JP2002278158A - Toner for image formation and two-component developer using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner for image formation which is useful as recycled toner. SOLUTION: This toner for image formation is used for an image forming method which recycles toner cleaned by a cleaning part and obtained by adding external additives to toner base particles composed of at least a coloring agent, binding resin, and an electric charge control agent; and respective values are substituted in X=(B/A)×(ΣC/D), where A is the toner electrostatic charging quantity of the toner base particles, B the toner electrostatic charging quantity after the addition of >=1 additive to the toner base particles, ΣC the sum of the mean particle sizes of the external additives, and D the mean particle size of the toner base body, and X is within a range of -2.3<=X<=2.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for forming a monochrome image and a color image used in an electrophotographic system, and a two-component developer using the toner.

[0002]

2. Description of the Related Art Generally, in an electrophotographic apparatus, a latent image on an electrostatic latent image carrier is developed with colored particles (toner), and the toner image is transferred to a transfer member. Thereafter, the toner image is fixed by a fixing device. . The electrostatic latent image carrier after the transfer of the toner is cleaned by a cleaning device to remove the remaining toner without being transferred, collected in a collection container, and discarded. If the recycled toner for reusing the residual toner can be used effectively, resources can be effectively used.

However, when the recycled toner is used, paper dust of the transfer paper is mixed in, and the toner in which the external additive is buried or peeled is mixed in, so that problems such as background fouling and toner scattering are likely to occur. It is said to be.

In using recycled toner, Japanese Patent Application Laid-Open No. 7-209902 states that the amount of a release agent and the amount of an external additive are specified to suppress deterioration of the carrier and improve the durability. In Japanese Patent Application Laid-Open No. H11-95553, the fluidity and charge stability of the toner are improved by a combination of toners that keeps the external additive amount of the initial toner smaller than the external additive amount of the replenishing toner. Japanese Patent Application Laid-Open No. H11-153881 discloses that, in a toner to which two types of fine particles are added and a toner to which two types of fine particles are added, the charge amount of the toner is the same as that of the toner base particles without additives. The transfer efficiency is high and the amount of waste toner is reduced by a combination between the charge amounts of

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for developing an electrostatic latent image on an electrostatic latent image carrier by a developing section having a developer carrier layer formed thereon. The developing section contains a two-component developer composed of a carrier and a toner. The developer is circulated and conveyed on the developer carrier, and a developing region in a gap between the developer and the opposing electrostatic latent image carrier. To develop the electrostatic latent image, and the toner image formed on the electrostatic latent image carrier is
Transferred to the transfer member one or more times,
The electrostatic latent image carrier is cleaned by a cleaning unit, and the toner cleaned by the cleaning unit is returned to a developing unit or a replenishing toner unit via a toner collecting device, and is extremely useful for reuse as recycled toner. An object of the present invention is to provide a useful image forming toner.

It is common practice to add an external additive to the toner base particles as described above. The purpose is to improve the fluidity and appropriately polish the surface of the carrier or the surface of the electrostatic latent image carrier to prevent the deterioration of the carrier or the electrostatic latent image carrier. Also, this is because the chargeability is improved. The external additive added to the toner base particles is separated from the toner base particles by the stirring in the developing device, the mechanical stress in the cleaning device, or the recovery path recovered from the cleaning device to the developing device, or the toner is removed. Embedding (embedding) in the base particles occurs.

When such a result occurs, in particular, the chargeability of the toner particles becomes unstable, so that, for example, the image density in the copy quality becomes low, or the image density becomes too high, and the background becomes dirty. I do. Further, the toner is scattered significantly in the apparatus, and the toner transfer efficiency is further reduced. As a result, it takes too much load to clean the latent image carrier in the cleaning process, and the toner cannot be sufficiently cleaned. Further, in a place where the use environment is different, a change in the amount of charge is remarkably changed in each environment, and the above problem is promoted.

[0008]

The inventors of the present invention have studied the toner from various angles. As a result, the present inventors have specified the binder resin of the toner, the charge amount (A) of the toner base particles and the toner base particles. The ratio (B / A) of the charge amount (B) to which the external additive is added, and the sum of the average particle size of the external additive (Σ
C), a ratio (Σ) where the average particle size of the toner base particles is (D).
It has been found that by defining the two products of C / D), good image quality can be obtained even when used as a recycled toner. The present invention has been made based on this.

Therefore, according to the present invention, the following (1) to
(14) is provided. (1) A toner used in an image forming method for reusing a toner collected by a cleaning unit of an electrostatic latent image carrier as a recycled toner, wherein the toner matrix includes at least a colorant, a binder resin, and a charge control agent It is composed of particles having an external additive added thereto, wherein the binder resin is an epoxy resin,
A polyol (A) obtained by reacting an alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof, a dihydric phenol, and a compound having one active hydrogen that reacts with an epoxy group in a molecule; A polyol (B) obtained by reacting a dihydric phenol with a compound having one active hydrogen in the molecule that reacts with an epoxy group, and the toner base particles have a toner charge amount of A; When the toner charge amount after adding at least one or more external additives to the base particles is B, the sum of the average particle diameters of the external additives is ΔC, and the average particle size of the toner base particles is D, X = (B / A) × (ΔC / D) The value of X is in the range of −2.3 ≦ X ≦ 2.3.

(2) The epoxy resin constituting the polyol (A) is at least two kinds of bisphenol A type epoxy resins having different number average molecular weights, and the number average molecular weight of the low molecular weight component is from 360 to 2,000, The image forming toner according to (1), wherein the number average molecular weight of the molecular weight component is 3,000 to 10,000.

(3) The epoxy resin constituting the polyol (A) is at least two or more bisphenol A type epoxy resins having different number average molecular weights, wherein the low molecular weight component is 20 to 60 wt% and the high molecular weight component is 5 to 5 wt%. The image forming toner according to the above (1) or (2), wherein the amount is 40 wt%.

(4) The alkylene oxide adduct of dihydric phenol or the glycidyl ether thereof constituting the polyol (A) is a diglycidyl ether of an alkylene oxide adduct of bisphenol A, and is represented by the following general formula (1). (1) characterized in that
The image forming toner according to any one of (1) to (3). General formula (1)

Embedded image (In the formula, n and m are the numbers of repeating units, each is 1 or more, and n + m = 2 to 6.)

(5) The alkylene oxide adduct of a dihydric phenol constituting the polyol (A) or its glycidyl ether is added to the epoxy resin in an amount of 10 to 50.
(1) to (1) above, wherein
The image forming toner according to any one of (4) and (4).

(6) The above (1), wherein the number average molecular weight of the polyol (B) is from 200 to 10,000.
The image forming toner according to any one of (1) to (5).

(7) The toner binder resin is a polyol (B)
(1) to (10), characterized by containing 20 to 50% by weight of
The image forming toner according to any one of the above (6).

(8) The image forming toner according to any one of the above (1) to (7), which comprises a metal salt of salicylic acid and / or a metal salt of a salicylic acid derivative as a charge control agent.

(9) The image forming toner according to any one of the above (1) to (8), wherein the colorant is black.

(10) Yellows whose colorants are different from each other,
(1) to (1), which are magenta and cyan.
(8) The toner for forming a color image according to any of (8).

(11) Yellows whose colorants are different from each other,
The color image forming toner according to any one of the above (1) to (8), which is magenta, cyan, and black.

(12) Consisting of carrier particles and toner particles, the carrier particles being silicon, fluorine or fluorine /
It has a coating layer of styrene / acryl, amino resin or resin composed of amino resin / styrene / acryl, and the toner particles are made of the toner described in any one of the above (1) to (11). Two-component developer.

(13) The two-component developer as described in (12) above, wherein the coating layer of the carrier particles contains a conductive material.

(14) The carrier particles consist of spherical particles having irregularities formed by a discontinuous phase in which the crystal state of the surface is molten, and a resin coating layer is provided on the surface thereof. The two-component developer as described in any one of (1) to (13) above, wherein the two-component developer has a coating layer such that the uneven portion can be recognized.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As pointed out in the above-mentioned prior art, when an external additive added to the toner base particles was detached or embedded in the toner base particles, the charge amount became unstable. It was confirmed that when the ratio (B / A) of the charge amount (A) of the base particles and the charge amount (B) after adding the external additive to the toner base particles was far apart, the charge amount was remarkably unstable. If this ratio is close to 1, almost A
= B, and even if the external additive added to the toner base particles is detached or buried in the toner base particles, the charge amount is almost A = B. The change in the charge amount between the particle surface and the carrier particles is small.

On the other hand, when the ratio is small or large, the difference in charge amount from the carrier particles is remarkably large (the charge amount is far apart). Therefore, when a phenomenon occurs in which the external additive added to the toner base particles is detached or buried in the toner base particles, the charge amount is dominated by the charge of the toner base particles and the carrier. Will contribute to the quantity (A). As a result, the charge (amount) in the developer becomes unstable, and the above-described problem occurs. In addition, addition of a plurality of external additives is sometimes and occasionally caused. For this reason, different particles may aggregate to increase the particle size of the additive. If the ratio (ΔC / D) of the sum (ΔC) of the average particle diameters of the external additives to the average particle diameter (D) of the toner base is too small, the external additives will not be used when mixing the toner base and the external additives. Easy to be buried in. Also,
When the temperature rises during use in the machine due to agitation in the developing section, it is very easy to be buried even when the temperature rises, so that the effect of adding an external additive is unlikely to appear.

On the other hand, if this ratio is too large, the external additive is less likely to adhere to or adhere to the toner matrix when the toner matrix and the external additive are mixed, and the amount of free external additive in the developer increases, resulting in charging of the developer. Of the toner, or damage to the electrostatic latent image carrier, or filming of a free external additive may significantly impair the formation of a latent image. Further, in roller fixing, if the roller surface is damaged, or if a release agent (silicone oil) is applied, the release agent adheres to the application member and the release agent cannot be supplied, thereby causing an offset. Further, since the external additive is remarkably easily detached even during use in the machine, the above-mentioned problem is likely to occur at the same time. For this reason, it is necessary to satisfy the condition of −2.3 ≦ (B / A) × (ΔC / D) ≦ 2.3.

Next, the toner binder resin will be described. The present invention relates to a polyol (A) which caps the end of an epoxy resin and has a polyoxyalkylene moiety in the main chain, and a polyol (B) which caps the end of an epoxy resin and does not have a polyoxyalkylene moiety. Environmental stability, stable fixing image, prevention of transfer of toner image to the sheet when copy-fixed image adheres to vinyl chloride sheet, and high production with improved pulverizability by using the combined toner binder resin It is effective in color reproducibility, stable gloss, and prevents curling of a copy-fixed image, not only when it is used for a black toner, but also especially when it is used for a color toner.

