JP2003330223A - Toner and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for forming an image by which uniform triboelectrification of a toner can be obtained and images with high definition and high quality can be obtained even for long-term use in a development method by bringing a toner regulating member into contact with a toner carrying body. <P>SOLUTION: In the method for forming an image including at least a developing process to develop an electrostatic latent image formed on a latent image holding body by a toner layer formed on a toner carrying body to form an image, the thickness of the toner layer formed on the surface of the toner carrying body is regulated by a toner layer thickness regulating member pressed and in contact with the surface of the toner carrying body through the toner layer. The toner contains at least a binder resin and a colorant. The binder resin contains at least one kind of vinyl resin selected from a group comprising a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin in which a carboxyl group reacts with an epoxy group. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an image forming method for developing with a toner an electrostatic charge image formed in a recording method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet recording method, And a toner used in the image forming method.

[0002]

2. Description of the Related Art A number of electrophotographic methods have been known so far, but generally, an electro latent image (electrostatic latent image) is formed on a photoconductor by various means using a photoconductive substance. Then, the latent image is developed with toner, and the toner image is transferred to a transfer material such as paper, if necessary, and then fixed by heating, pressure, heating / pressurizing, solvent vapor or the like to obtain a copy. The toner remaining on the photosensitive member without being transferred is cleaned by various methods, and the above steps are repeated.

Various methods are known as a developing method for converting an electrostatic latent image into a visible image using toner. As these developing methods, for example, a magnetic brush method using a developer mainly composed of toner and carrier, a cascade developing method, a liquid developing method and the like have been widely put into practical use. Although it is an excellent method that can stably obtain a good image. There are common problems associated with two-component developers such as carrier deterioration and variation in the mixing ratio of toner and carrier.

In order to solve such a problem, the one-component developing method is preferably used because the developing machine having a simple structure has no trouble, has a long life and is easy to maintain.

Even in the one-component developing method, the toner carrier and the electrostatic latent image carrier are arranged at a certain distance, and a thin layer of toner that does not come into contact with the latent image carrier is formed on the toner carrier. Further, a jumping development method (Japanese Patent Publication No. 58-32375) in which an alternating electric field is applied between the toner carrier and the latent image carrier to perform development is preferably used.

According to this method, the toner is thinly applied on the sleeve which is the toner carrier to increase the chances of contact between the sleeve and the toner, enabling sufficient triboelectrification, and improving the resolution and sharpness of the image. Can be achieved.
Therefore, this method for forming a thin layer of toner is essential, and some proposals have been made for this.

For example, as disclosed in Japanese Patent Laid-Open No. 54-43038, an elastic blade made of rubber or metal is brought into contact with a developing sleeve which is a toner carrier, and an abutting portion between the elastic blade and the developing sleeve. There is a method in which a thin layer of toner is formed on the developing sleeve by allowing the toner to pass therethrough and being regulated, and sufficient tribo is imparted to the toner by the friction of the contact portion.

However, in the recent high-speed and highly durable developing method, the triboelectric charging ability of the toner between the sleeve and the elastic blade is insufficient, and the uniform toner charging is not performed. In addition, image fog or image density unevenness is likely to occur. Further, there is a problem in that the toner is likely to be fused to the elastic blade and the sleeve due to an increase in the share of the toner on the contact surface between the sleeve and the elastic blade and an increase in the number of contacts.

In recent years, such a copying machine reflects the changing needs of the market, such as complexization and personalization,
There is a strict demand for smaller size, lighter weight, higher speed, and higher reliability, and as a result, not only the performance of developing devices but also the performance required for toner is becoming more sophisticated.
Furthermore, there is a demand for a developing method that further identifies the interaction between the developing device and the toner.

Many proposals for toner have been made in the past. For example, Japanese Examined Patent Publication No. 51-23354 discloses a toner comprising a vinyl polymer which is appropriately crosslinked by adding a crosslinking agent for a binder resin and a molecular weight modifier in the toner. Many blend-type toners that combine Tg, molecular weight, and gel content have been proposed.

The toner containing such a crosslinked vinyl polymer or gel has an excellent effect in offset resistance. However, when the crosslinked vinyl polymer is used as a toner raw material in incorporating them, internal friction in the polymer becomes extremely large in the melt-kneading step during toner production, and a large shearing force is generated in the polymer. Take For this reason, in many cases, molecular chain breakage occurs, which causes a decrease in melt viscosity and adversely affects offset resistance.

Therefore, in order to solve this, Japanese Patent Laid-Open No.
5-90509, 57-178249, 57-
In Japanese Patent Nos. 178250 and 60-4946, it is disclosed that a resin having a carboxylic acid and a metal compound are used as a toner raw material, and the mixture is heated and reacted at the time of melt kneading to form a crosslinked polymer, which is contained in the toner. .

It is also known that a binder containing a vinyl-based resin monomer and a more specific monoester compound as an essential constituent unit is reacted with a polyvalent metal compound to crosslink through a metal. 110155 and 61-1.
It is disclosed in Japanese Patent No. 110156.

Further, Japanese Patent Laid-Open No. 63-214760,
No. 63-217362, No. 63-217363, and No. 63-217364 have a molecular weight distribution that is divided into two groups, a low molecular weight and a high molecular weight, and have a large number of carboxylic acid groups contained on the low molecular weight side. It is disclosed that a valent metal ion is reacted and crosslinked (a dispersion liquid of a metal compound is added to a solution obtained by solution polymerization and heated to react).

Further, JP-A-2-168264, JP-A-2-235069, JP-A-5-173363,
In JP-A-5-173366 and JP-A-5-241371, the molecular weight, the mixing ratio, the acid value and the ratio of the low molecular weight component and the high molecular weight component in the binder resin are controlled to improve the fixability, offset resistance and the like. Improved toner binder compositions and toners have been proposed.

Further, in Japanese Patent Laid-Open No. 62-9256,
It discloses a binder composition for toner in which two kinds of vinyl resins having different molecular weights and resin acid values are blended.

Further, Japanese Patent Laid-Open Nos. 3-66361 and 3
-63662, 3-63663, 3-
Japanese Patent No. 118552 discloses that a carboxyl group-containing vinyl copolymer and a glycidyl group-containing vinyl copolymer are reacted with a metal compound to crosslink.

Further, JP-A-7-225491 and 8-44107 disclose that a carboxyl group-containing resin and an epoxy resin react to form a crosslinked structure.

Further, Japanese Patent Laid-Open No. 62-194260,
JP-A-6-11890, JP-A-6-222612, JP-A-7-20654, JP-A-9-185182, JP-A-9-244295, JP-A-9-319410 and JP-A-10-87837, Ibid 10-90943
In the publication, a glycidyl group-containing resin is used as a cross-linking agent, and in a resin composition composed of a carboxyl group-containing resin, molecular weight distribution, gel content, acid value, epoxy value, etc. are controlled, and fixability, offset resistance, etc. A binder composition for a toner and a toner having improved the above have been proposed.

The above-mentioned proposals have advantages and disadvantages in terms of improving offset resistance, but it is a fact that excellent effects can be obtained. However,
In the developing method in which the toner control member is brought into contact with the toner carrier in addition to the problem of ultra-high speed and high durability, it is possible to suppress the occurrence of fusion of the toner to the toner carrier and the toner control member. Difficult and needs further improvement.

Further, JP-A-1-256978, JP-A-4-124681, and JP-A-6-51556 disclose toners having a good chargeability by controlling the dielectric loss tangent of the toner. If only the control is applied to a high-speed machine with a large copy volume, the durability is poor and the image quality is likely to deteriorate.

[0022]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above problems and to provide an image forming method excellent in developability and durability and a toner applicable to the image forming method.

That is, the object of the present invention is also to provide a developing method in which a toner regulating member is brought into contact with a toner carrier.
An object of the present invention is to provide an image forming method capable of uniform triboelectrification of a toner and obtaining a high-definition, high-quality image even in long-term durability, and a toner adapted thereto.

Further, an object of the present invention is to provide an image forming method in which toner is not fused to the toner carrier and the toner regulating member even in the developing method in which the toner carrier is brought into contact with the toner regulating member, and a toner applicable thereto. To provide.

[0025]

According to the present invention, at least a developing step of forming an image by developing an electrostatic latent image formed on a latent image carrier with a toner layer formed on a toner carrier. In the image forming method, the toner carrier has a toner layer thickness regulated by a toner layer thickness regulating member pressed against the surface of the toner carrier via a toner layer, and the toner is at least a binder resin. The binder resin contains a vinyl resin having a carboxyl group and an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin having a reaction between a carboxyl group and an epoxy group. And at least one vinyl resin selected from the group consisting of
OH / g, and the frequency of the toner is 1.0 × 10 ³ (H
The dielectric loss tangent (tan δ _T ) in z) is the maximum value (tan δ) at T _MAX (° C) in the temperature range of 20 to 150 (° C).
δ _T (T _MAX )), and the dielectric loss tangent (tan δ _B (T _MAX )) at the frequency of the toner layer regulating member of 1.0 × 10 ³ (Hz) and T _MAX (° C) is 1.0 × 10 ^{-3 to} 5.0
The present invention relates to an image forming method characterized by being × 10 ⁰ .

Further, the present invention has at least a developing step of developing an electrostatic latent image formed on a latent image holding member by a toner layer formed on a toner carrying member to form an image. In the toner applied to the image forming method in which the toner layer thickness is regulated by the toner layer thickness regulating member in which the carrier is pressed against the surface of the toner carrier via the toner layer, the toner is at least a binder resin. And a colorant, wherein the binder resin is a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin having a reaction between a carboxyl group and an epoxy group. And at least one vinyl resin selected from the group consisting of
mgKOH / g, the dielectric loss tangent (tan δ _B ) of the toner layer regulating member at a frequency of 1.0 × 10 ³ (Hz).
At a frequency range of 1.0 × 10 ^{−3 to} 5.0 × 10 ⁰ at T _MAX (° C.), the toner frequency is 1.0 × 1.
The present invention relates to a toner having a maximum dielectric loss tangent (tan δ _T ) at 0 ³ (Hz).

[0027]

DETAILED DESCRIPTION OF THE INVENTION As a result of earnest studies, the present inventors
In a developing method in which a toner regulating member is pressed against a toner carrier via a toner, the toner has at least a binder resin, and as the binder resin, a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, The toner contains at least one vinyl resin selected from the group consisting of a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin in which a carboxyl group and an epoxy group are reacted, and the THF-soluble component of the toner contains a specific acid. By controlling the dielectric loss tangent of the toner and the toner regulating member in a specific temperature range, it is possible to perform sufficient triboelectric charging on the toner even in high-speed, high-durability systems regardless of environmental temperature changes. No fogging or uneven development occurs, and toner fusion to the toner carrier and toner control member and toner contamination can be suppressed. It revealed that.

