is apt to occur. When the number variation coefficient of the toner exceeds 35%, the tendency is further increased. Strengthen.

The particle size distribution of the toner particles can be measured by various methods. In the present invention, the measurement was performed using a Coulter counter.

For example, a Coulter Counter TA-II type (manufactured by Coulter) is used as a measuring device, and an interface (manufactured by Nikkaki) for outputting a number distribution and a volume distribution and a CX-1 personal computer (manufactured by Canon) are maintained. For the electrolyte, an approximately 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON
II (manufactured by Coulter Scientific Japan)
Can be used. The measuring method is 100 to 100
In 150 ml, 0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) is added as a dispersant,
Further, 2 to 20 mg of a measurement sample is added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the Coulter Counter TA-II was used, and a 100 μ aperture was used as an aperture. The particle size distribution is measured and the value according to the invention is determined therefrom.

Coefficient of variation A in the number distribution of toner particles
Is calculated from the following equation.

Coefficient of variation A = [S / D ₁ ] × 100 where S represents the standard deviation value in the number distribution of toner particles, and D ₁ is the number average particle size (μm) of the toner particles.
Show)

The toner of the present invention includes a lubricant powder such as Teflon powder, zinc stearate powder and polyvinylidene fluoride powder; an abrasive such as cerium oxide, silicon carbide and strontium titanate; a silica powder such as silica, titanium oxide and aluminum oxide. It is preferable to externally add a fluidity improver; an anti-caking agent; a conductivity-imparting agent such as carbon black, zinc oxide, and tin oxide.

In particular, as the inorganic fine powder, inorganic fine powder such as silicic acid fine powder, titanium oxide and aluminum oxide is preferable. The inorganic fine powder is preferably hydrophobized with a hydrophobizing agent such as a silane coupling agent, silicone oil, or a mixture thereof.

The external additive is usually used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the toner particles.

The toner of the present invention can be used as a one-component developer or a two-component developer toner.

As a one-component developing method, there is a method in which a magnetic toner in which a magnetic substance is contained in toner particles is transported and charged by using a developing sleeve containing a magnet. When a non-magnetic toner containing no magnetic material is used, a method of forcibly charging the toner on the developing sleeve using a coating blade, a coating roller, or a fur brush and causing the toner to adhere to the developing sleeve to convey the toner. is there.

On the other hand, in the case of a two-component developer, a carrier is used together with the toner of the present invention. The carrier used is not particularly limited, but mainly,
A magnetic carrier produced solely of iron, copper, zinc, nickel, cobalt, manganese or chromium element, or a magnetic ferrite carrier produced by mixing them is preferred. Saturation magnetization,
The shape of the carrier is also important because the electrical resistance can be controlled over a wide range. For example, it is preferable to select a spherical shape, a flat shape, an irregular shape, and the like, and also to control the fine structure (for example, surface unevenness) of the carrier surface. Generally, a method is used in which the inorganic oxide is calcined and granulated to generate carrier core particles in advance and then coat the resin. In order to reduce the load on the toner of the carrier, after kneading the inorganic oxide and the resin, pulverize and classify to obtain a low-density dispersed carrier, or directly knead the inorganic oxide and the monomer in an aqueous medium. It is also possible to use a method of obtaining a polymerized carrier which is subjected to suspension polymerization to obtain a true spherical dispersion carrier.

Coated carriers in which the surface of the carrier particles is coated with a resin are particularly preferred. As the method, a method in which a resin is dissolved or suspended in a solvent and applied and adhered to a carrier, a method in which the resin is simply mixed with a powder, and the like can be applied.

The substance fixed to the surface of the carrier particles varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide resin , Polyvinyl butyral, nigrosine, amino acrylate resin and the like are used alone or in combination.

The amount of the fixing substance used is generally 0.1 to 30% by weight (preferably 0.5% by weight) based on the total amount of the carrier.
-20% by weight).

