JP2002372806A - Toner, method for manufacuring toner and method for forming image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner having excellent low temperature fixing properties and high temperature offset resistance. SOLUTION: The toner is prepared by polymerizing a polymerizable monomer composition containing at least polymerizable monomers, a coloring agent, a polar resin, ester-based wax and a crosslinking agent expressed by the formula. The melt index(MI) of the toner at 135 deg.C and 68.6 N (7 kg load) ranges from 10 to 100 g/10 min. In the formula, R1 represents a hydrogen atom or 1-3C alkyl group, R2 represents a 2-6C straight chain or branched alkylene group and n represents 0 to 20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a toner jet method and the like, a method for producing the toner, and an image forming method.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
It is known by a number of methods as described in Japanese Patent Application Publication No. JP-B-43-24748 and Japanese Patent Publication No. 43-24748. In general, using a photoreceptor, an electrostatic charge image is formed on the photoreceptor by various means, and then the electrostatic charge image is developed using a toner. After a toner image is transferred onto a transfer material such as described above, the image is fixed by heating, pressure, heat and pressure, or solvent vapor to obtain a copy or print. The toner remaining on the photosensitive member without being transferred is cleaned by various methods, and the above-described steps are repeated.

Conventionally, in order to prevent toner from adhering to the surface of a fixing roller, the surface of the roller is formed of a material having excellent releasability (such as silicone rubber or fluorine-based resin) with respect to the toner. In order to prevent surface fatigue, the roller surface is coated with a thin film of a highly releasable liquid such as silicone oil or fluorine oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device for supplying an anti-offset liquid is required. Needless to say, this oil application causes delamination between the layers constituting the fixing roller, and consequently has a disadvantage that the life of the fixing roller is shortened.

In view of this, instead of using a silicone oil supply device, instead of supplying the offset preventing liquid from the toner particles during heating, a releasing agent such as low molecular weight polyethylene or low molecular weight polypropylene is contained in the toner particles. Has been proposed.

[0005] It is known that wax is contained as a release agent in toner particles. For example, Japanese Patent Publication No. 52-33
04, JP-B-52-3305, JP-A-57
No. 52574.

Further, JP-A-3-50559, JP-A-2-79860, JP-A-1-109359, JP-A-62-14166, and JP-A-61-2
73554, JP-A-61-94062, JP-A-61-138259, and JP-A-60-2523
No. 61, JP-A-60-252360 and JP-A-60-217366 disclose that wax is contained in toner particles.

[0007] Waxes are used to improve the offset resistance during low-temperature fixing and high-temperature fixing of toner, and to improve the fixing property during low-temperature fixing. On the other hand, the blocking resistance of the toner is reduced, the developing property of the toner is reduced by increasing the temperature inside the machine, and the wax migrates to the surface of the toner particles when the toner is left for a long time, and the developing property is reduced. I do.

To solve the above problem, a toner produced by a suspension polymerization method has been proposed (JP-B-36-10231).
No.). In this suspension polymerization method, a polymerizable monomer and a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) are uniformly dissolved or dispersed to prepare a monomer composition. After that, this monomer composition is dispersed in a continuous phase (for example, an aqueous phase) containing a dispersion stabilizer using a suitable stirrer, and simultaneously undergoes a polymerization reaction, thereby obtaining toner particles having a desired particle size. Is what you get. Further, Japanese Unexamined Patent Publication No.
According to Japanese Patent No. 341573, when a polar component is added to a monomer composition in an aqueous dispersion medium, a component having a polar group contained in the monomer composition is added to a surface layer portion at an interface with an aqueous phase. It is easy to exist, and the non-polar component hardly exists in the surface layer portion. Therefore, the toner particles can have a core / shell structure.

[0009] The toner produced by the suspension polymerization method can achieve both of the contradictory performances of blocking resistance and high temperature offset resistance by encapsulating wax in the toner particles. It is possible to prevent high-temperature offset without applying a release agent as described above.

However, in recent years, users have high expectations for smaller, lighter, higher quality, higher reliability, and the like of image forming apparatuses.

Further, a copying machine or a printer for forming a full-color image has been used.
In general, a full-color image is obtained by uniformly charging a photoconductor with a primary charger, performing image exposure with a laser beam modulated by a magenta image signal of a document, forming an electrostatic charge image on the photoconductor, and holding magenta toner. The magenta developing device develops the electrostatic charge image to form a magenta toner image. Next, the magenta toner image on the photosensitive member is transferred directly or via an intermediate transfer member to the transferred transfer material by a transfer charger.

After the electrostatic image has been developed, the photoreceptor is neutralized by a neutralizing charger, cleaned by a cleaning unit, and then charged again by a primary charger to form a cyan toner image similarly. The cyan toner image is transferred to the transfer material on which the above-described magenta toner image has been transferred, and further, yellow and black colors are sequentially developed to transfer the four color toner images to the transfer material. A full-color image is formed by fixing the transfer material having the four color toner images by the action of heat and pressure by a fixing unit.

In recent years, such image forming apparatuses have begun to be used not only as office work copying machines for copying original manuscripts but also as printers as personal computer outputs or personal copies for individuals. Was.

Such a device is being applied to a plain paper fax machine in addition to a field represented by a laser beam printer.

Therefore, miniaturization, weight reduction, high speed, high image quality, and high reliability have been strictly pursued. In addition, machines are becoming simpler in various respects. As a result, the performance required of the toner has become higher, and if the performance of the toner cannot be improved, excellent image formation cannot be realized. In recent years, demands for color copying have rapidly increased with various copying needs. In order to copy the original color image more faithfully, further higher image quality, higher resolution and the like are desired.
From these viewpoints, the toner used in the color image forming method needs to be mixed in color when heat is applied.

In the case of a fixing device in a color image forming apparatus, since a magenta toner, a cyan toner, a yellow toner, and a black toner are formed on a transfer material in a plurality of layers, an offset occurs due to an increase in toner layer thickness. Tends to be easy.

To prevent the toner from adhering to the surface of the fixing roller, the roller surface is formed of a material having excellent releasability from the toner (such as silicone rubber or fluorine-based resin). In order to prevent the fatigue of the roller, the surface of the roller is coated with a thin film of a liquid having high releasability such as silicone oil and fluorine oil. However, this method is extremely effective in preventing toner offset, but has a problem that a fixing device is complicated because a device for supplying an anti-offset liquid is required. . As the transfer material on which the toner image is fixed, various papers, coated papers, plastic films and the like are generally used. Transparency film (OHP) that uses an overhead projector for presentation
Film images). In particular, unlike paper, the OHP film has a low oil absorption capacity, so that a large amount of oil is present on the OHP film surface after fixing. Silicone oil evaporates due to heat and contaminates the inside of the image forming apparatus, and there is also a problem of processing collected oil. Instead of using a silicone oil supply device, instead of supplying the anti-offset liquid from the toner particles at the time of heat and pressure fixing, a release agent such as low molecular weight polyethylene or low molecular weight polypropylene is added to the toner particles. A method has been proposed. If a large amount of such a release agent is added in order to obtain a sufficient effect, filming on the photoreceptor and contamination of the surface of the toner carrier such as a carrier and a developing sleeve are likely to occur, and the image tends to deteriorate. At present, a small amount of release agent is added to the toner particles so as not to cause image deterioration, a small amount of release oil is supplied to the fixing roller, and the offset toner is taken up using a member such as a take-up web. Cleaning is performed using an apparatus or a cleaning pad.

However, in view of recent demands for downsizing, weight reduction, and high reliability, it is preferable to remove even these auxiliary devices even in a full-color image forming apparatus, and there is a long-awaited need for a toner that can cope with such an auxiliary apparatus.

In order to enhance the color mixing of the toner and to obtain a toner having excellent low-temperature fixability, it is preferable that the binder resin of the toner is instantaneously melted at the time of fixing. However, on the other hand, a binder resin having such properties is inferior in high-temperature offset resistance, blocking resistance, and durability.

In order to solve these problems, Japanese Patent Application Laid-Open No. 5-1582
79 and JP-A-6-236066 propose a toner using a crosslinking agent. 7-239
No. 66 and Japanese Patent Publication No. 7-23967 propose a toner having excellent magnetic material dispersibility by using a crosslinking agent.

Although these toners are toners having excellent fixing properties, none of them can sufficiently be said to satisfy the above-mentioned problems.

Further, in order to cope with recent downsizing of the apparatus, high printing speed, and networking, the anti-offset area of the toner is widened to a low temperature side so that the fixing device can be simplified easily, and the toner can be fixed. Reducing the temperature to make the fixing process faster is an effective method.

For this purpose, JP-A-9-265209 discloses a low molecular weight vinyl polymer component having a weight average molecular weight of 3 × 10 ^{3 to} 5 × 10 ⁴ and a weight average molecular weight of 3 × 10 3
^An antioxidant is added to 100 parts by mass of a vinyl polymer mainly containing ^{5 to} 5 × 10 ⁶ high molecular weight vinyl polymer components.
It has been proposed that a toner resin composition containing 0.5 to 1 part by mass of a toner as a main component is melted and kneaded, then cooled and finely pulverized so that the fixing temperature range can be widened. However, in this method, only the fixing area is shifted to the low temperature side, and the offset on the high temperature side is likely to be deteriorated.

On the other hand, Japanese Patent Application Laid-Open No. 8-262799 discloses a high molecular weight styrene-acrylic resin having a molecular weight peak in a region of 500,000 or more in molecular weight distribution measured by gel permeation chromatography, and a molecular weight of 50,000. A toner comprising a styrene-acrylic resin having a molecular weight peak in a region of 500,000, a styrene-acrylic resin having a crosslinked structure, and a polyester resin binder resin having a molecular weight peak in a region having a molecular weight of 50,000 or less has been proposed. However, the response to high-speed fixing is still insufficient.

As described above, in the fixing process,
Although there is a demand for a toner having a wide fixing temperature range and excellent anti-offset properties, at present, none of them satisfy these points sufficiently.

On the other hand, Japanese Patent Application Laid-Open No. Hei 5-271313 describes a polymer particle obtained by seed polymerization in which a stirring speed and an amount of a monomer to be added are specified, and a method for producing the same. However, although the described contents provide a certain effect on the chargeability of the toner, they do not contribute to the improvement of the durability or the fixability at all, and the effect on the contamination of the image forming apparatus is recognized. Not something.

Further, Japanese Patent Application Laid-Open No. Hei 10-177228 proposes a toner having a low fixing temperature defined by the ratio of the volume average particle diameter to the number average particle diameter and the film thickness of the shell portion. It is difficult to lower the fixing temperature and maintain high image quality only by the regulation.

In JP-A-2-201378, JP-A-3-237467, JP-A-237468 and JP-A-7-64336, a condensate of phenol and formaldehyde such as a calixarene derivative is used as a charge controlling agent. It has been proposed to use as However, the charging ability and matching with the image forming apparatus are not sufficient. Further, no consideration is given to a method for producing a toner using a polymerization method, and further improvement has been desired.

Several methods have been proposed to improve the dispersibility and adhesion between the binder resin and the colorant. JP-A-54-84731 discloses a method of treating a magnetic substance with a silane-based coupling agent and using the same. JP-A-55-26519 and JP-A-55-28019 disclose a method using a titanium-based coupling agent. A method of treating and using a magnetic material, and JP-A-54-122129,
No. 130130, No. 55-6344, No. 5
JP-A-5-11218 describes a method of coating a magnetic substance with an appropriate coating substance and using the same. Japanese Patent Publication No. 6-95223 discloses a polymerized toner obtained by using a magnetic material treated with a compound containing an isocyanate group, and Japanese Patent Publication No. 7-27273 discloses a magnetic toner treated with an epoxy compound. Are described.

However, these methods can provide a magnetic toner having improved dispersibility to some extent, but have not obtained a magnetic toner that is sufficiently satisfactory in all respects.

Patent No. 2802543 describes hematite particles containing iron as a main component in which Mn is dissolved in order to improve the blackness of iron oxide pigments.
However, even if the hematite particles are used as they are as a colorant for a toner, the compatibility with the binder resin is not sufficient, and there is still room for improvement in dispersibility and adhesion.

Further, in the case of carbon black having a large surface area and an aggregated higher-order structure, uniform treatment is more difficult, and there is still much room for improvement when used in toner.

As described above, in particular, in the case of long-term use under high humidity, adaptation to high-speed development, and the like, the actual situation is that a toner having sufficient performance has not yet been obtained.

[0034]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which can satisfy the above-mentioned requirements.

An object of the present invention is to provide a toner having excellent low-temperature fixability and high-temperature offset resistance.

An object of the present invention is to provide a toner having a good charge amount, and a developing property (toner charge amount,
(Image density) and transferability.

An object of the present invention is to provide a toner capable of providing a high-quality transparency image excellent in transparency of an OHP film fixed image.

An object of the present invention is to provide a high-resolution and high-definition image, satisfy charging stability, have a wide fixing temperature range, extremely minimize contamination of an image forming apparatus, and highly match an image forming method. It is an object of the present invention to provide a toner to be used, a method for efficiently manufacturing the toner, and an image forming method using the toner.

It is an object of the present invention to provide an image forming apparatus which does not impair the low-temperature fixability, does not cause fusing to the photosensitive member even at high temperatures, and does not easily cause contamination on the surface of a toner carrier such as a carrier or a sleeve. An object of the present invention is to provide a toner excellent in developability and a method for producing the toner.

An object of the present invention is to form an electrostatic latent image on a photoreceptor, and in the process of developing the electrostatic latent image, the surface of the photoreceptor comes into contact with a toner layer on a toner carrier, and In the image forming method using the one-component contact developing method in which the surface of the body and the surface of the toner carrier are moved relative to each other to achieve the development of the electrostatic latent image, a high-quality image is stably obtained for a long period of time. An object of the present invention is to provide a toner used in an image forming method to be realized and an image forming method.

[0041]

According to the present invention, a polymerizable monomer composition comprising at least a polymerizable monomer, a colorant, a polar resin, an ester wax and a crosslinking agent represented by the following formula is polymerized. The resulting toner, comprising:
A toner having a melt index (MI) value at 10 ° C. and 68.6 N (load 7 kg) of 10 to 100 g / 10 min (Invention 1).

[0042]

Embedded image [In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₂ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and n represents 0 to 20. ]

The present invention relates to a toner comprising at least one kind of binder resin, colorant, and wax component. Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
Having a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ ; In the scattergram of the circular equivalent-circularity based on the number of toners measured by the flow type particle image measuring device for the toner, the circle-equivalent number average diameter D1 (μm) of the dry toner
Is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
It relates to a toner characterized by being less than 0 (Invention 2).

According to the present invention, at least one polymerizable monomer and at least one polymerizable monomer are added to fine particles containing at least one binder resin, a colorant, a wax component, and at least one specific charge control agent. The present invention relates to a method for producing a toner, wherein a surface layer is formed by adding a polymerizable monomer composition containing an initiator as an essential component and performing seed polymerization.

According to the present invention, at least a charging step of applying a voltage to the charging member from the outside to charge the electrostatic latent image carrier, and forming an electrostatic latent image on the charged electrostatic latent image carrier. A latent image forming step, a developing step of developing the electrostatic image with toner to form a toner image on the electrostatic latent image carrier, and a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material And a fixing step of heating and fixing the toner image on the transfer material, wherein the toner is a dry toner comprising at least one kind of binder resin, a colorant, and a wax component. Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
Having a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ ; In the scattergram of the circular equivalent-circularity based on the number of toners measured by the flow type particle image measuring device for the toner, the circle-equivalent number average diameter D1 (μm) of the dry toner
Is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
The image forming method is less than 0.

According to the present invention, at least a charging step of externally applying a voltage to the charging member to charge the electrostatic latent image carrier, and forming an electrostatic latent image on the charged electrostatic latent image carrier. A latent image forming step, a developing step of developing the electrostatic charge image with toner to form a toner image on the electrostatic latent image carrier, and a developing step of transferring the toner image on the electrostatic latent image carrier to the intermediate transfer body An image forming method comprising: one transfer step; a second transfer step of transferring a toner image on the intermediate transfer member to a transfer material; and a fixing step of heating and fixing the toner image on the transfer material. A dry toner comprising at least one binder resin, a colorant, and a wax component; Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
It has a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ , and in a circle-equivalent diameter-circularity scattergram based on the number of toners measured by a flow-type particle image measuring device for the toner,
The average particle diameter D1 (μm) of the dry toner is equivalent to 2-1.
0 μm, and the average circularity of the toner is 0.92
The present invention relates to an image forming method, wherein the circularity standard deviation is 0 to 0.995 and less than 0.040.

According to the present invention, in a toner comprising at least a binder resin, a colorant and a release agent, at least a part of the binder resin has a cross-linked structure by a cross-linking agent, and the cross-linking agent has the following general formula [a]:

[0048]

Embedded image (Wherein at least one of R _{1 to} R ₅ and at least one of R _{6 to} R ₁₀ are a substituent having a vinyl group, and the others are each independently a hydrogen atom, a halogen atom, C ₁
Saturated / unsaturated alkyl group having -C _20, alkoxy groups, aromatic hydrocarbon group, a hydroxyl group, a carboxyl group, 1
It is selected from the group consisting of a tertiary amino group, a nitro group, a sulfone group, a sulfamide group, a cyano group, an alkyl carboxylate, and an acyl group. The present invention relates to a toner which is a biphenyl compound represented by the formula (3).

According to the present invention, in a toner having toner particles containing at least a binder resin and a colorant, a composite oxide having at least a surface treated with an organic compound is used as the colorant. At least Fe and Mn are contained, and the content of Mn in the composite oxide is 2 to the total amount of Fe in the composite oxide.
To 55 atomic% (the present invention 4).

The present invention provides at least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; and (b) an exposure for forming an electrostatic latent image on the charged image carrier by image exposure. (C) developing the electrostatic latent image by contacting a toner layer formed by toner carried on the surface of the toner carrier with the electrostatic latent image on the surface of the image carrier; A developing step of forming a toner image; (d) a transferring step of transferring the toner image formed on the surface of the image carrier to a transfer material with or without an intermediate transfer body; and (e) a transferring step. A cleaning step of cleaning and removing toner remaining on the surface of the image carrier later;
A toner used in an image forming method in which the above steps (a) to (e) are repeated using a cleaned image carrier, the toner comprising at least a binder resin, a colorant, a wax component, and a phenol. A derivative condensate, wherein the phenol derivative condensate in the toner is a cyclic condensate represented by the following general formula <A>, a chain condensate represented by the following general formula <B>, and a general formula <C>: A mixture of low-molecular-weight condensates represented by the general formula <A>: 5 to 95% by mass; a chain condensate represented by the general formula <B>: 5 to 95% by mass. % By mass of the low molecular weight condensate represented by the general formula <C>: 0 to 5% by mass (the present invention 5).

The present invention provides at least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; and (b) an exposing step of forming an electrostatic latent image on the charged image carrier by image exposure. (C) developing the electrostatic latent image with a toner included in a developing device to form a toner image;
(D) transferring the toner image formed on the surface of the image carrier to a transfer material with or without an intermediate transfer member, and remaining on the surface of the image carrier after the transfer process. A toner used in an image forming method using a developing and cleaning method in which the developing device also collects toner in a developing step, wherein the toner includes at least a binder resin, a colorant, a wax component, And a phenol derivative condensate in the toner, wherein a cyclic condensate represented by the following general formula <A>, a chain condensate represented by the general formula <B>, and a general formula <C> A low-molecular-weight condensate represented by the general formula <A>: 5 to 95% by mass; a chain condensate represented by the general formula <B>: 5 -95% by mass represented by the general formula <C> That low molecular weight condensate: a toner, which is a 0-5 wt% (Invention 6).

[0052]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention 1, the structure (formula 1)
Binder resin obtained by using a cross-linking agent having a, compared with a cross-linking agent such as divinylbenzene generally used, that a soft cross-linking component is obtained by increasing the distance between cross-links, MI value of toner is 10 to 100 g
/ 10 min, the low-temperature fixability is excellent.

Furthermore, since the crosslinking agent has an ester or ether moiety in the molecular chain, the ester wax contained in the binder resin can easily come out on the toner surface with a small amount of heat or pressure during fixing. It is considered that the low-temperature fixability is excellent synergistically.

Further, since it has a soft cross-linking component and contains wax, it has excellent offset resistance, and it is necessary to apply sufficient heat and pressure by means such as slowing down the fixing speed. Is possible, and the color mixing property of the toner is good, and an OHP sheet having excellent transparency can be obtained. Further, since the toner has a soft crosslinking component, the toner has excellent blocking resistance and durability without impairing the low-temperature fixing property.

When the MI value is less than 10 g / 10 min, the charging member and the photoreceptor are easily contaminated, and the durability is deteriorated. Conversely, if it exceeds 100 g / 10 min, the low-temperature fixability and the transparency of the OHP sheet will be poor.

As for the molecular weight distribution of the THF-soluble component of the toner, the main peak molecular weight Mp is 5,000 to 5,
0000 and a weight average molecular weight Mw of 50,000 to 1
It is preferably 000000.

If the main peak molecular weight Mp is less than 5,000 or the weight average molecular weight Mw is less than 50,000, the durability is impaired, and conversely, the main peak molecular weight Mp exceeds 50,000 or the weight average molecular weight Mw is reduced. 1
If it exceeds 000000, the low-temperature fixability and the transparency of the OHP sheet are undesirably poor.

The toner is preferably obtained by polymerizing the monomer composition in an aqueous medium.

This is because, as described above, since the crosslinking agent has an ester or ether moiety in the molecular chain, it is likely to be localized near the toner surface during polymerization. Because it is excellent.

Further, in the circle equivalent diameter-circularity scattergram based on the number of toners measured by the flow type particle image measuring apparatus, the average circularity is preferably 0.95 to 1.00. This is because the strength of the toner surface is made uniform, the stress resistance is excellent, and the developability and transferability are also improved.

The polar resin is a polyester resin, and preferably has an acid value of 1 to 35 (mgKOH / g). Since the toner is obtained by polymerization in an aqueous medium, the polar resin is likely to be localized on the surface layer of the toner. When the acid value is 1 to 35 (mgKOH / g), the balance between the polar resin in the vicinity of the toner surface layer and the abundance of the crosslinking agent is maintained,
It is considered that a surface layer strength that does not impair the low-temperature fixability can be obtained.

When the acid value is less than 1 (mgKOH / g), the ratio of the amount of the crosslinking agent in the surface layer increases, and the surface layer becomes too hard, and conversely, the acid value exceeds 35 (mgKOH / g). Then, the ratio of the amount of the crosslinking agent in the surface layer decreases, and the surface layer strength becomes insufficient.

Further, when the crosslinker has an ester or ether moiety in the molecular chain and the surface layer of the toner is a polyester resin, the ester wax easily emerges on the toner surface with a small amount of heat or pressure during fixing. Synergistically by becoming
It is considered that the low-temperature fixability is excellent.

The amount of the crosslinking agent to be added is preferably 0.01 to 5 parts by mass based on 100 parts by mass of the polymerizable monomer. When the amount is less than 0.01 part by mass, the durability is impaired. On the other hand, when the amount exceeds 5 parts by mass, the low-temperature fixability, OHP
The transparency of the sheet is poor, which is not preferable.