Further, the toner exhibits a specific circularity, or the molecular weight distribution measured by GPC of the THF-soluble component in the toner has a specific molecular weight distribution, or
The binder resin component of the toner has a specific THF-insoluble content, and the above effect can be further improved.

The reason why the effects of the present invention are exhibited will be described below.

One feature of the present invention is that the toner contains at least a binder resin and a colorant, and the binder resin contains a vinyl resin having a carboxyl group, a vinyl resin having an epoxy group, and a carboxyl group. The toner containing at least one vinyl resin selected from the group consisting of a vinyl resin having an epoxy group and a vinyl resin in which a carboxyl group and an epoxy group are reacted,
The F soluble component has a specific acid value, and when this toner is used in a developing method in which a blade, which is a toner regulating member, is brought into pressure contact with a developing sleeve, which is a toner carrier, through a toner, a high speed and long time It is possible to maintain excellent image quality even in durability. This is a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group,
Due to the mutual relationship between the vinyl resin having a carboxyl group and an epoxy group, the vinyl resin in which a carboxyl group and an epoxy group have reacted, and the hydroxyl group and other raw materials contained in the toner, the dispersibility and adhesion of the materials can be improved. Due to its excellent and moderate toner toughness, even when used in a blade pressure contact type developing method which has a large share of toner in the developing section, toner deterioration due to durability and blade abrasion are excellent, and the toner has excellent durability. Since the material is not detached from the sleeve, sleeve contamination does not occur.

That is, the toner of the present invention is melt-kneaded in a kneading step in the toner manufacturing process, and the binder resin causes a crosslinking reaction. At that time, the affinity between the binder resin and the other material is increased by including another material under the crosslinking reaction between the carboxyl group unit and the epoxy group unit in the binder resin, and the good dispersibility in the toner particles is obtained. Can be achieved.
Furthermore, detachment from the binder resin can be suppressed, and as a result, contamination of the sleeve and the like can be suppressed.

Further, the toner of the present invention can be made tougher by performing the crosslinking reaction as described above, and when applied to a high speed machine or the like, it is stable even when the copy volume is increased. Durability can be achieved.

One of the features of the present invention is that the T of the toner is
Acid value of HF soluble component is 1.0 to 50 mgKOH / g
And preferably 1.0 to 40 mg KO
H / g. When the toner of the present invention has a desired acid value, good developability and durability can be achieved.

The acid value of the THF-soluble component of the toner is 1.0 m
When it is less than gKOH / g, the dispersibility is not improved due to the mutual reaction between the carboxyl group and the other material and the effect of preventing desorption from the toner particles is not exhibited. If it exceeds 50 mgKOH / g, the toner tends to absorb moisture in a high humidity environment, resulting in a decrease in density.

Further, one of the features of the present invention is that the dielectric loss tangent (tan δ _T ) of the toner has a maximum value (tan δ) at T _MAX (° C.) in the temperature range of 20 to 150 (° C.).
_{T (T MA X))} has, the toner regulating member T _MAX (° C.)
Has a dielectric loss tangent (tan δ _B (T _MAX )) of 1.0 ×
It is 10 ^{−3 to} 5.0 × 10 ⁰ . The dielectric loss tangent (tan δ of the blade that is the toner regulating member)
_{When B} (T _MAX )) is less than 1.0 × 10 ⁻³ , the toner is not sufficiently charged, and the toner is reduced in density and fog due to long-term durability. On the other hand, when it is more than 5.0 × 10 ⁰ , the amount of overcharged toner particles is increased, the density is lowered due to a charge-up phenomenon, and uneven sleeve coat such as blotches is likely to occur.

The toner dielectric loss tangent of the present invention has a frequency of 100.
The value at 0 (Hz), which indicates the dielectric charge polarization at the toner particle interface, changes depending on the measurement frequency, but its maximum value is near the melting temperature of the toner where the toner agglomerates collapse. Indicates. That is, the toner has a particle shape in a temperature range equal to or lower than the temperature T _{MAX at} which the maximum value is obtained, and within the temperature range having the particle shape, T
_{At MAX} (° C), the toner has the largest charge relaxation.

On the other hand, in the portion where the blade comes into contact with the sleeve via the toner, the toner agglomeration is released, and the toner solid can sufficiently come into contact with the sleeve and the blade, which is an important opportunity when the toner is triboelectrically charged. . Therefore, by controlling the charge imparting ability of the blade in accordance with the present invention in accordance with the mitigation of the charge due to the environmental change of the toner, the charge amount of the toner can be stably controlled under any temperature environment, and more uniform charging becomes possible. Become. Further, in particular, in the developing means, when an alternating current is applied between the photoconductor and the sleeve, this blade portion is also under an alternating electric field, and by controlling the dielectric loss of the toner and the blade, dot reproducibility and fine line reproducibility are improved. Can be improved.

The toner layer regulating member of the present invention has a dielectric loss tangent (tan δ _B ) of 5.0 × 10 ^{-2 to} 2.0 × 10 at a frequency of 1.0 × 10 ³ (Hz) and T _MAX (° C.). It is preferably ⁰ . tan δ _B (T _MAX ) is 5.0 × 10
If it is less than ^-2 , the charge amount distribution becomes broad in a high temperature environment, and the image tends to scatter and fogging is likely to occur.

If tan δ _B (T _MAX ) is more than 2.0 × 10 ⁰ , the toner is likely to be excessively charged in a low temperature environment, the charge amount distribution is disturbed, and defective blotch sleeve coating is likely to occur.

The frequency of the toner of the present invention is 1.0 × 1.
The maximum value (tan δ _T (T _MAX )) in the temperature range of 0 ³ (Hz) and 20 to 150 (° C.) is 1.0 × 10 ^0.
The following is preferable, and 5.0 × 1 is more preferable.
It is preferably 0 ⁻¹ or less, particularly preferably 1.0 × 10 ⁻¹ or less.

The maximum value of the dielectric loss tangent of the toner tan δ _T (T
_{When MAX} ) is 1.0 × 10 ⁰ or less, good developability can be achieved, and particularly in a high temperature and high humidity environment, good developability is exhibited. When tan δ _T (T _MAX ) is more than 1.0 × 10 ⁰ , the charge relaxation becomes large with respect to the environmental temperature change, it becomes difficult to maintain stable charge, and the developability easily deteriorates. Also, the dot reproducibility is likely to deteriorate.

The toner of the present invention preferably has 85% by number or more of particles having a circularity a of 0.90 or more among particles having a particle diameter of 3 μm or more. Circularity a = L ₀ / L (where L ₀ represents the perimeter of a circle having the same area as the projected image of the particle, and L represents the perimeter of the projected image of the particle.)

When the number of particles having a circularity a of 0.90 or more is less than 85% by number, the toner particles have a distorted shape, which causes frictional charging between the toner and the blade or the toner and the sleeve. The contact size becomes large, and it becomes difficult for each toner to be uniformly charged, and the toner charge amount distribution tends to be broad. As a result, image fog and image unevenness are likely to occur. Further, in the blade pressure contact type developing method as in the present invention, the blade and the sleeve are worn by the toner due to long-term use, and the sleeve coat unevenness and the toner conveyance failure are likely to occur.

Further, in the present invention, THF in the toner
In the molecular weight distribution measured by GPC of the soluble component,
The number average molecular weight is preferably 1,000 to 40,000.
0, more preferably 2,000 to 20,000, particularly preferably 3,000 to 15,000, and the weight average molecular weight is preferably 10,000.
To 10,000,000, more preferably 20,000
0 to 5,000,000, particularly preferably 30,000
It is preferably 0 to 1,000,000.

In the GPC chromatogram of the THF-soluble component of the toner used in the present invention, when the above-mentioned average molecular weight is exhibited, it becomes possible for the toner to retain an appropriate amount of charge and toughness, and the toner in the developing section can be retained. Even in a high-speed and high-durability system, which has a large share of toner, good developability and durability can be achieved, and toner fusion does not occur.

When the number average molecular weight is less than 1,000 or the weight average molecular weight is less than 10,000, the melt viscosity of the toner is lowered, resulting in an uneven charge distribution, which leads to deterioration of fog suppression and the like. When the number average molecular weight that makes it easy to develop toner fusion on the sleeve exceeds 40,000 or the weight average molecular weight exceeds 10,000,000, the phase of the high molecular component and the low molecular component in the binder resin The solubility deteriorates, the component distribution of the binder resin itself becomes non-uniform, the material dispersibility in the toner deteriorates, and the dot reproducibility deteriorates.

Further, in the present invention, THF in the toner
In the molecular weight distribution measured by GPC of the soluble component,
It preferably has a main peak in the molecular weight range of 4,000 to 30,000, and more preferably has a main peak in the molecular weight range of 5,000 to 20,000.

When the main peak has a molecular weight of less than 4,000, sleeve fusion or the like tends to occur in a high temperature environment.
If the molecular weight exceeds 30,000, the material dispersibility deteriorates and the dot reproducibility deteriorates.

In the above molecular weight distribution, the molecular weight is 3
It is preferable that the peak area of 20,000 or less is 60 to 100% of the total peak area. When the peak area with a molecular weight of 30,000 or less is within the above range, good material dispersibility can be achieved in the toner particles, and when it is less than 60%, the melt viscosity of the resin increases,
It becomes difficult to uniformly disperse with other materials at the time of melt-kneading at the time of toner production.

Further, the resin component of the toner of the present invention is TH
You may contain 0.1 to 60 mass% of F insoluble matter. The content is more preferably 5 to 60% by mass, and particularly preferably 10 to 45% by mass. When the THF-insoluble content is within the above range, it is possible to achieve uniform dispersibility of the material in the toner particles, and to have appropriate toughness of the toner itself, thereby achieving good developability and durability. .

When the THF insoluble content exceeds 60% by mass,
The melt viscosity of the resin increases, and the dispersed state of the material inside the toner particles deteriorates, resulting in uneven charging, resulting in uneven charge distribution on the photoconductor and dot reproducibility. Getting worse.

Glass transition temperature (Tg) of the toner of the present invention
Is preferably 50 to 70 ° C. When Tg is less than 50 ° C., storage stability deteriorates, and when Tg exceeds 70 ° C., fixability deteriorates.

Further, in the toner of the present invention, the epoxy value of the THF-soluble component is preferably 0.0001 to 5.0. When the epoxy value is less than 0.0001, the dielectric loss of the toner tends to decrease, and in combination with the elastic blade of the present invention, fog or the like occurs due to excessive charging of some toner particles in a low humidity environment. easy. On the other hand, when the epoxy value is more than 5.0, similarly, in a high humidity environment, similarly, fog or the like is likely to occur due to insufficient charge amount of a part of the toner.