The epoxy resin used for the polyol (A) used in the present invention is preferably bisphenol A
And bisphenol F such as bisphenol F and epichlorohydrin. Epoxy resins are at least two or more bisphenol A type epoxy resins having different number average molecular weights in order to obtain stable fixing characteristics and gloss, and the number average molecular weight of the low molecular weight component is 360 to 360.
2000, and the number average molecular weight of the high molecular weight component is 300
It is preferably from 0 to 10,000. Furthermore, the low molecular weight component is 20 to 60 wt%, and the high molecular weight component is 5 to 40 w
It is preferably t%. If the molecular weight is too high, or if the molecular weight is lower than 360, the gloss will be too high and the toner storability will be poor. Further, when the amount of the high molecular weight component is too large, or when the molecular weight is higher than 10,000, gloss is hardly produced, and the toner fixability is not good.

Examples of the alkylene oxide adduct of dihydric phenol used in the present invention include the following. Examples include reaction products of ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof with bisphenols such as bisphenol A and bisphenol F. The resulting adduct may be glycidylated with epichlorhydrin or β-methylepichlorohydrin before use. In particular, a glycidyl ether of an alkylene oxide adduct of bisphenol A represented by the general formula (1) is preferable. It is preferable that the alkylene oxide adduct of dihydric phenol or its glycidyl ether is contained in an amount of 10 to 40% by weight based on the epoxy resin. If the amount is too small, problems such as large curl of the copy paper may occur. Also, in the above general formula (I), n + m is more than 8, or if the amount is too large, the gloss becomes too high, and the toner storability becomes poor. Not good.

Examples of the dihydric phenol used in the present invention include reaction products with bisphenols such as bisphenol A and bisphenol F.

Further, as the compound having one active hydrogen which reacts with an epoxy group in the molecule used in the present invention, the following compounds are exemplified. Examples include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol and the like.

To obtain the polyol (A) of the present invention, various combinations of raw materials are possible, but an epoxy resin having glycidyl groups at both terminals and a glycidyl group having two terminals at both terminals are available.
It is most preferable to react a divalent phenol with an alkylene oxide adduct of a divalent phenol, a compound having one active hydrogen which reacts with an epoxy group in a molecule, and a divalent phenol.

The polyol (B) used in the present invention preferably has a number average molecular weight of 2,000 to 10,000, and contains 10 to 50% by weight of the polyol (B) in the toner binder resin. Here, if the molecular weight is too small, the gloss will be too high and the storage stability of the toner will be poor. Further, the fixability of the toner is not good. Further, if the content of the polyol (B) is too small, the pulverizability is not good.

Synthesis Example of Polyol Resin: The following methods are used to measure the softening point and Tg of the polyol resin. As a device for measuring the softening point, a fully automatic dropping device FP5 / FP53 manufactured by Metra Co., Ltd. is used and the softening point is measured according to the following procedure.

After the pulverized sample is placed in a melting pot and left for 20 minutes, the sample is poured to the edge of the sample cup (droplet diameter: 6.35 mm), cooled to room temperature, and set in a cartridge. Set the temperature rise rate (1 ° C./min) measurement start temperature (set the initial softening temperature to 15 ° C.) in the FP-5 control unit. After mounting the cartridge in the FP-53 heating furnace and leaving it for 30 seconds, the start lever is depressed to start the measurement (the following measurements are automatically performed). When the measurement is completed, remove the cartridge.

The softening point (° C.) is calculated as follows. F
P-5 value of the result display panel A + correction value (adding the above correction value to the obtained result corresponds to the result of the Duran mercury method. In addition, the value of the result display panel A and the measurement start temperature (panel B If the difference between the two values is not more than 15 ° C, repeat the test.)

Next, as a device for measuring Tg, a DSC-200 manufactured by Seiko Electronics Co., Ltd. is used, and the Tg is measured according to the following procedure. The sample is crushed, weighing 10 ± 1 mg is weighed in an aluminum sample container, and an aluminum lid is placed on the sample container. The glass transition point (Tg) is measured by a DSC method in a nitrogen atmosphere.

The analysis conditions were as follows.
After heating to 150 ° C. at 150 ° C./min, the sample was left at 150 ° C. for 10 minutes, cooled to 0 ° C. at a cooling rate of 50 ° C./min, left for 10 minutes, and then placed in a nitrogen atmosphere (200 cc / mi).
In step n), the sample is heated again to a temperature of 150 ° C. at a heating rate of 20 ° C./min, and the DSC is measured. As for Tg, the peak rising temperature is read using analysis software (Tg job).

(Synthesis Example 1) A low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 360) was placed in a separal flask equipped with a stirrer, a thermometer, a nitrogen inlet, and a condenser.
378.4 g, high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight: about 2700) 86.0
g, a diglycidylation product of a bisphenol A type propylene oxide adduct (in the general formula (1), n +
m: about 2.1) 191.0 g, bisphenol F27
4.5 g, 70.1 g of p-cumylphenol and 200 g of xylene were added. The temperature was raised to 70 to 100 ° C. in a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
The temperature was raised to 0 ° C., xylene was distilled off under reduced pressure, and polymerization was carried out at a reaction temperature of 180 ° C. for 6 to 9 hours.
1000 g of a modified epoxy polyol resin having a Tg of 58 ° C. was obtained (hereinafter referred to as “resin 1”).

(Synthesis Example 2) Using the apparatus of Synthesis Example 1,
205.3 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 360), high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight:
About 3000) 54.0 g, a diglycidylation product of a bisphenol A-type propylene oxide adduct (in the general formula (1), n + m: about 2.2) 432.0 g, bisphenol F 282.7 g, p-cumylphenol 2
6.0 g and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 109 ° C. and a Tg of 58 ° C. (hereinafter referred to as “resin 2”).

(Synthesis Example 3) Using the apparatus of Synthesis Example 1,
252.6 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 360), high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight:
About 10000) 112.0 g, a diglycidylated product of a bisphenol A-type propylene oxide adduct (in the general formula (1), n + m: about 5.9) 336.0 g,
255.3 g of bisphenol AD, 44.1 g of p-cumylphenol, and 200 g of xylene were charged into a separal flask. In a nitrogen atmosphere, the temperature was raised to 70 to 100 ° C,
0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and the mixture was polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours to obtain a softening temperature of 109 ° C. and a Tg of 58.
Thus, 1000 g of a modified epoxy polyol resin at a temperature of ° C was obtained (hereinafter referred to as resin 3).

(Synthesis Example 4) Using the apparatus of Synthesis Example 1,
289.9 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 2400), 232.0 g of high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight: about 10,000), and bisphenol A type ethylene oxide adduct Diglycidylated product (in the general formula (1), n + m: about 6.0) 309.0
g, bisphenol AD 117.5 g, p-cumylphenol 51.6 g, and xylene 200 g were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
The xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours.
1000 g of a modified epoxy polyol resin at 61 ° C. was obtained (hereinafter referred to as “resin 4”).

(Synthesis Example 5) Using the apparatus of Synthesis Example 1,
430.0 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: 460), 188.0 g of high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight: about 6500), diglycidyl of bisphenol A type ethylene oxide adduct (In the above general formula (1), n + m: about 5.9) 116.0 g, bisphenol F 209.2 g, p-cumylphenol 4
7.5 g and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 107 ° C and a Tg of 57 ° C (hereinafter referred to as resin 5).

(Synthesis Example 6) Using the apparatus of Synthesis Example 1,
244.5 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 680), high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight:
188.0 g of bisphenol A type ethylene oxide adduct (n + m: about 7.9 in the general formula (1)) 348.0 g, bisphenol AD 169.9 g, p-cumylphenol 49.6 g And 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Softening temperature 112 ° C, Tg 59 ° C
Thus, 1000 g of a modified epoxy polyol resin was obtained (hereinafter referred to as resin 6).

(Synthesis Example 7) Using the apparatus of Synthesis Example 1,
258.3 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 680), high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight:
199.0 g of a diglycidylated bisphenol A-type ethylene oxide adduct (in the general formula (1), n + m: about 4.2) 276.0 g, 198.3 g of bisphenol A, and p-cumylphenol 6
8.3 g and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization was conducted for 9 hours to obtain 1,000 g of a modified epoxy polyol resin having a softening temperature of 114 ° C. and a Tg of 60 ° C. (hereinafter referred to as “resin 7”).

(Synthesis Example 8) Using the apparatus of Synthesis Example 1,
17.6 g of low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 2000) 423.0 g of high molecular weight bisphenol A type condensed diglycidyl ether (number average molecular weight: about 11000), diglycidyl of bisphenol A type ethylene oxide adduct 385.0 g of a compound (n + m: about 6.2 in the general formula (1)), 109.6 g of bisphenol F, p-cumylphenol 6
4.7 g and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization was conducted for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 118 ° C and a Tg of 62 ° C (hereinafter referred to as resin 8).

(Synthesis Example 9) Using the apparatus of Synthesis Example 1,
438.1 g of low molecular bisphenol A type diglycidyl ether (number average molecular weight: about 300), high molecular bisphenol A type condensed diglycidyl ether (number average molecular weight:
53.0 g of bisphenol A type ethylene oxide adduct (n + m: about 1.9 in the general formula (1)), 108.0 g, 347.9 g of bisphenol AD, and 51.9 g of p-cumylphenol. And 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Softening temperature 112 ° C, Tg 59 ° C
Thus, 1,000 g of a modified epoxy polyol resin was obtained (hereinafter referred to as resin 9).

(Synthesis Example 10) Using the apparatus of Synthesis Example 1, 251.2 g of low-molecular bisphenol A type diglycidyl ether (number average molecular weight: about 400) and high molecular bisphenol A type condensed diglycidyl ether (number Average molecular weight: about 6500) 50.0 g, diglycidylated bisphenol A type ethylene oxide adduct (n + m in the above general formula (1): about 2.0) 400.0 g,
276.0 g of bisphenol F, 22.7 g of p-cumylphenol, and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Softening temperature 112 ° C, Tg 59 ° C
Thus, 1000 g of a modified epoxy polyol resin was obtained (hereinafter referred to as resin 10).

(Synthesis Example 11) Using the apparatus of Synthesis Example 1, 82.3 g of a low molecular weight bisphenol A type diglycidyl ether (number average molecular weight: about 680) and a high molecular weight bisphenol A type condensed diglycidyl ether (number 683.0 g of an average molecular weight: about 6500), 125.0 g of a diglycidylation product of a bisphenol A-type ethylene oxide adduct (in the general formula (1), n + m: about 4.0),
9.3 g of bisphenol A, p-cumylphenol 18
0.0 g and 200 g of xylene were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C, and xylene was distilled off under reduced pressure.
Polymerization was carried out for 9 hours to obtain 1000 g of a modified epoxy polyol resin having a softening temperature of 118 ° C and a Tg of 63 ° C (hereinafter referred to as resin 11).