The average particle size of these carriers is 10 to 100.
μm, preferably 20 to 50 μm.

For example, the surface of ternary ferrite particles of Cu—Zn—Fe is coated with a combination of a resin such as a fluororesin and a styrene resin (for example, polyvinylidene fluoride and styrene-methyl methacrylate resin; polytetrafluoroethylene). Styrene-methyl methacrylate resin,
90: a fluorine-based copolymer and a styrene-based copolymer;
10-20: 80, preferably 70: 30-30: 70
Is a mixture of 0.01 to 5% by weight,
Preferably, 0.1 to 1% by weight of coating, 250 mesh pass, 400 mesh on carrier particles 70
It is a coated ferrite carrier having the above average particle size of not less than% by weight. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (10: 9
0 to 90:10). Examples of the styrene-based copolymer include styrene-2-ethylhexyl acrylate (20:90).
80-80: 20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-3
0:10 to 50).

The coated ferrite carrier has a favorable triboelectrification property with respect to the toner of the present invention, and further has an effect of improving electrophotographic characteristics.

When a two-component developer is prepared by mixing a toner and a carrier, the mixing ratio is 2 to 15% by weight, preferably 4 to 13% by weight as the toner concentration in the developer. Would normally give good results.

The magnetic characteristics of the magnetic carrier are preferably as follows. The magnetization strength (σ ₁₀₀₀ ) at 1000 Oe after magnetic saturation is 30 to 300 emu / c.
m ³ is preferred. In order to achieve higher image quality, it is preferably 100 to 250 emu / cm ³ . When it is larger than 300 emu / cm ^3, it is difficult to obtain a high quality toner image. 30e
If it is less than mu / cm ³ , the magnetic binding force is also reduced, and carrier adhesion is likely to occur.

The method for evaluating the image density, fog, coloring power (image density), low-temperature fixability, high-temperature offset resistance, transparency, and blocking resistance of the toner will be described below.

Image Density A durability test of 10,000 multi-sheets was performed by a modified machine of a commercially available digital full-color copier (CLC-500) manufactured by Canon without the silicone oil coating device, and the image density at the initial stage and at the end of the endurance was measured by Macbeth. It is measured with a reflection densitometer (manufactured by Macbeth).

Using a remodeled commercial digital full-color copier (CLC-500) manufactured by Canon without the fogging silicone oil coating device, the whiteness of the transfer paper measured by a reflexometer (manufactured by Tokyo Denshoku Co., Ltd.) And fog is calculated from a comparison of the whiteness of the transfer paper after printing the solid white.

100 parts by weight of coloring power toner and external additives such as hydrophobic silica fine powder, hydrophobic titanium oxide fine powder and hydrophobic alumina fine powder.
1 to 3 parts by weight to prepare a toner having an external additive on the surface of the toner particles.

Using the prepared toner, an unfixed image of the toner is formed on the surface of the transfer paper by a commercially available copying machine.

For example, SK paper (manufactured by Nippon Paper Industries Co., Ltd.) is used as the transfer paper, and the transfer weight of the toner in the solid image portion is about 0.5.
An unfixed image of 5 mg / cm ² is formed on transfer paper.

As an external fixing device, the fixing device shown in FIG. 2 is used. In the fixing device shown in FIG. 2, a silicone rubber layer 4 having a thickness of 2 mm and a hardness of 30 degrees is provided on a core metal 5 having a heater 6 variably adjustable in temperature.
A fixing roller 1 having a diameter of 40 mm having a PFA resin layer 3 of 0 μm, and a silicone rubber layer 8 having a thickness of 1 mm on a cored bar 9 having a heater 10 variably adjustable in temperature are provided. A pressure roller 2 having a diameter of 40 mm and a PFA resin layer 7 having a thickness of 50 μm is provided.