In the present invention, the dielectric loss tangents of the toner and blade are measured under the following conditions.

<Measurement of dielectric loss tangent> Using a 4284A precision LCR meter (manufactured by Hewlett-Packard Co.), after calibrating at a frequency of 1000 Hz and 1 MHz, a dielectric loss (tan δ = ε ”was obtained from the measured value of the complex dielectric constant at a frequency of 1000 Hz. / Ε ') is calculated.

The toner is weighed at 1.0 g, and the weight is 19600 k.
A load of Pa (200 kgf / cm ² ) is molded for 1 minute, and the diameter is 25 mm and the thickness is 2 mm or less (preferably 0.1 mm or less).
(5 mm to 1.5 mm) disk-shaped measurement sample. Similarly, the blade has a diameter of 25 mm and a thickness of 2 mm.
The following (preferably 0.5 mm to 1.5 mm) disk-shaped molded sample was used as a measurement sample, and this measurement sample was mounted with an ARES (rheometric scientific It is attached to FFE Co., Ltd., heated to a temperature of 80 ° C., and melted and fixed. afterwards,
Cool to a temperature of 20 ° C., 0.49 to 1.96 N (50 to
With a load of 200 g) applied, frequency 1000 Hz
In the temperature range of 20 to 150 ° C, which is constant,
It can be obtained by heating at a heating rate of 2.0 ° C./1 min and measuring.

<Measurement of Toner Circularity> A surfactant, preferably 0.1 to 0.5 ml of an alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of water in which impure solids have been removed in advance in a container. Furthermore, 0.1 to 0.1
Add about 0.5 g. The suspension in which the sample is dispersed is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and the dispersion liquid concentration is set to 3
It is obtained by measuring the shape and particle size of the toner using a flow type particle image analyzer FPIA-1000 manufactured by Toa Medical Electronics Co., Ltd.

The circularity in the present invention is an index of the degree of unevenness of the toner particles, and when the toner is a perfect sphere, 1.
00, the circularity has a smaller value as the surface shape becomes more complicated.

The standard deviation SD of the circularity distribution is 0.
It is preferably 050 or less in terms of image quality and transferability. In the present invention, as the standard deviation SD of the circularity distribution, a value obtained from the following equation (2) from the circularity and average circularity of each particle is used.

[0060]

[Equation 1]

The SD of the circularity distribution in the present invention is an index of the breadth of the distribution, and the smaller the numerical value, the sharper the distribution without variation.

In the present invention, T of the toner and the binder resin is
The molecular weight distribution by GPC using HF as a solvent is measured under the following conditions.

<Measurement of molecular weight distribution by GPC> 40 ° C.
The column is stabilized in the heat chamber of the above, and THF as a solvent is caused to flow through the column at a flow rate of 1 ml per minute, and about 100 μl of a THF sample solution is injected for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count value of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve,
For example, the molecular weight of Tosoh or Showa Denko is 1
It is suitable to use a standard polystyrene sample of at least about 10 points, using a sample of 0 ² to 10 ⁷ . Also,
An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns, for example, shod manufactured by Showa Denko KK
ex GPC KF-801, 802, 803, 80
Combination of 4,805,806,807,800P and TSKgel G1000H made by Tosoh Corporation
(H _XL ), G2000H (H _XL ), G3000H
(H _XL ), G4000H (H _XL ), G5000H
(H _XL ), G6000H (H _XL ), G7000H
(H _XL ), a combination of TSKgurd column.

The sample is prepared as follows.

The sample is placed in THF, left for a few hours, then shaken well and mixed well with THF (until the coalescence of the sample disappears), and then left still for 12 hours or more. Then th
The time for leaving in F should be 24 hours or more. Then sample processing filter (pore size 0.2 ~
0.5 μm, for example, Mysholydisc H-25-2
(Manufactured by Tosoh Corporation) can be used. ) Is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the present invention, the THF insoluble content of the binder resin component in the toner and the THF insoluble content of the raw material binder resin are measured as follows.

<Measurement of THF-insoluble matter> Toner 1.0 to
Weigh 2.0 g (W1 g), put a cylindrical filter paper (eg Toyo Roshi Kaisha No. 86R) into a Soxhlet extractor, and extract with THF 200 ml as a solvent for 10 hours, and the soluble component solution extracted by the solvent Is evaporated and then vacuum dried at 100 ° C. for several hours, and the amount of the THF-soluble resin component is weighed (W2g). The weight of incineration residual ash in the toner is calculated (W3g).

The incineration residual ash content is obtained by the following procedure. Approximately 2.0 g of the sample is placed in a 30 ml magnetic crucible that has been precisely weighed in advance, and the sample is precisely weighed, and the mass (Wa) g of the sample is precisely weighed. The crucible is placed in an electric furnace, heated at about 900 ° C. for about 3 hours, allowed to cool in the electric furnace, allowed to cool in a desiccator at room temperature for 1 hour or more, and the mass of the crucible is precisely weighed. From this, the incineration residual ash content (Wb) g is obtained. (Wb / Wa) x 100 = Incineration residual ash content (mass%)

From this content, the mass (W3g) of the incineration residual ash in the sample can be obtained.

The THF-insoluble matter is obtained from the following formula. THF insoluble matter = (W1- (W3 + W2)) / (W1-W
3) x 100 (%)

In the present invention, the THF soluble component of the toner and the acid value (JIS acid value) of the binder resin are determined by the following method. The acid value of the binder resin is the THF in the binder resin.
It means the acid value of the soluble component.

<Measurement of acid value> The basic operation is JIS K-0.
According to 070. (1) The sample is used by removing the THF-insoluble component of the toner and the binder resin in advance, or the soluble component extracted by the THF solvent by the Soxhlet extractor obtained by the measurement of the THF-insoluble component is used as the sample. To do. Precisely weigh 0.5-2.0 (g) of the crushed sample and weigh the soluble component by W
(G). (2) Put the sample in a beaker of 300 (ml) and dissolve it by adding 150 (ml) of a mixed solution of toluene / ethanol (4/1). (3) Using 0.1 mol / l KOH in ethanol, titration is performed using a potentiometric titrator. (For example, potentiometric titrator AT-400 (wi
nworkstation) and automatic titration with an ABP-410 electric burette is available. (4) The amount of KOH solution used at this time is S (ml),
At the same time, the blank is measured, and the amount of the KOH solution used at this time is B (ml). (5) The acid value is calculated by the following formula. f is a factor of KOH. Acid value (mgKOH / g) = {(S−B) × f × 5.6
1} / W

The method for measuring the glass transition temperature of the toner of the present invention is shown below.

<Measurement of Glass Transition Temperature of Toner> The glass transition temperature (Tg) of the toner is measured by a differential scanning calorimeter (DSC).
Measurement device), DCS-7 (manufactured by Perkin Elmer Co., Ltd.) are used for measurement according to ASTM D3418-82.

The measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg. Put it in an aluminum pan and use an empty aluminum pan as a reference.
The measurement is performed under normal temperature and normal humidity at a temperature rising rate of 10 ° C./min between 200 ° C. and 200 ° C. During this temperature raising process, the temperature is 40 to 100 ° C.
A specific heat change can be obtained in the range of ° C. At this time, the intersection of the line at the midpoint of the baseline before and after the change in specific heat and the differential heat curve is taken as the glass transition temperature Tg of the toner of the present invention.

<Measurement of Epoxy Value> Basic operation is JIS
According to K-7236. (1) The sample is used by removing the THF-insoluble component of the toner and the binder resin in advance, or the soluble component extracted by the THF solvent by the Soxhlet extractor obtained by the measurement of the THF-insoluble component is used as the sample. To do. 0.5 sample
~ 2.0 (g) is precisely weighed, and the weight is defined as W (g). (2) Put the sample in a 300 (ml) beaker and dissolve in 10 ml of chloroform and 20 ml of acetic acid. To this solution is added 10 ml of tetraethylammonium bromide acetic acid solution. Titration is performed using a potentiometric titrator using a 0.1 mol / l acetic acid perchlorate solution. (For example, potentiometric titrator AT-400 (win
automatic titration can be used with an ABP-410 electric burette. ). The amount of perchloric acid / acetic acid solution used at this time was S (ml), and at the same time, the blank was measured.
(Ml).

The epoxy value is calculated by the following formula. f is a factor of acetic acid perchlorate solution. Epoxy value (eq / kg) = 0.1 × f × (SB) /
W

In the present invention, the toner is a group consisting of a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, or a resin obtained by reacting these functional groups. At least one vinyl resin selected from the above is included.

The following are examples of the monomer having a carboxyl group unit which constitutes the vinyl resin having a carboxyl group.

Examples of the monomer having a carboxyl group unit include acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid, cinnamic acid, vinylacetic acid,
Acrylic acids such as isocrotonic acid, tiglic acid and angelic acid, their anhydrides and α- or β-alkyl derivatives, fumaric acid, maleic acid, citraconic acid, alkenylsuccinic acid, itaconic acid, mesaconic acid, dimethyl maleic acid, dimethyl Examples thereof include unsaturated dicarboxylic acids such as fumaric acid, monoester derivatives thereof, anhydrides and α- or β-alkyl derivatives.

A vinyl resin having a carboxyl group can be obtained by copolymerizing a monomer having such a carboxyl group unit, alone or in combination, with another vinyl monomer by a known polymerization method.

The acid value of the vinyl resin having a carboxyl group is preferably 0.5 to 60 mgKOH / g. 0.5
When the amount is less than mgKOH / g, the crosslinking reaction site between the carboxyl group and the epoxy group is reduced, so that the amount of the crosslinking component is small and the durability of the toner is hard to be expressed. Some compensation can be achieved by using a vinyl resin having a high epoxy group.
When it exceeds 60 mgKOH / g, when it is applied to a positively chargeable toner, the negative chargeability of the binder resin in the toner particles becomes strong, the image density tends to decrease, and the fog tends to increase.

The glass transition temperature (Tg) of the vinyl group having a carboxyl group is preferably 40 to 70 ° C. If the Tg is less than 40 ° C, the blocking resistance of the toner deteriorates, and if the Tg exceeds 70 ° C, the fixing property of the toner deteriorates.

In the vinyl resin having a carboxyl group, the number average molecular weight is preferably 1,000 to 40,000 in order to achieve good fixability and developability, and the weight average molecular weight is good offset resistance, To achieve blocking resistance and durability, 10,000 to 10,
, 000,000 is preferred.