(Synthesis Example 12) Using the apparatus of Synthesis Example 1, 528.0 g of bisphenol A-type diglycidyl ether (number average molecular weight: about 340), 472.0 g of p-cumylphenol, and 200 g of xylene were separated by separal. The flask was charged. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
Then, xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours to obtain 1000 g of an epoxy polyol resin having a molecular weight of about 350 (hereinafter referred to as resin 12).

(Synthesis Example 13) Using the apparatus of Synthesis Example 1, 590.3 g of low-molecular bisphenol A-type diglycidyl ether (number average molecular weight: about 340), 263.9 g of p-cumylphenol and 200 g of xylene were used. It was charged in a separal flask. The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
The temperature was raised to 60 ° C, and xylene was distilled off under reduced pressure.
At a reaction temperature of 6 to 9 hours to give a molecular weight of about 110
Thus, 1000 g of an epoxy polyol resin (hereinafter referred to as resin 13) was obtained.

(Synthesis Example 14) Using the apparatus of Synthesis Example 1, 627.3 g of low-molecular bisphenol A-type diglycidyl ether (number average molecular weight: about 340), 232.5 g of bisphenol A, 140 p-cumylphenol. 2
g and xylene 200 g were charged into a separal flask.
The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Thus, 1000 g of an epoxy polyol resin having a molecular weight of about 2000 was obtained (hereinafter referred to as resin 14).

(Synthesis Example 15) Using the apparatus of Synthesis Example 1, 647.6 g of low-molecular bisphenol A-type diglycidyl ether (number average molecular weight: about 340), 280.0 g of bisphenol A, and 72.000 g of p-cumylphenol. 4
g and xylene 200 g were charged into a separal flask.
The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Thus, 1000 g of an epoxy polyol resin having a molecular weight of about 4000 was obtained (hereinafter referred to as Resin 15).

(Synthesis Example 16) Using the apparatus of Synthesis Example 1, 660.5 g of low-molecular bisphenol A-type diglycidyl ether (number average molecular weight: about 340), 310.0 g of bisphenol A, and 290.0 g of p-cumylphenol. 5
g and xylene 200 g were charged into a separal flask.
The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Thus, 1000 g of an epoxy polyol resin having a molecular weight of about 10,000 was obtained (hereinafter referred to as resin 16).

(Synthesis Example 17) Using the apparatus of Synthesis Example 1, 661.9 g of low-molecular bisphenol A type diglycidyl ether (number average molecular weight: about 340), 313.4 g of bisphenol A, p-cumylphenol 24. 7
g and xylene 200 g were charged into a separal flask.
The temperature was raised to 70 to 100 ° C. under a nitrogen atmosphere, 0.183 g of lithium chloride was added, the temperature was further raised to 160 ° C., xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours. Thus, 1000 g of an epoxy polyol resin having a molecular weight of about 12,000 was obtained (hereinafter referred to as resin 17).

(Synthesis Example 18) Using the apparatus of Synthesis Example 1, 411.9 g of a low-molecular bisphenol A-type diglycidyl ether (number average molecular weight: about 684) and a diglycidylated product of a bisphenol A-type ethylenoxide adduct ( In the general formula (1), n + m: about 3.8) 35
0.0 g, 199.2 g of bisphenol A, 180.0 g of p-cumylphenol, and 200 g of xylene were charged into a separal flask. 313.4 g, p-cumylphenol 38.9 g, and xylene 200 g were charged into a separal flask. The temperature was raised to 70 to 100 ° C under a nitrogen atmosphere, and 0.183 g of lithium chloride was added.
The xylene was distilled off under reduced pressure, and polymerized at a reaction temperature of 180 ° C. for 6 to 9 hours.
1000 g of a modified epoxy polyol resin at 58 ° C. was obtained. (Hereinafter referred to as resin 18)

The above resin may be mixed with another resin in the binder resin. For example, as an example, homopolymers of styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene and a substituted product thereof; styrene / p-chlorostyrene copolymer, styrene / propylene copolymer, and styrene / vinyl toluene copolymer Polymer, styrene / vinylnaphthalene copolymer, styrene / methyl acrylate copolymer,
Styrene / ethyl acrylate copolymer, styrene / butyl acrylate copolymer, styrene / octyl acrylate copolymer, styrene / methyl methacrylate copolymer, styrene / ethyl methacrylate copolymer, styrene / butyl methacrylate Copolymer, styrene / α-chloromethyl methacrylate copolymer, styrene / acrylonitrile copolymer, styrene / vinyl methyl ketone copolymer, styrene / butadiene copolymer, styrene / isoprene copolymer, styrene / maleic acid Styrene-based copolymers such as copolymers; acrylate-based homopolymers such as polymethyl acrylate, polybutyl acrylate, polymethyl methacrylate, and polybutyl methacrylate; and copolymers thereof; polyvinyl chloride, poly Polyvinyl derivatives such as vinyl acetate;
Examples include polyester-based polymers, polyurethane-based polymers, polyamide-based polymers, polyimide-based polymers, aliphatic or alicyclic hydrocarbon resins, and aromatic petroleum resins. It is not limited to. Among them, a styrene-acrylic copolymer resin and a polyester resin are more preferable in terms of good binding properties, electrical properties, cost and the like.

The following are specific examples of the coloring agent.

(Examples of Black Colorant) Carbon black, spirit black, aniline black (CI PIGMENT BLACK 1)

(Example of Yellow Colorant) I. PIGMENT YELLOW 1 Symuller Fast Yellow GH-B
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. PIGMENT YELLOW 3 Simulator Fast Yellow 10GH
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. Pigment Yellow 12 Linol Yellow GRO (manufactured by Toyo Ink Mfg. Co., Ltd.) Symler Fast Yellow GF (manufactured by Dainippon Ink and Chemicals, Inc.) C.I. I. PIGMENT YELLOW 13 Simulator Fast Yellow GRF
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. PIGMENT YELLOW 14 Symler Fast Yellow 5GF
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. PIGMENT YELLOW 17 Symler Fast Yellow 8GF
(Manufactured by Dainippon Ink and Chemicals, Inc.) Linol Yellow FGN (manufactured by Toyo Ink Manufacturing Co., Ltd.) I. Pigment Yellow 154 Chromofine Yellow 2080 (manufactured by Dainichi Seika) C.I. I. Pigment Yellow 180 PV Fast Yellow HG (Clariant)

(Colorant for magenta) I. Pigment Red 5 Symler Fast Red 4188N (manufactured by Dainippon Ink and Chemicals) C.I. I. PIGMENT RED 22 Seikafast Scarlet G (manufactured by Dainichi Seika Co., Ltd.) Symler Fast Scarlet BG
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. PIGMENT RED 48: 1 Linol Red 2B FG-3303-G (manufactured by Toyo Ink Mfg. Co., Ltd.) Symler Red 3109 (manufactured by Dainippon Ink and Chemicals, Inc.) I. PIGMENT RED 57: 1 Linol Red 6B FG-4215 (manufactured by Toyo Ink Mfg. Co., Ltd.) Symler Brilliant Carmine
6B273 (Dainippon Ink) PV Ruby L6B (Clariant) C.I. I. Pigment Red 112 Oriental Fast Red GR (Toyo Ink Mfg. Co.) C.I. I. Pigment Red 114 Pollux Pink PM-2B (Sumika Color) C.I. I. PIGMENT RED 122 Hostaperm Pink E02 (manufactured by Clariant) Fastogen Super Magenta R
(Manufactured by Dainippon Ink and Chemicals, Inc.) I. Pigment Red 166 Fastogen Super Red R (manufactured by Dainippon Ink and Chemicals, Inc.) C.I. I. PIGMENT RED 184 Permanent Rubin F6B (manufactured by Clariant)

(Example of Cyan Colorant) I. PIGMENT BLUE 15: 3 Chromofine Blue 4920 (manufactured by Dainichi Seika) Fastogen Blue FGF (manufactured by Dainippon Ink and Chemicals) Linol Blue FG-7351 (manufactured by Toyo Ink Mfg.) C.I. I. Pigment Blue 16 Heliogen Blue 16 (manufactured by BASF) C.I. I. Pigment Green 7 Phthalocyanine Green (manufactured by Toyo Ink Mfg. Co., Ltd.) C.I. I. PIGMENT GREEN 36 Cyanine Green 2 YL (manufactured by Toyo Ink Mfg. Co., Ltd.)

Of the colorants, yellow, magenta, and cyan are useful for obtaining a full-color image, and black toner is useful in addition to yellow, magenta, and cyan to obtain a full-color image. . The amount of the coloring agent is suitably from 0.1 to 50 parts by weight, more preferably from 0.5 to 25 parts by weight, based on 100 parts by weight of the binder resin.

The toner of the present invention may contain a charge control agent, if necessary. As the charge control agent, any known charge control agents can be used. For example, nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxy amines, quaternary ammonium salts (fluorine-modified) Quaternary ammonium salts), alkylamides, phosphorus simple substances or compounds,
A simple substance or compound of tungsten, a fluorine-based activator, a metal salt of salicylic acid such as a metal compound of an aromatic carboxylic acid, a metal salt of a salicylic acid derivative, and the like are preferable. In particular, salicylic acid metal salts such as aromatic carboxylic acid metal compounds, and
The metal salt of the salicylic acid derivative has a high charging speed and a uniform charging distribution, so that it does not cause stains on the electrostatic latent image carrier, toner scattering in the machine, and background stains on the image area.

In the present invention, the amount of the charge control agent used is determined by the method of producing the toner, including the type of the binder resin, the additive used, and the dispersion method, and is not specifically limited. Preferably, it is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 100 parts by weight of the binder resin.
If the amount is less than 0.1 part by weight, the charging of the toner is insufficient, which is not practical. When the amount exceeds 10 parts by weight, the chargeability of the toner is too large, and in the case of a two-component developer, the electrostatic attraction force with the carrier increases, so that the fluidity of the developer decreases and the image density decreases. Invite. Further, the charge control agent may be used in combination with a plurality of charge control agents as needed.

The amount of the additive to the toner base particles is 0.02 to 100 parts by weight of the toner base.
6.5 parts by weight, more preferably 0.05 to 4.8 parts by weight, is preferred. This additive has a good effect when it has a specific surface area of 25 to 450 m ² / g by nitrogen adsorption measured by the BET method. Also, if necessary, hydrophobization,
It may be treated with a treating agent such as silicone oil, a coupling agent, an organic titanium compound or the like for the purpose of charge control or the like, which is a preferable form. For example, colloidal silica, hydrophobic silica, fatty acid metal salts (zinc stearate, aluminum stearate, etc.), metal oxides (titanium oxide,
Cerium oxide, silicon carbide, strontium titanate, aluminum oxide, tin oxide, antimony oxide), a fluoropolymer, or the like.