In the case of a non-magnetic toner, a fixed image having a gloss level of 9 measured by irradiating incident light at an incident angle of 60 degrees is formed, and the image density is measured. And In the case of a magnetic toner, a fixed image having a gloss level of 1 is formed, the image density is measured, and the value is used as the coloring power of the magnetic toner. The glossiness is measured using a handy gloss meter gloss checker IG-310 (manufactured by Horiba, Ltd.), and the image density is measured using Macbeth RD918 (manufactured by Macbeth).

Fixing Property and Offset Resistance An unfixed image 12 having a toner transfer amount of 0.75 mg / cm ² is fixed on a transfer sheet 11 by heat and pressure using the external fixing device shown in FIG. The nip between the fixing roller 1 and the pressure roller 2 is set to 7.0 mm, and the fixing speed is 140 mm / sec.
Then, the temperature is adjusted from 120 ° C. to 250 ° C. every 5 ° C. to perform fixing.

In the case of double-sided fixing, an unfixed image 12 having a toner transfer amount of 0.75 mg / cm ² is heat-pressurized and fixed on one surface of the transfer paper 11, and then the toner is applied on the other surface of the transfer paper 11. Is heated and pressed so that the unfixed image having a transfer amount of 0.75 mg / cm ² is on the fixing roller 1 side.

The fixing property was evaluated by applying a load of 50 g / cm ² to a fixed image (including a low-temperature offset image) and applying it to a silbon paper [Lenz Cleaning Paper “das”.
per (R) "(Ozu Paper Co. Ltd.
d)], the temperature at which the density reduction rate before and after rubbing is less than 10% is defined as the fixing start point.

For the offset resistance, the temperature at which the offset disappears visually is set as the low temperature starting point, the temperature is raised, and the highest temperature without the offset is set as the high temperature end point.

Blocking Resistance 5 g of a toner having a predetermined amount of an external additive is placed in a 100 cc polyethylene cup, and allowed to stand in a dryer at a temperature of 50 ° C. for 3 days.

Next, the degree of aggregation of the toner after standing is measured using a vibration sieve of a powder tester (manufactured by Hosokawa Micron Corporation) to evaluate the blocking resistance.

The measuring method is as follows:
h, 200 mesh, 100 mesh in order of narrow opening, that is, 400 mesh, 200 mesh, 100 mesh so that 100 mesh is at the top.
Set in the order of the screen.

The above sample was added to the set 100 mesh screen, the input voltage to the shaking table was adjusted to 15 V, and the amplitude of the shaking table at that time was adjusted so as to fall within the range of 0.5 mm. Vibration is applied for 15 seconds, and thereafter, the weight of the toner aggregate remaining on each screen is measured, and the toner aggregation degree is obtained based on the following equation.

At this time, the degree of blocking resistance is evaluated in three steps based on the rate of change in the degree of aggregation, based on the degree of aggregation of the toner not placed in the dryer at 50 ° C.

○ (Good): Cohesion degree is 0% to 30% Δ (Normal): Cohesion degree is 31% to 40% x (Poor): Cohesion degree is 41% or more

[0118]

[Outside 16]

The measuring environment is 23 ° C. and 55% RH.

An unfixed image on a transparent OHP sheet (trade name: CG3300, manufactured by 3M) was nipped at 7.0 mm and fixed at a fixing speed of 35 mm /
Then, the image is fixed by heating and pressing at a fixing temperature of 180 ° C. to form a fixed image on the OHP sheet.

The obtained fixed image (0.7 mg / cm ² )
Was measured for transmittance and haze (haze) for each image density, and the transparency was evaluated using the numerical value at an image density of 1.2. The method for measuring the transmittance and haze is described below.

The transmittance was measured using a Shimadzu self-recording spectrophotometer UV.
Using a 2200 (manufactured by Shimadzu Corporation), the transmittance of the OHP film alone is set to 100%, and the transmittance at the maximum absorption wavelength at magenta toner: 650 nm, cyan toner: 500 nm, yellow toner: 600 nm Is measured.

The haze was measured using a haze meter NDH-3.
It is measured using 00A (manufactured by Nippon Shikara Kogyo).