Further, the aqueous medium has a pH of 4.5 to 8.5.
It is preferably adjusted to. pH is lower than 4.5,
On the other hand, when it is higher than 8.5, the surface component of the toner is liable to undergo hydrolysis and the like, and as a disadvantage thereof, the developability is inferior.

Specific examples of the crosslinking agent used in the present invention 1 include ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene. Glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate,
And polypropylene glycol diacrylate. These crosslinking agents may be used in combination with other crosslinking agents.

As the polar resin used in the present invention 1, a copolymer of styrene and (meth) acrylic acid, a maleic acid copolymer, a saturated polyester resin, and an epoxy resin are preferably used. Among these polar resins, polyester resins are particularly preferred. Further, it becomes possible to obtain a toner having a core / shell structure in which wax is included. This is because, because the toner is manufactured in an aqueous medium, wax having a lower polarity than the polar resin is pushed into the toner.

In the present invention 2, the component extracted from the toner during the initial 15 to 60 minutes of reflux with chloroform is a chloroform-soluble binder resin component present near the toner surface, and is similarly extracted in 24 hours with reflux. Is the entirety of the chloroform-soluble binder resin component present in the toner. Further, in the toner of the present invention 2, the relationship between the former glass transition temperature (T ₁ ) and the latter glass transition temperature (T ₂₄ ) is as follows: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ < 75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C.)

The reason for this is that if T ₂₄ is less than 40 ° C., the chargeability of the toner will not be stable, and the durability of the toner will be insufficient. If it exceeds 70 ° C., the fixing temperature of the toner will increase, and , The fixability is extremely deteriorated. Further (T
_{When 1-} T ₂₄ ) is 5 ° C. or less, there is no difference in thermal stability between the components near the surface and the components inside even if the inside is covered with a surface layer. blocking resistance of the toner deteriorates when the T ₂₄ to a lower, setting to a higher T ₂₄ in order to improve the blocking resistance Conversely, fixability is deteriorated to the contrary. On the other hand, (T ₁ −
When T ₂₄ ) exceeds 75 ° C., T ₁ is set even if T ₂₄ is set low.
, And as a result, the fixing property is deteriorated.

In order to quantify the relationship between the fixing property and the blocking resistance as described above, (T ₁
+ T ₂₄ ). That is, over 100 ° C, 1
When the temperature is lower than 80 ° C., it is possible to achieve both the fixing property and the blocking resistance.

[0071] The reason why the T ₁ in the present invention 2 was defined as the glass transition temperature of the soluble matter extracted from the toner at any time between 15 and 60 minutes from chloroform reflux started, as follows is there.

Under chloroform reflux, the speed at which the binder resin is extracted near the surface of the toner varies depending on the glass transition temperature of the binder resin and the amount of insoluble matter. This is because sampling at any time during 60 minutes extracts chloroform-soluble components near the surface of the toner. More specifically, it is preferable that the component extracted from the toner at this time is 3 to 20% by mass with respect to the total mass of the toner because the vicinity of the surface is extracted with good reproducibility. 5-12
It is more preferable that the content is mass%. The extraction time at this time is preferably 20 to 50 minutes, more preferably 25 to 45 minutes.

On the other hand, the reason why T ₂₄ was defined as the glass transition temperature measured by a differential scanning calorimeter of the soluble matter extracted after 24 hours of reflux in chloroform is as follows. This is because all the soluble components have been extracted.

As a specific method, Soxhlet extraction or the like is preferable.

In the present invention 2, among the components that determine T ₁ , the main component of the resin component must be a polymer of a vinyl monomer. In the toner obtained by the production method of the present invention 2, it is possible to include a polar resin such as a polyester resin in the binder resin in order to adjust the physical properties. However, in the toner in which the surface layer is formed by seed polymerization, Is a component other than the polymer of the vinyl monomer as a main component of the resin component to be extracted, that is, the fact that the polar resin or the like is contained indicates that the formation of the surface layer is insufficient, In the present invention 2, the main component of the resin component, that is, 50% by mass or more of the components that determine T ₁ must be a polymer of a vinyl monomer.

The qualitative and quantitative analysis of the vinyl monomer can be carried out by various methods.

For example, components that determine T1 include nuclear magnetic resonance spectrum ( ¹ H-NMR, ¹³ C-NMR), infrared absorption spectrum (IR), Raman spectrum, ultraviolet absorption spectrum (UV), and mass spectrum (MS). The analysis may be performed by various methods such as spectrum analysis, elemental analysis, GPC, gas chromatography (GC), liquid chromatography (HPLC), and other chemical analysis.

(Method of Determining the Glass Transition Temperature) In the present invention 2, the measurement of the glass transition point of the extract, the binder resin and the toner was carried out by using DSC-7 (manufactured by PerkinElmer) at a temperature rate of 10 ° C. / ASTM in minutes (D3418-8
Performed according to the temperature setting pattern of 2).

The Tg was defined as the Tg based on the DSC curve at the second temperature rise, the intersection between the baseline before the endothermic peak, the contents of the baseline after the endothermic peak, and the rising curve.

The molecular weight distribution of the THF-soluble component of the toner of the present invention 2 in the molecular weight distribution determined by gel permeation chromatography (GPC) described below is such that the molecular weight in terms of polystyrene falls within the range of 2 × 10 ^{3 to} 5 × 10 ^5. Must have. If the peak molecular weight is lower than 2 × 10 ³ , the charging characteristics may be adversely affected, and the 5 × 1
0 ⁵ high and the melt viscosity is too high than, may cause problems in fixability. In producing the diene resin used in the present invention 2, a suitable molecular weight regulator, a molecular weight distribution regulator, a branching agent for improving viscoelasticity, a catalyst for accelerating the reaction, and the like are used as required. can do.

The toner of the present invention 2 has a T₁Components that determine
Acid value (AV₁), Hydroxyl value (OHV ₁), Reflux for 24 hours
The acid value (AV_{twenty four}), Hydroxyl value (O
HV_{Two Four}) Is the following relational expression │AV_{twenty four}-AV₁│ ≦ 5 (mgKOH / (soluble matter 1g
)) │OHV_{twenty four}-OHV₁│ ≦ 5 (mgKOH / (soluble matter 1
g)) must be satisfied.

The reason is that if the value of | AV ₂₄ −AV ₁ | exceeds 5, in the case of (AV ₂₄ > AV ₁ , OHV ₂₄ > OHV ₁ ),
The polarity of the resin present inside is higher, the formation of the surface layer is insufficient, and the blocking resistance of the toner deteriorates. (AV ₂₄ <AV ₁ , OHV ₂₄ <OHV ₁ )
T ₁ are extracted high polar component is by chloroform extraction time of the components that determine the high polarity, and have a degree of polymerization there are many low components, the charging property of the toner becomes insufficient. It is mentioned. However, this is not always the case when a carboxyl group-containing polymerizable monomer or a hydroxyl group-containing polymerizable monomer is actively used.

In a toner, a toner having a crosslinked structure and a portion having a two-dimensional or three-dimensional structure becomes stronger than a binder resin consisting of only one-dimensionally polymerized one. In particular, it has been found that fusing to a photoreceptor member or a carrier is reduced even in a severe environment such as a high temperature.

On the other hand, especially in a polymerization toner containing a wax, the polymerization time affects the fluidity of the toner. That is, as described above, the encapsulation of the wax is not completely performed at the time of polymerization, and particularly, the phenomenon that the low melting point component is diffused / adhered to the toner surface is a major controlling factor of the polymerization time. It has been found that the amount of wax present on the surface increases, which causes a decrease in the fluidity of the toner and an increase in blocking. Therefore, the present inventors have proposed a method of solving the above problem at the same time as the following general formula [a]

[0085]

Embedded image (Wherein at least one of R _{1 to} R ₅ and at least one of R _{6 to} R ₁₀ are a substituent having a vinyl group, and the others are each independently a hydrogen atom, a halogen atom, C ₁
Saturated / unsaturated alkyl group having -C _20, alkoxy groups, aromatic hydrocarbon group a hydroxyl棊, carboxyl group, 1-3
Secondary amino group, nitro group, sulfone group, sulfamide group,
It is selected from the group consisting of a cyano group, an alkyl carboxylate, and an acyl group. It has been found that the biphenyl compound represented by the formula (1) is used as a cross-linking agent for providing a cross-linked structure to the binder resin constituting the toner according to the third aspect of the invention. That is, the cross-linking agent is characterized in that the speed of forming a cross-linked structure with a binder resin is significantly higher than that of a conventionally used monocyclic aromatic cross-linking agent such as divinylbenzene. Therefore, when the crosslinking agent is used, the polymerization time in the polymerization method toner can be shortened, whereby the diffusion / adhesion of the wax to the toner surface is significantly reduced, and the fluidity and the blocking resistance of the toner are improved. I do. Further, since the cross-linking structure is reliably formed, the structure of the toner is strengthened, and the fusion of the toner to a photoreceptor or a carrier under a high temperature is reduced.

As a result of extensive studies by the present inventors, it has been found that a composite oxide containing at least Fe and Mn and having a surface treated with an organic compound is dispersible and adhesive to a binder resin for toner. Therefore, it has been found that a toner using this composite oxide as a colorant can solve various problems as described above. The reason is unknown at present, and it is considered that the compatibility between the organic compound serving as the treating agent and the Mn atom on the surface of the composite oxide is different from the compatibility with the Fe atom, At present it has not been determined.

Here, it has been clarified that a silicon-containing compound is preferable as the organic compound for surface treatment, and a silane coupling agent is more preferable among the silicon-containing compounds. Although it is known that the colorant treated with the silicon-containing compound has improved dispersibility in the resin to some extent, for example, the affinity between the silicon-containing compound and iron oxide is not so good. Therefore, when a physical share is added to disperse the iron oxide surface-treated with the silicon-containing compound in the toner, the silicon-containing compound peels off from the iron oxide surface, and as a result, the affinity between the iron oxide particles and the binder resin decreases. It seems that the effect of the surface treatment does not increase so much. On the other hand, in the toner according to the fourth embodiment, a complex oxide containing Mn is used as a coloring agent. Silicon compounds are relatively easily oxidized,
It has been found that the bond of the silicon moiety is easily cleaved as a result of the oxidation reaction. Also in the present invention 4, when the surface of the Mn-containing composite oxide is treated with the silicon-containing compound, the silicon-bonded portion is oxidatively cleaved by the Mn oxide having a high oxidizing power, and the surface of the composite oxide is strong. It may be creating a bond.

Further, among the silicon-containing compounds, particularly when a silane coupling agent is used, since there are originally many functional groups capable of bonding to the OH groups on the surface of the composite oxide, the silicon-containing compound Strong adhesion of the compound, less likely to peel off from the colorant surface even under physical share during toner production, and maintain compatibility between the colorant and the binder resin, resulting in improved dispersibility of the colorant It is presumed.

The content of Mn in the composite oxide was 2 to 55 atomic% with respect to the total amount of Fe in the composite oxide.
Is preferable, and 3 to 50 atomic% is more preferable. When the content of Mn is less than 2 atomic% with respect to the total Fe content, the blackness of the composite oxide tends to decrease, and in particular, the smaller the particle size of the composite oxide, the more brownish it becomes. When reducing the diameter of the toner for the purpose of high image quality, it is considered that reducing the diameter of the colorant particles used is also an essential technology, but even if the colorant has a good dispersibility in the toner, the coloring power is small. There is a problem if only a brown toner can be obtained.

In addition, the content of Mn is 2 to the total amount of Fe.
When the content is less than atomic%, the compatibility or adhesion between the surface of the composite oxide and the treatment agent is insufficient, and the treatment agent is peeled off from the surface of the composite oxide when dispersed in the binder resin by physical sharing. As a result, the effect of improving the dispersibility of the colorant in the toner is hardly seen.

On the other hand, when the content of Mn is 5
If it exceeds 5 atomic%, it becomes difficult to control the resistance and magnetic properties of the composite oxide. Particularly, when the composite oxide is used as a toner material, the resistance as a toner also decreases, and the reduction in charge amount cannot be completely prevented under high humidity and the like. It is not preferable because it leads.

The average diameter of the composite oxide used in the toner of the fourth invention is preferably 0.01 to 0.13 μm, and the nitrogen adsorption specific surface area (= BET specific surface area) is 6 to 80.
It is preferably in the range of m ² / g. More preferable average diameter and BET specific surface area are 0.015 to 0.10 μm and 10 to 75 m ² / g.

When the average diameter is less than 0.01 μm, the decrease in blackness becomes remarkable, the coloring power of the black and white toner becomes insufficient, and the aggregation of the composite oxide particles becomes strong. , Dispersibility tends to deteriorate. On the other hand, when the average diameter exceeds 0.13 μm, the coloring power becomes insufficient similarly to a general coloring agent. In addition, it is probabilistically difficult to disperse the same number of composite oxide particles in individual toner particles, particularly when used as a colorant for small particle size toners.

When the BET specific surface area is less than 6 m ² / g, the composite oxide particles are liable to peel off from the toner when the toner is agitated in a developing device, for example, because the adhesive area with the binder resin is small. . In addition, when a toner is produced by the polymerization method, the composite oxide particles are likely to pop out from the polymerized monomer droplets due to centrifugal force or the like during high-speed stirring in the polymerization liquid, and it is difficult to include the composite oxide particles as a colorant. . On the other hand, BE
If the T specific surface area exceeds 80 m ² / g, the contact area between the composite oxide particles increases, and the particles tend to aggregate, so that the dispersibility also tends to deteriorate.

By selecting the weight average particle diameter of the toner according to the present invention in the range of 1 to 9 μm, it is possible to obtain a very high-quality image stably for a long period of time.

It is generally known that the finer the particle size of the toner, the higher the resolution during development. As described above, in order to reduce the particle size of the toner, it is important to uniformly disperse the raw material in the individual toner particles as described above. One method is to reduce the diameter of the raw material. On the other hand, as described above, iron oxides such as carbon black and magnetite have a tint closer to brown with a reduction in diameter, and thus a toner using such a coloring agent also has a lower degree of blackness and a lower coloring. Insufficient power. However,
In the composite oxide used as a colorant in the toner of the present invention 4, a Mn oxide coexists, and blackness is high even with a fine particle diameter. Therefore, if this composite oxide having a small particle diameter is used as a colorant in a small particle diameter toner having an average diameter of 9 μm or less, it is possible to obtain a high-definition, high-density, high-quality image for a long time by using the toner. Become. If the average diameter of the toner exceeds 9 μm, it is not possible to achieve much higher image quality. On the other hand, when the average diameter of the toner is less than 1 μm, it is more difficult to uniformly disperse the toner raw materials, which is not preferable. For this improvement, it is necessary to reduce the diameter of materials other than the colorant and to improve the dispersibility.

The surface treatment of the composite oxide used as the colorant in the toner of the present invention 4 can be carried out by any method, but a wet treatment is preferred. This is also because the treatment in a large amount of the solvent containing the treatment agent comes into contact with the surface of the entire composite oxide particles more uniformly than in the dry method.

The aqueous wet treatment without using an organic solvent is also preferable because the post-treatment is simple and preferable. In the case of the aqueous wet treatment, the preferable pH in the aqueous system is 8 or less. Under alkaline conditions with a pH higher than 8, the rate of hydrolysis of the silane coupling agent is too fast, so that condensation of the silane coupling agent occurs preferentially, and the amount of the treatment agent attached to the surface of the composite oxide. And the effect of improving dispersibility is reduced. Furthermore, as a result of the condensation reaction product serving as a so-called glue, aggregation of the composite oxide particles is likely to occur.
Further, an alkoxy-type silane coupling agent itself that does not generate gas is generally insoluble in water,
Under the condition that is not more than 8, the alkoxy group is hydrolyzed at an appropriate rate, becomes water-soluble, and is uniformly dispersed in water, so that more uniform surface treatment of the composite oxide particles becomes possible. Further, under neutral to acidic conditions having a pH of 8 or less, the surface of the inorganic compound fine particles is generally protonated,
It is considered that the coupling reaction is more likely to proceed as described below.

[0099]

Embedded image

Here, the amount of the treating agent in the surface treatment of the composite oxide is 0.1 to 100 parts by mass of the composite oxide.
The amount is preferably from 0.5 to 20 parts by mass, more preferably from 0.1 to 10 parts by mass. If the amount is less than 0.05 part by mass, the effect of improving the dispersibility of the composite oxide in the binder resin for the toner by the surface treatment is insufficient. Easily occur, and the effect of improving the dispersibility becomes insufficient.

The surface treating agents used in the present invention 4 include the following.

First, a silicone resin, a rosin resin,
Styrene resin, acrylic resin, methacrylic resin,
Styrene-acrylic copolymers, styrene-methacrylic copolymers, epoxy resins, and mixtures of these as appropriate. Further, fatty acids and metal salts thereof, surfactants and the like may be used.

Examples of the coupling agent include a silane coupling agent and a titanium coupling agent. As described above, the silane coupling agent is more preferably used and has the general formula R _m SiY _n [Wherein, R represents an alkoxy group, a halogen atom, m represents an integer of 1 to 3, Y represents an alkyl group, a vinyl group, a glycidoxy group, a methacryl group, a hydrocarbon group such as a phenyl group, and n represents Indicates an integer of 1 to 3. ]. For example, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane,
Examples thereof include dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, and n-octadecyltrimethoxysilane.

In particular, the formula C _p H _{2p + 1} -Si- (OC
_q H _{2q + 1} ) _{3 wherein} p is an integer of 2 to 20, and q is 1
The complex oxide particles are preferably subjected to a hydrophobic treatment in an aqueous medium using an alkyl trialkoxysilane coupling agent represented by the following formula: When p in the above formula is smaller than 2, the affinity between the treating agent and the surface of the composite oxide is good, and the surface treatment is easy. However, in general, the affinity of the treated surface with the binder resin is low due to the high hydrophilicity. Poor, dispersibility does not improve much. On the other hand, when p is larger than 20, the treating agent molecular chains become entangled with each other, and the agglomeration of the composite oxide particles increases, so that the effect of improving the dispersibility tends to decrease. On the other hand, when q is larger than 3, the reactivity of the silane coupling agent and the solubility in water are reduced, and it is difficult to perform the surface treatment sufficiently uniformly.

When the surface-treated composite oxide thus obtained is used alone as a colorant or a magnetism-imparting agent, it is preferably used in an amount of 1 part by weight per 100 parts by weight of the binder resin for toner.
0 to 200 parts by mass, more preferably 20 to 160 parts by mass.
Parts by weight. If the amount is less than 10 parts by mass, sufficient coloring power cannot be obtained only with the surface-treated composite oxide, and if it exceeds 200 parts by mass, the fixability of the toner tends to decrease.

The binder resin that can be used in the toner of the present invention includes:
All known ones can be used.

Further, in an image forming apparatus using a developing and cleaning system in which a developing device also serves in a developing process to collect toner remaining on the surface of the image carrier after the transfer process, a phenol derivative having a specific structure is condensed. By applying a toner containing a specific ratio of the material, the charge state of the toner is improved, and quick charge control becomes possible, and the load of toner collection is reduced by reducing the transfer residual toner, In addition, the present inventor has found out that it is possible to stably form a high-quality image for a long period of time by smoothly recovering the transfer residual toner.
Was completed.

The present inventors have improved the charging characteristics of a toner by using a toner in which a phenol derivative condensate having a specific structure is present in a specific content ratio in an image forming method using a one-component contact development system. In particular, since the charge control characteristics of the toner in a low-temperature and low-humidity environment are improved, high-quality image reproduction is possible, and the charge amount of the developed toner on the photoconductor is appropriately controlled, and the transfer is performed. The present inventor has found that it is possible to prevent the cleaning property from being deteriorated due to the excessive charging of the remaining toner, and reached the fifth aspect of the present invention.

The toners of Nos. 5 and 6 of the present invention include at least
A dry toner containing a binder resin, a colorant, a wax component, and a phenol derivative condensate, wherein the phenol derivative condensate in the toner comprises a cyclic condensate represented by the following general formula <A> and a general formula < A mixture of a chain condensate represented by B> and a low molecular weight condensate represented by the general formula <C>,
Each content ratio is such that the cyclic condensate represented by the general formula <A>: 5 to 95% by mass The chain condensate represented by the general formula <B>: 5 to 95% by mass The low condensate represented by the general formula <C> Molecular weight condensate: 0 to 5% by mass.

[0110]

Embedded image [Wherein, R _{1 to} R ₁₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X1 and Y1 are integers of 0 to 8, and the sum of X1 and Y1 is 3 to 12. ]

[0111]

Embedded image [Wherein, R _{21 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X2 and Y2 are integers of 0 to 8, and the sum of X2 and Y2 is 3 to 12. ]

[0112]

Embedded image [In the formula, R _{41 to} R ₅₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X3 and Y3 are integers of 0 to 2, and the sum of X3 and Y3 is 1 to 2. ]

The phenol derivative condensate as described above is obtained by condensing phenols and formaldehydes. In order to obtain the above structure, a raw material having a predetermined substituent can be used in advance. Specific examples of phenols include p-phenylphenol, alkylphenylphenol, halogenated phenylphenol, and halogenated alkylphenyl. Phenol, phenyl sulfonate, aminophenylphenol, cyanophenylphenol, phenylphenol isocyanate, nitrophenylphenol, cumylphenol, benzylphenol, styrenated phenol, phenol substituted with an alicyclic group, aminophenol, phenolsulfone Acid, hydroxybenzoic acid ester, hydroxyphenylacetic acid, hydroxyphenylacetic acid derivative, formylphenol, methoxyethylphenol, trialkylsilylated pheno It can be used Le like.

After these are used as raw materials and condensed, a substituent may be further introduced or eliminated.

Examples of the substituent to be added include an alkyl group, an aryl group which may have a substituent, an alkyl group having 1 to 8 carbon atoms substituted with an aryl group, and an aryl which may have a substituent. Examples include a cyclic group, a halogen atom, a fluoroalkyl group, a nitro group, an optionally substituted sulfone group, a phenylcarbamoyl group, an optionally substituted amino group, and a trialkylsilyl group.

The phenol derivative condensates according to the present inventions 5 and 6 include the cyclic condensate represented by the general formula <A>, the chain condensate represented by the general formula <B> and the general formula <C>. It is a mixture of low molecular weight condensates, each content ratio of which is 5 to 95% by mass of a cyclic condensate represented by the general formula <A>: 5 to 95% by mass. The low molecular weight condensate represented by the general formula <C> is adjusted to be 0 to 5% by mass.

The cyclic condensate represented by the general formula <A> is slightly inferior in dispersibility in toner particles, but is excellent in charge imparting property,
In particular, it is preferable because the charging speed is good. Also,
The chain condensate represented by the general formula <B> is inferior in chargeability to the cyclic condensate represented by the general formula <A>, but is excellent in dispersibility in toner particles, so that a uniform charge state can be obtained. . Therefore, in order to effectively exert these effects, it is possible to improve the chargeability in a well-balanced manner by using both of them in the above content ratio.

In the general formulas <A> and <B>, the substituents R ₂ , R ₁₂ , R ₂₂ , R ₃₂ , R ₄₂ and R _{52 represent} an alkyl group, an aryl group which may have a substituent, Aralkyl groups,
When it is an alisalic group, the chargeability is likely to be good. In particular, a phenyl group, cumyl group and the like which may have a substituent are excellent in charge controllability, and among them, those having at least one kind of phenyl group are preferable because they maintain an appropriate charge amount.