The vinyl resin having a carboxyl group is preferably composed of a low molecular weight component and a high molecular component. The peak molecular weight of the low molecular weight component is preferably 4,000 to 30,000 in order to achieve good fixability.
The peak molecular weight of the high molecular weight component is 10 in order to achieve good offset resistance, blocking resistance and durability.
It is preferably from 10,000 to 1,000,000.

As a polymerization method which can be used in the present invention as a method for synthesizing a high molecular weight component copolymer, a bulk polymerization method,
A solution polymerization method, an emulsion polymerization method and a suspension polymerization method can be mentioned.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is performed using a water-soluble polymerization initiator. . In this method, the heat of reaction can be easily adjusted, and the phase in which the polymerization is carried out (oil phase composed of polymer and monomer)
And the aqueous phase are different, the termination reaction rate is low, and as a result, the polymerization concentration is high and a high polymerization degree is obtained. Further, in the production of toner, due to the relatively simple polymerization process and the fine particles of the polymerization product,
Since it is easy to mix with a colorant, a charge control agent and other additives, it is advantageous as a method for producing a binder resin for toner.

However, the added emulsifier tends to impure the polymer, and an operation such as salting out is required to remove the polymer. To avoid this inconvenience, solution polymerization and suspension polymerization are performed. Is convenient.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is added to 100 parts by mass of the aqueous solvent.
0 to 90 parts by mass) is preferable. As dispersants that can be used, polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like are used, and generally 0.05 to 1 part by mass relative to 100 parts by mass of the aqueous solvent. The polymerization temperature is suitably 50 to 95 ° C., but it is appropriately selected depending on the initiator used and the target polymer.

In order to achieve the object of the present invention, the high molecular weight polymer of the resin composition used for preparing the resin composition is a polyfunctional polymerization initiator alone or a monofunctional polymerization as exemplified below. It is preferably produced in combination with an initiator.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,5-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-t-
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butylperoxyoctane and various polymer oxides;
And a functional group having a polymerization initiation function such as a peroxide group in one molecule such as diallyl peroxydicarbonate, t-butyl peroxy maleic acid, t-butyl peroxy allyl carbonate and t-butyl peroxy isopropyl fumarate. And a polyfunctional polymerization initiator having both a polymerizable unsaturated group.

Of these, the more preferable ones are:
1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-butylperoxycyclohexane, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxy Azelate and 2,2-bis- (4,4-di-t-butylperoxycyclohexane) propane and t-butylperoxyallyl carbonate.

These polyfunctional polymerization initiators are preferably used in combination with a monofunctional polymerization initiator in order to satisfy various performances required as a binder for toner.
Particularly, it is preferably used in combination with a polymerization initiator having a half-life of 10 hours, which is lower than the decomposition temperature for obtaining the half-life of 10 hours of the polyfunctional polymerization initiator.

Specifically, benzoyl peroxide,
1,1-di (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-di (t
-Butylperoxy) valerate, dicumyl peroxide, α-α'-bis (t-butylperoxydiisopropyl) benzene, t-butylperoxycumene, di-t
Examples include organic peroxides such as -butyl peroxide, azo and diazo compounds such as azobisisobutyronitrile and diazoaminoazobenzene.

These monofunctional polymerization initiators may be added to the monomer at the same time as the polyfunctional polymerization initiator, but in order to keep the efficiency of the polyfunctional polymerization initiator proper,
It is preferably added after the half-life indicated by the polyfunctional polymerization initiator has elapsed in the polymerization step.

From the viewpoint of efficiency, these initiators are preferably used in an amount of 0.01 to 10 parts by mass with respect to 100 parts by mass of the monomer.

As a method for synthesizing the low molecular weight component, a known method can be used. However, in the bulk polymerization method, polymerization is performed at a high temperature to accelerate the termination reaction rate,
Although a low molecular weight polymer can be obtained, there is a problem that it is difficult to control the reaction. In that respect, in the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in radical chain transfer depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferable to obtain a low molecular weight component in a vinyl resin having a carboxyl group.

As a solvent used in solution polymerization, xylene,
Toluene, cumene, cellosolve acetate, isopropyl alcohol or benzene are used. If styrene monomers are used, xylene, toluene or cumene are preferred. The solvent is appropriately selected depending on the polymer to be polymerized. The reaction temperature varies depending on the solvent used, the polymerization initiator, and the polymer to be polymerized, but is usually 70 to 230 ° C.
Good to do in. The solution polymerization is preferably performed with 30 to 400 parts by mass of the monomer based on 100 parts by mass of the solvent.

Further, it is also preferable to mix another polymer in the solution at the end of the polymerization, and several polymers can be mixed.

The epoxy group in the vinyl resin having an epoxy group used in the present invention is a functional group in which an oxygen atom is bonded to carbon atoms of two atoms in the same molecule and has a cyclic ether structure. Typical cyclic ether structures include a 3-membered ring, a 4-membered ring, a 5-membered ring and a 6-membered ring, and among them, a 3-membered ring structure is preferable.

The following are examples of the monomer having an epoxy group unit which constitutes the vinyl resin having an epoxy group.

Glycidyl acrylate, glycidyl methacrylate, β-methylglycidyl acrylate, β-methylglycidyl methacrylate, allyl glycidyl ether,
Allyl β-methyl glycidyl ether and the like can be mentioned.
Further, the glycidyl monomer represented by the general formula (1) is preferably used.

[0103]

[Chemical 1] (In the general formula (1), R ₁ , R ₂ and R ₃ are hydrogen,
An alkyl group, an aryl group, an aralkyl group, a carboxyl group and an alkoxycarbonyl group are shown. )

Monomers having such an epoxy group unit may be used alone or in admixture, and the vinyl resin having the epoxy groups may be obtained by copolymerizing with a vinyl monomer by a known polymerization method.

The weight average molecular weight (Mw) of the vinyl resin having an epoxy group is preferably 2,000 to 10.
10,000, more preferably 2,000 to 50,000
It is preferably 0, and more preferably 3,000 to 40,000. If the Mw is less than 2,000, the molecular weight increases due to the crosslinking reaction in the binder resin, and many molecules are cleaved during the kneading step, resulting in poor durability. Mw is 10
When it exceeds 50,000, the fixing property is affected.

The epoxy value is 0.05 to 5.0.
eq / kg is preferable. If it is less than 0.05 eq / kg, the cross-linking reaction is difficult to proceed, resulting in high molecular weight components or THF.
The amount of insoluble matter produced is reduced, and the toughness of the toner is reduced. If it exceeds 5.0 eq / kg, the crosslinking reaction is likely to occur, but on the other hand, many molecular breakages occur in the kneading step, and the dispersibility with other materials deteriorates.

Further, when used in the above range, the epoxy groups can be dispersed uniformly in the toner, whereby the dielectric loss of the toner can be appropriately increased and controlled. By using the elastic blade as in the present invention together with the elastic blade, it becomes possible to uniformly charge the toner regardless of the environmental temperature change.

The epoxy group-containing vinyl resin of the present invention contains 0.01 to 10.0 equivalents of epoxy groups, preferably 0.03 to 5.0 equivalents, relative to 1 equivalent of carboxyl groups in the carboxyl group-containing vinyl resin. It is preferable to use an equivalent mixing ratio.

When the epoxy group is less than 0.01 equivalent, the number of cross-linking points in the binder resin is small, and the effect of the cross-linking reaction such as durability is difficult to be exhibited. On the other hand, if it exceeds 10 equivalents, the crosslinking reaction is likely to occur, but the dispersibility is deteriorated due to the generation of an excessive THF insoluble component, and the pulverizability is deteriorated and the development stability is problematic.

In the vinyl resin having a carboxyl group and an epoxy group, the number average molecular weight is preferably 10,000 to 40,000 in order to achieve good developability and durability. Further, the weight average molecular weight is the offset resistance,
10,0 to achieve blocking resistance and durability
00 to 10,000,000 is preferable.

The vinyl resin having a carboxyl group and an epoxy group can be obtained by mixing a monomer having a carboxyl group unit and a monomer having an epoxy group unit and copolymerizing with another vinyl monomer by a known polymerization method.

In the present invention, a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group may be previously reacted at the time of resin production. As the reaction means, a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group are mixed in a solution state, and heat is applied in a reaction vessel to cause a cross-linking reaction. A vinyl resin having a group may be taken out of the reaction kettle, dry-blended with a Henschel mixer or the like, and melt-kneaded with a twin-screw extruder to cause a cross-linking reaction.

When the vinyl resin obtained by reacting the vinyl resin having a carboxyl group with the resin having an epoxy group is used, it is preferable that the THF-insoluble content is contained in an amount of 0.1 to 60% by mass. When the THF insoluble content is in the above range,
In the kneading process during the manufacturing process, the resin itself can have an appropriate melt viscosity, so that uniform dispersibility of the material can be achieved.

When the THF insoluble content exceeds 60% by mass,
The melt viscosity of the resin itself increases and the dispersibility of the material deteriorates.

Examples of the vinyl monomer to be copolymerized with the monomer having a carboxyl group unit and the monomer having an epoxy group unit include the following.

Examples of the monomer other than the monomer having a carboxyl group unit and the monomer having an epoxy group unit include, for example, styrene; o-methylstyrene, m-
Methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene,
3,4-dichlorostyrene, p-ethylstyrene, 2,
4-dimethylstyrene, pn-butylstyrene, p-
Styrene derivatives such as tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene. , Ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; vinyl acetate,
Vinyl esters such as vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate,
Isobutyl methacrylate, n-octyl methacrylate,
Α-Methylene aliphatic monocarboxylic acid esters such as dodecyl methacrylate, (2-ethylhexyl) methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, 1-octyl acrylate,
Acrylic esters such as dodecyl acrylate, acrylic acid (2-ethylhexyl), stearyl acrylate, acrylic acid (2-chloroethyl), phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and methyl isopropenyl ketone; N-
N-vinyl compounds such as vinylpyrrol, N-vinylcarbazole, N-vinylindole and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid derivatives or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile and acrylamide. . These vinyl monomers may be used alone or in admixture of two or more.

Among these, a combination of monomers that forms a styrene copolymer and a styrene-acrylic copolymer is preferable, and in this case, at least a styrene copolymer component or a styrene-acrylic copolymer component is used. It is preferable that the content is at least mass% in terms of fixability and mixability.

As the binder resin used in the toner of the present invention, the following polymers may be added.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and their substitution products; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene. Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used.

In order to maintain the positive charging property or the negative charging property of the toner used in the present invention, it is preferable that the toner is controlled to contain a charge control agent.

There are the following substances for controlling the toner to be positively charged.