Further, in order to use a so-called oil-less fixing method in which a releasing agent such as oil is not used at the time of fixing the toner, wax such as polyethylene wax, propylene wax and carnauba wax is contained in the toner particles. It can be realized by things. As the usage of these,
Although it depends on the type of material to be used and the fixing method, it may be about 0.
It is preferable to use about 5 to 10.0% by weight,
It is more preferable to use about 8.0% by weight.

The method for producing the toner particles of the present invention includes:
The raw materials as described above are kneaded by a known method such as a twin roll, a twin screw extruder, a single screw extruder or the like, and this is pulverized and classified by a known method such as a mechanical method or an air flow method to form toner base particles. Can be created. Alternatively, a method of directly manufacturing a toner from a monomer, a colorant, and an additive by a suspension polymerization method or a non-aqueous dispersion polymerization method may be used.

The particle size of the toner is preferably 3 to 10 μm,
If m is exceeded, it is difficult to obtain a smooth gradation, and the resolution is reduced. If it is less than 3 μm, the rise of the charge amount is good, but the tendency of toner scattering and contamination of the carrier surface becomes significant.

The measurement of the particle size of the toner is carried out by COULTER.
COUNTER MODELTA2 (Coulter)
And an interface for outputting a number distribution and a volume distribution is used, and an aperture (pore) of 10 μm is used. First, a toner measurement sample is dispersed in a surfactant added to an electrolytic aqueous solution. The sample was added to another 1% Nac
Injecting into the electrolytic solution, a current is passed between the electrodes through the electrolytic solution in which electrodes are placed on both sides of the aperture of the aperture tube, and the particle size distribution of 2 to 40 μm particles is measured from this resistance change, The volume average particle size is determined from the volume average distribution. The toner having a particle size distribution of 5 μm or less is preferably 60% by number or less. Above this level, the toner tends to adhere to the carrier, and the carrier in the developer is not efficiently charged with respect to the replenished toner, so that toner is scattered in the machine and background contamination on the image area is likely to occur. Would. Further, the toners tend to agglomerate, it is difficult to obtain a smooth image, and the character portion may have a void. It is desirable that the content of toner particles having a particle size of 16 μm or more be 2% by volume or less. If it is more than this, the resolution is reduced and the image is rough. Further, the developed toner is less likely to be transferred to the transfer paper.

Further, at the time of kneading, a colorant or a dispersant for controlling the dispersion state of the magnetic material may be used in combination. Further, the toner base particles may be added with the above-mentioned additives and subjected to mixing and surface modification by a mixer or the like.

The carrier particles include inorganic / metal particles having a suitable resistance, resin particles in which particles having a relatively low resistance are dispersed, and particles having a coating layer provided on a core material having these as a core. Can be used.

Examples of the materials used for these are as follows. First, examples of inorganic / metal particles that can be used for carrier particles include conventionally known inorganic / metal particles, for example, metals such as iron, cobalt, and nickel; alloys and compounds such as magnetite, hematite, and ferrite. The core of such a coated carrier is generally made by powder metallurgy. That is, a raw material having a fine primary particle size of 0.3 to 9 Miciron is weighed,
After mixing and pre-sintering, pulverize. This is then granulated into spherical particles of approximately 20 to 75 microns in a spray granulation process. Next, sintering is performed in a firing machine. During the sintering, the temperature is defined so that the primary particles on the carrier surface keep the shape as it is (so that the primary particles do not become a continuous molten phase). Thereafter, the particles are classified into arbitrary particles to obtain a carrier core material.

Next, as the resin forming the resin particles of the carrier particles and / or the coating layer, for example, polyethylene,
Polyolefin resins such as polypropylene, chlorinated polyethylene, and chlorosulfonated polyethylene; polystyrene, acrylic (for example, polymethyl methacrylate), polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether, polybiriketone, etc. Polyvinyl and polyvinylidene resins; vinyl chloride-vinyl acetate copolymers; silicone resins comprising organosiloxane bonds or modified products thereof (for example, modified products by alkyd resins, polyester resins, epoxy resins, polyurethanes, etc.); polytetrafluoroethylene Fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polychlorotrifluoroethylene; polyamides; polyesters; Urethane; polycarbonate;
Amino resins such as urea-formaldehyde resin, melamine-formaldehyde, melamine-formaldehyde-alcohol co-condensation, and epoxy resins. Among them, silicone resin or its modified product, fluorine resin, amino resin, especially silicone resin or its modified product are preferable as the material for the coating layer in terms of preventing toner spent.

As the silicone resin, any conventionally known silicone resin may be used, such as straight silicone comprising only an organosiloxane bond represented by the following formula and silicone modified with alkyd, polyester, epoxy, urethane or the like. Resins.

Embedded image In the above formula, R1 is a hydrogen atom, an alkyl group or phenyl group having 1 to 4 carbon atoms, R2 and R3 are a hydrogen group, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, a phenoxy group,
An alkenyl group having 2 to 4 carbon atoms, an alkenyloxy group having 2 to 4 carbon atoms, a hydroxy group, a carboxyl group,
It is an ethylene oxide group, a glycidyl group or a group represented by the following formula.

Embedded image (R4 and R5 are a hydroxy group, a carboxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, and 2 carbon atoms.
The alkenyloxy group, phenyl group, phenoxy group, k, l, m, n, o, and p represent an integer of 1 or more. )
Is a group represented by

Each of the above substituents has, in addition to unsubstituted ones, substituents such as amino group, hydroxy group, carboxyl group, mercapto group, alkyl group, phenyl group, ethylene oxide group, glycidyl group and halogen atom. You may.

As described above, the low-resistance material used to control the volume resistivity of the resin particles and / or the carrier particles dispersed in the coating layer may be a conventionally known material.
Examples include metals such as iron, gold and copper; iron oxides such as ferrite and magnetite; white conductive agents (titanium oxide,
Tin oxide, zinc oxide); and pigments such as carbon black. Among them, in particular, by using a mixture of furnace black and acetylene black, which are one of the carbon blacks, the conductivity can be effectively adjusted by adding a small amount of a low-resistance fine powder, and the resistance of the resin particles / coating layer can be further improved. Obtain carrier particles with excellent wear properties. These low-resistance fine powders preferably have a particle size of about 0.01 to 10 μm, and 1 to 100 parts by weight of the resin particles or the coating resin.
It is preferable to add 30 parts by weight, more preferably 2-2.
0 parts by weight is preferred. In addition, a silane coupling agent, a titanium coupling agent, or the like is added to the resin particles and / or the coating layer of the charge imparting member for the purpose of improving the adhesion to the core particles and improving the dispersibility of the conductivity imparting agent. You may.

The silane coupling agent used in the present invention
Are compounds represented by the following general formula. YRSix_Three  (However, X is a hydrolyzable group bonded to a silicon atom.
Lol group, alkoxy group, acetoxy group, alkylamino
Group, propenoxy group, etc., and Y is an organic matrix
Vinyl, methacrylic, epoxy
Xy group, glycidoxy group, amino group, mercapto group, etc.
R represents an alkyl group having 1 to 20 carbon atoms or an alkyl group.
Is a ren group. )

Among these silane coupling agents, an aminosilane coupling agent having an amino group in Y is preferable for obtaining a developer having a negative charge property, and an epoxy silane coupling agent having an amino group for Y is preferable for obtaining a developer having a positive charge property. Epoxysilane coupling agents having groups are preferred. As a method for forming the coating layer, the coating layer forming liquid may be applied to the surface of the carrier core particles by a spraying method, a dipping method, a heating type kneader, a heating type Henschel mixer, or the like, as in the related art. Further, the thickness of the coating layer is preferably 0.1 to 20 μm.

The present invention comprises a carrier particle having a spherical particle and an irregular portion formed by a discontinuous phase in which the surface state is melted. A resin coating layer is provided on the surface, and the irregular portion of the spherical particle surface after coating is formed. It has a coating layer that can be distinguished. Therefore, even if the surface of the core material is a convex portion, the coating layer is present, and the carrier resistance is appropriately maintained, the spent is suppressed, and a long life (high durability) carrier is provided. In other words, a uniform coating layer is provided along the circumferential shape of the core material, and the convex portion has a thinner coating layer than the concave portion, while the concave portion has a thicker coating layer. With such a configuration, by the presence of the convex portion, the increase in the carrier resistance is appropriately suppressed, and by the balance between the presence of the concave portion and the convex portion, the charge rising property with the toner is favorably maintained, and Does not cause spent toner to adhere. If any part of the projection has an exposed portion, toner adheres to the carrier in that portion, leading to a decrease in charge amount and a cause of toner scattering. Also, if a coating layer is provided like a shell without conforming to the circumferential shape of the surface of the core material (the yolk is the core material in the image of an egg), the spent toner will not adhere and the coating layer will be thicker, so Due to the agitation, the coating layer slightly shaved the film,
There is no problem if it occurs. However, the problem that the carrier resistance increases, the charge amount increases, the image density decreases, or an edge effect occurs. Occurs remarkably. The present invention moderately suppresses the rise of the carrier resistance in particular due to the presence of the convex portion,
The present invention provides a carrier having a long life (high durability) by maintaining good chargeability with the toner by the balance of the existence of the concave portions.

The resistance of the carrier particles is 1 × 10 ⁸ to 1 × 1
0 ¹⁵ Ωcm is good. When it is 1 × 10 ¹⁵ Ωcm or more, the edge effect is large and the roughness of the image is large. Also,
This is not a particularly serious problem in character copying, but in the case of color copying, when a picture is copied, the above-mentioned disadvantages are large and close up. Further, the carrier ears become hard at the time of development, so that streaks and unevenness are likely to occur. 1x
When the resistivity is 10 ⁸ Ωcm or less, the carrier is apt to adhere to the latent image carrier, and the latent image carrier is easily damaged, whereby the latent image is easily disturbed and the image quality is remarkably deteriorated.

The resistance is measured in the following manner. In an environment of 20 ° C / 60% RH, the area is 10
The sample is poured into a cell formed by opposing two electrode plates (4 cm in length and 2.5 cm in width) at an interval of 2 mm, and then the cell is placed on a flat plate from a position of 15 mm in height in this state. The carrier sample is filled into the cell by repeating the tapping operation of dropping the carrier sample 30 times. Next, 500 V is applied to the electrode plate after removing excess carriers on the cell.
A DC electric field of / cm is applied to determine the resistance.

[0082]

Next, the present invention will be described more specifically with reference to examples. Parts here are by weight.

(Example 1) Toner was prepared by kneading a mixture of the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying. Is 12.85, and the volume% of 16 μm or more is 0.0
7 were obtained. Binder resin: Resin 1 resin 70 parts: Resin 15 resin 30 parts Colorant: Carbon black 11 parts Charge control agent: Chromium-containing metal complex 1.5 parts

Silica having an average particle size of 0.015 μm was mixed in a ratio of 0.3 part to 100 parts of the toner base particles to prepare a negatively chargeable black toner for development.