In the general formulas <A> and <B>, the substituents R ₁ , R ₁₁ , R ₂₁ , R ₃₁ , R ₄₁ and R _{51 represent} a hydrogen atom, an alkyl group, an aralkyl group and a substituent R ₃ ,
_{R 4, R 13, R 14} , R 23, R 24, R 33, R 34, R 43, R
_{In 44} , R ₅₃ and R ₅₄ , a hydrogen atom, an alkyl group, a halogen atom, a nitro group, and further a substituent R ₅ , R ₁₅ , R ₂₅ ,
In _{R 35, R 4 5, R} 55, preferred for hydrogen atoms prevents improvement in and charging stability, the production of low molecular weight condensate of the formula <3> by inhibition of the condensation reaction.

When two or more substituents are used as these substituents, not only the electronic effect of the substituents but also the crystallinity is deteriorated due to the steric effect, and the dispersibility in toner particles and the charging characteristics are reduced. Can be adjusted.

On the other hand, the low molecular weight condensate represented by the general formula <C> corresponds to the low molecular weight component of the condensate represented by the general formula <A> or <B>, but has a sufficient charging ability. If the content ratio is more than 5% by mass, it is difficult to uniformly charge the toner. Further, since it acts as a plastic component in the toner particles, it interferes with matching with the image forming apparatus.

On the other hand, in the general formulas <A> and <B>, if the sum of X1 and Y1 or the sum of X2 and Y2 corresponding to the number of repeating units of the phenol derivative condensate exceeds 12, the toner particles The dispersibility in the image is significantly reduced, and the chargeability of the toner becomes uneven, and the matching with the image forming apparatus is hindered.

The condensates of the phenol derivatives used in the toners of the present inventions 5 and 6 are prepared by adjusting the conditions of synthesis and purification.
After isolating the desired phenol derivative condensate, it is preferable to use a mixture having a structure as described above in a specific content ratio.

Incidentally, the number of repeating units of the phenol derivative condensate as described above can be determined by electrolytic desorption mass spectrum analysis (FD-MS) or the like.

As a method for incorporating the phenol derivative condensate according to the present invention into the toner, there are a method of adding the toner inside the toner (internal addition) and a method of adding the toner externally (external addition).
The preferable addition amount in the case of internal addition is as follows.
0.1 to 10 parts by mass relative to parts by mass, more preferably,
It is used in the range of 0.5 to 5 parts by mass. On the other hand, when externally added, the amount is preferably 0.01 to 5 parts by mass, and particularly preferably mechanochemically fixed to the toner surface.

The specific structures of the phenol derivative condensates according to the present inventions 5 and 6 and the comparative phenol derivative condensate are illustrated below, but the present inventions 5 and 6 are not limited thereto.

Cyclic condensate (A1-4) A condensation reaction is carried out in the presence of an alkali catalyst using the following phenol derivative (p-phenylphenol: compound 1) and formaldehyde as starting materials, and the obtained reaction product is separated by column. After that, recrystallization is performed to obtain a condensate (the number of repeating units of the phenol derivative condensate: 4), which corresponds to the cyclic condensate represented by the general formula <A>.

[0128]

Embedded image

Cyclic condensate (A1-n) Using the phenol derivative (compound 1) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the reaction product obtained is separated by a column and recrystallized. A cyclic condensate represented by the general formula <A> obtained by performing the above process, wherein the number of repeating units of the phenol derivative condensate is n.

Specifically, the cyclic condensate (A1-
3), a cyclic condensate having 6 repeating units (A1
-6), a cyclic condensate having 3 repeating units (A
1-8), a cyclic condensate (A1-12) having 12 repeating units, and the like, all of which can be obtained by changing reaction conditions and purification conditions.

Cyclic condensate (A2-4) Using the following phenol derivatives (compounds 1 and 2) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the obtained product is separated into columns. A condensate obtained by recrystallization (the number of repeating units of the phenol derivative condensate: 4), wherein the general formula <A
> Corresponds to the cyclic condensate represented by

[0132]

Embedded image

Cyclic condensate (A2-n) Using the phenol derivative (compound 1 and compound 2) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the resulting reaction product is subjected to column separation.
A cyclic condensate represented by the general formula <A> obtained by recrystallization, wherein the number of repeating units of the phenol derivative condensate is n.

Specifically, the cyclic condensate (A2-
3) a cyclic condensate having 6 repeating units (A2
-6), a cyclic condensate having 3 repeating units (A
2-8), a cyclic condensate (A2-12) having 12 repeating units and the like, all of which can be obtained by changing reaction conditions and purification conditions.

Chain Condensate (B1-4) Using the phenol derivative (compound 1) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the resulting product is subjected to column separation and recrystallization. This is a condensate (number of repeating units of the phenol derivative condensate: 4) obtained by the reaction, and corresponds to the chain condensate represented by the general formula <B>.

[0136]

Embedded image

Chain Condensate (B1-n) Using the phenol derivative (compound 1) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the resulting reaction product is separated into columns and then recrystallized. A cyclic condensate represented by the above general formula <B>, wherein the number of repeating units of the phenol derivative condensate is n.

Specifically, the phenol derivative condensate is a chain condensate (B1-
3) a chain condensate having 6 repeating units (B1
-6), a chain condensate having 3 repeating units (B
1-8), a chain condensate (B1-12) having 12 repeating units, and the like, all of which can be obtained by changing reaction conditions and purification conditions.

Chain Condensate (B2-4) Using the following phenol derivatives (compounds 1 to 5) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst, and the resulting product is subjected to column separation. This is a condensate obtained by recrystallization (the number of repeating units of the phenol derivative condensate: 4), and corresponds to the chain condensate represented by the general formula <B>.

[0140]

Embedded image

Chain Condensate (B2-n) Using the phenol derivative (compounds 1 to 5) and formaldehyde as starting materials, a condensation reaction is carried out in the presence of an alkali catalyst. A chain condensate represented by the general formula <B> obtained by crystallization, wherein the number of repeating units of the phenol derivative condensate is n.

More specifically, a chain condensate (B2-
3) a chain condensate having 6 repeating units (B2
-6), a chain condensate having 8 repeating units (B
2-8), a chain condensate (B2-12) having 12 repeating units, and the like, all of which can be obtained by changing reaction conditions and purification conditions.

Low molecular weight condensate (C1-n) Condensation reaction is carried out using the phenol derivative (compound A) and formaldehyde as starting materials, in the presence of an alkali catalyst, and the resulting reaction product is subjected to column separation and recrystallization. A low-molecular-weight condensate represented by the general formula <C>, wherein the number of repeating units of the phenol derivative condensate is n.

Specifically, a low molecular weight condensate (C1-
1) A low-molecular-weight condensate (C1-2) having two repeating units, which can be obtained by changing reaction conditions or purification conditions.

Low molecular weight condensate (C2-n) A condensation reaction is carried out in the presence of an alkali catalyst using the phenol derivative (compounds 1 to 5) and formaldehyde as starting materials, and the resulting reaction product is subjected to column separation. A low molecular weight condensate represented by the general formula <C> obtained by recrystallization, wherein the number of repeating units of the phenol derivative condensate is n.

Specifically, a low molecular weight condensate (C2-
1) A low-molecular-weight condensate (C2-2) having two repeating units, which can be obtained by changing reaction conditions or purification conditions.

Comparative cyclic condensate (a) A cyclic condensate obtained by subjecting the phenol derivative (compound 1) and formaldehyde as starting materials to a condensation reaction in the presence of an alkali catalyst, followed by recrystallization, When the number of repeating units of the phenol derivative condensate is 13 to 16
Is a comparative cyclic condensate (a).

Comparative chain condensate (b) A chain condensate obtained by subjecting the phenol derivative (compounds 1 to 5) and formaldehyde as starting materials to a condensation reaction in the presence of an alkali catalyst and recrystallization. Wherein the number of repeating units of the phenol derivative condensate is 13 to 2
0 is a comparative chain condensate (b).

Further, the toners of the present inventions 5 and 6 have a circle-equivalent number average diameter D1 (μm) in a circle equivalent diameter-circularity scattergram based on the number of toners measured by a flow type particle image measuring apparatus. ) Is 2 to 10 μm, and
By precisely controlling the toner particle shape so that the average circularity of the toner is 0.920 to 0.995 and the circularity standard deviation is less than 0.040, the developability and the transferability are improved in a well-balanced manner. At the same time, matching with the image forming apparatus is significantly improved. In addition, since the charge control characteristic of the toner when passing through the charging member is also improved, the toner is smoothly collected in the developing device, so that the durability is synergistically improved.

By reducing the toner-equivalent number average diameter D1 (μm) of the toner to 2 to 10 μm, the reproducibility of the outline portion of an image, particularly, the development of a character image or a line pattern becomes good. . However, in general, when the particle size of the toner particles is reduced, the abundance ratio of the fine particle toner is inevitably increased, so that it is difficult to uniformly charge the toner, causing not only image fogging but also the surface of the electrostatic latent image carrier. And the adhesion to the toner carrier is increased, resulting in an increase in transfer residual toner and the above-described problems.

However, in the toners of the present inventions 5 and 6, since the phenol derivative condensate having a specific structure is present in the toner at a specific content ratio, the circularity standard deviation is less than 0.040, preferably When the thickness is less than 0.035, it is possible to make the toner charge amount appropriate when forming a thin layer of toner on the toner carrier, and it is possible to greatly improve the problem relating to developability. .

The average circularity of the circularity frequency distribution of toner particles is 0.920 to 0.995, preferably 0.95.
0 to 0.995, more preferably 0.970 to 0.99
By setting the value to 0, the transferability of a toner having a small particle diameter, which has been difficult in the past, is greatly improved, and the developing ability for a low-potential latent image and the recoverability of the toner are remarkably improved. In particular, the above tendency is very effective when developing a digital minute spot latent image or when forming a full-color image in which an intermediate transfer body is used to perform multiple transfers, and the matching with the image forming apparatus is also good. It becomes something.

In the inventions 5 and 6, the equivalent circle diameter of the toner
The circularity and the frequency distribution thereof are used as a simple method for quantitatively expressing the shape of the toner particles. In the present invention, the flow type particle image measuring device FPIA-10 is used.
The measurement was performed using Model 00 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following equation.

[0154]

(Equation 1)

Here, the “particle projection area” is the area of the binarized toner particle image, and “the perimeter of the particle projection image”.
Is defined as the length of the contour obtained by connecting the edge points of the toner particle image.

The circularity in the present inventions 5 and 6 is an index indicating the degree of unevenness of the toner particles. When the toner particles are perfectly spherical, the circularity is 1.000. Is a small value.

In the present inventions 5 and 6, the circle-equivalent number average diameter D means the average value of the particle size frequency distribution based on the number of toners.
1 (μm) and the particle size standard deviation SDd are calculated from the following equation, where di is the particle size (central value) at the dividing point i of the particle size distribution and fi is the frequency.

[0158]

(Equation 2)

[0159]

[0160]

(Equation 3)

As a specific measuring method, 10 ml of ion-exchanged water from which impurity solids and the like have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant thereto. Further, 0.02 g of the measurement sample is added and uniformly dispersed. As a dispersing means, an ultrasonic dispersing machine UH-50 (manufactured by SMT Co., Ltd.) equipped with a titanium alloy chip of 5φ as a vibrator is subjected to a dispersing treatment for 5 minutes to obtain a dispersion for measurement.
At this time, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.

The shape of the toner particles was measured using the above-mentioned flow type particle image measuring apparatus.
The concentration of the dispersion liquid is readjusted so as to be 100 to 10,000 particles / μl, and 1,000 or more toner particles are measured. After the measurement, this data is used to determine the equivalent circle diameter and circularity frequency distribution of the toner particles.

The wax components according to the present inventions 5 and 6 show that the wax components are substantially spherical and insoluble in the binder resin when observed on a tomographic plane of the toner using a transmission electron microscope (TEM). And / or dispersed in the form of spindles and islands.

In the present inventions 5 and 6, the dispersion state of the wax component as described above is defined as follows. That is,
It is D4 × 0.9 or more with respect to the circle-equivalent weight average diameter D4 (μm) which means the average value of the weight-based particle size frequency distribution of the toner measured by the above-mentioned flow type particle image measuring apparatus, and Twenty tomographic planes of toner having a major axis of D4 × 1.1 or less are selected. Then, the major axis R of the selected tomographic plane of each toner and the largest major axis r of the phase separation structure caused by the wax component present in the tomographic plane of the toner having the major axis R are measured. An arithmetic mean value of r / R (r / R) _ST is obtained. When the obtained arithmetic mean value of r / R (r / R) _ST is in a dispersed state satisfying 0.05 ≦ (r / R) _ST ≦ 0.95, the wax component is compatible with the binder resin. In a non-dispersed state, a substantially spherical and / or spindle-shaped island-shaped dispersion state is assumed.

The arithmetic mean value of the above r / R (r / R)
_ST is, 0.05 ≦ (r / R) ST ≦ 0.95 by dispersing the wax component so as to satisfy the phenol derivative condensates represented by such general formula <1> or formula <2> Can be efficiently localized on the toner surface, which can contribute to stabilization of the chargeability of the toner. In addition, since the wax component is included in the toner particles, deterioration of the toner surface and contamination of the image forming apparatus can be prevented, so that the effect of fixing the phenol derivative condensate near the toner particle surface can be maintained. Can be done. If the low-molecular-weight condensate represented by the general formula <3> is present in an amount exceeding 5% by mass, it is difficult to obtain the above-described dispersed state of the wax component due to its plasticity. Furthermore, the arithmetic mean value of r / R (r / R) _ST is 0.25 ≦
(R / R) In a dispersion state satisfying _ST ≦ 0.90,
It is preferable because good chargeability can be maintained and a toner image excellent in dot reproduction can be formed for a long period of time. In addition, the wax component acts efficiently at the time of heating, so that low-temperature fixability and offset resistance are satisfactory.

As a method for observing the tomographic plane of the toner,
It is necessary to use an electron dyeing method that increases the electron density of one component with heavy metal and makes contrast between the materials by utilizing the difference in the microstructure of the crystalline phase and the amorphous phase of the wax component used and the resin constituting the outer shell. preferable. Specifically, after sufficiently dispersing the toner particles in a room-temperature curable epoxy resin, the toner particles are cured at an ambient temperature of 40 ° C. for 2 days, and the obtained cured product is ruthenium tetroxide (RuO ₄ ), If necessary, osmium tetroxide (OsO ₄ ) is used for electron staining, and then a flaky sample is cut out using an ultramicrotome equipped with a diamond knife. Observe the cross-sectional layer morphology.

A typical example is shown in FIG. In the toner particles obtained in Examples described later, it was observed that the wax component was included in the binder resin.

The wax component used in the present invention includes DS measured in accordance with ASTM D3418-8.
The main endothermic maximum peak (melting point) in the C curve is 30 to
Compounds in the range from 120 ° C, more preferably from 40 to 90 ° C, are preferred. Maximum peak value of wax component (melting point)
Is less than 30 ° C., the self-cohesive force of the wax component becomes weak, and as a result, the hot offset resistance becomes weak, which is not preferable. The maximum peak value (melting point) of the wax component is 120
If the temperature exceeds 100 ° C., the fixing temperature increases, and it becomes difficult to appropriately smooth the surface of the fixed image, which is not preferable in terms of lowering the color mixing.

Further, when toner particles are obtained by a polymerization method, since the granulation and polymerization are performed in an aqueous medium, if the endothermic maximum peak value (melting point) is high, the release agent is mainly deposited during granulation. It is not preferable because it comes.

For measuring the temperature (melting point) of the maximum peak value of the wax component, for example, DSC-manufactured by PerkinElmer Co., Ltd.
7 is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the heat quantity correction uses the heat of fusion of indium. An aluminum pan was used as a sample, an empty pan was set as a control, and measurement was performed at a temperature increasing rate of 10 ° C./min from 20 ° C. to 180 ° C.

The wax component used in the toner of the present invention includes petroleum waxes and derivatives thereof such as paraffin wax, microcrystalline wax and petrol tact, montan wax and derivatives thereof, and hydrocarbon wax and derivatives thereof by the Fischer-Tropsch method. , Polyolefin wax represented by polyethylene and its derivatives, carnauba wax, candelilla wax, etc., natural waxes and their derivatives, etc., derivatives such as oxides, block copolymers with vinyl monomers,
Alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, etc. Can be

Examples of the ester wax used in the present invention include those formed from compounds represented by the following formulas (I) to (VI).

[0173]

Embedded image (Where a and b are integers from 0 to 4, and a + b is 4
It is. R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the difference between R ₁ and R ₂ is 3 or more. m and n are integers from 0 to 25, and m and n are not simultaneously 0.

[0174]

Embedded image(Where a and b are integers from 0 to 3, and a + b is 1
It is three. R₁And R_TwoIs an organic group having 1 to 40 carbon atoms
Yes, R₁And R_TwoIs 3 or more. R _ThreeIs water
Elemental atoms and organic groups having 1 or more carbon atoms. Where a + b
= 2, R_ThreeOne of which has 1 or more carbon atoms
Organic group. k is an integer of 1 to 3. m and n are 0
Is an integer of ~ 25, and m and n cannot be 0 at the same time.
I)

[0175]

Embedded image (Wherein R ₁ and R ₂ are organic groups having 6 to 32 carbon atoms, and R ₁ and R ₃ may or may not be the same.
₂ represents an organic group having 1 to 20 carbon atoms)

[0176]

Embedded image Or - (CH _{2) n} - is. m represents an integer of 1 to 10, and n represents an integer of 1 to 20. )

[0177]

Embedded image (In the formula, a is an integer of 0 to 4, b is an integer of 1 to 4, a + b is 4. R ₁ is an organic group having 1 to 40 carbon atoms. M and n are 0. An integer of 〜25, m and n
Do not become 0 at the same time)

[0178]

Embedded image (Wherein R ₁ and R ₂ are the same or different and each have 15 to 4 carbon atoms)
(Shows 5 hydrocarbon groups)

Examples of the ester wax as a release agent comprising an ester compound include the following.

[0180]

Embedded image

[0181]

Embedded image

When the release agent is an ester wax having an ester compound having the above structural formula, it exhibits good transparency, and exhibits good fixability when incorporated in toner particles. is there. After the release agent and the polar resin are dissolved in the polymerizable monomer, the polymerization reaction of the polymerizable monomer is advanced in a hydrogen medium. It is possible to obtain an excellent toner for developing an electrostatic image with a high speed until the charge value is reached and a small variation in the triboelectric charge amount during the durability of a large number of sheets.

The release agent is blended in an amount of 5 to 40 parts by mass (more preferably, 10 to 30 parts by mass) with respect to the toner, and as a result, per 100 parts by mass of the binder resin formed from the polymerizable monomer. 5 to 40 parts by mass of a release agent (more preferably, 1 to 40 parts by mass)
(0 to 30 parts by mass) It is preferred that it is contained in the toner particles.

As the polymerizable monomer used in the toner of the present invention, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-
Methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, pn-butyl styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, p- Styrene derivatives such as n-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene and p-phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-
Propyl acrylate, n-butyl acrylate, is
o-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate Acrylic polymerizable monomers such as ethyl acrylate, dibutyl phosphate ethyl acrylate and 2-benzoyloxyethyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate , Tert
-Butyl methacrylate, n-amyl methacrylate,
Methacrylic polymerizable monomers such as n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate, n-nonyl methacrylate, diethyl phosphate ethyl methacrylate, dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; acetic acid Vinyl esters such as vinyl, vinyl propionate, vinyl butyrate, vinyl benzoate and vinyl formate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropyl ketone. No.

These can be used alone or in general in the published Polymer Handbook, 2nd edition III-P139-192.
The monomers are appropriately mixed and used so that the theoretical glass transition temperature (Tg) described in (John Wiley & Sons) shows 40 to 75 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems arise in terms of the storage stability of the toner and the durability stability of the developer. In this case, the color mixture of each color toner is insufficient and the color reproducibility is poor, and the transparency of the OHP image is remarkably reduced, which is not preferable from the viewpoint of high image quality. The molecular weight of the toner is GP
It is measured by C (gel permeation chromatography). As a specific GPC measurement method, a toner is prepared in advance using a Soxhlet extractor with a toluene solvent.
After the extraction with time, toluene is distilled off by a rotary evaporator, and an organic solvent such as chloroform, which dissolves the low softening point substance but does not dissolve the outer shell resin, is sufficiently washed, and then washed with THF (tetrahydrofuran). )
A solution obtained by filtering a solution that was dissolved in a solvent-resistant membrane filter having a pore diameter of 0.3 μm was used as a sample, and 150 C manufactured by Waters Co., Ltd. was used. The column configuration was A-801 manufactured by Showa Denko.
802, 803, 804, 805, 806, 807 can be connected to measure the molecular weight distribution using a standard polystyrene resin calibration curve.

The melt index in the present invention is:
Japanese Industrial Standard Thermoplastic Flow Test Method J
The measurement was performed by a manual cutting method using an apparatus described in IS K7210.

As the polymerization initiator used in the polymerization of the polymerizable monomer, an oil-soluble initiator and / or a water-soluble initiator are used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis-2,4-dimethylvaleronitrile, 1,
Azo compounds such as 1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonylper oxide,
Lauroyl peroxide, stearoyl peroxide, propionyl peroxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, Peroxide initiators such as dicumyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide and cumene hydroperoxide are exemplified.

Examples of the water-soluble initiator include ammonium persulfate, potassium persulfate and 2,2′-azobis (N, N′-
Dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloride, azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, sulfuric acid Ferrous or hydrogen peroxide.

In the present invention, in order to control the degree of polymerization of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like may be further added and used.

As the colorant used in the present invention, carbon black, a magnetic substance, and a copper colored black using a yellow / magenta / cyan colorant shown below are used.

Examples of yellow colorants include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 and the like are preferably used.

Examples of the magenta coloring agent include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
22, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used.
Specifically, C.I. I. Pigment Blue 1, 7, 15,
15: 1, 15: 2, 15: 3, 15: 4, 60, 6
2, 66 and the like are particularly preferably used. These colorants can be used alone or as a mixture or in the form of a solid solution. The colorant of the present invention is selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the coloring agent is 1 to 100 parts by mass of the resin.
Used in an amount of up to 20 parts by mass.

Further, the toner of the present invention may be used as a magnetic toner by containing a magnetic material as a colorant. In this case, the magnetic material can also serve as a colorant. In the present invention, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, hematite, and ferrite; metals such as iron, cobalt, and nickel; and aluminum, cobalt, copper, lead, magnesium, and tin of these metals. , Zinc, antimony, beryllium, bismuth,
Cadmium, calcium, manganese, selenium, titanium,
Alloys of metals such as tungsten and vanadium and mixtures thereof can be given.

The magnetic material used in the present invention is more preferably a surface-modified magnetic material. When the magnetic material is used in a polymerization toner, it is hydrophobized by a surface modifier which is a substance having no polymerization inhibition. Those that have been treated are preferred. Examples of such a surface modifier include a silane coupling agent and a titanium coupling agent.

These magnetic materials have an average particle size of 2 μm or less,
Preferably, the thickness is about 0.1 to 0.5 μm.
The amount contained in the toner particles is preferably about 20 to 200 parts by weight, more preferably 40 to 150 parts by weight, based on 100 parts by weight of the binder resin.