For example, modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and analogs thereof. Onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid,
Ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; diorganotinborates such as dibutyltin borate, dioctyltin borate, dicyclohexyltin borate. There are guanidine compounds and imidazole compounds. These can be used alone or in combination of two or more. Among these,
A triphenylmethane compound, an imidazole compound, and a quaternary ammonium salt whose counter ion is not halogen are preferably used.

Further, there are the following substances for controlling the toner to be negatively charged.

Organic metal complexes and chelate compounds are effective, for example, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acid metal complexes, and aromatic dicarboxylic acid metal complexes. Others include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids and aromatic polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

As a method of incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally.
The amount of these charge control agents used is determined by the type of binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not uniquely determined, but is preferably determined. 0.1 to 100 parts by weight of binder resin
It is used in an amount of 10 parts by mass, more preferably 0.1 to 5 parts by mass.

In the present invention, the following waxes are preferably contained in order to impart releasability to the toner. A wax having a melting point of 70 to 165 ° C. and a melt viscosity at 160 ° C. of 1000 mPa · s or less, and specific examples thereof include paraffin wax, microcrystalline wax, Fischer-Tropsch wax, montan wax, ethylene, propylene, butene, and petroleum. Homopolymers of straight-chain α-olefins such as pentene, hexene, heptene, octene, nonene, decene and branched α-olefins having a branched moiety at their ends and olefins having different positions of their unsaturated groups. Alternatively, copolymers thereof and the like can be mentioned. Others, alcohol wax,
Fatty acid wax, ester wax, and natural wax are also used.

Further, a modified wax obtained by forming a block copolymer with a vinyl-based monomer, a graft modification, or an oxidation treatment may be used.

These waxes are used in the production of toner.
It is also possible to add and mix the polymer components in advance.
In that case, it is preferable to pre-dissolve the wax and the high molecular weight polymer in a solvent when preparing the polymer component, and then mix them with the low molecular weight polymer solution. This alleviates phase separation in the microscopic region, controls reaggregation of the high molecular weight component, and obtains a good dispersion state with the low molecular weight polymer.

The amount of the above wax added is preferably 0.5 to 10 parts by mass, and more preferably 1 to 8 parts by mass with respect to 100 parts by mass of the binder resin.
Two or more types of wax may be used in combination.

The colorant that can be used in the toner of the present invention includes any appropriate pigment or dye. For example, as the pigment, carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red iron oxide,
There are phthalocyanine blue and indanthrene blue. These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and are 0.1 to 100 parts by mass of the resin.
The addition amount of 20 parts by mass, preferably 0.2 to 10 parts by mass is good. Further, a dye is further used for the same purpose. For example, there are azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes.
0.1 to 20 parts by mass, preferably 0.3 to 10 parts by mass may be added.

Further, in the toner of the present invention, a magnetic material may be used as a colorant and used as a magnetic toner.

Further, the toner of the present invention can be used as a one-component developer as a magnetic toner containing a magnetic material. In this case, the magnetic material can also serve as a coloring agent. In the present invention, as the magnetic material used in forming the magnetic toner, magnetite, hematite, iron oxide of ferrite; metals such as iron, cobalt, nickel or these metals and aluminum, cobalt, copper, lead, magnesium, Tin, zinc, antimony,
Alloys with metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof are mentioned.

These magnetic materials preferably have an average particle size of 2 μm or less, preferably about 0.1 to 0.5 μm. The amount of resin component to be contained in the toner is 100
It is preferably about 20 to 200 parts by mass, and particularly preferably 40 to 150 parts by mass with respect to parts by mass.

Further, the saturation magnetization of these magnetic materials is 5 Am ² / kg (5 emu / g) to 200 Am ² / k in a magnetic field of 7.96 × 10 ² kA / m (10 kOe).
g (200 emu / g), further 10 Am ² / kg
(10 emu / g) to 150 Am ² / kg (150 em
u / g) are preferred.

The residual magnetization of the magnetic material is 7.96 ×
With a magnetic field of 10 ² kA / m (10 kOe), 1 Am ² / kg
(1 emu / g) to 100 Am ² / kg (100 emu / g
/ G), and further 1 Am ² / kg (1 emu / g) to 7
It is preferably 0 Am ² / kg (70 emu / g).

The magnetic characteristics of the magnetic material were determined by using an “oscillating sample magnetometer VSM-3S-15” (manufactured by Toei Industry Co., Ltd.) and an external magnetic field of 7.96 × 10 ² kA / m (10 kOe).
It is the value measured under. The amount of the magnetic substance contained in the toner of the present invention is 10 to 2 with respect to 100 parts by mass of the binder resin.
00 parts by mass, preferably 20 to 170 parts by mass, desirably 30 to 150 parts by mass.

In the toner of the present invention, the charging stability,
In order to improve developability, fluidity and durability, it is preferable to add fine silica powder.

[0138] Silica fine powder used in the present invention has a specific surface area by the BET method by nitrogen adsorption 30 m ² / g or more, particularly in the range of 50 to 400 m ² / g give good results. The fine silica powder is used in an amount of 0.01 to 8 parts by mass, preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the toner.

Further, the silica fine powder used in the present invention contains, if necessary, a silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, for the purpose of hydrophobizing and controlling the charging property. It is also preferable that the treatment is carried out with a treating agent such as a silane compound having a functional group or another organic silicon compound, or in combination with various treating agents.

If necessary, other external additives may be added to the toner of the present invention.

Examples thereof include resin fine particles and inorganic fine particles that act as a charging aid, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a releasing agent at the time of hot-roller fixing, a lubricant, an abrasive and the like. .

Examples of the lubricant include polyvinyl fluoride powder, zinc stearate powder, polyvinylidene fluoride powder, and the like, and polyvinylidene fluoride powder is preferable. Examples of the polishing agent include cerium oxide powder, silicon carbide powder, and strontium titanate powder.
Of these, strontium titanate powder is preferable. Examples of the fluidity-imparting agent include titanium oxide powder and aluminum oxide powder, and among them, hydrophobic ones are preferable. Examples of the conductivity imparting agent include carbon black powder, zinc oxide powder, antimony oxide powder, tin oxide powder and the like. Furthermore, a small amount of reverse polarity white fine particles and black fine particles can be used as a developing property improver.

To prepare the toner of the present invention, a binder resin, a colorant, other additives and the like are thoroughly mixed with a mixer such as a Henschel mixer or a ball mill, and then a heating roll, a kneader or an extruder is used. Melt kneading using a simple heat kneader, crushing and classifying after cooling and solidifying,
Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner of the present invention.

For example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Co., Ltd.); a ribocon (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); The spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); the Ledige mixer (manufactured by Matsubo Co., Ltd.), and the kneaders include KRC Kneader (Kurimoto Iron Works Co., Ltd.); Bus Co Kneader (Bus Co., Ltd.); TEM type extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Japan Steel Works); PCM kneader (manufactured by Ikegai Iron Works Co., Ltd.); three-roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); Kneedex (Mitsui Mining Co., Ltd.); MS type pressure kneader, Nider Ruder (Moriyama Seisakusho); Banbury mixer (Kobe) As a crusher, examples of the crusher include a counter jet mill, a micron jet, an inomizer (made by Hosokawa Micron Co.); an IDS type mill, a PJM jet crusher (made by Nippon Pneumatic Mfg. Co., Ltd.); a cross jet mill (Kurimoto Tekko Co., Ltd.). Ulmax (manufactured by Nisso Engineering); SK Jet
O-mill (made by Seishin Enterprise Co., Ltd.); Kriptron (made by Kawasaki Heavy Industries, Ltd.); Turbo Mill (made by Turbo Engineering Co., Ltd.), and classifiers include Classels, Micron Classifiers, and Spedic Classifiers (made by Seishin Enterprises). ); Turbo classifier (manufactured by Nisshin Engineering Co., Ltd.); Micron separator, Turboplex (ATP), TSP separator (manufactured by Hosokawa Micron); Elbow Jet (manufactured by Nittetsu Mining Co., Ltd.), Dispersion separator (Nippon Pneumatic Mfg. Co., Ltd.) Company);
YM Micro Cut (manufactured by Yasukawa Shoji Co., Ltd.) is mentioned, and as a sieving device used for sieving coarse particles and the like, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonator Sieve, Gyro Shifter (Dekuju Kosakusho Co., Ltd.); Vibra Sonic system (manufactured by Dalton); Soniclean (manufactured by Shinto Kogyo Co., Ltd.); Turbo Screener (manufactured by Turboe Industry Co., Ltd.); Micro Shifter (manufactured by Makino Sangyo Co., Ltd.); circular vibrating sieve and the like.

The developing step of the image forming method using the toner of the present invention will be described in detail.

The developing method using the toner of the present invention includes a method using a magnetic toner and a method using a non-magnetic toner.

The method using the magnetic toner will be described.

In FIG. 1, the substantially right half peripheral surface of the toner carrier 102 is constantly in contact with the toner pool in the toner container 106, and the toner near the surface of the toner carrier is magnetically attracted to the surface of the toner carrier. It is attached and held by the magnetic force of the generating means 103 and / or by the electrostatic force. When the toner carrier 102 is rotationally driven, the magnetic toner layer on the surface of the toner carrier is layered as a thin layer T1 having a uniform thickness in each part while passing through the position of the toner regulating member 104.
The magnetic toner is charged mainly by frictional contact between the surface of the toner carrier and the magnetic toner in the toner pool in the vicinity of the surface of the toner carrier as the toner carrier 102 rotates.
The magnetic toner thin layer surface on 2 rotates to the side of the photoconductor 101 as the toner carrier rotates, and passes through the developing area A, which is the closest part between the photoconductor 101 and the toner carrier 102.
In the course of this passage, the magnetic toner in the thin layer of the magnetic toner on the surface side of the toner carrier 102 is transferred to the photoreceptor 101 and the toner carrier 102.
It flies by a direct current and an alternating voltage applied by a direct current and an alternating voltage, and reciprocates between the surface of the photoconductor 101 in the developing area A and the surface of the toner carrier 102 (gap α). Finally, the magnetic toner on the side of the toner carrier 102 is transferred to the photoconductor 10.
The toner image T2 is sequentially formed on the surface of the first surface by selectively transferring and adhering in accordance with the potential pattern of the latent image.

The surface of the toner carrier on which the magnetic toner has been selectively consumed after passing through the developing area A is the toner container 106.
When the magnetic toner is re-supplied by re-rotating to the toner reservoir, the surface of the magnetic toner thin layer T1 of the toner carrier 102 is transferred to the developing area A, and the developing process is repeated.

It is considered that the toner regulating member used in the image forming method of the present invention, in the toner of the present invention, further improves the charging characteristics of the toner and improves the image density.

As the toner regulating member, a rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel or steel can be used. Moreover, even those composites can be used. A rubber elastic body is preferable.