[0124]

Next, the present invention will be described in more detail with reference to examples.

Example 1 177 parts by weight of a styrene monomer, 10 parts by weight of a cyan colorant (copper phthalocyanine pigment, primary average particle diameter: 0.3 μm) and a negative charge control agent (metal compound of di-tert-butyl salicylic acid, primary average particle diameter: 0) .3 μm) was placed in an attritor, and mixed by stirring at a temperature of 30 ° C. and a rotation speed of 200 rpm for 3 hours in the presence of spherical zirconia particles having a diameter of 2 mm. The obtained mixture was transferred to another container, and 23 parts by weight of n-butyl acrylate monomer and polar resin [terephthalic acid and propylene oxide-modified bisphenol A were used.
10 parts by weight of a saturated polyester resin (weight average molecular weight of about 7000, acid value of about 14 mg KOH / g)] and 40 parts by weight of a solid ester wax (A-1), and paddle stirring while heating to a temperature of 60 ° C. Stir for 2 hours using wings. The solid ester wax (A-1) was dissolved in the monomer, and the cyan colorant and the negative charge control agent were uniformly dispersed.

Next, the stirring device was changed to a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.), and 12 parts by weight of a polymerization initiator [2,2'-azobis (2,4-dimethylvaleronitrile)] was added. The mixture was stirred at 200 rpm for 1 minute to prepare a polymerizable monomer composition.

On the other hand, 0.10 parts by weight of ion-exchanged water
540 parts by weight of a 1M-Na ₃ PO ₄ aqueous solution is added, and 60
After heating to ° C, the mixture was stirred at 12000 rpm using a TK homomixer (manufactured by Tokushu Kika Kogyo). To this, 80 parts by weight of a 1.3 M CaCl ₂ aqueous solution was gradually added to prepare an aqueous medium containing fine particles of Ca ₃ (PO ₄ ) ₂ .

The polymerizable monomer composition was charged into an aqueous medium, and the mixture was stirred at 10,000 rpm for 10 minutes at 60 ° C. in a N ₂ atmosphere using a TK homomixer to granulate the polymerizable monomer composition. did. Thereafter, while stirring with a paddle stirring blade, the temperature was raised to 70 ° C., and a suspension polymerization reaction was performed for 11 hours to produce a styrene-n-butyl acrylate copolymer in the particles.

After the completion of the polymerization reaction, the mixture was cooled, hydrochloric acid was added to dissolve calcium phosphate, and then filtered, washed with water and dried to obtain cyan toner particles. When the cross section of the cyan toner particles was observed by TEM, as shown in FIG. 1, the ester wax (A-1) was replaced with the outer shell resin (styrene-n).
-Butyl copolymer and a polar resin).

100 parts by weight of the obtained cyan toner particles and 1.5 parts by weight of hydrophobic silica having a specific surface area of 212 m ² / g by a BET method were mixed to prepare a negatively chargeable electrically insulating cyan toner. Obtained. The weight average particle diameter of the obtained cyan toner was 6.4 μm, and SF-1 was 111.

5 parts by weight of this cyan toner and 95 parts by weight of a silicone resin-coated magnetic ferrite carrier were mixed to prepare a two-component developer for magnetic brush development.

Examples 2 to 4 I. Pigment Yellow 17 (primary average particle size: 0.3 μm), C.I. I. Pigment Red 202 (primary average particle size: 0.3 μm), graft carbon black (primary average particle size: 0.05 μm), and in the same manner as in Example 1, an electrically insulating yellow toner, an electrically insulating magenta toner, and an electrically insulating material. A black toner was obtained. The physical properties of each color toner are shown in Table 2 below. Further, a two-component developer for magnetic brush development was prepared in the same manner as in Example 1.

[0133]

[Table 2]

Evaluation Example 1 A two-component developer for magnetic brush development prepared in Examples 1 to 4 was replaced with a commercially available Canon digital full-color copying machine (C
LC-500), and the toner was successively replenished to form an unfixed image and a fixed image in a single-color mode for each color.