The magnetic properties when 795.8 kA / m (10 k Oersted) was applied showed a coercive force (Hc) of 1.6 to 24 k.
A / m (20-300 Oersted), saturation magnetization (σ
s) 50 to ²⁰⁰ Am ² / kg, remanent magnetization (σr) 2
A magnetic material of ²⁰ Am ² / kg is preferred.

The toner of the present invention may contain a charge control agent.

The following substances control the toner to be negatively charged.

For example, organic metal compounds and chelate compounds are effective, and examples thereof include monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid-based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

Further, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds,
Quaternary ammonium salts, calixarenes and the like.

The following substances control the toner to be positively charged.

Nigrosine modified with nigrosine and fatty acid metal salts, etc., guanidine compounds, imidazole compounds, quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate,
And onium salts such as phosphonium salts, which are analogs thereof, and lake pigments thereof, triphenylmethane dyes, and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten 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; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate And diorganotin borates. These can be used alone or in combination of two or more.

In the combination with the polar resin of the present invention, a metal-containing salicylic acid compound is preferred.

The charge control agent is preferably used in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

In the present invention, compounds represented by the following general formula (I) are more preferable among the above charge control agents.

[0207]

Embedded image

Typical examples of the charge control agent include the following compounds.

[0209]

Embedded image

[0210] From the viewpoint of durability, the additive for improving various characteristics of the toner preferably has a particle diameter of 1/5 or less of the volume average diameter of the toner particles. The particle size of the additive means the average particle size of the toner particles obtained by observing the surface of the toner particles with an electron microscope. As additives for imparting these properties, for example, the following are used.

Examples of the fluidity-imparting agent include metal oxides (such as silicon oxide, aluminum oxide, and titanium oxide), carbon black, and carbon fluoride. Those subjected to a hydrophobic treatment are more preferable.

Examples of the abrasive include metal oxides (such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide and chromium oxide), nitrides (such as silicon nitride), carbides (such as silicon carbide), and metal salts (calcium sulfate). , Barium sulfate, calcium carbonate, etc.).

Examples of the lubricant include fluororesin powders (eg, vinylidene fluoride, polytetrafluoroethylene) and fatty acid metal salts (eg, zinc stearate, calcium stearate).

Examples of the charge control particles include metal oxides (such as tin oxide, titanium oxide, zinc oxide, silicon oxide, and aluminum oxide) and carbon black.

These additives are used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the toner particles.
0.1 to 5 parts by mass are used. These additives may be used alone or in combination of two or more.

In the method for producing the toner of the present invention, the shape of the toner particles can be controlled uniformly, a sharp particle size distribution with a number variation coefficient of 35% or less (preferably 30% or less) can be easily obtained, and the weight average A suspension polymerization method in which toner particles having a small particle size of 3 to 8 μm can be easily obtained is particularly preferable. Further, a seed polymerization method in which a monomer is further adsorbed on the polymer particles once obtained and then polymerized using a polymerization initiator can also be suitably used in the present invention. At this time, it is also possible to use a compound having polarity dispersed or dissolved in the monomer to be adsorbed. When suspension polymerization is used as a method for producing toner particles, toner particles can be directly produced by the following production method. A monomer composition in which a low-softening point substance such as wax, a colorant, a polymerization initiator, a crosslinking agent, and other additives are added to a monomer, and the mixture is uniformly dissolved or dispersed with a homogenizer, an ultrasonic disperser, or the like. Is dispersed in an aqueous medium containing a dispersion stabilizer using a conventional stirrer, homomixer, homogenizer, or the like. Preferably, the agitation speed and time are adjusted so that the droplets of the monomer composition have the desired size of the toner particles, and granulation is performed. After that, due to the action of the dispersion stabilizer, the particle state is maintained,
In addition, stirring may be performed to such an extent that settling of particles is prevented.
The polymerization is carried out at a polymerization temperature of 40 ° C. or higher, usually 50 to 90 ° C. (preferably 55 to 85 ° C.). The temperature may be raised in the latter half of the polymerization reaction, and may be further increased in the latter half of the reaction or after the end of the reaction to remove unreacted polymerizable monomers and by-products that cause odor at the time of fixing the toner. The partial aqueous medium may be distilled off. After the reaction, the generated toner particles are collected by washing and filtration, and dried.

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

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

As for the colorant used in the toner produced by the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant. The colorant is preferably subjected to a surface modification (for example, a hydrophobic treatment that does not inhibit polymerization). In particular, dyes and carbon black need to be carefully used because many of them have polymerization inhibitory properties. As a preferable method for surface-treating the dye, a method in which a polymerizable monomer is polymerized in advance in the presence of the dye is mentioned, and the obtained colored polymer is added to the monomer composition. The carbon black may be treated with a substance (for example, polyorganosiloxane) that reacts with the surface functional group of the carbon black, in addition to the treatment similar to the above-described dye.

(Method of Measuring Acid Value) The acid value is determined by mg of potassium hydroxide required to neutralize the acid contained in 1 g of the sample.
(JIS K676), for example, toluene / n-
It is determined by dissolving a sample in a mixed solvent of butanol (50/50: mass ratio) at a concentration of 3%, and titrating with an ethanol solution of KOH using phenolphthalein as an indicator.

(Measurement method of hydroxyl value)
g of potassium hydroxide required to neutralize the acetic acid consumed to acetylate the hydroxyl group contained in g, for example, in a mixed solvent of toluene / n-butanol (50/50: mass ratio). The sample was dissolved at a concentration of 3%, acetylation was performed by adding a trace amount of pyridine as a catalyst and heating with an excess acetylating agent (such as acetic anhydride), and the saponification value of the produced acetylated product was measured. Calculate according to the formula.

[0222]

(Equation 4) Here, A represents the saponification value after acetylation, and B represents the saponification value before acetylation.

When used as a two-component developer, a carrier is used together with the toner of the present invention as a developer. The magnetic carrier is composed of an element consisting of iron, copper, zinc, nickel, cobalt, manganese, and chromium alone or in a composite ferrite state. The shape of the magnetic carrier is spherical, flat, or irregular. Furthermore, the fine structure of the surface state of the magnetic carrier particles (for example, surface unevenness)
Is also preferably controlled. In general, a method is used in which magnetic carrier core particles are generated in advance by baking and granulating the inorganic oxide, and then coating the resin with a resin. From the viewpoint of reducing the load on the toner of the magnetic carrier, after kneading the inorganic oxide and the resin, pulverizing and classifying to obtain a low-density dispersed carrier, and further, directly kneading the inorganic oxide and the monomer. It is also possible to use a method of obtaining a spherical magnetic carrier by suspension polymerization in an aqueous medium.

Coated carriers for coating the surface of the carrier particles with a resin are particularly preferred. As the method, a method of dissolving or suspending the resin in a solvent, applying the resin, and attaching the resin to the carrier, or a method of simply mixing the resin powder and the carrier particles and attaching the mixture is applicable.

The substance fixed to the surface of the carrier particles varies depending on the toner material. For example, polytetrafluoroethylene, monochloro-triple-ethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin, styrene resin, acrylic resin, polyamide resin , Polyvinyl butyral, amino acrylate resin and the like. These may be used alone or in combination.

The magnetic properties of the carrier are preferably as follows.
79.58 kA / m after magnetic saturation (1000
(Oersted) has a magnetization strength (σ1000) of 3
It needs to be 0 to 300 emu / cm ³ .
In order to achieve higher image quality, it is preferably 100 to 250 emu / cm ³ . 300 em
When it is larger than u / cm ^3, it becomes difficult to obtain a high quality toner image. When it is less than ³⁰ emu / cm ³ ,
Since the magnetic binding force is also reduced, carrier adhesion is likely to occur.

When a two-component developer is prepared by mixing the toner of the present invention and a magnetic carrier, the mixing ratio is 2% by mass to 15% by mass, preferably 4% by mass, as the toner concentration in the developer. When it is 13% by mass, usually good results are obtained.

The image forming method to which the toner of the present invention can be applied will be described below with reference to the accompanying drawings.

The toner of the present invention can be mixed with a magnetic carrier and applied to an image forming method using, for example, developing means 37 as shown in FIG. Specifically, while applying an alternating electric field, the magnetic brush is used to hold the electrostatic image holder (for example,
It is preferable that the development is performed in a state of being in contact with the photosensitive drum 33. The distance (S-D distance) B between the developer carrier (developing sleeve) 31 and the photosensitive drum 33 is 100 to 1
000 μm is good in preventing carrier adhesion and improving dot reproducibility. If it is smaller than 100 μm, the supply of the developer tends to be insufficient and the image density is reduced. If it is larger than 1000 μm, the magnetic field lines from the magnet S1 are widened and the density of the magnetic brush is reduced, resulting in poor dot reproducibility or restrained carrier. And the carrier is likely to adhere. The toner 41 is sequentially supplied to the developing device,
The toner is mixed with the carrier by the stirring means 35 and 36 and transported to the developing sleeve 42 containing the fixed magnet 34.

The voltage between the peaks of the alternating electric field is 500 to 50.
00V is preferable, the frequency is 500 to 10000 Hz,
The frequency is preferably 500 to 3000 Hz, and can be appropriately selected and used for each process. In this case, the waveform may be triangular, rectangular, sine, or Duty.
Various selections such as waveforms with different ratios can be used. If the applied voltage is lower than 500 V, it is difficult to obtain a sufficient image density, and it may not be possible to satisfactorily collect fog toner in the non-image area. If the voltage exceeds 5000 V, the electrostatic image may be disturbed via the magnetic brush, which may cause deterioration in image quality.

By using a two-component developer having a well-charged toner, the fog removal voltage (Vback)
And the primary charge of the photoconductor can be reduced, so that the life of the photoconductor can be extended. Vbac
k is preferably 150 V or less, more preferably 100 V or less, depending on the developing system.

As the contrast potential, 200 V to 500 V is preferably used so that a sufficient image density can be obtained.

If the frequency is lower than 500 Hz, although it is related to the process speed, charge injection into the carrier may occur, so that the image quality may be deteriorated by carrier adhesion or disturbing the latent image. If the frequency exceeds 10,000 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

In order to obtain a sufficient image density, achieve excellent dot reproducibility, and perform development without carrier adhesion, the contact width (developing nip C) of the magnetic brush on the developing sleeve 31 with the photosensitive drum 33 is preferably set. 3 to 8 mm. If the developing nip C is narrower than 3 mm, it is difficult to sufficiently satisfy a sufficient image density and dot reproducibility.
If the width is larger than mm, packing of the developer occurs to stop the operation of the machine, and it is difficult to sufficiently suppress carrier adhesion. As a method of adjusting the development nip,
The nip width is appropriately adjusted by adjusting the distance A between the developer regulating member 32 and the developing sleeve 31 or adjusting the distance B between the developing sleeve 31 and the photosensitive drum 33.

In the output of a full-color image in which halftone is particularly important, three or more developing units for magenta, cyan, and yellow are used, and the toner of the present invention is used to form a digital latent image. In combination with the developing system described above, there is no influence of the magnetic brush and the latent image can be faithfully developed with respect to the dot latent image without disturbing the latent image. In the transfer step, a high transfer rate can be achieved by using the toner of the present invention, so that high image quality can be achieved in both the halftone portion and the solid portion.

Further, by using the toner of the present invention together with the initial improvement of the image quality, the effect of the present invention without deterioration in image quality can be sufficiently exhibited even when copying a large number of sheets.

The toner image on the electrostatic image holding member 33 is transferred to a transfer material by transfer means 43 such as a corona charger.
The toner image on the transfer material is fixed by a heat and pressure fixing unit having a heating roller 46 and a pressure roller 45, and a fixed image is formed on the transfer material. The transfer residual toner on the electrostatic image holder 33 is removed from the electrostatic image holder 33 by cleaning means 44 such as a cleaning blade. The toner of the present invention has a high transfer efficiency in the transfer step, a small amount of untransferred toner, and an excellent cleaning property, so that filming hardly occurs on the electrostatic image holding member. Further, even when a multi-sheet durability test is performed, the toner of the present invention has less embedding of the external additive on the surface of the toner particles than the conventional toner, so that good image quality can be maintained for a long time.

In order to obtain a good full-color image, it is preferable that a developing device for magenta, cyan, yellow, and black is provided, and a tight image is obtained by performing black development last. it can.

An example of an image forming apparatus capable of favorably performing a multi-color or full-color image forming method will be described with reference to FIG.

The color electrophotographic apparatus shown in FIG. 4 includes a transfer material transport system I provided from the right side of the apparatus main body to substantially the center of the apparatus main body, and the transfer material transport system I provided substantially at the center of the apparatus main body. And a developing unit (that is, a rotary developing device) III disposed in close proximity to the latent image forming unit II. It is roughly divided.

The transfer material transport system I has the following configuration. An opening is formed in a right wall (right side in FIG. 4) of the apparatus main body, and detachable transfer material supply trays 302 and 303 are provided in the opening so as to partially protrude outside the apparatus. Feed rollers 304 and 305 are disposed almost directly above the trays 302 and 303, and the feed rollers 304 and 305 are linked to a transfer drum 305 disposed on the left and rotatable in the direction of arrow A. For this purpose, a paper feed roller 306 and paper feed guides 307 and 308 are provided. In the vicinity of the outer peripheral surface of the transfer drum 315, the contact roller 309, the gripper 310, the transfer material separating charger 311, and the separating claw 31 from the upstream to the downstream in the rotation direction.
2 are sequentially arranged.

A transfer charger 313 and a transfer material separating charger 314 are provided on the inner peripheral side of the transfer drum 315. A transfer sheet (not shown) made of a polymer, such as polyvinylidene fluoride, is attached to a portion of the transfer drum 315 around which the transfer material is wound, and the transfer material is electrostatically placed on the transfer sheet. It is stuck on. At the upper right side of the transfer drum 315, a conveyor belt unit 316 is disposed in close proximity to the separation claw 312. At the end (right side) of the conveyor belt unit 316 in the transfer material transport direction (right side), a fixing device 318 is disposed. I have. A discharge tray 317 that extends outside the apparatus main body 301 and that is detachable from the apparatus main body 301 is provided downstream of the fixing device 318 in the transport direction.

Next, the configuration of the latent image forming section II will be described. A photosensitive drum (for example, an OPC photosensitive drum) 319, which is a latent image carrier rotatable in the direction of the arrow in FIG. 4, is provided with its outer peripheral surface in contact with the outer peripheral surface of the transfer drum 315. Above the photosensitive drum 319 and in the vicinity of the outer peripheral surface thereof, from the upstream side to the downstream side in the rotation direction of the photosensitive drum 319, the charge removing charger 320 and the cleaning unit 321 are arranged.
And a primary charger 323 are sequentially arranged. Further, an image exposure unit 324 such as a laser beam scanner for forming an electrostatic latent image on the outer peripheral surface of the photosensitive drum 319 and an image exposure reflection unit 325 such as a mirror are provided. It is arranged.

The structure of the rotary developing device III is as follows. A rotatable housing (hereinafter referred to as a “rotating body”) 3 is provided at a position facing the outer peripheral surface of the photosensitive drum 319.
26, and four types of developing devices are mounted in the rotating body 326 at four positions in the circumferential direction.
9, the electrostatic latent image formed on the outer peripheral surface is visualized (that is, developed). The four types of developing devices include a yellow developing device 327Y, a magenta developing device 327M, a cyan developing device 327C, and a black developing device 327BK, respectively.

The sequence of the entire image forming apparatus having the above configuration will be described by taking a full color mode as an example. When the above-described photosensitive drum 319 rotates in the direction of the arrow in FIG.
Charged by In the apparatus shown in FIG. 4, the distance around the photosensitive drum 319 (hereinafter referred to as process speed) is 1
00 mm / sec or more (for example, 130 to 250 mm /
sec). When the photosensitive drum 319 is charged by the primary charger 323, image exposure is performed by the laser light E modulated by the yellow image signal of the document 328, and an electrostatic latent image is formed on the photosensitive drum 319,
By the rotation of the rotating body 326, the electrostatic latent image is developed by the yellow developing device 327Y fixed at the developing position in advance, and a yellow toner image is formed.

The transfer material conveyed via the paper feed guide 307, the paper feed roller 306, and the paper feed guide 308 is held at a predetermined timing by the gripper 310, and is brought into contact with the contact roller 309 and the corresponding contact roller. The transfer drum 315 is electrostatically wound by the electrode 309 and the facing electrode. The transfer drum 315 rotates in the direction indicated by the arrow in FIG. 4 in synchronization with the photosensitive drum 319.
The yellow toner image formed by 27Y is transferred onto the transfer material by the transfer charger 313 at a position where the outer peripheral surface of the photosensitive drum 319 and the outer peripheral surface of the transfer drum 315 are in contact. The transfer drum 315 continues to rotate, and prepares for the transfer of the next color (magenta in FIG. 4).

The photosensitive drum 319 is provided with the charge removing device 3 for discharging.
After being removed by the cleaning device 20 and cleaned by the cleaning means 321 using a cleaning blade, it is charged again by the primary charger 323, image exposure is performed by the next magenta image signal, and an electrostatic latent image is formed. The rotary developing device rotates while an electrostatic latent image is formed on the photosensitive drum 319 by image exposure based on a magenta image signal, and causes the magenta developing device 327M to be disposed at the above-described predetermined developing position. Develop with magenta toner. Subsequently, the above-described process is also performed for cyan and black, respectively. When the transfer of the four-color toner image is completed, the three-color visual image formed on the transfer material is transferred to each of the chargers 322 and 314. , The transfer material is released from being held by the gripper 310, and the transfer material is separated from the transfer drum 315 by the separation claw 312.
18 and is fixed by heat and pressure to complete a series of full-color print sequences, and a required full-color print image is formed on one surface of the transfer material.

Next, another image forming method will be described with reference to FIG.

In the apparatus system shown in FIG. 5, the developing units 74-1, 74-2, 74-3, and 74-4 respectively include a developer having a cyan toner, a developer having a magenta toner, and a developing device having a yellow toner. A developer having a developer and a black toner is introduced, and the electrostatic charge image formed on the photoconductor 71 is developed by a magnetic brush development system or a non-magnetic one-component development system, so that a toner image of each color is formed on the photoconductor 71. . The photoconductor 71 is made of a-Se, Cds, ZnO ₂ ,
A photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as OPC or a-Si. The photoconductor 71 is rotated in a direction indicated by an arrow by a driving device (not shown).

As the photosensitive member 71, a photosensitive member having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

As the organic photosensitive layer, the photosensitive layer contains a charge generating substance and a substance having charge transport performance in the same layer.
It may be a single-layer type or a function-separated type photosensitive layer having a charge transport layer as a component of the charge transport layer. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated on a conductive substrate in this order is one of preferred examples.

The binder resin for the organic photosensitive layer is preferably a polycarbonate resin, a polyester resin, or an acrylic resin, particularly having good transferability and cleaning properties, and poor cleaning, fusion of a toner to a photoreceptor, and filming of an external additive. Less likely.

In the charging step, there are a system that is not in contact with the photoreceptor 71 using a corona charger, and a contact system that uses a roller or the like, and either system is used. For efficient uniform charging, simplification, and low ozone generation, a contact type as shown in FIG. 5 is preferably used.

The charging roller 72 has a basic configuration in which a central core bar 72b and a conductive elastic layer 72a forming the outer periphery thereof are provided. The charging roller 72 is pressed against the surface of the photoconductor 71 with a pressing force, and is rotated by the rotation of the photoconductor 71.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 4.9 to 490 N / m
(5 to 500 g / cm), when an AC voltage superimposed on a DC voltage is used, AC voltage = 0.5 to 5 kVp
p, AC frequency = 50 Hz to 5 kHz, DC voltage = ±
0.2 to ± 1.5 kV, and when a DC voltage is used, the DC voltage is ± 0.2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are effective in that high voltage is not required and generation of ozone is reduced.

As the material of the charging roller and the charging blade as the contact charging means, conductive rubber is preferable, and a release coating may be provided on the surface thereof. As the release coating, a nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride) or the like can be applied.

The toner image on the photosensitive member is applied with a voltage (for example, ±
(0.1 to ± 5 kV). The surface of the photoreceptor after the transfer is cleaned by cleaning means 79 having a cleaning blade 78.

The intermediate transfer member 75 comprises a pipe-shaped conductive core 75b and a medium-resistance elastic layer 75 formed on the outer peripheral surface thereof.
a. The core metal 75b may be formed by applying a conductive plating to a plastic pipe.

The medium-resistance elastic layer 75a is made of silicone rubber, fluorine rubber, chloroprene rubber, urethane rubber,
An elastic material such as PDM (a terpolymer of ethylene propylene diene) is mixed with a conductive material such as carbon black, zinc oxide, tin oxide, and silicon carbide to disperse the material so that the electric resistance value (volume resistivity) is 10%. ^{It is} a solid or foamed layer adjusted to a medium resistance of ⁵ to 10 ¹¹ Ω · cm.

The intermediate transfer member 75 is arranged in parallel with the photosensitive member 71 so as to be in contact with the lower surface of the photosensitive member 71, and rotates counterclockwise at the same peripheral speed as the photosensitive member 71. I do.

The first color toner image formed and carried on the surface of the photosensitive member 71 is transferred by the transfer bias applied to the intermediate transfer member 75 while passing through the transfer nip portion where the photosensitive member 71 contacts the intermediate transfer member 75. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer body 75 by the electric field formed in the nip area.

If necessary, the surface of the intermediate transfer member 75 is cleaned by the detachable cleaning means 80 after the transfer of the toner image onto the transfer material. When there is a toner image on the intermediate transfer member, the cleaning unit 80 is separated from the surface of the intermediate transfer member so as not to disturb the toner image.

A transfer means is provided in parallel with the intermediate transfer body 75 and is brought into contact with the lower surface of the intermediate transfer body 75. The transfer means 77 is, for example, a transfer roller or a transfer belt. It rotates clockwise with the same peripheral speed as the arrow. The transfer unit 77 may be disposed so as to directly contact the intermediate transfer body 75, or a belt or the like may be disposed so as to contact between the intermediate transfer body 75 and the transfer unit 77.

In the case of the transfer roller, the basic structure is a core metal 77b at the center and a conductive elastic layer 77a forming the outer periphery thereof.

A general material can be used for the intermediate transfer member and the transfer roller. By setting the volume resistivity of the elastic layer of the transfer roller smaller than the volume resistivity of the elastic layer of the intermediate transfer member, the voltage applied to the transfer roller can be reduced, and a good toner image can be formed on the transfer material. At the same time, the winding of the transfer material around the intermediate transfer member can be prevented. In particular, it is particularly preferable that the volume resistivity of the elastic layer of the intermediate transfer member is at least 10 times the volume resistivity of the elastic layer of the transfer roller.

The hardness of the intermediate transfer member and the transfer roller is determined by JI
It is measured according to SK-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to the range of 10 to 40 degrees. On the other hand, the hardness of the elastic layer of the transfer roller is higher than the hardness of the elastic layer of the intermediate transfer member.
Those having a value of from 80 to 80 degrees are preferable in order to prevent the transfer material from being wound around the intermediate transfer member. When the hardness of the intermediate transfer member and that of the transfer roller are reversed, a concave portion is formed on the transfer roller side, and the winding of the transfer material around the intermediate transfer member is likely to occur.