The material of the toner regulating member has a great influence on the charging of the toner on the toner carrier. Therefore, an organic substance or an inorganic substance may be added to the elastic body, and may be melt-mixed or dispersed. For example, metal oxide, metal powder, ceramics, carbon allotrope, whiskers,
There are inorganic fibers, dyes, pigments, surfactants and the like. Furthermore,
For the purpose of controlling the chargeability of the toner, rubber, synthetic resin, or metal elastic body may be used in which a substance such as resin, rubber, metal oxide, or metal is attached so as to contact the toner carrier contact portion. When durability is required for the elastic body and the toner carrier, it is preferable to bond the resin and rubber to the metal elastic body so as to contact the toner carrier contact portion.

When the toner is negatively charged, urethane rubber, silicone rubber, urethane resin, polyamide resin, nylon resin or the like that is easily charged to the positive polarity is preferable. When the toner is positively charged, urethane rubber and urethane resin as well as silicone rubber, silicone resin, polyester resin, fluorine resin, polyimide resin and the like which are easily negatively charged are preferable.

When the contact portion of the toner carrier is a molded body of resin, rubber or the like, a metal such as silica, alumina, titania, tin oxide, zirconia oxide, zinc oxide or the like is used to adjust the chargeability of the toner. It is also preferable to contain an oxide, carbon black, a charge control agent generally used in toner, and the like.

The base portion which is the upper side portion of the toner regulating member is fixedly held on the toner container side, and the lower side portion is flexed in the forward or reverse direction of the toner carrier against the elasticity of the toner regulating member. It is brought into contact with the surface of the toner carrier with an appropriate elastic pressure. An example of the image forming apparatus is shown in FIGS.

The contact pressure between the toner regulating member and the toner carrier is 0.98 N as the linear pressure in the toner carrier generatrix direction.
/ M (1 g / cm) or more, preferably 1.27 to 245
N / m (3 to 250 g / cm), more preferably 4.9
Effectiveness is to 118 N / m (5 to 120 g / cm).
When the contact pressure is less than 0.98 N / m (1 g / cm), it becomes difficult to uniformly apply the toner, which causes fog and scattering. The contact pressure is 245 N / m (250 g / c
When it exceeds m), a large pressure is applied to the toner, and the toner is apt to deteriorate, which is not preferable.

The gap α between the photoconductor and the toner carrier is preferably set to, for example, 50 to 500 μm.

The layer thickness of the magnetic toner layer on the toner carrier is
It is preferable that the gap is smaller than the gap α between the photoconductor and the toner carrying member, but it is also possible to use the form in which a part of the toner layer is in contact with the photoconductor surface.

In the present invention, it is preferable that an electric field containing an AC component is applied between the toner carrier and the photoconductor. The peak-to-peak magnitude (Vpp) of the electric field at the closest point of both the AC component between the toner carrier and the photoconductor is preferably 2 to 8 MV / m or more. The frequency of the AC bias is 1.0 kHz-
5.0 kHz, preferably 1.5 kHz to 3.0 kHz
Used in. As the AC bias waveform, a rectangular wave, a sine wave, a sawtooth wave, a triangular wave, or the like can be applied. In addition, an asymmetrical AC bias with different times of applying positive / reverse voltages can also be used.

In the present invention, the toner carrier is a metal,
Materials such as ceramics are used, but aluminum, SUS and the like are preferable from the viewpoint of chargeability to the toner. The toner carrier can be used as it is pulled out or cut, but in order to control the toner transporting property and the triboelectric charging property, polishing, roughening in the circumferential direction or longitudinal direction, and blasting treatment are performed. It is applied and coated. In the present invention, a blast treatment may be performed, and the regular particles and the irregular particles are used as the blasting agent, and they may be used alone or in combination, and may be overlaid.

A form in which a coating layer containing conductive fine particles is formed on the surface of the toner carrier can also be used.

As the conductive fine particles contained in the resin layer for coating the surface of the toner carrier, conductive metal oxides such as carbon black, graphite and conductive zinc oxide, and metal complex oxides may be used alone or in combination of two or more. It is preferably used. Further, as the resin in which the conductive fine particles are dispersed, phenol resin, epoxy resin, polyamide resin, polyester resin, polycarbonate resin,
Known resins such as polyolefin resin, silicone resin, fluorine resin, styrene resin, and acrylic resin are used. Particularly, a thermosetting or photocurable resin is preferable.

Next, an example of developing with non-magnetic toner will be described.

FIG. 4 shows an apparatus for developing an electrostatic image formed on a photoconductor. Reference numeral 401 denotes a photoconductor, and latent images are formed by electrophotographic process means or electrostatic recording means (not shown). A toner carrier 402 is composed of a non-magnetic sleeve made of aluminum or stainless steel.

The toner carrier may be a rough tube made of aluminum or stainless steel as it is, but preferably the surface is uniformly roughened by blowing glass beads or the like, a mirror-finished one, or coated with a resin or the like. The material used is the same as that used in the developing method of magnetic toner.

The toner 406 is stored in the toner container 403, and is supplied onto the toner carrier by the supply roller 404. The supply roller is made of a foam material such as polyurethane foam and rotates in a forward or reverse direction at a relative speed that is not 0 with respect to the toner carrier, and at the same time as the toner supply, the toner (developed toner on the toner carrier is not developed). Toner) is also stripped off. The toner applied onto the toner carrier is uniformly and thinly applied by the toner applying blade 405.

Of the components such as the electrostatic latent image carrier such as the photosensitive drum, the developing device, the primary charging means, and the cleaning means, a plurality of components are integrally combined as a device unit to form a process cartridge, The process cartridge may be detachably attached to the apparatus main body. For example, the primary charging means and the developing device are integrally supported together with the photosensitive drum to form a process cartridge,
A single unit that can be attached / detached to / from the apparatus main body may be configured so that it can be attached / detached using a guide means such as a rail of the apparatus main body. At this time, the above process cartridge may be provided with a cleaning means.

FIG. 5 shows an embodiment of the process cartridge of the present invention. In this embodiment, the developing device 1, the drum-shaped electrostatic latent image holder (photosensitive drum) 3, the cleaner 1
4, a process cartridge 18 in which the primary charger 11 is integrated is illustrated.

The process cartridge is replaced with a new cartridge when the magnetic toner 13 of the developing device 1 is used up.

[0170]

The present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.

Production of Resin for Toner <Production Example A-1 of Polymer Component> Styrene 78.4 parts by mass n-Butyl acrylate 19.6 parts by mass Methacrylic acid 2.0 parts by mass 2,2- Bis (4,4-di-t-butylperoxycyclohexyl) propane 0.8 parts by mass The above components are sufficiently replaced with nitrogen while stirring 200 parts by mass of xylene in a 4-neck flask. 120 ° C
After the temperature was raised to 4, the mixture was added dropwise over 4 hours. Further, the polymerization was completed under reflux of xylene, and the solvent was distilled off under reduced pressure. The resin thus obtained is designated as A-1.

<Production Example A-2 of Polymer Component> Production Example A-
1, styrene 79.7 parts by mass, acrylic acid n-
Butyl 19.9 parts by mass, acrylic acid 0.5 parts by mass, 2,
Production Example A except that the amount of 2-bis (4,4-di-t-butylperoxycyclohexyl) propane was changed to 0.8 part by mass.
Resin A-2 was obtained in the same manner as in -1.

<Production Example A-3 of Polymer Component> Production Example A-
1, styrene 74.4 parts by mass, acrylic acid n-
Butyl 18.6 parts by mass, acrylic acid 7 parts by mass, 2,2-
Production Example A-1 except that the amount of bis (4,4-di-t-butylperoxycyclohexyl) propane was changed to 0.8 part by mass.
Resin A-3 was obtained in the same manner as in.

<Production Example A-4 of Polymer Component> Production Example A-
1, except that the amount of styrene was changed to 80 parts by mass, n-butyl acrylate was 20 parts by mass, and 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane was 1 part by mass. Resin A-4 was obtained in the same manner as in 1.

<Production Example A-5 of Polymer Component> Production Example A-
1, styrene 72.8 parts by mass, acrylic acid n-
Butyl 18.2 parts by mass, acrylic acid 9 parts by mass, 2,2-
Production Example A-1 except that the amount of bis (4,4-di-t-butylperoxycyclohexyl) propane was changed to 0.8 part by mass.
Resin A-5 was obtained in the same manner as.

<Production Example B-1 of Vinyl Resin Having Carboxyl Group> Polymer Component Resin A-1 30 parts by mass, styrene 55.4 parts by mass, n-butyl acrylate 13.9 parts by mass, methacrylic acid 0 0.7 parts by mass / di-t-butyl peroxide 1.4 parts by mass The above raw materials were dropped into 200 parts by mass of xylene over 4 hours. Further, the polymerization was completed under reflux of xylene, the solvent was distilled off under reduced pressure, and the resin thus obtained was treated with B.
-1.

<Production Example B-2 of Vinyl Resin Having Carboxyl Group> In Production Example B-1, polymer component resin A
-30 parts by mass, styrene 56 parts by mass, acrylic acid n
Resin B-2 was obtained in the same manner as in Production Example B-1 except that 14 parts by mass of -butyl and 1.4 parts by mass of di-t-butyl peroxide were used.

<Production Example B-3 of Vinyl Resin Having Carboxyl Group> In Production Example B-1, polymer component resin A
-3 was changed to 30 parts by mass, styrene 52.8 parts by mass, n-butyl acrylate 13.2 parts by mass, acrylic acid 4 parts by mass, and di-t-butyl peroxide 1.4 parts by mass. Resin B-3 was obtained in the same manner as B-1.

<Production Example B-4 of Vinyl Resin Having No Carboxyl Group> In Production Example B-1, 50 parts by mass of polymer component resin A-4, 40 parts by mass of styrene, and 10 parts by mass of n-butyl acrylate. Resin B-4 was obtained in the same manner as in Production Example B-1 except that the amount of di-t-butyl peroxide was changed to 1.0 part by mass.

<Production Example B-5 of Vinyl Resin Having Carboxyl Group> In Production Example B-1, polymer component resin A
-5 was changed to 30 parts by mass, styrene 52.8 parts by mass, n-butyl acrylate 13.2 parts by mass, acrylic acid 4.0 parts by mass, and di-t-butyl peroxide 1.4 parts by mass. Resin B-5 was obtained in the same manner as in Production Example B-1.

<Production Example B-6 of Vinyl Resin Having Carboxyl Group> In Production Example B-1, polymer component resin A
-50 parts by mass, styrene 40 parts by mass, acrylic acid n
Resin B-6 was obtained in the same manner as in Production Example B-1 except that 10 parts by mass of -butyl and 1.0 part by mass of di-t-butyl peroxide were used.