On the other hand, as a carrier, a resin obtained by mixing a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene at a weight ratio of 75/25 was used. 0.75% by weight of ferrite core material
(Based on core material) to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and the carrier becomes 50 g. The toner concentration was 1.5% by weight (toner = 0.75 g,
The carrier is set to 49.25 g, the toner and the carrier are charged into a pot, and mixed at 150 rpm for 10 minutes, and then the charge amount of the developer (Q / M, unit μc /
g, the same applies hereinafter). At this time, the toner is composed of only the toner base particles and the toner particles after the addition of the external additive, and the charge amount (Q / M) of each developer is measured. The results are as follows. A: Q / M of toner base particles = -17 B: Q / M of toner particles after adding external additives = -21 C: silica having an average particle diameter of 0.015 μm D: toner base having an average particle diameter of 7.75 μm Particle X = 0.0024

For testing by setting the developer in a copying machine, a developer was prepared by mixing 2.5 parts of the toner at a ratio such that the total amount with the carrier was 100 parts. Then, Imagio 420 (copier made by Ricoh Company) was modified so that the recycled toner returned to the toner supply section. When a developer was set in this electrophotographic apparatus and an initial image was formed, a good image was obtained. Furthermore, 10
When a continuous paper passing test of 0000 sheets was performed, a good image was obtained, and no toner scattering was observed in the copying machine.
When the copying process was stopped halfway and the latent image carrier was observed, no contamination by toner was observed, and it was confirmed that there was no problem. Then 10 ° C / 15%, 30 ° C
A test was conducted on each of 10,000 sheets of continuous paper passing in each environment of / 90%, but no particular problem occurred.

(Example 2) In Example 1, only the resin was changed as follows. Binder resin: Resin 2 resin 60 parts: Resin 13 resin 40 parts A toner was prepared in the same manner as in Example 1.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1.
Obtained similar results.

(Example 3) In Example 1, only the resin was changed as follows. Binder resin: Resin 3 resin 70 parts: Resin 12 resin 30 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

Example 4 In Example 1, only the resin was changed as follows. Binder resin: Resin 4 resin 60 parts: Resin 14 resin 40 parts A toner was prepared in the same manner as in Example 1.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 5) In Example 1, only the resin was changed as follows. Binder resin: Resin 5 resin 85 parts: Resin 16 resin 15 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 6) In Example 1, only the resin was changed as follows. Binder resin: Resin 6 resin 75 parts: Resin 17 resin 25 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 7) In Example 1, only the resin was changed as follows. Binder resin: Resin 8 resin 60 parts: Resin 15 resin 40 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 8) In Example 1, only the resin was changed as follows. Binder resin: Resin 9 resin 60 parts: Resin 15 resin 40 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

Example 9 In Example 1, only the resin was changed as follows. Binder resin: Resin 10 resin 60 parts: Resin 14 resin 40 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

Example 10 In Example 1, only the resin was changed as follows. Binder resin: Resin 11 resin 70 parts: Resin 16 resin 30 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 11) In Example 1, only the resin was changed as follows. Binder resin: Resin 2 resin 45 parts: Resin 13 resin 55 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 12) In Example 1, only the resin was changed as follows. Binder resin: Resin 18 resin 60 parts: Resin 15 resin 40 parts A toner was prepared in the same manner as in the first embodiment.
The same additives as in Example 1 were added, and a test was performed in the same manner as in Example 1 using the same carrier as in Example 1. As a result, similar results to Example 1 were obtained.

(Example 13) In Example 1, only the resin was changed as follows. Binder resin: Resin 1 resin 60 parts: Resin 13 resin 30 parts: Resin 16 resin 10 parts A toner was prepared in the same manner as in Example 1, and the same additives as in Example 1 were added. A test was performed in the same manner as in Example 1 using the same carrier as in Example 1, and the same results as in Example 1 were obtained.

(Comparative Example 1) A toner having the following formulation was kneaded under heating with two rolls, then cooled, coarsely pulverized, and pulverized and classified to obtain toner base particles having an average particle diameter of 3.6 μm. Was. Binder resin: 100 parts of styrene / acrylic resin Colorant: 11 parts of carbon black Charge control agent: 0.2 part of chromium-containing metal complex

To 100 parts of the above toner base particles, 0.7 parts of silica having an average particle diameter of 0.29 μm was mixed to prepare a negatively chargeable developing toner.

On the other hand, as the carrier, a resin obtained by mixing a copolymer of 2hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene at a weight ratio of 80/20 was used. 0.75% by weight of ferrite core material
(Based on core material) to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and the carrier becomes 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g), the toner and the carrier are charged in a pot, and mixed at 150 rpm for 10 minutes, and then the charge amount of the developer is set. Measure (Q / M). At this time, the toner is composed of only the toner base particles and the toner particles after the addition of the external additive, and the charge amount (Q / M) of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = −35 C: silica having an average particle size of 0.29 μm D: toner base particles having an average particle size of 3.6 μm X = −2.8

For testing with a developer set in a copying machine, a developer was prepared by mixing 2.5 parts of the toner at a ratio such that the total amount with the carrier was 100 parts. Then, Imagio 420 (copier made by Ricoh Company) was modified so that the recycled toner returned to the toner supply section. When the developer was set in this electrophotographic apparatus and an initial image was formed, the image density was low and the image was extremely uneven. Further, when a continuous paper passing test was performed on 1000 sheets, the image became more soiled, and toner scattering occurred remarkably in the copying machine. In addition, the copying process was stopped halfway, and the latent image carrier was observed. As a result, it was confirmed that the toner was contaminated and the amount of additives was remarkably large. At this time, when the developer was observed with an electron microscope (SEM), many floating additives were confirmed.

(Comparative Example 2) A toner having the following formulation was kneaded under heating with two rolls, then cooled, coarsely pulverized, and pulverized and classified to obtain toner base particles having an average particle diameter of 3.7 μm. Was. Binder resin: 100 parts of styrene / acrylic resin Colorant: 11 parts of carbon black Charge control agent: 0.2 part of quaternary ammonium salt

To 100 parts of the toner base particles, 0.7 parts of silica having an average particle diameter of 0.31 μm was mixed at a ratio of 0.7 parts to prepare a positively chargeable developing toner. On the other hand, as a carrier, a copolymer of 2hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene were used in a ratio of 20/80.
A resin having a weight ratio of 0.75% by weight (based on the core material) was coated on a ferrite core material having an average particle size of 50 μm to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and the carrier becomes 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g), the toner and the carrier are charged in a pot, and mixed at 150 rpm for 10 minutes, and then the charge amount of the developer is set. Measure (Q / M). At this time, the toner is composed of only the toner base particles and the toner particles after the addition of the external additive, and the charge amount (Q / M) of each developer is measured. The results are as follows. A: Q / M of toner base particles = 1 B: Q / M of toner particles after adding an external additive = 31 C: Silica having an average particle size of 0.31 μm D: Toner base particles X having an average particle size of 3.7 μm = 2.6

For testing with a developer set in a copying machine, a developer was prepared by mixing 2.5 parts of the toner at a ratio such that the total amount with the carrier was 100 parts. The Spirio 2210 (copier made by Ricoh Company) was modified so that the recycled toner returned to the toner replenishing section. When the developer was set in this electrophotographic apparatus and an initial image was formed, the image density was low and the image was extremely uneven. Further, when a continuous paper-passing test was performed on 1000 sheets, the image became more soiled, and toner scattering occurred remarkably in the copying machine. In addition, the copying process was stopped halfway and the latent image carrier was observed on the latent image carrier. However, it was confirmed that the toner was stained and the amount of additives was remarkably large. At this time, when the developer was observed with an electron microscope (SEM), many floating additives were confirmed.

Example 14 Toner was prepared by kneading a mixture of the following formulation under heating with two rolls, cooling, coarsely pulverizing and pulverizing and classifying to obtain toner base particles having an average particle diameter of 4.5 μm. Was. Binder resin: Resin 2 resin 70 parts: Resin 13 resin 30 parts Coloring agent: Carbon black 11 parts Charge control agent: Chromium-containing metal complex 0.2 parts Average particle diameter 0 with respect to 100 parts of the toner base particles. .3
0.7 μm silica was mixed in a ratio of 0.7 part to prepare a negatively chargeable developing toner.

On the other hand, as a carrier, a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene in a weight ratio of 75/25 was used as a resin.
0.75% by weight of 0μm ferrite core (based on core)
Was coated on the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and the carrier becomes 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g), the toner and the carrier are charged in a pot, and mixed at 150 rpm for 10 minutes, and then the charge amount of the developer is set. Measure (Q / M). At this time, the toner is composed of only the toner base particles and the toner particles to which the external additives are added. The toners are charged, and the charge amount (Q / M) of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after addition of an external additive = −35 C: silica having an average particle diameter of 0.3 μm D: toner base particles of an average particle diameter of 4.5 μm X = −2.3

For testing with a developer set in a copying machine, a developer was prepared by mixing 2.5 parts of the toner at a ratio such that the total amount with the carrier was 100 parts. Then, Imagio 420 (copier made by Ricoh Company) was modified so that the recycled toner returned to the toner supply section. When a developer was set in this electrophotographic apparatus and an initial image was formed, a good image was obtained. Furthermore, 10
When a continuous paper passing test of 0000 sheets was performed, a good image was obtained, and no toner scattering was observed in the copying machine.
When the copying process was stopped halfway and the latent image carrier was observed, no contamination by toner was observed, and it was confirmed that there was no problem. Then 10 ° C / 15%, 30 ° C
A test was conducted on each of 10,000 sheets of continuous paper passing in each environment of / 90%, but no particular problem occurred.

Example 15 Toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 4.5 μm. Was. Binder resin: Resin 2 resin 70 parts: Resin 13 resin 30 parts Colorant: Carbon black 11 parts Charge control agent: Quaternary ammonium salt 0.2 parts

0.7 parts by weight of silica having an average particle diameter of 0.3 μm was mixed with 100 parts by weight of the toner base particles to prepare a positively chargeable developing toner.

On the other hand, as a carrier, a resin obtained by mixing a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene at a weight ratio of 20/80 was used. 0.75% by weight of ferrite core material
(Based on core material) to coat the carrier.