The transfer means 77 rotates the intermediate transfer member 75 at a constant speed or at a different peripheral speed. The transfer material 76 is conveyed between the intermediate transfer body 75 and the transfer means 77, and at the same time, a bias having a polarity opposite to the frictional charge of the toner is applied to the transfer means 77 from the transfer bias means. The toner image is transferred to the front side of the transfer material 76.

As the material of the transfer rotary member, the same material as that of the charging roller can be used. The preferable transfer process condition is that the contact pressure of the roller is 4.9 to 490 N.
/ M (5-500 g / cm) and the DC voltage is ± 0.2-
± 10 kV.

For example, the conductive elastic layer 77b of the transfer roller
Is polyurethane, ethylene-propylene-diene terpolymer (EPDM) in which conductive material such as carbon is dispersed
It is made of an elastic material having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the core 77a from a constant voltage power supply. The bias condition is ± 0.2 ~
± 10 kV is preferred.

Next, the transfer material 76 is conveyed to a fixing unit 81 having a heating roller having a built-in heating element such as a halogen heater and an elastic pressure roller pressed against the heating roller with a pressing force. The toner image is heated and pressed on the transfer material by passing between the roller and the pressure roller. A fixing method using a heater via a film may be used.

Next, the one-component developing method will be described. The toner of the present invention can be applied to a one-component developing method such as a magnetic one-component developing method and a non-magnetic one-component developing method. The magnetic one-component developing method will be described with reference to FIG.

In FIG. 6, the substantially right half peripheral surface of the developing sleeve 83 is always in contact with the toner reservoir in the toner container 84, and the toner T near the surface of the developing sleeve 83 is brought into contact with the developing sleeve surface by the magnetic generating means in the sleeve. With a magnetic force of 85 and /
Or, it is attached and held by electrostatic force. Developing sleeve 83
Is rotated, the magnetic toner layer on the sleeve surface is formed as a thin magnetic toner T1 having a substantially uniform thickness in the process of passing through the position of the regulating member 86. The magnetic toner is charged mainly by frictional contact with the sleeve surface accompanying the rotation of the developing sleeve 83, and the thin magnetic toner layer surface on the developing sleeve 83 moves toward the latent image holding member 87 along with the rotation of the developing sleeve 83. It rotates and passes through the developing area A, which is the closest part between the latent image holding member 87 and the developing sleeve 83. During this passage process, the magnetic toner of the magnetic toner thin layer on the side of the developing sleeve 83 is applied by the bias applying means 96 to the latent image holding member 87.
It flies by the DC and AC electric fields generated by the DC and AC voltages applied between the developing sleeve 83 and the developing sleeve 83, and reciprocates between the surface of the latent image holding member 87 in the developing area A and the surface of the developing sleeve 83 (gap α). Finally, the magnetic toner on the side of the developing sleeve 83 is selectively transferred and adhered to the surface of the latent image holding member 87 in accordance with the potential pattern of the latent image, and a toner image T2 is sequentially formed.

The developing sleeve surface, on which the magnetic toner has been selectively consumed after passing through the developing area A, is re-rotated into the toner reservoir of the toner container 84 to be re-supplied with the magnetic toner. The surface of the magnetic toner thin layer T1 of the developing sleeve 83 is transferred, and the developing step is repeatedly performed.

The regulating member 86 as the toner thinning means used in FIG. 6 is a doctor blade such as a metal blade or a magnetic blade disposed at a predetermined gap from the sleeve. Alternatively, a roller made of metal, resin or ceramic may be used instead of the doctor blade.

Further, an elastic blade (for example, 80 in FIG. 7) or an elastic roller which comes into contact with the surface of the developing sleeve (toner carrier) by an elastic force may be used as the toner thinning regulating member.

As the material for forming the elastic blade or the elastic roller, silicone rubber, urethane rubber, NBR
Rubber elastic body such as polyethylene terephthalate; and metal elastic body such as stainless steel, steel and phosphor bronze. A composite of them may be used.
Preferably, the sleeve contact portion is a rubber elastic body or a resin elastic body.

FIG. 7 shows an example in which an elastic blade is used.

The base on the upper side of the elastic blade 80 is fixed and held on the developer container side, and the lower side of the elastic blade 80 is
The inner surface of the elastic blade 80 (in the case of the reverse direction, the outer surface) is pressed against the surface of the developing sleeve 89 with an appropriate elasticity by bending the developing sleeve 89 in the forward or reverse direction against the elasticity of 0. To make contact. According to such an apparatus, a thin and dense toner layer can be obtained more stably with respect to environmental fluctuations.

When an elastic blade is used, a sleeve,
Although the toner easily fuses to the blade surface, the toner of the present invention is preferably used because of excellent releasability and stable triboelectric charging.

In the case of the magnetic one-component developing method, the blade 20
The contact pressure between the sleeve 19 and the sleeve 19 is 0.1 kg / m or more, preferably 0.3 to 2 as a linear pressure in the sleeve generatrix direction.
It is preferably 5 kg / m, more preferably 0.5 to 12 kg / m.

The gap α between the latent image holder 88 and the developing sleeve 89 is set to, for example, 50 to 500 μm.

It is most preferable that the thickness of the magnetic toner layer on the developing sleeve 89 is smaller than the gap α between the latent image holding member 88 and the developing sleeve 89. The thickness of the magnetic toner layer may be restricted to such an extent that some of the ears contact the latent image holding member 88.

The developing sleeve 89 is rotated at a peripheral speed of 100 to 200% with respect to the latent image holding member 88. The alternating bias voltage by the bias applying means 86 is 0.1 kV or more in peak to peak, preferably 0.2 to 3.0 k.
V, more preferably 0.3 to 2.0 kV. The alternating bias frequency is 0.5 to 5.0 kHz, preferably 1/0 to 3.0 kHz, and more preferably 1.5 to 5.0 kHz.
Used at ~ 3.0 kHz. As the alternating bias waveform, a waveform such as a rectangular wave, a sine wave, a sawtooth wave, and a triangular wave can be applied. Also, asymmetrical AC biases having different positive and reverse voltages and times can be used. It is also preferable to superimpose a DC bias.

Next, an example of a developing method for performing non-magnetic one-component development will be described with reference to FIG. Reference numeral 95 denotes a latent image holding member, and a latent image is formed by an electrophotographic process unit or an electrostatic recording unit (not shown). A developing sleeve 94 is made of a non-magnetic sleeve such as aluminum or stainless steel.

As the developing sleeve 94, a rough tube of aluminum or stainless steel may be used as it is, but preferably the surface is uniformly roughened by spraying spherical particles such as glass beads, mirror-finished, or resin. What is coated with is good.

The toner T is stored in the hopper 91 and is supplied onto the developing sleeve (toner carrier) 94 by the toner application roller 92. Toner application roller 92
A roller made of a foamed material of a porous elastic body (for example, a flexible polyurethane foam or the like) is preferably used.
The roller is rotated with respect to the developing sleeve 94 in a forward or reverse direction at a relative speed other than 0, and the developing sleeve 9 is rotated.
Along with the supply of the toner onto the developing sleeve 4, the toner on the developing sleeve 94 after the development (undeveloped toner) is also removed. At this time, the contact width (nip width) of the toner application roller 92 to the developing sleeve 94 is preferably 2.0 to 10.0 mm in consideration of the balance between toner supply and stripping.
4.0 to 6.0 mm is more preferable. Stress is applied to the toner, and the aggregation of the toner due to the deterioration of the toner is increased, or the toner is easily fused and fixed to the developing sleeve 94 and the toner application roller 92. However, the toner of the present invention has poor fluidity and releasability. Since it has excellent stability and durability, it is preferably used also in the developing device shown in FIG. Also,
Instead of the toner application roller 92, a brush roller made of a resin fiber such as nylon or rayon may be used.
The developing method shown in FIG. 9 is extremely effective in a one-component developing method using a non-magnetic one-component toner.

The toner supplied onto the developing sleeve 94 is thinly and uniformly applied by the regulating member 93. It is particularly preferable that the toner regulating member 93 presses the toner onto the surface of the developing sleeve 94 with an elastic blade or an elastic roller. As the elastic blade or the elastic roller, it is preferable to use a material of a triboelectric series suitable for charging the toner to a desired polarity. The regulating member 93 is preferably made of silicone rubber, urethane rubber, styrene-butadiene rubber, or the like. Furthermore, even if an organic resin layer such as polyamide, polyimide, nylon, melamine, melamine crosslinked nylon, phenolic resin, fluorine resin, silicone resin, polyester resin, urethane resin, styrene resin, and acrylic resin is provided on the regulating member 93. good.

The contact pressure between the elastic blade or the elastic roller and the developing sleeve 94 is 0.1 to 25 kg / m, preferably 0.5 to 12 kg, as the linear pressure in the sleeve generatrix direction.
/ M is effective, and by adjusting the contact pressure to 0.1 to 25 kg / m, it is possible to effectively loosen the aggregation of the toner, and to instantaneously raise the triboelectric charge amount of the toner. Becomes possible.

In a system in which a thin layer of toner is coated on the developing sleeve 94 with a blade, particularly in the non-magnetic one-component developing method, the developing sleeve 94 is attached to the latent image holding member 95 in order to obtain a sufficient image density. , 100-300
It is rotated at a peripheral speed of%. Preferably, it is rotated at a peripheral speed of 120 to 250%.

It is preferable that the thickness of the toner layer on the developing sleeve 94 is smaller than the length of the gap between the developing sleeve 94 and the latent image holding member 95 and an alternating electric field is formed in this gap. By applying an alternating electric field or a developing bias in which the alternating electric field is superimposed on a DC electric field to the developing sleeve 94 by the bias power supply 96, the transfer of the toner from the developing sleeve 94 to the latent image holding member 95 is facilitated, and further high quality is achieved. Images can be obtained.

In the present invention, it is preferable that the surface of the photoreceptor is provided with a releasability, and the contact angle of water on the surface of the photoreceptor is preferably 85 degrees or more. More preferably, the contact angle of water on the surface of the photoreceptor is 90 degrees or more.

The fact that the photosensitive member surface has a high contact angle
This indicates that the surface of the photoreceptor has high release properties, and this effect can significantly reduce the amount of toner remaining after transfer, greatly reducing the load in the cleaning process, and more reliably preventing the occurrence of defective cleaning. Can be prevented.

Further, since the surface of the photoreceptor has a high releasability, the amount of toner remaining after transfer can be remarkably reduced. Occasionally, the recovery efficiency of the transfer residual toner in the development area is also improved, and a positive ghost image is prevented.

Here, the mechanism of generation of a ghost image will be described.

The problem of light shielding by the transfer residual toner is particularly problematic when the surface of the photoreceptor is used repeatedly for one transfer material, that is, the length of one circumference of the photoreceptor is longer than the length of the transfer material in the traveling direction. If the transfer residual toner is short, the charge, exposure and development must be performed in a state where the transfer residual toner is present on the photoreceptor. Therefore, the potential on the surface of the photoreceptor where the transfer residual toner exists is not sufficiently reduced and the development contrast is insufficient. Therefore, the reversal development appears on the image as a negative ghost having a lower density than the surroundings.

On the other hand, if the cleaning effect of the transfer residual toner is insufficient at the time of development, the toner is developed on the surface of the photoreceptor where the transfer residual toner is present, so that the density is higher than the surrounding area and a positive ghost occurs. .

With the structure of the present invention, the ghost image described above can be essentially prevented.

In the image forming method of the present invention, it is effective when the surface of the photoreceptor is mainly composed of a polymer binder. For example, (i) a case where a protective film mainly composed of a resin is provided on an inorganic photoreceptor such as selenium or amorphous silicon; (ii) a charge transport material and a resin are used as a charge transport layer of a functionally separated organic photoreceptor. Having a surface layer with
(Iii) There is a case where the above-mentioned protective layer is further provided thereon. As means for imparting releasability to such a surface layer, a resin having a low surface energy is used for the resin constituting the film, additives for imparting water repellency and lipophilicity are added, and high releasability is provided. And dispersing the material having the above into a powder form. Is achieved by introducing a fluorine-containing group and a silicone-containing group into the structure of the resin.
, A surfactant may be added as an additive. For example, a compound containing a fluorine atom such as polytetrafluoroethylene, polyvinylidene fluoride and carbon fluoride may be used.

[0300] By these means, the contact angle of water on the surface of the photoreceptor can be made 85 degrees or more. If the contact angle of the photoreceptor surface with water is less than 85 degrees, the toner and the toner carrier are likely to deteriorate due to durability.

Of these, fluorine-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride are particularly preferred.
In the present invention, when a fluorine-containing resin is used as the releasable powder as the powder, the dispersion in the outermost surface layer is preferable.

In order to incorporate these powders on the surface, a layer in which the powders are dispersed in a binder resin is provided on the outermost surface of the photoreceptor, or an organic photosensitive material originally composed mainly of resin is used. In the case of a body, the powder may be dispersed in the outermost surface layer without newly providing a surface layer.

The amount of the powder added to the surface layer is 1 to 60% by mass, and more preferably 2 to 50% by mass, based on the total mass of the surface layer.
Is preferred. When the amount is less than 1% by mass, the residual toner of the transfer is not sufficiently reduced, the cleaning efficiency of the residual toner is not sufficient, and the ghost prevention effect is insufficient. When the amount is more than 60% by mass, the strength of the film is reduced. This is not preferable because the amount of light incident on the photosensitive member is significantly reduced. The particle size of the powder is preferably 1 μm or less, and more preferably 0.5 μm or less from the viewpoint of image quality. If it is larger than 1 μm, the line will be cut poorly due to scattering of incident light, which is not practical.

The present invention is particularly effective when the charging means is a contact charging method in which a charging member is brought into contact with a photosensitive member. That is, if there is a large amount of residual toner after cleaning, the residual toner adheres directly to the charging member in a later process, causing charging failure. Therefore, compared to corona discharge in which the charging means does not contact the photoconductor, the amount of residual toner is smaller,
It is necessary to make it hard to adhere.

One preferred embodiment of the photosensitive member used in the present invention will be described below.

As the conductive substrate, a metal such as aluminum or stainless steel; a plastic having a coating layer of an aluminum alloy or an indium oxide-tin oxide alloy;
Cylindrical cylinders and films of paper or plastic impregnated with conductive particles; plastic with conductive polymer;

On these conductive substrates, the adhesion of the photosensitive layer was improved, the coating property was improved, the substrate was protected, the defect was coated on the substrate,
An undercoat layer may be provided for the purpose of improving the charge injection property from the substrate and protecting the photosensitive layer against electrical breakdown.

The undercoat layer may be made of polyvinyl alcohol, poly-N-vinylimidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, nitrocellulose, ethylene-acrylic acid copolymer, polyvinyl butyral, phenol resin, casein, polyamide, copolymer nylon, glue, Made of gelatin, polyurethane or aluminum oxide material. The thickness of the undercoat layer is usually 0.1 to 10 μm, preferably 0.1 to 3 μm.
Is good.

The charge generation layer may be made of an azo pigment, a phthalocyanine pigment, an indigo pigment, a perylene pigment, a polycyclic quinone pigment, a squarylium dye, a pyrylium salt, a thiopyrylium salt, a triphenylmethane dye or selenium or amorphous. An inorganic charge generating substance such as silicon is dispersed in a suitable binder and coated or formed by vapor deposition. Of these, phthalocyanine pigments are preferred for adjusting the sensitivity of the photoreceptor to a sensitivity suitable for the present invention. As the binder, a wide range of binder resins can be selected, for example, polycarbonate resin, polyester resin, polyvinyl butyral resin, polystyrene resin, acrylic resin, methacryl resin, phenol resin, silicone resin, epoxy resin, vinyl acetate resin. No. The amount of the binder contained in the charge generation layer is 80% by mass or less, preferably 0% by mass.
The content is preferably up to 40% by mass. The thickness of the charge generation layer is 5
μm or less, particularly preferably 0.05 to 2 μm.

[0310] The charge transport layer has a function of receiving charge carriers from the charge generation layer in the presence of an electric field and transporting them. The charge transporting layer is formed by dissolving a charge transporting substance in a solvent together with a binder resin if necessary, and applying the solution. The film thickness is generally 5 to 40 μm. As the charge transport material, biphenylene,
Polycyclic aromatic compounds such as anthracene, bilen and phenanthrene; nitrogen-containing cyclic compounds such as indole, carbazole, oxadiazole and pyrazoline; hydrazone compounds; styryl compounds; selenium; selenium-tellurium;
Amorphous silicon; cadmium sulfide.

Examples of the binder resin for dispersing these charge transport materials include polycarbonate resin, polyester resin,
Resins such as polymethacrylate, polystyrene resin, acrylic resin and polyamide resin; organic photoconductive polymers such as poly-N-vinylcarbazole and polyvinylanthracene.

[0312] A protective layer may be provided as a surface layer. As the resin of the protective layer, polyester, polycarbonate, acrylic resin, epoxy resin, phenol resin, or a curing agent of these resins is used alone or in combination of two or more.

The conductive particles may be dispersed in the resin of the protective layer. Examples of the conductive fine particles include metals and metal oxides. Preferably, zinc oxide, titanium oxide,
There are ultrafine particles of tin oxide, antimony oxide, indium oxide, bismuth oxide, tin oxide-coated titanium oxide, tin-coated indium oxide, antimony-coated tin oxide, or zirconium oxide. These may be used alone or as a mixture of two or more. In general, when particles are dispersed in the protective layer, it is necessary that the particle size of the particles is smaller than the wavelength of the incident light in order to prevent scattering of the incident light by the dispersed particles, and the conductivity dispersed in the protective layer The particle size of the insulating particles is preferably 0.5 μm or less. The content in the protective layer is preferably from 2 to 90% by mass, more preferably from 5 to 80% by mass, based on the total mass of the protective layer. The thickness of the protective layer is preferably from 0.1 to 10 μm, more preferably from 1 to 7 μm.

The surface layer can be applied by spray coating, beam coating or permeation (dipping) coating of the resin dispersion.

The preferable conditions of the developing step used in the present invention are that the developer and the surface of the photoreceptor are in contact, and that the reversal developing method is used. When the two-component magnetic brush developing method is used, ferrite, magnetite, iron powder or those coated with an acrylic resin, a silicone resin, a fluororesin or the like are used as the carrier. At this time, at the time of development or at the time of blank before and after the development, a bias of a DC or AC component is applied to control the potential so that the development and the remaining toner on the photoreceptor can be collected. At this time, the DC component is located between the light portion potential and the dark portion potential.

In the case of a one-component developer, a method is also used in which an elastic roller is used as a toner carrier, and a toner layer formed by coating the surface of the elastic roller with toner is brought into contact with the surface of the photoreceptor. At this time, the toner may be either magnetic or non-magnetic, and it is important that the toner layer is in contact with the surface of the photoreceptor. The toner carrier is substantially in contact with the photoconductor surface, which means that the toner carrier is in contact with the photoconductor surface when the toner layer is removed from the toner carrier. At this time, in order to obtain an image having no edge effect due to an electric field acting between the photosensitive member surface and the elastic roller facing the photosensitive member surface via the toner layer, the surface of the elastic roller or the vicinity thereof has a potential. It is necessary to have an electric field between the photoreceptor surface and the toner carrying surface. For this reason, it is also possible to use a method in which the elastic rubber of the elastic roller is resistance-controlled in the medium resistance region to keep the electric field while preventing conduction with the photoreceptor surface, or to provide a thin insulating layer on the surface layer of the conductive roller. . In addition, a conductive resin sleeve whose outer surface facing the photoconductor surface of the conductive roller is coated with an insulating material, or a configuration in which a conductive layer is provided on the inner surface of the insulating sleeve that does not face the photoconductor surface are also possible. It is. It is also possible to adopt a configuration in which a rigid roller is used as the toner carrier and the photosensitive member is made flexible such as a belt. Developing roller 29 as toner carrier
Is preferably in the range of 10 ² to 10 ⁹ Ω.

The electric resistance of the developing roller is measured by the following method. That is, as shown in FIG. 25, the aluminum roller 131 having a diameter of 16 mm and the developing roller 132 are brought into contact with each other.
9 N (500 g), and the aluminum roller 131 is rotated at 2 rps. Next, V ₁ =
A DC voltage of 400 V is applied. Variable resistor R on earth side
Are arranged, the voltage V ₂ at both ends thereof is measured while adjusting the resistance value of the variable resistor R according to the developing roller 132, and the current value is calculated to calculate the electric resistance of the developing roller 132.

When the one-component contact developing method is used, the surface of the developing roller carrying the toner may be rotated in the same direction as the moving direction of the surface of the photoreceptor, or may be rotated in the opposite direction. When the rotation is in the same direction, it is desirable that the peripheral speed ratio is higher than 100% with respect to the peripheral speed of the photoconductor. 1
If it is less than 00%, the image quality is poor. The higher the peripheral speed ratio, the greater the amount of toner supplied to the development site, the more frequently the toner is attached to and detached from the latent image, and unnecessary portions are scraped off and added to necessary portions repeatedly. As a result, an image faithful to the latent image can be obtained. Specifically, the moving speed of the surface of the toner carrier is preferably 1.05 to 3.0 times the moving speed of the surface of the photoconductor.

Hereinafter, the transfer step applicable to the image forming method of the present invention will be specifically described.

In the transfer step, it is preferable to use a contact transfer method in which a toner image is electrostatically transferred to a transfer material while a transfer means is in contact with the surface of the photoreceptor via a transfer material.
The contact pressure of the transfer means against the photoreceptor surface is preferably at least a linear pressure of 2.9 N / m (3 g / cm), and more preferably 9.8 to 490 N / m (10 to 490 N / m).
(500 g / cm). If the linear pressure as the contact pressure is less than 2.9 N / m (3 g / cm), it is not preferable because the transfer of the transfer material and the occurrence of transfer failure tend to occur. If the contact pressure is too high, the surface of the photoconductor is deteriorated and toner adheres, and as a result, the toner is fused to the surface of the photoconductor.

As a transfer means in the contact transfer step,
An apparatus having a transfer roller or a transfer belt is used. The transfer roller has at least a core metal and a conductive elastic layer covering the core metal, and the conductive elastic layer has a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm such as urethane or EPDM in which conductive particles such as carbon are dispersed. Made of elastic material.

The present invention is particularly effectively used in an image forming apparatus in which the surface of a photoreceptor is an organic compound. That is, when the organic compound forms the surface layer of the photoreceptor, since the adhesiveness to the binder resin contained in the toner particles is higher than that of another photoreceptor using an inorganic material, the transferability is improved. It has a technical problem that it tends to decrease. Therefore, the effect of high transferability by the toner used in the present invention becomes more remarkable.

Examples of the surface material of the photoreceptor according to the present invention include silicone resin, vinylidene chloride, ethylene-vinyl chloride, styrene-acrylonitrile, styrene-methyl methacrylate, styrene, polyethylene terephthalate, and polycarbonate. There is no limitation, and other monomers or copolymers and blends of the above-mentioned binder resins can be used.

In the present invention, the present invention is particularly effectively used for an image forming apparatus having a drum-shaped photosensitive member having a small diameter of 50 mm or less. That is, in the case of a small-diameter photosensitive drum, pressure concentration at the contact portion of the contact member at the same linear pressure is likely to occur. Although it is considered that the same phenomenon occurs in the belt photoconductor, the present invention is also effective for an image forming apparatus using a photoconductor belt having a radius of curvature of 25 mm or less at the contact portion.