The unfixed image was fixed by an external fixing device to evaluate the single-sided fixing and the double-sided fixing. Table 4 shows the evaluation results.

Comparative Example 1 A cyan toner was produced and evaluated in the same manner as in Example 1 except that the following compound was used instead of the solid ester wax (A-1). Table 4 shows the results.

[0137]

[Outside 17]

Comparative Example 2 A cyan toner was prepared and evaluated in the same manner as in Example 1 except that the following compound was used instead of the solid ester wax (A-1). Table 4 shows the results.

[0139]

[Outside 18]

Comparative Example 3 A cyan toner was prepared and evaluated in the same manner as in Example 1 except that a low molecular weight polyethylene wax (PE130 manufactured by Hoechst) was used instead of the solid ester wax (A-1). Was. Table 4 shows the results.

Comparative Example 4 A low molecular weight polypropylene wax (Viscol 550 manufactured by Sanyo Chemical Co., Ltd.) was used instead of the solid ester wax (A-1).
A cyan toner was prepared and evaluated in the same manner as in Example 1 except that P) was used. Table 4 shows the results.

Comparative Example 5 A cyan toner was prepared and evaluated in the same manner as in Example 1 except that paraffin wax (weight average molecular weight: 550) was used instead of the solid ester wax (A-1). Table 4 shows the results.

Comparative Example 6 A cyan toner was prepared in the same manner as in Example 1 except that an ester wax mainly containing an ester compound represented by the following formula was used instead of the ester wax (A-1). An evaluation was performed. Table 4 shows the results.

[0144]

[Outside 19]

Examples 5 to 8 Cyan toner, yellow toner and magenta toner were prepared in the same manner as in Examples 1 to 4, except that the solid ester wax (A-6) was used instead of the solid ester wax (A-1). And a black toner. Table 3 shows the physical properties of each color toner. Table 4 shows the evaluation results of the obtained color toners.

Examples 9 to 12 Cyan, yellow, and magenta toners were prepared in the same manner as in Examples 1 to 4, except that the solid ester wax (B-1) was used instead of the solid ester wax (A-1). And a black toner. Table 3 shows the physical properties of each color toner. Table 4 shows the evaluation results of the obtained color toners.

[0147]

[Table 3]

[0148]

[Table 4]

Evaluation Experimental Example 2 Using the respective color toners of Examples 1 to 4 and the respective color toners of Examples 5 to 8, an image output test was performed in a full-color mode. The properties and color mixing were evaluated.

In one-side fixing and two-side fixing, good results were obtained, and a full-color image faithful to the original document was obtained.

[0151]

The toner of the present invention contains the above-mentioned solid ester wax (A) or (B), thereby exhibiting good coloring power, high-temperature offset resistance against high speed, and blocking resistance. Improvement can be achieved.

[Brief description of the drawings]

FIG. 1 is a schematic view of a sectional surface of a toner of the present invention in which an ester wax is included in an outer shell resin.

FIG. 2 is a schematic diagram schematically showing an external fixing device for fixing a toner image on a transfer material by heating and pressing.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Fixing roller 2 Pressure roller 6 Heater 10 Heater

────────────────────────────────────────────────── ─── of the front page continued (51) Int.Cl. ⁷ identification mark FI G03G 9/08 361 384 (72) inventor rapids KataSatoru Ota-ku, Tokyo Shimomaruko 3-chome No. 30 No. 2 Canon within Co., Ltd. (56) References JP-A-6-3856 (JP, A) JP-A-6-337540 (JP, A) JP-A-6-337541 (JP, A) JP-A-61-279864 (JP, A) (58) Survey Field (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (19)