Next, a stainless steel pot is prepared (diameter 60 mm, height 60 mm, volume 50 cm ³ ) and weighed so that the total amount of the toner and the carrier is 50 g. The toner concentration is set to 1.5% (toner = 0.75 g, carrier = 49.25 g), the toner and the carrier are charged in a pot, and mixed at 150 rpm for 10 minutes, and then the charge amount of the developer is set. Measure (Q / M). At this time, the toner is composed of only the toner base particles and the toner particles after the addition of the external additive, and the charge amount (Q / M) of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = 35 C: silica having an average particle diameter of 0.3 μm D: toner base particles having an average particle diameter of 4.5 μm X = 2.3

In order to set a developer in a copying machine and test it, a developer was prepared by mixing 2.5 parts of the toner at a ratio such that the total amount with the carrier was 100 parts. Then, the Spirio 2210 Ricoh Co.) was modified so that the recycled toner returned to the toner supply section.

Example 16 Example 16 was the same as Example 1 except that the charge controlling agent was changed from a chromium-containing metal complex to a zinc salicylate derivative (Bontron E84, manufactured by Orient Chemical Co.) in the toner formulation. And a similar test was carried out to obtain the same result as in Example 1.

(Example 17) Toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain a toner having an average particle size of 7.75 μm and a number% of 5 μm or less. Is 12.85, and the volume% of 16 μm or more is 0.0
7 were obtained. Binder resin: Resin 2 resin 70 parts: Resin 13 resin 30 parts Colorant: Carbon black 11 parts Charge control agent: Chromium-containing metal complex 1.5 parts

With respect to 100 parts by weight of the toner base particles, 0.6 part of silica having an average particle size of 0.018 μm and 0.2 part of titanium having an average particle size of 0.023 μm were mixed at a ratio of negative charge. Developing toner was prepared. The carrier used in Example 1 was used, and the toner consisted of toner base particles only and toner particles obtained by adding an external additive to the toner base particles. The charge amount (Q /
Measure M). The result is as follows. A: Q / M of toner base particles = -17 B: Q / M of toner particles after adding external additives = -19 C: (silica having an average particle size of 0.018 μm) + (average particle size of 0.023 μm) ) = 0.041 D: toner base particle having an average particle diameter of 7.75 μm X = 0.0059 Next, the same test as in Example 1 was performed, and the same result as in Example 1 was obtained.

(Example 18) In Example 1, silica was treated with an organic silicon compound (TS-7).
20, manufactured by Cabot Corporation), and the same results as in Example 1 were obtained.

Example 19 A toner was prepared in the same manner as in Example 1 except that the charge controlling agent was changed from a chromium-containing metal complex to an iron salt of a zinc salicylate derivative in the toner formulation. Then, the same test was performed, and the same result as in Example 1 was obtained.

Example 20 Toner was prepared by kneading a mixture having the following formulation under heating with two rolls, then cooling, coarsely pulverizing, and pulverizing and classifying to obtain toner base particles having an average particle diameter of 7.75 μm. Was. Binder resin: Resin 2 resin 70 parts: Resin 13 resin 30 parts Coloring agent: Carbon black 11 parts Charge control agent: Chromium-containing metal complex 1.5 parts Wax: Paraffin wax 5.5 parts The toner base particles 100 0.3 parts by weight of silica having an average particle diameter of 0.015 μm was mixed with parts by weight to prepare a negatively chargeable black toner for development. On the other hand, when the test was conducted in the same manner as in Example 1 using the carrier of Example 1, the same results as in Example 1 were obtained.

(Example 21) The toner used in Example 1 was used. On the other hand, a coating solution was prepared for the carrier according to the following formulation. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning Co., Ltd.) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle diameter of 50 μm and having a core material surface having irregularities. After coating 230
The silicon film was cured under heating at 2 ° C. for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), unevenness of the surface was clearly observed even after coating. In addition, it was confirmed by an electron beam microanalyzer that the Si element was also present in the projection. Using this carrier and toner, a test was conducted in the same manner as in Example 1, and the same results as in Example 1 were obtained.

(Example 22) The toner used in Example 1 was used. On the other hand, a coating solution was prepared for the carrier according to the following formulation. Then, the same core material as in Example 9 was coated. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Conductive agent: Ketjenblack ECDJ600 4 parts (manufactured by Lion Akzo) Toluene 1500 parts The same test as in Example 1 was performed using this carrier and toner. The same results as in Example 1 were obtained.

(Example 23) The toner used in Example 1 was used. On the other hand, a coating solution was prepared for the carrier according to the following formulation. Then, the same core material as in Example 21 was coated. Silicone resin liquid: SR2411 (Toray Dow Corning) 300 parts Conductive agent: Ketjenblack ECDJ600 4 parts (Lion Akzo) Coupling agent: KBM603 (Shin-Etsu Chemical) 8 parts Toluene 1500 parts The test was performed in the same manner as in Example 1 to obtain the same result as in Example 1.

(Example 24) The toner used in Example 1 was used. On the other hand, for the carrier, a coating solution was prepared according to the following formulation and the core material was coated. Cu-Zn ferrite (Powdertech Co., Ltd., average particle size 50 μm, F-300) 1000 parts Completely substituted methylated benzoguanamine (degree of polymerization 1.65, solid content 77%) 2.6 parts Acrylic resin (the following synthetic product: (Solid content 50%) 10 parts Toluene 300 parts Example of synthesizing acrylic resin having a hydroxyl group: While stirring with a stirrer, 700 g of xylene and 300 g of butanol were charged in a nitrogen stream, the temperature was raised to 100 ° C., 400 g of styrene, 400 g of methyl A mixture of 160 g of methacrylate, 200 g of n-butyl acrylate, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator was added to the mixture.
It was dropped over time. Thereafter, the content was further reacted for 6 hours to obtain a resin having a solid content of 50% (hydroxyl value: 41 KOH).
mg / g, number average molecular weight 1400).

The above-mentioned methylated guanamine, acrylic resin and toluene were mixed to prepare a coating solution. The temperature of the fluidized bed coating apparatus into which the ferrite was charged was maintained at about 60 ° C., and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled, and crushed to obtain a resin-coated carrier having a thickness of 0.2 μm. Using this carrier and toner, a test was conducted in the same manner as in Example 1, and the same results as in Example 1 were obtained.

(Example 25) The toner used in Example 1 was used. On the other hand, for the carrier, a coating solution was prepared according to the following formulation and the core material was coated. Cu-Zn ferrite (Powdertech, average particle size 50 m, F-300) 1000 parts Completely substituted methylated benzoguanamine (polymerization degree 1.65, solid content 77%) 2.6 parts Acrylic resin (synthetic product: (Solid content 50%) 10 parts Conductive agent: Ketjen Black ECDJ600 2.5 parts (manufactured by Lion Akzo) Toluene 300 parts

Synthesis Example of Acrylic Resin Having Hydroxyl Group: 700 g of xylene and 300 g of butanol were charged in a nitrogen stream while stirring with a stirrer, the temperature was raised to 100 ° C., 400 g of styrene, 160 g of methyl methacrylate
g, n-butyl acrylate 200 g, methacrylic acid 3
A mixture of 0 g, 100 g of 2-hydroxyethyl acrylate and 10 g of azobisisobutyronitrile as a polymerization initiator was added dropwise over 5 hours. Then add 6 more
The resin was reacted for 50 hours to obtain a resin having a solid content of 50% (hydroxyl value:
41 KOH mg / g, number average molecular weight 1400).

The above-mentioned methylated guanamine, acrylic resin and toluene were mixed to prepare a coating solution. The temperature of the fluidized bed coating apparatus into which the ferrite was charged was maintained at about 60 ° C., and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled, and crushed to obtain a resin-coated carrier having a thickness of 0.2 μm. Using this carrier and toner, a test was conducted in the same manner as in Example 1, and the same results as in Example 1 were obtained.

Example 26 A coating solution was prepared for the carrier according to the following formulation. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Toluene 1500 parts The coating liquid was coated on a ferrite having an average particle size of 50 μm and having a core material surface having irregularities. After coating 230
The silicon film was cured under heating at 2 ° C. for 2 hours to obtain carrier particles having a coating layer. When the surface of the coated carrier particles was observed with a scanning electron microscope (SEM) and a scanning tunneling microscope (STM), unevenness of the surface was clearly observed even after coating. In addition, it was confirmed by an electron beam microanalyzer that the Si element was also present in the projection.

On the other hand, the yellow toner is
The toner was created. Binder resin: Resin 1 resin 70 parts: Resin 15 resin 30 parts Yellow colorant: C.I. I. Pigment Yellow 180 5 parts Charge control agent: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co., Ltd.) 2 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, and further pulverized and classified to give an average particle size of 7.75.
A yellow toner having a number% of μm and 5 μm or less of 12.85 and a volume% of 16 μm or more of 0.07 was obtained. Negatively chargeable toner was obtained by mixing 0.016 μm silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 0.5 part to 100 parts of the toner base particles.

On the other hand, the above-mentioned carrier is used.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = -18 B: Q / M of toner particles after adding external additives = -23 C: silica having an average particle size of 0.016 μm D: toner base having an average particle size of 7.75 μm Particle X = 0.00
26

A magenta toner was prepared according to the following toner prescription. Binder resin: Resin 1 resin 70 parts: Resin 15 resin 30 parts Magenta colorant: C.I. I. Pigment Red 122 4 parts Charge control agent: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co., Ltd.) 2 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, and further pulverized and classified to give an average particle size of 7.75.
The magenta toner base particles having a number% of μm and 5 μm or less of 12.85 and a volume% of 16 μm or more of 0.07 were obtained.
0.016 to 100 parts by weight of the toner base particles
A negatively chargeable toner was obtained by mixing 0.5 μm of silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) at a ratio of 0.5 part.

On the other hand, the above-mentioned carrier is used.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = -14 B: Q / M of toner particles after adding external additives = -19 C: silica having an average particle diameter of 0.016 μm D: toner base having an average particle diameter of 7.75 μm Particle X = 0.0028

A cyan toner was prepared according to the following toner prescription. Binder resin: Resin 1 resin 70 parts: Resin 15 resin 30 parts Cyan colorant: C.I. I. Pigment Blue 15: 3 3 parts Charge control agent: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co., Ltd.) 2 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified to give an average particle size of 7.75.
The mother toner particles were obtained in which the number% of μm and 5 μm or less was 12.85 and the volume% of 16 μm or more was 0.07. For 100 parts of the toner base particles, 0.56 μm of silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.) was added to 0.5 part
Parts of the toner were mixed to obtain a negatively chargeable toner.

On the other hand, the above-mentioned carrier is used.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = −18 B: Q / M of toner particles after adding external additives = −22 C: silica having an average particle diameter of 0.016 μm D: toner base having an average particle diameter of 7.75 μm Particle X = 0.0025

A black toner was prepared according to the following toner prescription. Binder resin: Resin 1 resin 70 parts: Resin 15 resin 30 parts Black colorant: Carbon black 8 parts Charge controller: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co.) 2 parts This is pre-kneaded with a mixer. Is carried out. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified to give an average particle size of 7.75.
Black toner mother particles having a number% of μm and 5 μm or less of 12.85 and a volume% of 16 μm or more of 0.07 were obtained.
0.016 μm with respect to 100 parts of the toner base particles.
Silica fine powder R972 (manufactured by Nippon Aerosil Co., Ltd.)
By mixing at a ratio of 5 parts, a negatively chargeable toner was obtained.