Further, in the present invention, it is desirable to control the total charge amount of the toner during development in order to impart high charge to the toner. Therefore, the surface of the toner carrier according to the present invention is preferably covered with a resin layer in which conductive fine particles and / or a lubricant are dispersed.

As a charging method, a known corona charging method called corotron or scorotron is used, and a method using a pin electrode can also be used. A contact charging method in which a charging member is skillfully brought into contact with the photoreceptor surface to perform charging can also be used.

In the present invention, it is particularly effective when the charging means is a contact charging method in which the charging member is brought into contact with the surface of the photosensitive member. That is, compared to non-contact corona discharge in which the charging means does not come into contact with the photoreceptor surface, the contact charging method is liable to cause deterioration of the photoreceptor surface, and from the viewpoint of durability, an increase in untransferred toner due to a decrease in transferability. There is a technical problem that cleaning performance is in a severe direction. Therefore, the effect of the high transferability used in the present invention becomes more remarkable.

As a preferable process condition when the charging roller is used as the contact charging member, the contact pressure of the charging roller is 4.9 to 490 N / m (5 to 500 g / cm), and more preferably 9.8 to 490 N / m. 392 N / m (10 to 400 g
/ Cm). Further, a DC voltage is preferably applied in order to make the polarity of the transfer residual toner the same as the charge polarity of the photoreceptor and facilitate recovery during development, but an AC voltage is superimposed on the DC voltage. 2 × Vth (V)
It is preferable that an AC voltage having a peak-to-peak voltage less than [Vth; discharge start voltage (V) in DC application] is superimposed on the DC voltage.

Other contact charging members include a method using a charging blade and a method using a conductive brush. These contact charging means have the effects of eliminating the need for high voltage and reducing the generation of ozone.

In the case of a roller or a blade as the contact charging member, a conductive metal such as iron, copper or stainless steel; a carbon dispersed resin; a metal or a metal oxide dispersed resin is used as the conductive substrate. In the case of a blade,
The shape can be a bar or a plate. As the configuration of the elastic roller, one having an elastic layer, a conductive layer, and a resistance layer provided on a conductive base is used.

The elastic layer may be made of rubber or rubber foam such as chloroprene rubber, isoprene rubber, EPDM rubber, polyurethane rubber, epoxy rubber and butyl rubber, sponge, styrene-butadiene thermoplastic elastomer, polyurethane thermoplastic elastomer, polyester It can be formed of a thermoplastic elastomer such as a thermoplastic thermoplastic elastomer and an ethylene-vinyl acetate thermoplastic elastomer.

[0332] The conductive layer preferably has a volume resistivity of 10
⁷ Ω · cm or less, more preferably 10 ¹ to 10 ⁶ Ω · cm
Good to be. As the conductive layer, for example, a metal deposition film, a conductive particle dispersed resin, a conductive resin, or the like is used.
Specific examples include vapor-deposited films of conductive metals such as aluminum, indium, nickel, copper, and iron; carbon,
Conductive particle-dispersed resin in which conductive particles such as aluminum, nickel and titanium oxide are dispersed in a resin such as urethane, polyester, vinyl acetate-vinyl chloride copolymer and polymethyl methacrylate; quaternary ammonium salt-containing polymethacrylic acid Examples include conductive resins such as methyl, polyvinylaniline, polyvinylpyrrole, polydiacetylene, and polyethyleneimine.

The resistive layer has a volume resistivity of 10 ⁶ to 10 ¹² Ω.
・ It is good to be a layer of cm. As the resistance layer, a semiconductive resin or a conductive particle dispersed insulating resin can be used. As the semiconductive resin, for example, ethyl cellulose,
Nitrocellulose, methoxymethylated nylon, ethoxymethylated nylon, copolymerized nylon, polyvinyl hydrin or casein is used. As the conductive particle dispersed resin, for example, carbon, aluminum, indium oxide, conductive particles such as titanium oxide in urethane, polyester, vinyl acetate-vinyl chloride copolymer, insulating resin such as polymethyl methacrylate. Examples thereof include those dispersed in a small amount.

As the conductive brush as a contact charging member, a brush whose resistance is adjusted by dispersing a conductive material in generally used fibers is used. As the fibers, generally known fibers can be used, and examples thereof include nylon, acrylic, rayon, polycarbonate, and polyester. As the conductive material, generally known conductive materials can be used. For example, conductive metals such as copper, nickel, iron, aluminum, gold and silver; iron oxide, zinc oxide, tin oxide, antimony oxide, and oxide An oxide of a conductive metal such as titanium; or a conductive powder such as carbon black may be used. In addition, these conductive materials may be subjected to a surface treatment for the purpose of hydrophobicity and resistance adjustment as required. At the time of use, it is selected and used in consideration of dispersibility with fibers and productivity.

The conductive brush may have a fiber thickness of 1 to 20 denier (fiber diameter of about 10 to 500 μm),
The length of the brush fiber is preferably 1 to 15 mm, and the brush density is preferably 10,000 to 300,000 per square inch (about 1.5 × 10 ^{7 to} 4.5 × 10 ⁸ per square meter). Used.

The image forming method of the sixth embodiment will be described with reference to the accompanying drawings.

FIG. 22 is a diagram schematically showing an image forming apparatus having a process cartridge from which a cleaning unit having a cleaning member such as a cleaning blade has been removed as an example of an embodiment of the image forming method of the present invention 6. .

The photosensitive member 36 is charged by the charging roller 31 as a contact charging means, and the image portion is exposed by the laser light 40 to form an electrostatic latent image. The toner 30 stored in the developing device 32 is applied to the toner application roller 35 and the application blade 3.
3 is applied onto the toner carrier 34, and the toner carrier 3
The toner image on the photoconductor 36 is formed by bringing the toner layer on the photoconductor 4 into contact with the surface of the photoconductor 36 and developing the electrostatic latent image on the photoconductor 36 by a reversal development method. At least a DC bias is applied to the toner carrier 34 by a bias applying unit 41. The toner image on the photoreceptor 36 is transferred onto a recording material 38 as a transferred transfer material by a bias applying unit 42.
The toner image transferred by the transfer roller 37, which is a transfer unit to which a bias is applied, and transferred onto the recording material is fixed by the heat and pressure fixing unit 43 having a heating roller and a pressure roller.

The transfer residual toner on the photoreceptor 36 after the transfer step is conveyed to the charging roller 31 without going through a cleaning step using a cleaning member such as a blade cleaning unit. The photoconductor 36 having the transfer residual toner is charged again by the charging roller 31, and after the charging, an electrostatic latent image is formed by exposure to the laser beam 40. The photoreceptor 36 having the transfer residual toner collects the transfer residual toner on the toner carrier 34 while developing the electrostatic latent image with the toner on the toner carrier 34. The toner image on the photoconductor 36 after the development simultaneous cleaning step is
The image is transferred onto the conveyed recording material 38 by the transfer roller 37. After the transfer process, the photosensitive member 36 is
, And the same steps are repeated thereafter.

In the reversal development method, preferable development conditions for performing simultaneous development cleaning include a dark portion potential (V _d ) and a bright portion potential (V ₁ ) on the surface of the photoreceptor, and a DC bias applied to the toner carrier. (V _DC ) and | V _d −
V _DC |> | V ₁ −V _DC | More preferably, the value of | V _d -V _DC |
It is better that the value is 10 V or more than the value of V ₁ −V _DC |.

FIG. 15 shows another example of the image forming apparatus capable of smoothly removing the toner that has contributed to the development from the developing sleeve in addition to supplying the toner to the developing sleeve as the toner carrier. .

In FIG. 15, reference numeral 1 denotes a photosensitive drum, around which a primary charging roller 2 as contact charging means, a developing device 8 as developing means, and a transfer charging roller 2 as contact transferring means.
1. A register roller 19 is provided. The photosensitive drum 1 is driven by the primary charging roller 2 to, for example, -700V.
Is charged. The applied voltage by the bias applying means 5 is, for example, a DC voltage of -1350V. Then, the photosensitive drum 1 is exposed by irradiating the photosensitive drum 1 with a laser beam 7 by a laser generator 6, and a digital electrostatic latent image is formed. The electrostatic latent image on the photosensitive drum 1 is developed with the non-magnetic one-component toner 15 by the developing device 8, and the bias voltage is applied to the photosensitive drum 1 via the recording material 20 as a transfer material by the bias applying means 24. Is transferred onto the recording material 20 by the transfer roller 21 to which is applied. Toner image 26
Is transported by a conveyor belt 25 to a heat-pressure fixing device 27 having a heating roller 28 and a pressure roller 29 and is fixed on the recording material 20.

The charging roller 2 basically has a core metal 4 at the center and a conductive elastic layer 3 forming the outer periphery thereof.

As shown in FIG. 19, the developing device 8 contacts the photosensitive drum 1 with the toner layer on the developing sleeve 9 as a toner carrier, and applies a bias to the core metal 10 and the elastic layer. A developing sleeve as a toner carrying member including an elastic roller 9 having an elastic roller 11 is provided. A toner application roller 13 having a core metal 13 to which a bias is applied by a bias applying unit 17 and an elastic layer 14 is provided in the developing device 8. A toner regulating blade 16 is provided as a member for regulating the amount of toner attached to and transported to the developing sleeve 9, and the amount of toner (toner layer) transported to the developing area by the contact pressure of the toner regulating blade 16 against the developing sleeve 9. Thickness) is controlled. In the developing area, at least a DC developing bias is applied to the developing sleeve 9, and the toner layer on the developing sleeve contacts the surface of the photosensitive drum 1 and transfers onto the photosensitive drum 1 according to the electrostatic latent image to form a toner image. Form.

In order to carry out the development simultaneous cleaning, when the potential of the light portion of the photosensitive drum 1 is 0 to 250 V and the potential of the dark portion is 300 to 1000 V, the supply bias voltage applied by the bias applying means 17 is reduced. 100
To 900 V, and the developing bias voltage applied by the bias applying means 18 is preferably 100 to 900 V. Further, the supply bias voltage applied by the bias applying means 17 is 10 to 40 in absolute value more than the developing bias voltage applied by the bias applying means 18.
A larger value of 0 V is preferable because the supply of the non-magnetic toner 15 to the developing sleeve 9 and the stripping of the non-magnetic toner from the developing sleeve 9 are performed smoothly.

With respect to the rotation direction of the developing sleeve 9, the surfaces of the toner application rollers 12 move in the counter direction as indicated by the arrows (the rotation directions are the same).
It is preferable in terms of supplying and stripping non-magnetic toner.

The image forming apparatus shown in FIG. 15 employs an image forming method of directly transferring a toner image formed on an image carrier to a recording material without using an intermediate transfer member.

Next, the toner image formed on the image carrier is subjected to a first transfer onto an intermediate transfer member as a transfer material, and the toner image transferred onto the intermediate transfer member is subjected to a second transfer onto a recording material. An image forming method for performing the following will be described using an image forming apparatus shown in FIG.

In FIG. 18, a charging roller 52, which rotates in contact with a photosensitive drum 51 as an image carrier, gives a surface potential on the photosensitive drum 51, and forms an electrostatic latent image by exposure means 53. The electrostatic latent image is developed with four color toners of magenta toner, cyan toner, yellow toner, and black toner by developing units 54, 55, 56, and 57 of a one-component contact developing system, and a full-color toner image is formed. At the time of development, each of the developing devices 54, 55,
When one of 56 and 57 moves, the toner carrier of the developing device comes into contact with the surface of the photosensitive drum 51 to perform the development, and after the development, the developing device moves to the original position again. The toner carrier is separated from the surface of the photosensitive drum 51. This operation is repeated four times for each developing device. The toner image is transferred onto the intermediate transfer material 58 for each color, and is repeated a plurality of times to form a multiple toner image.

As the intermediate transfer member 58, a drum-shaped one is used, and a holding member is stretched on the outer peripheral surface, and a conductivity providing member such as carbon black, zinc oxide, tin oxide,
What has an elastic layer (for example, nitrile butadiene rubber) in which silicon carbide or titanium oxide is sufficiently dispersed is used. A belt-shaped intermediate transfer member may be used.

The hardness of the intermediate transfer member 58 formed on the surface of the support member 59 is 10 to 50 degrees (JIS K-6301).
In the case of a transfer belt, it is preferable that the transfer portion to a transfer material (recording material) is formed of a support member having the elastic layer 60 having this hardness.

In the transfer from the photosensitive drum 51 to the intermediate transfer member 58, a transfer current is obtained by applying a bias from a power source 66 to a metal core 59 as a support member of the intermediate transfer member 58, and the transfer of the toner image is performed. Done. Corona discharge or roller charging from the back surface of the holding member or the belt may be used.

The multi-toner image on the intermediate transfer member 58 is collectively transferred onto the recording material S by the transfer means 61. As the transfer unit, a contact electrostatic transfer unit using a corona charger, a transfer roller, or a transfer belt is used.

The recording material S having the toner image was
A fixing nip portion between the fixing roller 68 and the pressure roller 69 of the heat fixing device 70 having a fixing roller 68 as a fixing member having the fixing member 7 therein and a pressure roller 69 for pressing the fixing roller 68 is formed. As the S passes, the toner image is fixed on the recording material S.

The toner containing carbon black used in the present invention is used as a black toner in one of the developing units 54, 55, 56 and 57 of the above-mentioned image forming apparatus, and the remaining toner is used as the black toner. The three developing units use three chromatic color toners. The black toner used in the present invention is used for forming a color image or a full-color image in combination with a chromatic color toner, or for forming a monochrome image using only the black toner.

In the image forming apparatus shown in FIG.
The developing device 54 moves to a position where development can be performed, development is performed, the developed toner image is transferred to the intermediate transfer member 58, and the toner remaining on the surface of the photosensitive drum 51 after the first transfer is The developer is collected and cleaned by the developing device 54. When the toner remaining on the surface of the photosensitive drum 51 is collected by the developing device 54, the developing device 54 moves and returns to the original position, and then moves to a position where the developing device 55 can perform development. The operation is the same as that of the developing device 54, and the developing devices 55 and 56 also operate in the same manner. 65 is the second
Is a cleaner (second cleaning means) having a cleaning member 64 for removing toner remaining on the surface of the intermediate transfer member 58 after the transfer of the toner image.

The image forming method using the two-component contact developing method will be described with reference to FIGS.

FIG. 20 shows image formation using a developing device using a two-component developer for magnetic brush development, which is used as an example of the image forming method of the present invention 6 and used in an example described later. The apparatus will be described with reference to a schematic diagram.

In FIG. 20, a charging brush roller 75 (charging means for charging the photoreceptor 72) (a fiber having a thickness of 6 denier and a brush having a length of 3 mm, the resistance of which is adjusted by dispersing carbon black in nylon fiber) is 3 mm. , Brush density is 1
(100,000 lines per square inch, rotated at a peripheral speed of 120% in the opposite direction to the rotation of the photoconductor), contacted with the photoconductor 72, applied with a bias, charged, and exposed to laser light 76 (600 dp).
i, binary), an electrostatic latent image is formed on the photoconductor 72. A magnetic brush formed of a two-component developer having a toner and a magnetic carrier on a developer carrier 71 of a developing device 85 is brought into contact with the photoconductor 72, and an electrostatic latent image on the photoconductor 72 is formed by a reversal development method. To form a toner image.

At least a DC bias is applied to the developer carrying member 71 by a bias applying means (setting is performed so that the developing contrast becomes 500 V as a DC component.
1.8 kV is applied as an AC component).

The toner image on the photosensitive member 72 is transferred to a recording material 74 as a transferred transfer material by a transfer corona charger 73 (not in contact with the photosensitive member 72) as a transfer means. The upper toner image is fixed on the recording material 74 by a heat-pressure fixing unit having a heating roller 77 including a heater 78 and a pressure roller 79. The transfer residual toner on the photoconductor 72 after the transfer process does not pass through the cleaning process. The photoconductor 72 that has been neutralized by the erase exposure 81 is charged again by the charging brush roller 75, and forms an electrostatic latent image by the exposure 76. The photoreceptor 72 having the transfer residual toner is subjected to the development of the electrostatic latent image by the magnetic brush on the developer carrier 71 and the transfer residual toner is collected on the developer carrier 71. The toner image on the photoconductor 72 after the development simultaneous cleaning step is transferred onto the conveyed recording material 74 by the transfer corona charger 73, and the photoconductor 72 after the transfer step is subjected to erase exposure 8
1, the charge is removed by the charging brush roller 75,
Thereafter, similar steps are repeatedly performed.

FIG. 21 is an enlarged view of the developing section of FIG. In FIG. 21, a photoconductor 72 and a developer carrier 71
It is in contact with the magnetic brush formed of the two-component developer 90 above.

The developer carrier 71 is made of a non-magnetic material such as aluminum or SUS316.
The developer carrier 71 has a horizontally long opening formed in the longitudinal direction of the container on the lower left wall of the developing device 85 so that a substantially right half circumferential surface protrudes into the developing device 85, and a left side half circumferential surface is exposed to the outside of the container and is rotatable. It is mounted horizontally on a bearing and is driven to rotate in the direction of the arrow.

A fixed permanent magnet (magnet) as a fixed magnetic field generating means inserted into the developer holding member 71 and positioned and held in the position and orientation shown in the drawing. Even when the developer holding member 71 is driven to rotate, this magnet 94 Is fixedly held at the position and posture shown in the figure. This magnet 94 has N magnetic poles 92,
95 and 96, and five magnetic poles 91 and 93 of the south pole. The magnet 94 may be provided with an electromagnet instead of a permanent magnet.

Reference numeral 83 denotes a non-magnetic blade as a developer regulating member having a base fixed to the side wall of the container on the upper edge side of the developer supply opening provided with the developer carrying member 71.
S316 is bent into an L-shape as shown in the cross section road map.

Reference numeral 84 denotes a non-magnetic blade (developer regulating member)
A magnetic carrier limiting member having an upper surface in contact with the lower surface side of 83 and a front end surface as a developer guide surface. Non-magnetic blade 83
The portion constituted by the magnetic carrier return member 84 and the like is a regulating portion.

Reference numeral 90 denotes a developer layer having a toner and a magnetic carrier. 86 is a non-magnetic toner.

Reference numeral 97 denotes a toner density detection sensor (not shown)
Is a toner supply roller that operates according to the output obtained from the toner supply roller. As the sensor, the developer volume detection method,
A piezoelectric element, an inductance change detection element, an antenna system using an alternating bias, and a system for detecting optical density can be used. The non-magnetic toner 86 is supplied by rotating or stopping the roller. The fresh developer supplied with the toner 86 is mixed and stirred while being transported by the developer transport roller 87. Accordingly, a tribo is applied to the replenished toner during this conveyance.
Reference numeral 88 denotes a partition plate which is cut out at both ends in the longitudinal direction of the developing device. At this portion, the fresh developer conveyed by the screw 87 is delivered to the screw 89.

The N magnetic pole 96 is a carrier pole. The collected developer after the development is collected in the container, and the developer in the container is further transported to the regulating section.

In the vicinity of the N magnetic pole 96, the fresh developer conveyed by the screw 89 provided close to the developer carrier 71 and the recovered developer after development are exchanged.

The distance d between the end of the non-magnetic blade 83 and the surface of the developer carrier 1 was 400 μm. A preferable setting range of d is 100 to 900 μm. This distance is 100μ
If the particle size is smaller than m, the carrier particles are clogged during this time, the developer layer tends to be uneven, and the developer necessary for good development cannot be applied, and only a developed image with a low density and many unevenness can be obtained. There is. On the other hand, if this distance is 9
When the thickness is larger than 00 μm, the amount of the developer applied on the developer carrying member 71 increases, and a predetermined developer layer thickness cannot be regulated. As a result, the adhesion of the magnetic particles to the latent image carrying member increases and the developer circulates. The development restriction by the developer limiting member 84 is weakened, and toner tribo tends to be insufficient and fogging tends to occur.

The thickness of the developer layer on the developer carrier 71 is
It is preferable that the gap distance between the developer carrier 71 and the photoconductor 72 be slightly larger than the gap distance between the developer carrier 71 and the photoconductor 72. This distance is 400μ
m. Preferably, the thickness is set to 50 to 800 μm.

The methods for evaluating various physical properties of the toner will be described below.

Measurement of Particle Size Distribution of Toner A Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Inc.) is used as a measuring device. Electrolyte is about 1% using primary sodium chloride
Prepare an aqueous NaCl solution. For example, ISOTON-I
I (manufactured by Coulter Scientific Japan) can be used. As a measuring method, the electrolytic solution 100
0.1 to 5 ml of a surfactant (preferably an alkylbenzene sulfonate) as a dispersant in ~ 150 ml
, And 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles were measured for each channel using the above-mentioned measuring device using a 100 μm aperture as an aperture. Then, the volume distribution and the number distribution of the toner are calculated. Then, the weight-average particle diameter (D) of the toner on a weight basis determined from the volume distribution of the toner particles.
4) (the median value of each channel is set as a representative value for each channel).

The channels are 2.00 to 2.52
μm; 2.52 to 3.17 μm; 3.17 to 4.00 μm
m; 4.00 to 5.04 μm; 5.04 to 6.35 μm
m; 6.35 to 8.00 μm; 8.00 to 10.08 μm
m; 10.08 to 12.70 μm; 12.70 to 16.
00 μm: 16.00 to 20.20 μm;
25.40 μm; 25.40 to 32.00 μm;
13 channels of 40.30 μm are used.

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

Coefficient of variation A = [S / D1] × 100 [where S represents a standard deviation value in the number distribution of toner particles, and D1 represents the number average particle diameter of toner particles (μm)]
Show)

Measurement of Toner Charge in Each Environment The environmental charge is measured by the following method after the toner and the carrier are allowed to stand all day and night under each environmental condition.

For example, room temperature and normal humidity (23 ° C./60% R
H), the triboelectric charge of the toner is measured based on the blow-off method in an environment of high temperature / high humidity (30 ° C./80% RH) and low temperature / low humidity (15 ° C./10% RH).

FIG. 1 is an explanatory view of an apparatus for measuring a triboelectric charge amount of a toner. First, in a metal measuring container 2 having a 500-mesh screen 3 at the bottom, a mixture of a toner and a carrier having a mass ratio of 1:19 to be measured for a triboelectric charge amount is put into a polyethylene bottle having a volume of 50 to 100 ml. Shake by hand for 5 to 10 minutes, add about 0.5 to 1.5 g of the mixture (developer) and close the metal lid 4. At this time, the mass of the entire measurement container 2 is weighed and is defined as W1 (g). Next, in the suction device 1 (at least a portion in contact with the measurement container 2 is an insulator), the pressure of the vacuum gauge 5 is adjusted to 250 mmAq by adjusting the air volume control valve 6 by suctioning from the suction port 7. In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction. The potential of the electrometer 9 at this time is set to V (volt). Here, reference numeral 8 denotes a capacitor, whose capacity is C (μF). The weight of the entire measurement container after suction is weighed and is referred to as W2 (g). The triboelectric charge (mC / kg) of this toner is calculated as in the following equation.