<Production Example C-1 of Vinyl Resin Having Epoxy Group> -Styrene 79.2 parts by mass-n-butyl acrylate 19.8 parts by mass-Glycidyl methacrylate 1 part by mass-Di-t-butyl peroxide 5 parts by mass The above components were thoroughly replaced with nitrogen while stirring 200 parts by mass of xylene in a four-necked flask,
After the temperature was raised to ℃, it was added dropwise over 4 hours. Further, the polymerization was completed under reflux of xylene, the solvent was distilled off under reduced pressure, and the resin thus obtained was designated as C-1. The epoxy value of Resin C-1 was 0.07 eq / kg.

<Production Example C-2 of Vinyl Resin Having Epoxy Group> 72 parts by mass of styrene in Production Example C-1
Resin C-2 was obtained in the same manner as in Production Example B-1 except that 18 parts by mass of n-butyl acrylate, 10 parts by mass of glycidyl methacrylate and 5 parts by mass of di-t-butyl peroxide were used. The epoxy value of the obtained resin C-2 is 0.7 eq / k.
It was g.

Manufacture of Elastic Blade <Manufacture Example 1 of Elastic Blade> 100 g (Mn = 1500, NCO 6.2 wt%) of rubber material / ethylene butylene adipate type urethane prepolymer Curing agent 1,4-butadiol 3. 9 g ・ Trimethylolpropane 2.1 g The above materials were mixed at 80 ° C. and poured into a mold heated in advance to 130 ° C., molding temperature 130 ° C./molding time 30 minutes / secondary heating temperature 130 ° C./secondary heating. Heat curing for 4 hours,
The elastic blade 1 was obtained by processing into a predetermined shape. The measurement chart of the dielectric loss of the obtained elastic blade 1 is shown in FIG.

<Production Example 2 of Elastic Blade> Rubber material: Ethylene butylene adipate-based polyol 19 g-Diphenylmethane diisocyanate 37 g-Modified silicone oil 44 g The above materials were mixed and reacted in a solvent, and after completion of the reaction, the solvent was removed by distillation to obtain a prepolymer. Got Curing agent ・ 1,4-butadiol 3.9 g ・ Trimethylolpropane 2.1 g Curing agent was mixed with the above prepolymer at 80 ° C.
It is cast in a mold heated to 0 ° C., and is heat-cured at a molding temperature of 130 ° C./molding time of 30 minutes / secondary feeding temperature of 130 ° C./secondary feeding time of 4 hours, and processed into a predetermined shape, and an elastic blade 2 Got The measurement chart of the dielectric loss of the obtained elastic blade 2 is shown in FIG.

<Production Example 3 of Elastic Blade> Rubber material: Ethylene butylene adipate-based polyol 8 g-Diphenylmethane diisocyanate 40 g-Modified silicone oil 52 g The above materials were mixed and reacted in a solvent, and after completion of the reaction, the solvent was removed by distillation to obtain a prepolymer. Got Curing agent ・ 1,4-butadiol 3.9 g ・ Trimethylolpropane 2.1 g Curing agent was mixed with the above prepolymer at 80 ° C.
It is cast in a mold heated to 0 ° C., and is heat-cured at a molding temperature of 130 ° C./molding time of 30 minutes / secondary feeding temperature of 130 ° C./secondary feeding time of 4 hours, and processed into a predetermined shape, and an elastic blade 2 Got The measurement chart of the dielectric loss of the obtained elastic blade 3 is shown in FIG.

[Example 1] 90 parts by mass of the vinyl resin having a carboxyl group obtained in Production Example B-1 and Production Example C
-10 parts by mass of the epoxy group-containing vinyl resin obtained in -1 was mixed with a Henschel mixer, then kneaded with a biaxial kneading extruder at 180 ° C., and cooled and pulverized to obtain a binder resin 1. Binder resin 1 100 parts by mass Magnetic substance (0.20 μm) 90 parts by mass Polyethylene wax 4 parts by mass Triphenylmethane lake pigment 2 parts by mass After thoroughly premixing the above materials with a Henschel mixer,
Melt-kneading was performed by a twin-screw kneading extruder set at 130 ° C. The obtained kneaded product was cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the fine pulverized product obtained was further classified by an air classifier, and the weight average was obtained. Classified fine powder (toner particles) with a diameter of 7.5 μm
Got

To 100 parts by mass of the obtained classified fine powder, silica fine powder produced by a dry method (BET specific surface area of 200 m
² / g) Amino-modified silicone oil per 100 parts by mass (amine equivalent 830, viscosity at 25 ° C. 70 mm ²
/ S) 0.8 parts by mass of hydrophobic silica treated with 17 parts by mass is added and mixed by a Henschel mixer, and the opening is 150 μm.
Sieve with a m mesh to obtain Toner 1. The toner physical properties are summarized in Table 1. The dielectric loss tangent measurement chart of this toner is shown in FIG.

The toner 1 thus obtained was subjected to the following evaluation tests.

<Image Evaluation Test> Commercially available copying machine GP-60
5 (manufactured by Canon Inc.); AC bias application (Vpp =
1,000 V, f = 2,700 Hz), halogen lamp fixing, process speed 300 mm / sec) was modified, and the elastic blade 1 of Production Example 1 was used as a developing blade.
The test chart with a printing ratio of 6% was used for 100% in each environment under normal temperature and low humidity environment (23 ° C / 5% RH) and high temperature and high humidity environment (30 ° C / 80% RH). 1,000 copies were made, and image density, fog, dot reproducibility, sleeve coatability, sleeve fusion, sleeve scraping amount, etc. were evaluated.

1) Image Density With a "Macbeth reflection densitometer" (manufactured by Macbeth Co.), an SPI filter was used to measure the reflection density of an image having a diameter of 5 mm.

2) Fog "reflection densitometer" (reflectometer model TC-6)
(DS manufactured by Tokyo Denshoku Co., Ltd.) was used to measure the reflection density (Dr) of the transfer paper before image formation and the worst value (Ds) of the reflection density after copying the solid white image, and the difference ( Ds-
Dr) was evaluated as the fog value.

3) Dot Reproducibility A checkered latent image composed of 1 dot, 2 dots, 3 dots, and 4 dots was formed on a photoconductor by a laser as an image for measurement. This sample is observed with a magnifying glass, and the number of dots in the image in which the checkered pattern can be clearly confirmed is defined as the dot reproducibility. The smaller this number is, the better the dot reproducibility is.

4) Evaluation of Sleeve Coatability After copying 100,000 sheets under a low temperature and low humidity environment and a high temperature and high humidity environment, the toner coat state of the developing sleeve was visually observed and evaluated by the blotch generation state. ⊚: Blotches are not generated at all ◯: Blotches are slightly generated at the end of the sleeve. Δ: Blotches are slightly generated but the image is not affected. X: Blotches are clearly generated and affect the image.

5) Sleeve Contamination Test After copying 100,000 sheets under a low temperature and low humidity environment and a high temperature and high humidity environment, a part of the surface of the developing sleeve was wiped and washed with ethanol, and the washed developing sleeve was used. The solid black print was performed again, the image densities of the solid black images before and after the wiping with ethanol were measured, and the difference was calculated to evaluate the sleeve contamination. ⊚: difference less than 0.03 ◯: difference 0.03 to 0.10 Δ: difference 0.10 to 0.20 x: difference 0.20 or more

6) Abrasion and chipping test of elastic blade After 100,000 copies were made in a low temperature and low humidity environment and a high temperature and high humidity environment, the elastic blade was removed and the sliding surface of the elastic blade against the developing sleeve was observed. It was evaluated according to the following criteria. ◎: No wear or chipping ○: No visible wear or chipping, but slightly visible by reflected light, but no effect on sleeve coat △: Partial wear or chipping, sleeve Slight streaks and unevenness occur on the coat. X: Abrasion and chipping were observed as a whole, and streaks and unevenness were considerably generated on the sleeve coat.

The image evaluation results are summarized in Table 2.

[Example 2] 90 parts by mass of the vinyl resin having a carboxyl group obtained in Production Example B-2 and Production Example C
10 parts by mass of the epoxy group-containing vinyl resin obtained in No. -1 was mixed with a Henschel mixer, kneaded with a twin-screw extruder at 180 ° C., and cooled and pulverized to obtain a binder resin 2.

Toner 2 was obtained in the same manner as in Example 1, except that the binder resin 2 was used instead. The toner 2 was evaluated in the same manner. Table 1 for toner properties
Table 2 shows the evaluation results.

[Example 3] 95 parts by mass of the carboxyl group-containing vinyl resin obtained in Production Example B-3 and Production Example C
5 parts by mass of the vinyl resin having an epoxy group obtained in -1 was mixed in a Henschel mixer, and then mixed in a twin-screw extruder.
The mixture was kneaded at 180 ° C., cooled and pulverized to obtain a binder resin 3.

A toner 3 was obtained in the same manner as in Example 1, except that the binder resin 3 was used instead. The toner 3 was evaluated in the same manner. Table 1 for toner properties
Table 2 shows the evaluation results.

Comparative Example 1 90 parts by mass of a carboxyl group-free vinyl resin obtained in Production Example B-4 and 10 parts by mass of the epoxy group-containing vinyl resin obtained in Production Example C-1 were used. The mixture was mixed with a mixer, kneaded with a twin-screw extruder at 180 ° C., cooled and pulverized to obtain a binder resin 4.

A toner 4 was obtained in the same manner as in Example 1, except that the binder resin 6 was used instead. The toner 4 was evaluated in the same manner. Table 1 for toner properties
The evaluation results are summarized in Table 2 [Comparative Example 2] 90 parts by mass of the vinyl resin having a carboxyl group obtained in Production Example B-5 and the vinyl resin having an epoxy group obtained in Production Example C-2. 10 parts by mass were mixed with a Henschel mixer, kneaded with a twin-screw extruder at 200 ° C., and cooled and pulverized to obtain a binder resin 5.

A toner 5 was obtained in the same manner as in Example 1, except that the binder resin 5 was used instead. The toner 5 was evaluated in the same manner. Table 1 for toner properties
Table 2 shows the evaluation results.

Example 4 In Example 1, the fine pulverization conditions among the toner production conditions were adjusted to obtain Toner 6 having the toner physical properties shown in Table 1. The toner 6 was evaluated in the same manner as in Example 1. The evaluation results are summarized in Table 2.

[Embodiment 5] Evaluation was made in the same manner as in Embodiment 1 except that the elastic blade 2 of Production Example 2 was used as the developing blade.

The evaluation results are summarized in Table 2.