On the other hand, the above-mentioned carrier is used.
The toner is composed of toner base particles only and toner particles obtained by adding an external additive to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = -13 B: Q / M of toner particles after adding external additives = -18 C: silica having an average particle size of 0.016 μm D: toner base having an average particle size of 7.75 μm Particle X = 0.0029

The carrier used above is used, and the total amount of 5 parts of the toner of each color and the carrier is 100%.
And yellow, magenta, cyan, and black developers were prepared. The developer for each color was modified from Pretail 750 (Ricoh color copier),
When the recycled toner was set in the copier where the toner returned to the toner supply section and the image was taken out, the toner transferability was good, there was no toner dust in the image area, there was no toner loss in the text area, and an appropriate image gloss was maintained. A good image was obtained without background contamination. In addition, 10 ° C / 30%, 30 ° C / 90
%, An image was obtained in each environment, and a good image was obtained even after copying 10,000 sheets in each environment.

Example 27 In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using the same carrier, and the same result as in Example 26 was obtained. Binder resin: Resin 2 resin 60 parts: Resin 13 resin 40 parts

(Example 28) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: 70 parts of resin 3: 30 parts of resin 12

(Example 29) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 4 resin 60 parts: Resin 14 resin 40 parts

(Example 30) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 5 resin 85 parts: Resin 16 resin 15 parts

(Example 31) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed to the following. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: 75 parts of resin 6: 25 parts of resin 17

(Example 32) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 8 resin 60 parts: Resin 15 resin 40 parts

(Example 33) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: 60 parts of resin 9: 40 parts of resin 14

(Example 34) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed to the following. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 10 resin 60 parts: Resin 14 resin 40 parts

(Example 35) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: 70 parts of resin 11: 30 parts of resin 16

(Example 36) In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed to the following. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: 45 parts of resin 2 resin: 55 parts of resin 13 resin

Example 37 In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 18 resin 60 parts: Resin 15 resin 40 parts

Example 38 In Example 26, yellow, magenta, cyan and black toners were prepared in the same manner as in Example 26 except that only the binder resin was changed as follows. The same test as in Example 26 was performed using this carrier, and the same result as that in Example 26 was obtained. Binder resin: Resin 1 resin 60 parts: Resin 13 resin 30 parts: Resin 16 resin 10 parts

(Example 40) In Example 26, the carrier was changed to that of Example 2 by changing the additives of the toner as follows.
The test was performed in the same manner as in Example 26 with 6 samples, and the same result as in Example 26 was obtained. Additive: 0.6 part of silica having an average particle size of 0.018 μm: 0.2 part of titanium having an average particle size of 0.023 μm X = 0.0059.

(Example 41) In Example 26, silica (TS-7) treated with an organic silicon compound was used.
20, manufactured by Cabot Corporation), and the same test as in Example 26 was carried out.

(Example 42) In Example 26, the toner used in Example 26 was used, and the carrier was a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and vinylidene fluoride / tetrafluoroethylene. The copolymer was coated with a resin at a weight ratio of 75/25 on a ferrite core material having an average particle diameter of 50 μm at 0.75% by weight (based on the core material) to coat the carrier. When a test was performed in the same manner as in Example 26 using this toner and carrier, the same results as in Example 26 were obtained.

(Example 42) In Example 26, the coating liquid was prepared according to the following formulation, using the toner of Example 26 as the toner. And Example 26
The same core material was coated. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical) 8 parts Toluene 1500 parts A test was performed in the same manner as in Example 26 using this toner and carrier. The same results as in Example 26 were obtained.

Example 43 In Example 26, the coating liquid was prepared according to the following formulation, using the toner of Example 26 as the toner. Then, the same core material as in Example 26 was coated. Silicon resin liquid: SR2411 (manufactured by Toray Dow Corning) 300 parts Coupling agent: KBM603 (manufactured by Shin-Etsu Chemical) 8 parts Toluene 1500 parts A test was conducted in the same manner as in Example 26 using this toner and carrier. The same results as in Example 26 were obtained.

(Example 44) In Example 26, the toner used in Example 26 was used, and a carrier was prepared according to the following formulation to coat the core material. Cu-Zn ferrite (Powdertech Co., Ltd., average particle size 50 μm, F-300) 1000 parts Completely substituted methylated benzoguanamine (degree of polymerization 1.65, solid content 77%) 2.6 parts Acrylic resin (the following synthetic product: (Solid content 50%) 10 parts Toluene 300 parts Example of synthesizing acrylic resin having a hydroxyl group: While stirring with a stirrer, 700 g of xylene and 300 g of butanol were charged in a nitrogen stream, the temperature was raised to 100 ° C., 400 g of styrene, 400 g of methyl A mixture of 160 g of methacrylate, 200 g of n-butyl acrylate, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate and 10 g of azobisisobutyronitrile as a polymerization initiator was added dropwise over 5 hours. Thereafter, the content was further reacted for 6 hours to obtain a resin having a solid content of 50% (hydroxyl value: 41 KOHm).
g / g, number average molecular weight 1400).

A coating solution was prepared by mixing the above methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed coating apparatus into which the ferrite was charged was maintained at about 60 ° C., and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled, and crushed to obtain a resin-coated carrier having a thickness of 0.2 μm. Using this carrier and toner, a test was conducted in the same manner as in Example 26, and the same result as in Example 26 was obtained.

Example 45 In Example 26, the toner used in Example 26 was used, and a carrier was prepared according to the following formulation, and the core material was coated. Cu-Zn ferrite (Powdertech Co., Ltd., average particle size 50 μm, F-300) 1000 parts Completely substituted methylated benzoguanamine (degree of polymerization 1.65, solid content 77%) 2.6 parts Acrylic resin (the following synthetic product: (Solid content: 50%) 10 parts Conductive agent: Ketjen Black ECDJ600 2.5 parts (manufactured by Lion Akzo) Toluene 300 parts Synthesis example of acrylic resin having hydroxyl group: 700 g of xylene in a nitrogen stream while stirring with a stirrer , 300 g of butanol, and the temperature was raised to 100 ° C .; 400 g of styrene, 160 g of methyl methacrylate, 200 g of n-butyl acrylate, 30 g of methacrylic acid, 100 g of 2-hydroxyethyl acrylate, and 10 g of azobisisobutyronitrile as a polymerization initiator. The mixture was added dropwise over 5 hours. Thereafter, the content was further reacted for 6 hours to obtain a resin having a solid content of 50% (hydroxyl value: 41 KOHm).
g / g, number average molecular weight 1400).

The coating was prepared by mixing the methylated guanamine, acrylic resin and toluene. The temperature of the fluidized bed coating apparatus into which the ferrite was charged was maintained at about 60 ° C., and the coating liquid was sprayed. After the spraying was completed, it was dried for about 10 minutes and taken out. Next, this carrier was treated in an electric furnace at 150 ° C. for 1 hour, cooled, and crushed to obtain a resin-coated carrier having a thickness of 0.2 μm. Using this carrier and toner, a test was conducted in the same manner as in Example 26, and the same result as in Example 26 was obtained.

(Embodiment 46) In Embodiment 26, Pretail 750 (a color copying machine manufactured by Ricoh Company) was remodeled.
The recycled toner is returned only to the black developing section to the toner replenishing section. The developer of each color was set in this, and when the image was taken out, the toner transferability was good, there was no toner dust in the image part, there was no toner loss in the character part, the image gloss was maintained properly, and there was no background stain And a good image was obtained. In addition, good images were obtained even after the images were formed in the respective environments of 10 ° C./30% and 30 ° C./90%, and after copying 10,000 sheets in the respective environments.

(Comparative Example 3) A resin obtained by mixing a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene at a weight ratio of 80/20 was used as a carrier. 0.7% for ferrite core material with average particle size of 50μm
The carrier was coated with 5% by weight (based on the core material).

On the other hand, the toner is
Toner base particles were prepared. Binder resin: styrene / acrylic resin 100 parts Yellow colorant: C.I. I. Pigment Yellow 180 5 parts Charge control agent: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co., Ltd.) 0.3 parts This is subjected to preliminary kneading with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and has an average particle diameter of 3.6 μm.
m of yellow toner base particles were obtained. To 100 parts of the toner base particles, 0.29 μm of silica fine powder was mixed at a ratio of 0.7 part to obtain a negatively chargeable yellow toner.

On the other hand, a carrier is used as described above.
The toner is composed of only toner base particles and toner particles after external additives are added to the toner base particle toner, and the charge amount of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = −35 C: silica having an average particle size of 0.29 μm D: toner base particles having an average particle size of 3.6 μm X = −2.8

A magenta toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Magenta colorant: C.I. I. Pigment Red 122 4 parts Charge control agent: Zn salt of salicylic acid (Bontron E84, manufactured by Orient Chemical Co.) 0.3 part This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and has an average particle diameter of 3.6 μm.
m magenta toner was obtained. The toner base particles 100
To each part, 0.29 μm silica fine powder was mixed at a ratio of 0.7 part to obtain a negatively chargeable toner.

On the other hand, a carrier is used as described above.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = −35 C: silica having an average particle size of 0.29 μm D: toner base particles having an average particle size of 3.6 μm X = −2.8

A cyan toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Cyan colorant: C.I. I. Pigment Blue 15: 3 3 parts Charge control agent: Salicylic acid Zn salt (Bontron E84, manufactured by Orient Chemical Co.) 0.3 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and has an average particle diameter of 3.6 μm.
m of cyan toner base particles were obtained. 0.29 μm of fine silica powder was added to 100 parts of the toner base particles in an amount of 0.1 μm.
Seven parts were mixed to obtain a negatively charged cyan toner.
On the other hand, the above-mentioned carrier is used, and the toner is composed of only the toner base particles and the toner particles after the external additive is added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = −35 C: silica having an average particle size of 0.29 μm D: toner base particles having an average particle size of 3.6 μm X = −2.8

A black toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Black colorant: carbon black 8 parts Charge control agent: Zn salt of salicylic acid (Bontron E84, manufactured by Orient Chemical Co.) 0.3 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture is melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and has an average particle diameter of 3.6 μm.
m of black toner base particles were obtained. To 100 parts of the toner base particles, 0.29 μm silica fine powder was mixed in a ratio of 0.7 part to obtain a negatively chargeable black toner.