[0381]

(Equation 5)

Measurement of Friction Charge of Toner on Development Sleeve The friction charge of toner on the development sleeve is obtained by using a suction type Faraday gauge method.

In the suction-type Faraday gauge method, the outer cylinder is pressed against the surface of the developing sleeve to suction toner on a fixed area on the developing sleeve, and the toner is collected by a filter of the inner cylinder, and the amount of suction is calculated based on the increase in the mass of the filter. The mass of the toner obtained can be calculated. At the same time, by measuring the amount of electric charge accumulated in the inner cylinder electrostatically shielded from the outside, the amount of triboelectric charge of the toner on the developing sleeve can be obtained.

[0384]

<Example 1> Deionized water 13 in a reaction vessel
To 000 parts by mass, 135 parts by mass of a 0.1M-Na ₃ PO ₄ aqueous solution and 130 parts by mass of a 1M-HCl aqueous solution were added, and the mixture was kept at 65 ° C. for 60 minutes while purging with N ₂ . TK
1200 using a homo homomixer (manufactured by Tokushu Kika Kogyo)
While stirring at 0 rpm, 80 parts by mass of a 1.0 M CaCl ₂ aqueous solution was added all at once to prepare an aqueous medium containing a calcium phosphate salt having a pH of 5.8.

・ Styrene 165 parts by mass ・ n-butyl acrylate 35 parts by mass ・ Coloring agent (copper phthalocyanine pigment) 13 parts by mass ・ Di-t-butylsalicylic acid metal compound 1 part by mass ・ Polyester resin 15 parts by mass (terephthalic acid-propylene) Oxide-modified bisphenol A, acid value 15, peak molecular weight 6000) 30 parts by mass of ester-based wax (release agent No. 5) 0.5 part by mass of crosslinking agent (diethylene glycol dimethacrylate)

In a separate container, the above material was kept at 65 ° C.
Using a K-type homomixer (manufactured by Tokushu Kika Kogyo), 12
It was uniformly dissolved and decomposed at 000 rpm. Into this, 5 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

In the above-mentioned aqueous medium in the reaction vessel, the above-mentioned polymerizable
The monomer composition is charged, and 65 ° C, N _TwoSmell under purge
For 3 minutes at 10,000 rpm with TK homomixer
After stirring, the polymerizable monomer composition was granulated. Then pad
6 hours at 70 ° C while stirring with a stirring blade
The temperature was raised and the reaction was carried out for 2 hours.

After the completion of the polymerization reaction, the reaction vessel was cooled, hydrochloric acid was added to dissolve the calcium phosphate salt, and then filtered, washed with water and dried to obtain cyan toner particles. When the cross section of the cyan toner particles was observed by TEM, FIG.
As shown in the figure, it was confirmed that the release agent was well encapsulated in the outer shell resin.

[0389] 100 parts by mass of the obtained cyan toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by a BET method were mixed to obtain a negatively triboelectrically-chargeable cyan toner. Obtained. The weight average particle size of the obtained cyan toner was 6.9 μm.

A developer was prepared by mixing 95 parts by mass of an acrylic-coated ferrite carrier with 5 parts by mass of the cyan toner, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

Example 2 As a crosslinking agent, polyethylene glycol dimethacrylate (n = 4 in the formula 1) was used in an amount of 0.8.
Parts by weight of wax and release agent No. A magenta toner was obtained in the same manner as in Example 1, except that the acid value of the polar resin was changed to 10, the pH of the aqueous medium was changed to 6.5, and the colorant was changed to dimethylquinacridone. When the cross section of the magenta toner particles was observed by TEM, it was confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

100 parts by mass of the obtained magenta toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the BET method were mixed to obtain a negatively triboelectrically-chargeable magenta toner. Obtained. The weight average particle size of the obtained magenta toner was 7.2 μm.

A developer was prepared by mixing 5 parts by weight of this magenta toner with 95 parts by weight of an acryl-coated ferrite carrier to prepare a developer. A commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a modified machine, a continuous paper passing test of 10,000 sheets of magenta toner (under normal temperature and normal humidity) was performed. Table 1 shows the results.

Example 3 The coloring agent was C.I. I. Pigment Yellow 17 and a yellow toner were obtained in the same manner as in Example 1 except that the acid value of the polar resin was changed to 10. When the cross section of the yellow toner particles was observed by TEM, it was confirmed that the release agent was well encapsulated in the shell resin as shown in FIG.

100 parts by weight of the obtained yellow toner particles and 1.5 parts by weight of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by a BET method were mixed to obtain a negatively triboelectrically-chargeable yellow toner. Obtained. The weight average particle size of the obtained yellow toner was 7.0 μm.

A developer was prepared by mixing 5 parts by weight of this yellow toner with 95 parts by weight of an acryl-coated ferrite carrier to prepare a developer. A commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. 4 was used. Using a modified machine, a 10,000-sheet continuous paper passing test (under normal temperature and normal humidity) of the yellow toner was performed. Table 1 shows the results.

Example 4 As a crosslinking agent, polyethylene glycol dimethacrylate (n = 9 in the formula 1) was used in an amount of 1.0
Parts by weight of wax and release agent No. 3. A black toner was obtained in the same manner as in Example 1, except that the colorant was changed to carbon black. The cross section of the black toner particles is represented by T
Observation by EM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

100 parts by mass of the obtained black toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the BET method were mixed to obtain a negative frictionally chargeable black toner. Obtained. The weight average particle size of the obtained black toner was 6.5 μm.

A developer was prepared by mixing 5 parts by mass of this black toner with 95 parts by mass of an acryl-coated ferrite carrier, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon Inc.) as shown in FIG. Using a modified machine, a continuous paper passing test of 10,000 sheets of black toner (under normal temperature and normal humidity) was performed. Table 1 shows the results.

<Example 5> A wax was used as a release agent No. 3,
The polar resin is a styrene-methacrylic acid copolymer (Mw =
Example 1 except for changing to 50000, acid value = 20)
In the same manner as in the above, a cyan toner was obtained. Observation of the cross section of the cyan toner particles by TEM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

[0420] 100 parts by mass of the obtained cyan toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the BET method were mixed to obtain a negatively triboelectrically charged cyan toner. Obtained. The weight average particle size of the obtained cyan toner was 7.3 μm.

A developer is prepared by mixing 5 parts by mass of this cyan toner with 95 parts by mass of an acryl-coated ferrite carrier to prepare a developer. A commercially available digital full-color copying machine (CLC500, manufactured by Canon Inc.) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

Example 6 Example 4 was repeated except that the amount of the crosslinking agent added was changed to 5.2 parts by mass and the acid value of the polar resin was changed to 10.
A black toner was obtained in the same manner as described above. Observation of the cross section of the black toner particles by TEM showed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

[0404] 100 parts by mass of the obtained black toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the BET method were mixed to obtain a negative frictionally chargeable black toner. Obtained. The weight average particle size of the obtained black toner was 6.7 μm.

A developer is prepared by mixing 95 parts by weight of an acryl-coated ferrite carrier with 5 parts by weight of the black toner, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a modified machine, a continuous paper passing test of 10,000 sheets of black toner (under normal temperature and normal humidity) was performed. Table 1 shows the results.

Example 7 A wax was used as a releasing agent No. 1,
A cyan toner was obtained in the same manner as in Example 1, except that the acid value of the polar resin was changed to 10, and the pH of the aqueous medium was changed to 10.5. Observation of the cross section of the cyan toner particles by TEM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG. 100 parts by mass of the obtained cyan toner particles have a specific surface area of 1 according to the BET method.
This was mixed with 1.5 parts by mass of a hydrophobic titanium oxide fine powder of 00 m ² / g to obtain a negative frictionally chargeable cyan toner. The weight average particle size of the obtained cyan toner was 7.5 μm.

A developer was prepared by mixing 95 parts by mass of an acrylic-coated ferrite carrier with 5 parts by mass of this cyan toner, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

Example 8 A cyan toner was obtained in the same manner as in Example 5, except that the number of revolutions of the paddle stirring blade during the polymerization reaction was changed. Observation of the cross section of the cyan toner particles by TEM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG. Also,
The shape was slightly distorted.

[0409] 100 parts by mass of the obtained cyan toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by a BET method were mixed to obtain a negatively triboelectrically-chargeable cyan toner. Obtained. The weight average particle size of the obtained cyan toner was 7.7 μm.

A developer is prepared by mixing 95 parts by mass of an acryl-coated ferrite carrier with 5 parts by mass of the cyan toner, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

<Embodiment 9> Using the developers of Examples 1, 2, 3, and 4, and using a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. When a 10,000-sheet continuous paper passing test (under normal temperature and normal humidity) was conducted, an image having a low image fog and a stable image density was obtained.

Example 10 Using the toners of Examples 1, 2, 3 and 4 and a non-magnetic one-component developing system as shown in FIG. (Under normal temperature and normal humidity), an image having a low image fog and a stable image density was obtained.

<Comparative Example 1> As a crosslinking agent, divinylbenzene and wax were used as release agents No. A cyan toner was obtained in the same manner as in Example 1, except that the toner was changed to 1. Observation of the cross section of the cyan toner particles by TEM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

[0414] 100 parts by mass of the obtained cyan toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by the BET method were mixed to obtain a negatively triboelectrically-chargeable cyan toner. Obtained. The weight average particle size of the obtained cyan toner was 7.0 μm.

A developer was prepared by mixing 5 parts by mass of this cyan toner with 95 parts by mass of an acryl-coated ferrite carrier, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

<Comparative Example 2> A cyan toner was obtained in the same manner as in Example 1, except that 0.005 parts by mass of divinylbenzene was used as a crosslinking agent and paraffin wax was used (melting point: 60 ° C). Observation of the cross section of the cyan toner particles by TEM confirmed that the release agent was well encapsulated in the outer shell resin as shown in FIG.

[0417] 100 parts by mass of the obtained cyan toner particles and 1.5 parts by mass of a hydrophobic titanium oxide fine powder having a specific surface area of 100 m ² / g by a BET method were mixed to obtain a negatively triboelectrically-chargeable cyan toner. Obtained. The weight average particle size of the obtained cyan toner was 7.4 μm.

A developer was prepared by mixing 5 parts by mass of this cyan toner with 95 parts by mass of an acryl-coated ferrite carrier, and a commercially available digital full-color copying machine (CLC500, manufactured by Canon Inc.) as shown in FIG. Using a remodeled machine, a continuous paper passing test (under normal temperature and normal humidity) of 10,000 sheets of cyan toner was performed. Table 1 shows the results.

[0419]

[Table 1]

Image Density The image density of the fixed image area at a toner mass of 0.60 mg / cm ² per unit area is determined by Macbeth RD918.
(Manufactured by Macbeth).

Image quality of halftone portion and solid portion In the case of two-component development; contamination of the carrier / drum due to durability greatly affects the solid portion image, and the solid portion image quality of the obtained image on transfer paper is visually determined. , A, B,
C and D were evaluated.

In the case of a non-magnetic one component: The fusion of the toner onto the sleeve due to the durability and the unevenness of the toner coating greatly affect the solid portion image, and the solid portion image quality of the obtained image on the transfer paper is visually determined. A, B, C, and D were evaluated.

Fog measurement method Fog was measured using REFLECTOME manufactured by Tokyo Denshoku Co., Ltd.
The measurement was performed using TER MODELTC-6DS, and the cyan toner image was calculated using the following formula using an amber filter. The smaller the value, the less fog.

Fog (reflectance) (%) = [Reflectance of standard paper (%)] − [Reflectance of non-image portion of sample (%)]

A: 1.2% or less, A: more than 1.2%, 1.6
% To B, 1.6% to 2.0% or less C, 2.0%
% Was evaluated as D.

Fixability and Offset Resistance Toner particles are obtained by externally adding an appropriate amount of an external additive to the toner particles. An unfixed image of the obtained toner is created by a commercially available copying machine.

The toner is evaluated for fixing and anti-offset properties by a heat roller external fixing device having no oil application function. Further, a fixed image for transparency evaluation is obtained.

At this time, the surface of both the upper roller and the lower roller is made of fluororesin or rubber. Both the upper roller and the lower roller have a diameter of 40 mm, and the fixing conditions are as follows.
0 mm / sec, and the transfer material is an OHP sheet (CG33
(00 / 3M), the nip is set to 5.5 mm, the fixing speed is set to 35 mm / sec, and the temperature is adjusted every 5 ° C. within a temperature range of 100 ° C. to 250 ° C.

[0429] The fixing property was determined by comparing the non-offset image with 5
0 g / cm ^{2 with} a load of silbon paper [Lenz Cl
eating Paper “desper (R)”
(Ozu Paper Co., Ltd.)], and the temperature at which the density reduction rate before and after the rubbing is less than 10% is defined as the fixing start point.

In the offset resistance, the temperature at which no offset is visually observed is defined as a low-temperature non-offset starting point, and the highest temperature at which no offset is generated by increasing the temperature is defined as a high-temperature non-offset end point.

Transparency The transmittance and the haze (haze) of the fixed image obtained on the OHP sheet with respect to the amount of each toner per unit area were measured, and the toner mass per unit area was 0.70 mg / cm.
^The transparency is evaluated using the value of ² . The methods for measuring the transmittance and haze are described below.

The transmittance was measured using a Shimadzu self-recording spectrophotometer UV.
Using a 2200 (manufactured by Shimadzu Corporation) with the transmittance of the OHP film alone as 100%, the transmittance at the maximum absorption wavelength at 650 nm was measured for the magenta toner; 550 nm for the yellow toner; 410 nm for the cyan toner; I do.

[0433]Production Example 1 of Toner High-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo)
Deionized water in a 2 liter four-necked flask equipped with
650 parts by mass and 0.1 mol / liter-Na _ThreePO_Fourwater
500 parts by mass of the solution are charged, and the number of revolutions is 12000 rpm.
And heated to 70 ° C. 1.0 mol here
/ Liter-CaCl_TwoAdd 80 parts by weight of aqueous solution
Contains a small water-insoluble dispersion stabilizer (calcium phosphate salt)
An aqueous dispersion medium was prepared.

On the other hand, dispersoids include: 82 parts by mass of styrene 18 parts by mass of 2-ethylhexyl acrylate 10 parts by mass of carbon black (BET specific surface area = 55 m ² / g) 5 parts by mass of wax (ester wax No. 1) 1.5 parts by mass of a negative charge control agent (compound [I] -1) After dispersing the above mixture for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), 2,2′-azobis (2,4- Dimethylvaleronitrile) (3 parts by mass) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer composition was charged into a pre-distribution dispersion medium, and a high-speed stirrer was maintained at 12,000 rpm under a nitrogen atmosphere at an internal temperature of 70 ° C.
After stirring for minutes, the polymerizable monomer composition was granulated. After that, when the stirrer was replaced with a propeller stirring blade and stirring was performed at 50 rpm for 4 hours at the same temperature, then polymerization was performed to a polymerizable monomer mixture consisting of: 28 parts by mass of styrene monomer 2 parts by mass of 2-ethylhexyl acrylate 2, as an initiator
2'-azobis (2,4-dimethylvaleronitrile)
1.2 parts by mass were added and dissolved. Using a metering pump (manufactured by Nippon Feeder), this solution was continuously and uniformly dropped over 1 hour, adsorbed and coated on the surface of the polymer particles, polymerized, heated to 80 ° C., and further polymerized for 6 hours.

After completion of the polymerization, the suspension was cooled, and then dilute hydrochloric acid was added to remove the dispersion stabilizer. Further, after washing with water was repeated several times, it was dried to obtain polymer particles (A). The polymer particles (A) had a weight average diameter of 6.7 μm.

The polymer particles (A) (100 parts by mass) and hydrophobic
Silica fine powder (BET; 240m ^Two/ G) 1.5 mass
Part is dry-mixed with a Henschel mixer to obtain the toner of the present invention.
(A).

The average circularity of the toner (A) is 0.990,
The circularity standard deviation was 0.025, the circle-equivalent number average diameter D1 was 6.1 μm, and the peak molecular weight was 27,000.

Toner Production Examples 2-6 Except for changing the type and amount of polymerizable monomer, wax and charge control agent, the type and amount of monomer to be subjected to seed polymerization, the timing of adding the monomer, etc. In the same manner as in Toner Production Example 1, toners (B) to (F) were obtained. Table 2 shows the types and amounts of the materials used together with the toner (A), and Tables 3 and 4 show the analysis results of the toner.

Comparative Production Examples 1 to 4 of polymerizable monomers, waxes, types and amounts of charge control agents, types and amounts of monomers to be subjected to seed polymerization, timing of monomer addition, etc. are changed. Except for the above, toners (G) to (J) were obtained in the same manner as in toner production example 1. Table 2 shows the types and amounts of materials used, and Tables 3 and 4 show the results of toner analysis.
Shown in

[0441]

[Table 2]

[0442]

[Table 3]

[0443]

[Table 4]

<Examples 11 to 16 and Comparative Examples 3 to 6> Evaluations of toners manufactured according to the above-described manufacturing examples will be described below.

FIG. 9 is a schematic diagram showing an example of an image forming apparatus using an intermediate transfer belt.

FIG. 9 shows a color image forming apparatus (copier or laser beam printer) using an electrophotographic process.

Reference numeral 1 denotes a drum-shaped electrophotographic photosensitive member (hereinafter, referred to as a photosensitive drum) as a first image carrier, which is driven to rotate at a predetermined peripheral speed (process speed) in the direction of an arrow.

The photosensitive drum 1 rotates in the primary charging
, And is uniformly charged to a predetermined polarity and potential, and then subjected to exposure 3 by image exposure means 3 (not shown). In this way, an electrostatic latent image corresponding to the first color component image (for example, a yellow color component image) of the target color image is formed.

Next, the electrostatic latent image is developed into a first color yellow component image by a first developing device (yellow color developing device 41). At this time, since the second to fourth developing devices, namely, the magenta developing device 42, the cyan developing device 43, and the black developing device 44 are not operating and do not act on the photosensitive drum 1, the first developing device is not used. The color yellow component image is not affected by the second to fourth developing units.

The intermediate transfer belt 20 is driven to rotate at the same peripheral speed as the photosensitive drum 1 in the direction of the arrow.

The yellow component image of the first color formed on the photosensitive drum 1 is transferred to the photosensitive drum 1 and the intermediate transfer belt 20.
In the process of passing through the nip portion, the electric field formed by the primary transfer bias applied to the intermediate transfer belt 20 from the bias power source 29 via the primary transfer roller 62 sequentially causes the outer peripheral surface of the intermediate transfer belt 20 to be Transfer (primary transfer) is performed.

The surface of the photosensitive drum 1 on which the transfer of the first color yellow toner image corresponding to the intermediate transfer belt 20 has been completed is cleaned by the cleaning device 13.

Thereafter, similarly, the magenta toner image of the second color, the cyan toner image of the third color, and the black toner image of the fourth color are sequentially superimposed on the intermediate transfer belt 20 and transferred to correspond to the target color image. Thus, a combined color toner image is formed.

Reference numeral 63 denotes a secondary transfer roller, which corresponds to the secondary transfer opposing roller 64 and is supported in parallel with the intermediate transfer belt 20.
Are disposed on the lower surface of the device so as to be separated therefrom.

A primary transfer bias for transferring a toner image from the photosensitive drum 1 to the intermediate transfer belt 20 is applied from a bias power supply 29 with a polarity opposite to that of the toner. The applied voltage is in a range of, for example, +100 V to +2 kV.

In the primary transfer process of the first to third color toner images from the photosensitive drum 1 to the intermediate transfer belt 20,
The next transfer roller 63 and the transfer residual toner charging member 52 can be separated from the intermediate transfer belt 20.

The full-color image transferred on the intermediate transfer belt 20 is transferred to the secondary transfer roller 63 by the intermediate transfer belt 20.
The transfer material P, which is the second image carrier, is fed from the paper feed roller 11 to the contact portion between the intermediate transfer belt 20 and the secondary transfer roller 63 at a predetermined timing, and the secondary transfer bias is applied. Is applied to the secondary transfer roller 63 from the bias power supply 28, so that the secondary transfer is performed on the transfer material P. The transfer material P to which the toner image has been transferred is introduced into the fixing device 15 (for example, FIGS. 10 and 11) and is heated and fixed.

After the image transfer to the transfer material P is completed, the transfer residual toner cleaning device 50 is brought into contact with the intermediate transfer belt 20, and the surface of the intermediate transfer belt 20 is cleaned.

At this time, the heating element 71 of the heat fixing device 15
The surface temperature of the temperature detecting element 71d is 130 ° C., and the heating element 71−
The total pressure between the pressure rollers 73 is 5 kg, the nip between the pressure rollers and the film is 3 mm, and the fixing film 72 has a low-resistance release layer in which a conductive material is dispersed in PTFE on the contact surface with the recording material. A heat-resistant polyimide film having a thickness of 50 μm was used.

Using the above-described image forming apparatus, the moving speed of the surface of the toner carrier is changed to the moving speed of the surface of the electrostatic latent image carrier.
It was set to be 120%.

Next, each of the toners (A) to (J) is filled in the developing device, and the peripheral speed of the toner carrier surface of the developing device is set to 19
The developing device was mounted on a driving device of a developing device having no electrostatic latent image carrier set to be 0 mm / sec, and the developing device was rotated without passing paper for 100 minutes under high temperature and high humidity. Later the image was printed out.

In this embodiment, the apparatus shown in FIG. 9 is used as an image forming apparatus, and is operated at normal temperature and normal humidity (25 ° C., 60% R
H), toners (A) to (O) at a printout speed of 28 sheets / min (A4 size) in an environment of high temperature and high humidity (30 ° C., 80% RH) and low temperature and low humidity (15 ° C., 10% RH) Was subjected to a printout test of 20,000 sheets in a continuous mode in a single color (that is, a mode in which the consumption of toner is promoted without stopping the developing device). Then, the obtained printout image was evaluated for items described below.

Further, the matching between the used image forming apparatus and the toner was evaluated after the completion of the printout test.

[Evaluation of Printout Image] (1) Image Density Image density was evaluated by maintaining image density at the end of 20,000 printouts on ordinary paper for copying machines (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00. A: 1.40 or more, B: 1.35 or more, less than 1.40, C: 1.00 or more, less than 1.35, D: less than 1.00

(2) Image fog The fog density (%) was calculated from the difference between the whiteness of the white background portion of the printout image measured by the “Reflectometer” (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper. Image fog was evaluated. A: less than 1.5% B: 1.5% or more, less than 2.5% C: 2.5% or more, less than 4.0% D: 4% or more

(3) Dot Reproducibility The electric field is easy to close due to the latent image electric field, making it difficult to reproduce.
An image of an isolated dot pattern having a small diameter (X = 50 μm) as shown in FIG. 2 was printed out, and the dot reproducibility was evaluated. A: 2 or less defects / 100 B: 3 to 5 defects / 100 C: 6 to 10 defects / 100 D: 11 or more defects / 100 defects

(4) Fixing Property The fixing property was evaluated by applying a load of 50 g / cm ² , rubbing the fixed image with soft thin paper, and evaluating the reduction rate (%) of the image density before and after rubbing. A: less than 5% B: 5% or more and less than 10% C: 10% or more, less than 20% D: 20% or more

(5) Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image after 5,000 sheets. A: not generated B: hardly generated C: slightly generated D: severely generated

[Evaluation of Matching of Image Forming Apparatus] <1> Matching with Developing Sleeve After the printout test was completed, the state of fixation of the residual toner on the surface of the developing sleeve was visually evaluated. A: not generated B: hardly generated C: some sticking D: many sticking

<2> Matching with Photosensitive Drum After the printout test was completed, the occurrence of scratches on the surface of the photosensitive drum and the adhesion of residual toner were visually evaluated. A: not generated B: slightly scratched C: sticking or scratching D: much sticking

<3> Matching with Intermediate Transfer Belt After completion of the printout test, the surface of the intermediate transfer member was visually evaluated for scratches and the state of fixation of residual toner. A: not generated B: presence of residual toner on the surface is observed C: sticking or flaw D: sticking too much

<4> Matching with Fixing Device After the completion of the printout test, the surface of the fixing film and the state of fixation of the residual toner were visually evaluated. A: Not generated B: Slightly adhered C: Adhered or damaged D: Adhered

<5> Evaluation of Blocking Resistance 10 g of toner was placed in a 50 ml polycup, left in a hot air drier set at 50 ° C. for one week, and then the removed toner was slowly rotated when the polycup was taken out. The state was visually evaluated. A: The fluidity is not impaired. B: Although the fluidity is reduced, the fluidity is gradually recovered as the cup rotates. C: Aggregates can be seen, but loosened with a needle. D: Granulation or caking so as not to be loosened even with a needle.