[Comparative Example 3] Evaluation was made in the same manner as in Example 1 except that the elastic blade 3 of Production Example 3 was used as the developing blade.

The evaluation results are summarized in Table 2.

Example 6 Binder Resin 1 100 parts by mass Magnetic substance (0.18 μm) 100 parts by mass Polyethylene wax 4 parts by mass Monoazo iron complex 2 parts by mass Before the above materials were mixed with a Henschel mixer. After mixing
Melt kneading was performed by a twin-screw kneading extruder set to 140 ° C. The obtained kneaded product was cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the fine pulverized product obtained was further classified by an air classifier, and the weight average was obtained. Classified fine powder (toner particles) with a diameter of 6.7 μm
Got

To 100 parts by mass of the obtained classified fine powder, silica fine powder produced by a dry method (BET specific surface area: 200 m
² / g) 1.2 parts by weight of hydrophobic silica treated with dimethyldichlorosilane per 100 parts by weight of dimethyldichlorosilane, then treated with hexamethylenedisilazane and treated with dimethylsilicone oil, mixed with a Henschel mixer, and opened with a mesh of 15
Sieve with a 0 μm mesh to obtain Toner 7. The toner physical properties are summarized in Table 1.

The toner 7 thus obtained was subjected to the following evaluation tests.

<Image evaluation test> Commercially available laser beam printer (LASER jet9000 (manufactured by HP), halogen lamp system fixing, process speed 236 mm /
sec) was used to fill the process cartridge with 1000 g of the above magnetic toner 7. The process cartridge filled with the magnetic toner 7 was attached to the printer body.

Therefore, in a room temperature and low humidity environment (23 ° C./5% R
H) and high-temperature and high-humidity environment (30 ° C / 80% RH), each test pattern with a print ratio of 4%
50,000 sheets were printed out and image evaluation was carried out in the same manner as in Example 1. The sleeve coatability test, sleeve contamination test, elastic blade wear, and chipping test were evaluated after the completion of 30,000 sheets in each environment. The evaluation results are shown in Table 2.

Example 7 Binder resin 100 parts by mass Copper phthalocyanine 3.5 parts by mass Polyethylene wax 3 parts by mass Triphenylmethane lake pigment 2 parts by mass The above materials were sufficiently premixed with a Henschel mixer. rear,
Melt kneading was performed by a twin-screw kneading extruder set to 120 ° C. The obtained kneaded product was cooled and coarsely pulverized by a cutter mill, then finely pulverized by a fine pulverizer using a jet stream, and the fine pulverized product obtained was further classified by an air classifier, and the weight average was obtained. Finely divided powder (toner particles) with a diameter of 8.5 μm
Got

To 100 parts by mass of the obtained classified fine powder, silica fine powder produced by a dry method (BET specific surface area of 200 m
² / g) Amino-modified silicone oil per 100 parts by mass (amine equivalent 830, viscosity at 25 ° C. 70 cs
t) 1.0 part by weight of hydrophobic silica treated with 17 parts by weight was added and mixed with a Henschel mixer, and the opening was 150 μm.
And a toner was obtained. Table 1 shows the physical properties of the toner.
Summarized in.

<Image Evaluation Test> Commercially available copying machine FC-33
0 (manufactured by Canon Inc.) and the elastic blade of the present invention was used as the developing blade, and toner was constantly supplied under normal temperature / low humidity environment and high temperature / high humidity environment to 50% each.
A copy test of 00 sheets was performed, and image evaluation was performed in the same manner as in Example 1. At this time, the sleeve coatability test and the sleeve contamination test were evaluated after 5,000 sheets were finished under each environment. Image evaluation was performed in the same manner as in Example 1. The sleeve coatability test, sleeve contamination test, elastic blade wear and chipping test were evaluated after the completion of 5,000 sheets in each environment. The evaluation results are summarized in Table 2.

[0218]

[Table 1]

[0219]

[Table 2]

[0220]

According to the present invention, in a developing system in which a toner regulating member is pressed against a toner carrier through a toner, the toner contains a vinyl resin having a carboxyl group, a vinyl resin having an epoxy group, and a carboxyl group. And at least one vinyl resin selected from the group consisting of a vinyl resin having an epoxy group and a vinyl resin in which a carboxyl group and an epoxy group are reacted, and the THF-soluble component of the toner has a specific acid value. By controlling the dielectric loss tangent of the toner and the toner regulating member in a specific temperature range, good developability and durability can be achieved.

Further, the toner has a specific circularity,
Alternatively, the THF-soluble component in the toner has a specific molecular weight distribution measured by GPC, or the binder resin component of the toner has a specific THF-insoluble component, and the above effect is further exerted. Can be improved.

[Brief description of drawings]

FIG. 1 is a schematic sectional view of an example of an image forming apparatus according to an embodiment of the present invention.

FIG. 2 is a partially enlarged schematic sectional view of the image forming apparatus according to the embodiment of the present invention.

FIG. 3 is a partially enlarged schematic cross-sectional view of the image forming apparatus according to the exemplary embodiment of the present invention.

FIG. 4 is a schematic sectional view of an example of an image forming apparatus according to an embodiment of the present invention.

FIG. 5 is a schematic sectional view of an example of a process cartridge according to the embodiment of the present invention.

FIG. 6 is a graph showing a dielectric loss tangent characteristic of Toner 1 in Example 1 of the present invention.

FIG. 7 is a graph showing a dielectric loss tangent characteristic of an elastic blade according to an example of the present invention.

[Explanation of symbols]

101 latent image holder 102 toner carrier 103 magnetism generating means 104 Toner regulating member 105 Stirrer 106 toner container 401 latent image holder 402 toner carrier 403 toner container 404 Toner distribution roller 405 Toner coating blade 406 toner 1 Development device 2 Toner container 3 Latent image holder 6 Toner carrier 7 cleaning blade 8 Toner regulating member 13 toner 14 cleaner 15 Magnetic generation means 18 Process cartridge

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaki Fujimoto             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Hiroyuki Fujikawa             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation (72) Inventor Nobuyuki Okubo             3-30-2 Shimomaruko, Ota-ku, Tokyo             Non non corporation F-term (reference) 2H005 AA01 AA15 CA04 CA17 EA01                       EA05 EA06 EA10                 2H077 AD02 AD06 AD13 AD17

Claims (10)

[Claims] 1. An image forming method comprising at least a developing step of developing an electrostatic latent image formed on a latent image holding member by a toner layer formed on a toner carrying member to form an image. The carrier has its toner layer thickness regulated by a toner layer thickness regulating member that is pressed against the surface of the toner carrier via a toner layer, and the toner contains at least a binder resin and a colorant. The binder resin is selected from the group consisting of a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin having a reaction between a carboxyl group and an epoxy group. Containing at least one vinyl resin and having an acid value of 1 to 50 mgKOH of the THF soluble component of the toner.
/ G and the dielectric loss tangent (tan δ _T ) of the toner at a frequency of 1.0 × 10 ³ Hz is in the temperature range of 20 to 150 ° C.
Maximum value (tan δ _T (T _MAX )) at T _MAX (° C) of
And the frequency of the toner layer regulating member is 1.0 × 10 ³ H
Dielectric loss tangent (tan δ at z, T _MAX (° C))
_B (T _MAX )) is 1.0 × 10 ^{−3 to} 5 × 10 ⁰ . 2. The toner layer regulating member has a frequency of 1.0 ×
Dielectric loss tangent (tan) at 10 ³ Hz, T _MAX (° C)
The image forming method according to claim 1, wherein δ _B ) is 5.0 × 10 ^{-2 to} 2.0 × 10 ⁰ . 3. The toner according to claim 1, wherein the toner has 85% by number or more of particles having a circularity a of 0.90 or more, which is determined by the following equation, among particles having a particle diameter of 3 μm or more.
Or the image forming method described in 2. Circularity a = L ₀ / L (In the formula, L ₀ represents the perimeter of a circle having the same area as the projected image of the particle, and L represents the perimeter of the projected image of the particle.) 4. Tetrahydrofuran (TH
F) The soluble component has a number average molecular weight (Mn) of 1,000 to 40,000 and a weight average molecular weight (Mw) of 10,000 to 10,000 in a molecular weight distribution measured by gel permeation chromatography (GPC). 10,
It is 1,000,000, It is characterized by the above-mentioned.
The image forming method according to any one of 1. 5. The image forming method according to claim 1, wherein the binder resin component of the toner contains 0.1 to 60% by mass of THF insoluble matter. 6. At least a developing step of forming an image by developing an electrostatic latent image formed on a latent image carrier with a toner layer formed on the toner carrier, wherein the toner carrier is A toner applied to an image forming method in which the toner layer thickness is regulated by a toner layer thickness regulating member that is pressed against the surface of the toner carrier via a toner layer, wherein the toner is at least a binder resin and a colorant. The binder resin is a group consisting of a vinyl resin having a carboxyl group and a vinyl resin having an epoxy group, a vinyl resin having a carboxyl group and an epoxy group, and a vinyl resin having a reaction between a carboxyl group and an epoxy group. At least one vinyl resin selected from the above, and the THF-soluble component of the toner has an acid value of 1 to 50 mgKOH
/ G and the toner tangent regulating member has a dielectric loss tangent (tan δ _B ) at a frequency of 1.0 × 10 ³ Hz of 1.0 × 10 ^{−3 to} 5 in a temperature range of T _MAX (° C.), the toner is Toner having a maximum dielectric loss tangent (tan δ _T ) at a frequency of 1.0 × 10 ³ Hz. 7. The frequency of the toner layer regulating member 1.0 × 1
0³Dielectric loss tangent (tan δ in Hz_B) Is 5.0 × 10
^-2To 2.0 x 10⁰T in the temperature range that satisfies _MAXTo (℃)
The frequency of the toner is 1.0 × 10³In Hz
Dielectric loss tangent (tan δ_T) Has a maximum value
The toner according to claim 6, wherein 8. The toner has 85% by number or more of particles having a particle size of 3 μm or more and having a circularity a of 0.90 or more determined by the following formula.
Or the toner according to item 7. Circularity a = L ₀ / L (In the formula, L ₀ represents the perimeter of a circle having the same area as the projected image of the particle, and L represents the perimeter of the projected image of the particle.) 9. Tetrahydrofuran (TH
F) The soluble component has a number average molecular weight (Mn) of 1,000 to 40,000 and a weight average molecular weight (Mw) of 10,000 to 10,000 in a molecular weight distribution measured by gel permeation chromatography (GPC). 10,
9,000,000, wherein
The toner according to any one of 1. 10. The toner according to claim 6, wherein the binder resin component of the toner contains 0.1 to 60% by mass of THF insoluble matter.