On the other hand, the carrier is the same as that described above.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M = 0 of toner base particles B: Q / M of toner particles after adding external additives = −35 C: silica having an average particle size of 0.29 μm D: toner base particles having an average particle size of 3.6 μm X = −2.8

The carrier used above is used, and the total amount of 5 parts of the toner of each color and the carrier is 100%.
And yellow, magenta, cyan, and black developers were prepared. The developer for each color was modified from Pretail 750 (Ricoh color copier),
When the recycled toner was set in a copying machine in which the toner returned to the toner replenishing section, and the image was taken out, the toner transferability was not good, toner dust in the image area was observed, the image density was low, and the image was extremely uneven. there were. In addition, 100
When a continuous paper passing test was performed on 0 sheets, the image became more soiled, and toner scattering was noticeably generated in the copying machine. Further, the copying process was stopped halfway, and the image was observed on the latent image carrier. However, it was confirmed that the toner was stained and the amount of additives was remarkably large. At this time, when the developer was observed with an electron microscope (SEM), many floating additives were confirmed.

(Comparative Example 4) The average particle size of the carrier was a resin obtained by mixing a copolymer of 2-hydroxyethyl metal acrylate / methyl methacrylate / styrene and a copolymer of vinylidene fluoride / tetrafluoroethylene at a weight ratio of 20/80. A carrier was coated by coating a ferrite core material having a diameter of 50 μm with 0.75% by weight (based on the core material).

On the other hand, the toner is
The toner was created. Binder resin: styrene / acrylic resin 100 parts Yellow colorant: C.I. I. Pigment Yellow 180 5 parts Charge control agent: quaternary ammonium salt 0.3 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture was melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and the average particle size was 3.7 μm.
m of yellow toner base particles were obtained. To 100 parts of the toner base particles, 0.31 μm of silica fine powder was mixed in a ratio of 0.7 part to obtain a positively chargeable yellow toner.

On the other hand, the carrier used is as described above.
The toner is composed of only the toner base particles and the toner particles after the external additive is added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = 1 B: Q / M of toner particles after adding an external additive = 31 C: Silica having an average particle size of 0.31 μm D: Toner base particles X having an average particle size of 3.7 μm = 2.6

A magenta toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Magenta colorant: C.I. I. Pigment Red 122 4 parts Charge control agent: quaternary ammonium salt 0.3 parts This is subjected to preliminary kneading with a mixer. Thereafter, the mixture was melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and the average particle size was 3.7 μm.
m magenta toner was obtained. The toner base particles 100
The toner base particles were obtained by mixing 0.31 μm of silica fine powder in a ratio of 0.7 part with respect to the parts.

On the other hand, the carrier is the same as that described above.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = 1 B: Q / M of toner particles after adding an external additive = 31 C: Silica having an average particle size of 0.31 μm D: Toner base particles X having an average particle size of 3.7 μm = -2.8

A cyan toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Cyan colorant: C.I. I. Pigment Blue 15: 3 3 parts Charge control agent: quaternary ammonium salt 0.3 parts This is subjected to preliminary kneading with a mixer. Thereafter, the mixture was melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and the average particle size was 3.7 μm.
m of cyan toner base particles were obtained. 0.31 μm of silica fine powder was added to 100 parts of the toner base particles in an amount of 0.1 μm.
Seven parts were mixed to obtain a positively chargeable cyan toner.

On the other hand, a carrier is used as described above.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = 1 B: Q / M of toner particles after adding an external additive = 31 C: Silica having an average particle size of 0.31 μm D: Toner base particles X having an average particle size of 3.7 μm = -2.8

A black toner was prepared according to the following toner prescription. Binder resin: styrene / acrylic resin 100 parts Black colorant: carbon black 8 parts Charge control agent: quaternary ammonium salt 0.3 parts This is preliminarily kneaded with a mixer. Thereafter, the mixture was melt-kneaded in a three-roll mill, cooled, coarsely pulverized to 0.5 to 3 mm, further pulverized and classified, and the average particle size was 3.7 μm.
m of black toner base particles were obtained. To 100 parts of the toner base particles, 0.31 μm of silica fine powder was mixed in a ratio of 0.7 part to obtain a positively chargeable black toner.

On the other hand, the above-mentioned carrier is used.
The toner consists of toner base particles only and toner particles after external additives are added to the toner base particles, and the charge amount of each developer is measured. The results are as follows. A: Q / M of toner base particles = 1 B: Q / M of toner particles after adding an external additive = 31 C: Silica having an average particle size of 0.31 μm D: Toner base particles X having an average particle size of 3.7 μm = -2.8

The carrier used above is used, and the total amount of 5 parts of the toner of each color and the carrier is 100%.
And yellow, magenta, cyan, and black developers were prepared. The developer for each color was modified from Pretail 750 (Ricoh color copier),
When the recycled toner was set in a copying machine in which the toner returned to the toner replenishing section, and the image was taken out, the toner transferability was not good, toner dust in the image area was observed, the image density was low, and the image was extremely uneven. there were. In addition, 100
When the continuous paper passing test was performed for 0 sheets, the image became more soiled, and toner scattering occurred remarkably in the copying machine. In addition, the copying process was stopped halfway and the latent image carrier was observed. It was confirmed that the toner stain and the amount of additives were remarkably large. At this time, when the developer was observed with an electron microscope (SEM), many floating additives were confirmed.

(Example 49) In Example 26, only the constitution of the base particles of the black toner was changed to the following formulation. The same test as in Example 26 was performed using the yellow toner, magenta toner, and cyan toner of Example 26, and the same results as in Example 26 were obtained. Binder resin: Resin 2 resin 70 parts: Resin 13 resin 30 parts Coloring agent: Carbon black 11 parts Charge control agent: Chromium-containing metal complex 1.5 parts Wax: Paraffin wax 5.5 parts

[0184]

(1) According to the first aspect of the present invention, the polyol (A) and the polyol (B) resins are defined so that even if the toner is a recycled toner, the charge stability, the environmental stability, and the fixation are satisfactory. Good image quality can be achieved by producing effects such as stability, no toner scattering, and no toner adhesion to the PVC sheet when storing copy paper.

(2) Claim 2 defines the molecular weight of the polyol (A). Claim 3 defines the low molecular weight / high molecular weight ratio of the polyol (A). Claim 4 defines the polyol (A). By defining the alkylene oxide adduct of a dihydric phenol of A), Claim 5 defines the content of the alkylene oxide adduct of a dihydric phenol of polyol (A).
In claim 6, the molecular weight of the polyol (B) is specified, and in claim 7, the content of the polyol (A) is specified, whereby the effect of claim 1 or more can be obtained.

(3) By defining the charge control agent in claim 8, the effect of claim 1 or more can be obtained, and the charging speed at the time of toner replenishment is high, and a developer having a uniform charge distribution can be obtained. Prevents toner from adhering to the surface. (4) According to the toner of the ninth aspect, a good monochrome image can be obtained. (5) According to the toner of the tenth and eleventh aspects, a good color image can be obtained. (6) According to the two-component developer according to claims 12, 13 and 14, good images can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Minoru Masuda 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Inventor Tomomi Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Company (72) Kosuke Suzuki 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh (72) Inventor Tamotsu Kajihara 1-3-6 Nakamagome, Ota-ku, Tokyo Stock Company Ricoh Company F Terms (reference) 2H005 AA01 AA06 AA08 AA21 AB10 BA06 BA07 BA15 CA07 CA15 CA21 CA25 CB18 DA02 DA07 DA09 EA01 EA05 EA06 EA07 FA01

Claims (14)

[Claims] 1. A toner used in an image forming method for reusing toner collected by a cleaning section of an electrostatic latent image carrier as a recycled toner, comprising at least a colorant, a binder resin, and a charge control agent. The binder resin comprises an epoxy resin, an alkylene oxide adduct of a dihydric phenol or its glycidyl ether, a dihydric phenol, and active hydrogen which reacts with an epoxy group. Is reacted with a polyol (A) obtained by reacting a compound having one in the molecule, an epoxy resin, a dihydric phenol, and a compound having one active hydrogen in the molecule to react with the epoxy group. A, and the toner base particles have a toner charge amount of A, and at least one or more external additives are added to the toner base particles. When the charge amount of the toner after the addition is B, the sum of the average particle diameters of the external additives is ΔC, and the average particle diameter of the toner base particles is D, the respective values are substituted into the following equations, and X = (B / A) × (ΔC / D) An image forming toner, wherein the value of X is in the range of −2.3 ≦ X ≦ 2.3. 2. The epoxy resin constituting the polyol (A) is at least two kinds of bisphenol A type epoxy resins having different number average molecular weights, the number average molecular weight of the low molecular weight component is 360 to 2000, and the high molecular weight 2. The image forming toner according to claim 1, wherein the number average molecular weight of the components is 3,000 to 10,000. 3. The epoxy resin constituting the polyol (A) is at least two or more bisphenol A type epoxy resins having different number average molecular weights, and the low molecular weight component is 20%.
3. The image forming toner according to claim 1, wherein the amount of the high molecular weight component is 5 to 40 wt%. 4. An alkylene oxide adduct of a dihydric phenol or a glycidyl ether thereof constituting the polyol (A) is a diglycidyl ether of an alkylene oxide adduct of bisphenol A and represented by the following general formula (1). The image forming toner according to claim 1, wherein: General formula (1) (In the formula, n and m are the numbers of repeating units, each is 1 or more, and n + m = 2 to 6.) 5. An alkylene oxide adduct of a dihydric phenol constituting the polyol (A) or its glycidyl ether is present in an amount of 10 to 50 wt.
5. The image forming toner according to claim 1, wherein 6. The polyol (B) having a number average molecular weight of 20
The image forming toner according to claim 1, wherein the number is from 0 to 10,000. 7. A toner binder resin comprising the polyol (B) as 2
The image forming toner according to claim 1, wherein the toner comprises 0 to 50 wt%. 8. The image forming toner according to claim 1, wherein the charge controlling agent contains a metal salt of salicylic acid and / or a metal salt of a salicylic acid derivative. 9. The image forming toner according to claim 1, wherein the colorant is black. 10. The color image forming toner according to claim 1, wherein the colorants are yellow, magenta, and cyan different from each other. 11. The color image forming toner according to claim 1, wherein the colorants are different yellow, magenta, cyan, and black. 12. Carrier particles and toner particles, said carrier particles having a coating layer of silicon, fluorine or fluorine / styrene / acryl, amino resin or resin consisting of amino resin / styrene / acryl, A two-component developer, wherein the toner particles comprise the toner according to any one of claims 1 to 11. 13. The two-component developer according to claim 12, wherein the coating layer of the carrier particles contains a conductive material. 14. The carrier particles are formed of spherical particles having an irregular portion formed by a discontinuous phase in which the crystalline state of the surface is molten. A resin coating layer is provided on the surface, and the surface of the spherical particles after coating is irregular. 14. The two-component developer according to claim 12, wherein the two-component developer has a coating layer capable of confirming the discrimination.