(57) [Claims] 1. A toner having a binder resin, a colorant, a polar resin and a solid wax represented by the following formula (A) or (B), which is formed of a styrene polymer or a styrene copolymer. A toner for developing electrostatic images, characterized by the following. [Outside 1] [Wherein R ₁ and R ₃ are straight-chain alkyl groups having 6 to 32 carbon atoms.
Indicates alkyl group, R ₁ and R ₃ may be different even if the same thing, R ₂ is a straight chain having 4 to 20 carbon atoms
Shows an alkylene group. [Outside 2] [In the formula, when R ₅ is the following group (1) or (2),
₄ and R ₆ represent a straight-chain alkyl group having 6 to 32 carbon atoms, R ₄ and R ₆ may be the same or different, and when R ₅ is the following group (3), ₄ and R ₆ represent a linear alkyl group having 10 to 25 carbon atoms;
₄ and R ₆ may be the same or different. —CH ₂ CH ₂ OC ₆ H ₄ OCH ₂ CH ₂ — (1) 2. The toner particles are prepared by dispersing a polymerizable monomer composition containing at least a polymerizable monomer containing styrene, a colorant, a polar resin and an ester wax in an aqueous medium. The electrostatic charge image according to claim 1, wherein the resin particles are colored resin particles having a binder resin formed by forming particles of the body composition and polymerizing the polymerizable monomer in the particles of the polymerizable monomer composition. Development toner. 3. The toner particles have a shape factor SF-1 of 10
0 to 150, and the shape factor SF-2 is 100 to 130.
The toner for developing an electrostatic charge image according to claim 1, wherein 4. The toner particles have a shape factor SF-1 of 10
0 to 150, and the shape factor SF-2 is 100 to 130.
The electrostatic image developing toner according to any one of claims 1 to 3, wherein the solid ester wax is encapsulated in the toner particles by an outer shell resin layer formed of a binder resin and a polar resin. 5. The electrostatic image developing toner according to claim 1, wherein the binder resin is a styrene-acrylate copolymer and the polar resin is a polyester resin. 6. The electrostatic image developing toner according to claim 1, wherein the binder resin is a styrene-methacrylate copolymer, and the polar resin is a polyester resin. 7. The solid ester wax is a binder resin 10
The toner according to any one of claims 1 to 6 , wherein the toner is contained in an amount of 5 to 40 parts by weight per 0 parts by weight. 8. The solid ester wax is a binder resin 10
2. The composition according to claim 1, wherein the content is 10 to 30 parts by weight per 0 parts by weight.
8. The toner for developing an electrostatic image according to any one of items 1 to 7 . 9. The toner particles The toner according to any one of claims 1 to 8 is a cyan toner particles of the non-magnetic. 10. The toner particles The toner according to any one of claims 1 to 8 which is yellow toner particles of non-magnetic. 11. The toner particles The toner according to any one of claims 1 to 8 which is a non-magnetic magenta toner particles. 12. The toner particles The toner according to any one of claims 1 to 8 is a black toner particles of the non-magnetic. 13. A solid ester wax having a melting point of 40.
The toner according to any one of claims 1 to 12 is to 90 ° C.. 14. A solid ester wax having a melting point of 55.
The toner for developing an electrostatic charge image according to any one of claims 1 to 12 , which has a temperature of from -85 ° C. 15. The solid ester wax has a solubility parameter (SP) value of the toner for electrostatic image development according to any one of claims 1乃<br/> optimum 14 is 7.5 to 10.5. 16. The solid ester wax has a temperature of 130.
2. The melt viscosity at a temperature of 1 to 300 cPs.
16. The electrostatic image developing toner according to any one of items 15 to 15 . 17. The solid ester wax has a temperature of 130.
The electrostatic image developing toner according to any one of claims 1 to 15 , having a melt viscosity at 3C of 3 to 50 cPs. 18. The solid ester wax, toner according to any one of claims 1 to 17 Vickers hardness of 0.3 to 5.0. 19. The solid ester wax, toner according to any one of claims 1 to 17 Vickers hardness of 0.5 to 3.0.