Tables 5 to 8 summarize the evaluation results.

[0475]

[Table 5]

[0476]

[Table 6]

[0477]

[Table 7]

[0478]

[Table 8]

[Composite Oxide Particle Production Examples a to e]
MnSO ₄ was added to an aqueous ferrous salt solution containing ₄ and NaOH, heated, and air was vented to obtain Fe and M
Thus, a suspension of composite oxide particles containing n was obtained. afterwards,
Through the steps of filtration, washing, drying, crushing, and baking, composite oxide particles a to f shown in Table 9 below were obtained.

The method for measuring the physical properties of the composite oxide particles is as follows.

(1) Nitrogen adsorption specific surface area (BET) of toner
Method for measuring specific surface area) The nitrogen adsorption specific surface area of the toner according to the present invention is determined by adsorbing nitrogen gas to the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method.
The specific surface area was calculated using the BET multipoint method.

(2) Measurement of atomic ratio of Fe and Mn in composite oxide The atomic ratio of Fe and Mn contained in the composite oxide used in the toner according to the present invention is measured by the following method. .

In a beaker, 0.2 g of the composite oxide was collected.
15 ml of a 12N aqueous hydrochloric acid solution is added, and the reaction is continued while heating and stirring until all the components are dissolved and become transparent. Water was added to the obtained liquid to make 100 ml, and Fe and M were determined by plasma emission spectroscopy (ICP) using this sample liquid.
The amount of dissolution of n metal elements is measured. And Fe and Mn
The atomic ratio is calculated using a calibration curve measured in the same manner for the standard solution of the metal element.

In some cases, after washing and removing deposits and the like on the surface of the composite oxide in an aqueous solution of sodium hydroxide having a pH of about 10, the content of metal elements of Fe and Mn is determined by plasma emission spectroscopy as described above. Should be measured.

When analyzing the composite oxide contained in the toner, an organic solvent such as xylene that dissolves the resin component of the toner is mixed with the toner, and the solution in which the resin component of the toner is dissolved is subjected to pore size analysis. The solution is filtered through a 0.1 μm membrane filter, and the composite oxide remaining on the filter is collected. The collected composite oxide is treated in an atmosphere of 500 ° C. to remove organic components, and then the obtained composite oxide is analyzed by the above-described method to determine the content of the metal elements Fe and Mn. And the atomic ratio is calculated.

(3) Method for Measuring Average Diameter of Composite Oxide Particles The average particle diameter of the composite oxide was measured using a transmission electron microscope.

That is, the measured powder sample was observed with a transmission electron microscope, and the particle diameter of 100 particles in the visual field was measured to determine the average particle diameter.

(4) Method for Measuring Content of Complex Oxide in Toner The content of complex oxide in the toner was measured with a thermal analyzer TGA7 manufactured by PerkinElmer. The measurement method is as follows. The toner is heated from normal temperature to 900 ° C. at a temperature rising rate of 25 ° C./min under a nitrogen atmosphere, and is heated from 100 ° C. to 750 ° C.
The mass% of the weight loss up to ° C. was defined as the amount of the binder resin. The remainder obtained by subtracting the amount of the binder resin from the entire toner (100% by mass) was approximately determined as the content of the composite oxide in the toner.

[0489]

[Table 9]

[Surface-treated composite oxide production example 1] A xylene solution in which an epoxy resin was dissolved was prepared and used as a treatment liquid.
After mixing the composite oxide particles a and the treatment liquid so that the amount of the epoxy resin becomes 2 parts by mass with respect to the composite oxide particles a, xylene is removed by heating and drying, and after crushing, the surface-treated composite oxide 1 is removed. Obtained.

[Surface-treated composite oxide production examples 2 and 3] Instead of the epoxy resin, methyl hydrogen polysiloxane or n-decyltrimethoxysilane was used. Surface-treated composite oxides 2 and 3 were obtained.

[Surface-treated composite oxide production examples 4 to 8] The composite oxide particles b to f were used in place of the composite oxide particles a, and the surface-treated composite oxide was treated using n-decyltrimethoxysilane as a treating agent. 4-8 were obtained.

Table 10 shows the physical properties of the resulting surface-treated composite oxides 1 to 8.

[0494]

[Table 10]

[Production Examples 9 and 10 of surface-treated composite oxide] The composite oxide particles a were dispersed in an aqueous solution adjusted to pH 10 or pH 6, to which n-decyltrimethoxysilane was added, stirred, filtered, and dried by heating. Thereafter, the resultant was crushed to obtain surface-treated composite oxides 9 and 10.

Table 11 shows the physical properties of the resulting surface-treated composite oxides 9, 10.

[0497]

[Table 11]

[Toner Production Example 7] (Resin) 100 parts by mass of styrene-butyl acrylate copolymer (copolymerization ratio: 80:20) (colorant) 50 parts by mass of surface-treated composite oxide 1 (charge control agent) monoazo dye Compound of Fe and Fe 2 parts by mass (release agent) Ester wax (softening point 75 ° C) 5 parts by mass The above materials are mixed in advance and 12 parts are extruded with a twin screw extruder.
Melt kneading was performed at 0 ° C. This melt-kneaded material was crushed by a hammer mill to obtain a crushed toner having a 1 mm mesh pass. Further, the coarsely crushed product is finely pulverized by a collision type pulverizer using a jet stream, and then subjected to air classification to obtain a weight average particle size of 9.
5 μm black ground particles were obtained. Obtained black ground particles 1
Hydrophobic titanium oxide having a specific surface area of about 100 m ² / g was obtained by subjecting the surface of the anatase-type titanium oxide base material to hydrophobic treatment with a silane coupling agent.
The toner 1 was obtained by externally adding 0 parts by mass.

[Toner Production Example 8] 0.1 M Na ₃ was added to 710 g of ion-exchanged water in a two-liter four-necked flask.
After pouring 200 g of PO ₄ aqueous solution and heating to 60 ° C.,
The mixture was stirred at 12,000 rpm using a high-speed stirrer TK homomixer (manufactured by Tokushu Kika Kogyo). 1.0
30 g of an aqueous solution of M-CaCl ₂ was gradually added to obtain an aqueous dispersion medium containing fine, slightly water-soluble dispersion stabilizers.

On the other hand, (monomer) styrene 60 g n-butyl acrylate 40 g (colorant) Surface-treated composite oxide 1 100 g (charge control agent) Compound of monoazo dye and Fe 2 g (release agent) ester wax (dispersoid) (Softening point: 75 ° C.) 10 g (Others) Saturated polyester resin: 10 g Of the above formulation, only the colorant, the charge control agent, and styrene were premixed using an Ebara Milder (manufactured by Ebara Corporation). Next, heat all the above formulations to 60 ° C, dissolve,
It was dispersed to obtain a monomer mixture. Further, while maintaining the temperature at 60 ° C., 8 g of an initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was added and dissolved to prepare a monomer composition.

The above monomer composition was added to the aqueous dispersion medium prepared in the 2-liter flask of the homomixer. The mixture was stirred at 8000 rpm for 20 minutes at 60 ° C. using a TK homomixer in a nitrogen atmosphere to granulate the monomer composition. Then, while stirring with paddle stirring blades, 60 ° C
For 6 hours, and then polymerized at 80 ° C. for 10 hours.

After the completion of the polymerization reaction, the reaction product was cooled, and Ca ₃ (PO ₄ ) ₂ was dissolved by adding hydrochloric acid, followed by filtration, washing and drying to obtain black suspended particles having a weight average diameter of about 9.4 μm. I got

To 100 parts by mass of the obtained black suspended particles, 1.0 part of the hydrophobic titanium oxide used in Toner Production Example 7 was added.
The toner 2 was obtained by external addition in parts by mass.

[Toner Production Example 9] Black suspended particles having a weight average diameter of about 6.9 µm were obtained in the same manner as in Toner Production 7, except that the concentration of the poorly water-soluble dispersion stabilizer in the aqueous system was increased. 1.3 parts by mass of the hydrophobic titanium oxide used in Toner Production Example 1 was externally added to 100 parts by mass of the obtained black suspended particles.
Toner 3 was obtained.

[Toner Production Examples 10 to 17] Toner 10 was produced in the same manner as in Toner Production Example 9 except that surface-treated composite oxides 2 to 8 and composite oxide particles a were used as colorants.
~ 17.

[Toner Production Examples 18 to 21] Black suspension particles were obtained in the same manner as in Toner Production Example 9 using surface-treated composite oxides 9, 10, and 3 and composite oxide particles a as coloring agents. , Having a specific surface area of 20 as a BET method as an external additive.
The surface of a silica matrix of 0 m ² / g is hydrophobized with a silane coupling agent and silicone oil, and 1.3 parts by mass of hydrophobic silica having a specific surface area of 120 m ² / g is externally added. 18-21 were obtained. The obtained toner is summarized in Table 12 below.

[0507]

[Table 12]

<Examples 17 to 25> First, an experiment using the toner of the present invention as a two-component developer will be described.

As a carrier, a ferrite carrier (average particle diameter 39 μm) obtained by coating a silicone core with a carrier core material by 0.5 part by mass was used, and mixed so that the toner concentration in the developer became 6%. Using the electrophotographic copying machine CLC-700 (manufactured by Canon)
In an environment of a temperature of 30 ° C. and a humidity of 90%, an original document having an image area ratio of 20% is used, and only 10
A 000-sheet printing test was performed.

[0510] When this printing durability test was performed using Toner 5, the charge amount of the toner showed a substantially constant value from the initial stage to the end of the printing durability test, and high image density and high definition image quality were stably obtained. Was done. Also, no fog or toner scattering was observed. After the printing test, the content of the composite oxide in the toner present in the developing device was analyzed by TGA.
A value of about 30% by mass was obtained with respect to the entire toner, and there was almost no change from the initial value, about 31% by mass.

[0511] Hereinafter, toners 1-4, toner 6, and toner 8
The same printing durability test was carried out for the samples No. 10 to No. 10, and almost satisfactory results were obtained.

[0512] The above results are summarized in Table 13.

<Comparative Examples 7 and 8> When a printing test similar to that of Example 17 was performed on Toner 7, the charge amount of the toner gradually decreased, and the image density and fog deteriorated, and the machine body was deteriorated. There was also toner scattering inside. After completion of the printing durability test with frequent maintenance, the content of the composite oxide in the toner present in the developing device was analyzed by TGA and found to be about 12% by mass based on the whole toner.

[0514] Since Mn is not contained in the composite oxide used as the coloring agent, the coloring power is low, and the adhesion of the surface treating agent is poor. This is considered to be due to the fact that the hydrophobicity did not increase, and the selectivity of the toner during development was not good due to poor dispersion of the composite oxide.

[0515] The same printing durability test was performed on the toner 11.

The results are shown in Table 13.

[0517]

[Table 13]

<Examples 26 to 28 and Comparative Example 9> Next, an experiment using the toner of the present invention as a one-component developer will be described.

First, the image forming apparatus will be described.

In the present invention, a commercially available laser beam printer LBP-SX (manufactured by Canon Inc.) was used as modified as shown in FIG. That is, the iron blade in the process cartridge portion is changed to an elastic blade 29 made of urethane rubber, the magnet included in the developer carrier 35 is removed, and the coating roller 26 and the cleaning roller 36 are removed.
Was installed. Further, the peripheral speed ratio of the peripheral speed of the developer carrying member to the peripheral speed of the photosensitive member is set to 200%.

[0521] The following is a more detailed description.

FIG. 13 schematically shows an apparatus for developing an electrostatic image formed on a latent image holding member. OP with primary charger 31
A developing device that charges the surface of the C photoconductor 23 to a negative polarity, forms a digital latent image by image scanning by exposure 25 with a laser beam, and includes a urethane rubber elastic blade 29 and a developing sleeve 35 installed in the counter direction. Thereby, the latent image is reversely developed with the one-component developer 33. In the developing section, between the conductive base of the photosensitive drum 23 and the developing sleeve 35, an alternating bias, a pulse bias and / or a DC bias are applied by the bias applying means 32. When the transfer paper P is conveyed and reaches the transfer section, the transfer paper P is charged by the electrostatic transfer means 24 from the back surface (the surface opposite to the photosensitive drum side) of the transfer paper P, so that a developed image (toner image) on the photosensitive drum surface is formed. ) Is electrostatically transferred onto the transfer paper P. Transfer paper P separated from photosensitive drum 23
Is subjected to a fixing process for fixing the toner image on the transfer paper P by a fixing device including the fixing roller 27.
The developer remaining on the photosensitive drum 23 after the transfer process is removed by a cleaning device 34 having a cleaning blade 28. In this experiment, a cleaning roller 36 is further provided. After the cleaning, the photosensitive drum 23 is neutralized by the erase exposure 37, and the process starting from the charging process by the primary charger 31 is repeated again.

As the developing bias used in this experiment, a DC bias (-400 V) superposed with an AC bias (rectangular wave having a frequency of 3200 Hz and a peak-to-peak voltage of 1800 V) was used. Further, the dark portion potential and the bright portion potential on the electrostatic latent image carrier are -600 V and -15 V, respectively.
Image output was performed at 0 V.

As the transfer material P, 75 g / m ² paper was used.

Under the above image forming conditions, the temperature was 30 ° C. /
Under a condition of 80% humidity, a printing durability test of 2,000 sheets was performed in character printing with a printing area ratio of 5%.

Here, the resolving power at the initial stage of the printing durability test is 600 dpi which is difficult to reproduce because the electric field is easily closed by the latent image electric field.
The evaluation was made based on the reproducibility of one small-diameter isolated dot. ◎ Very good: 5 or less defects in 100 ○ Good: 6 to 10 defects in 100 △ Practical acceptable: 11 to 20 defects in 100 × Not practical: defect in 100 Is 20 or more

Table 14 shows the results of the printing durability test performed using Toners 12 to 15.

Example 26 An aqueous dispersion medium and a polymerizable monomer composition were each prepared as described below.

(Preparation of Aqueous Dispersion Medium) In a container having an internal volume of 20 liters, the following components were mixed, heated to 60 ° C., and then a high-speed rotary shear stirrer CLEARMIX (manufactured by M Technic Co., Ltd.) And the mixture was stirred at 15,000 rpm. Water 97.4% by mass Na ₃ PO ₄ 1.0% by mass Hydrochloric acid 1.0% by mass Next, the inside of the container is replaced with nitrogen, and CaCl ₂ is added thereto.
0.6% by mass was added and reacted to obtain an aqueous dispersion medium containing fine particles of Ca ₃ (PO ₄ ) ₂ . The pH of the obtained aqueous dispersion medium was 5.8.

(Preparation of Polymerizable Monomer Composition) Styrene monomer 63.9 mass% n-butyl acrylate monomer 13.1 mass% quinacridone pigment 6.2 mass% terephthalic acid-propylene oxide-modified bisphenol A 3.9% by mass 4,4'-divinylbiphenyl 0.2% by mass Aluminum di-tert-butylsalicylate 0.8% by mass Ester wax (release agent No. 5, melting point: 73 ° C) 9.6% by mass A part of a styrene monomer, a quinacridone-based pigment, and an aluminum di-tert-butylsalicylate compound are mixed among the above components, and an attritor (Mitsui Miike Industry Co., Ltd.)
), And the remainder of the styrene monomer and other components were added, and the mixture was heated to 60 ° C and mixed until it was sufficiently compatible. Thereafter, 2.3% by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added thereto to obtain a polymerizable monomer composition.

The polymerizable monomer composition prepared above was charged into the aqueous dispersion medium prepared above, and the mixture was stirred for 3 minutes at a CLEAR MIX rotation speed of 15,000 rpm to perform granulation. Thereafter, the clear mix was stopped, and the polymerization was continued at a rotation speed of 50 rotations / minute and a liquid temperature of 60 ° C. using a normal stirring blade. Five hours later, the polymerization temperature was raised to 80 ° C, and heating and stirring were continued for 5 hours to complete the polymerization. After the temperature of the reaction product decreased, dilute hydrochloric acid was added to dissolve the dispersant, and after solid-liquid separation, washed with water, filtered and dried to obtain polymerized toner particles. When the particle size distribution of the toner particles was measured,
The D4 average diameter was 7.0 μm, the particle size distribution was sharp, and the triboelectric charge amount was as high as −40 (μC / g).

Next, hydrophobic silica was externally added to the obtained toner particles, and a ferrite carrier coated with an acrylic resin was mixed to obtain a two-component developer. 2 under high temperature / humidity
When an image output test was performed on 0000 sheets, the fog was 0.
At 3%, there was no fluctuation in image density throughout, and a clear and excellent fixability image was obtained stably. At this time, no fusion to the photosensitive drum, no blocking in the developing device, and no contamination of the carrier and the developing sleeve were observed. Also OH
The transparency of the fixed image on the P sheet was very good.

Comparative Example 9 Example 2 was repeated except that divinylbenzene was used instead of 4,4'-divinylbiphenyl.
In the same manner as in Example 6, a toner was obtained. D4 average diameter is 7.5
μm, and the triboelectric charge amount was −32 (μC / g). When the image output test of 20,000 sheets was performed under high temperature / high humidity,
Although fog was 1.0% and there was no fluctuation or unevenness in image density, slight fusion to the photosensitive drum occurred, and image defects caused by the fusion were recognized. The transparency of the fixed image on the OHP sheet was good.

Example 27 A toner was obtained in exactly the same manner as in Example 26 except that a polyethylene wax (melting point: 125 ° C.) was used instead of the ester wax. The D4 average diameter was 7.7 μm, and the triboelectric charge was −28 (μC / g). When an image output test was performed on 20,000 sheets under high temperature and high humidity, fog was 0.6% and the image quality was good. No fusing to the photosensitive drum, no blocking in the developing device, and no contamination of the carrier and the developing sleeve were observed. OH
The transparency of the fixed image on the P sheet was slightly inferior to Example 26.

Example 28 A toner was obtained in exactly the same manner as in Example 26 except that hydrochloric acid was not used when preparing the aqueous dispersion medium. The pH at the time of preparation of the aqueous dispersion medium was 9.2. D
4 The average diameter is 6.9 μm, and the triboelectric charge is −33 (μC /
g). When an image output test was performed on 20,000 sheets under high temperature and high humidity, fog was 0.8% and the image quality was good. Although the transparency of the fixed image on the OHP sheet was good, scattering of the toner from the developing device was slightly observed.

[0536]

[Table 14]

(Production Example 22 of Toner) In a two-liter four-necked flask equipped with a high-speed stirrer CLEARMIX (manufactured by M-Technic Co., Ltd.), 700 g of ion-exchanged water and 0.1 g of 0.1 ml water were added.
750 g of a 1 mol / L-Na ₃ PO ₄ aqueous solution was charged, and the number of revolutions of the high-speed stirring device was set to 15000 rpm, and
Warmed to ° C. Here, 1.0 mol / L-CaCl
₂ 70 parts by mass of an aqueous solution is added, and a minute poorly water-soluble dispersant C
An aqueous dispersion medium containing a ₃ (PO ₄ ) ₂ was prepared.

On the other hand, dispersoids include:-61 parts by mass of styrene monomer-19 parts by mass of 2-ethylhexyl acrylate monomer-0.1 parts by mass of divinylbenzene monomer-Carbon black (particle size = 55 nm, pH = 7.5) 7 parts by mass ・ Polycarbonate resin (molecular weight peak = 6000) 4 parts by mass ・ Ester wax (melting point = 65 ° C.) 5 parts by mass was dispersed for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.). Thereafter, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer was added to the aqueous dispersion medium.
The body composition is charged, and N at an internal temperature of 60 ° C. _TwoAtmosphere, high speed
While maintaining the rotation speed of the stirrer at 15,000 rpm, 1
The mixture was stirred for 5 minutes to granulate the polymerizable monomer composition. That
After that, replace the stirring device with a paddle stirring blade,
While maintaining the same temperature while stirring at 80 rpm, a polymerizable vinyl
When the polymerization conversion of the styrene-based monomer has reached 50%, 20 parts by mass of a styrene monomer 3 parts by mass of a phenol derivative condensation mixture having the following contents: 3 parts by mass of the cyclic condensate (A1-4): 70% by mass A solution mixture comprising the chain condensate (B1-4): 30% by mass is dropped into the aqueous dispersion medium,
Is absorbed into the granulated particles of the polymerizable monomer composition in progress.
Was. Thereafter, the reaction temperature was raised to 80 ° C., and the polymerization conversion rate was increased.
When it reached almost 100%, the polymerization reaction was completed.

After completion of the polymerization, the remaining monomers were distilled off under reduced pressure under heating, and then, after cooling, dilute hydrochloric acid was added to dissolve the poorly water-soluble dispersant. After repeating water washing several times,
Drying was performed using a conical ribbon dryer (manufactured by Okawara Seisakusho) to obtain polymer particles (5A).

The polymer particles (5A) (100 parts by mass) and hydrophobic oil-treated silica fine powder (BET: 200 m ² /
g) 2 parts by mass were dry-mixed with a Henschel mixer (manufactured by Mitsui Kinzoku Co., Ltd.) to obtain a toner (5A) of the present invention.

The toner (5A) had a circle-equivalent number average diameter of 5.8 μm, an average circularity in the circularity frequency distribution of 0.988, a circularity standard deviation of 0.027, and a circularity of less than 0.950. The number of toner particles was 6% by number, and the molecular weight distribution by GPC was found to have a peak molecular weight of 2,000,000 and Mw / Mn.
Was 15.

The total residual amount of the polymerizable monomer in the toner (5A) was 77 ppm (styrene monomer: 60 ppm,
2-ethylhexyl acrylate monomer and divinylbenzene monomer: 0 ppm). Further, when the dispersion state of the wax component was observed with a TEM, it was found to be substantially spherical and dispersed in the binder resin as shown in the schematic diagram of FIG.

(Production Examples 23 to 25 of Toner and Production Examples 1 and 2 of Comparative Toner) The same procedures as in Example 1 were carried out except that the types and amounts of the phenol derivative condensate and the wax component were changed. After obtaining the polymer particles (5B) to (5D), toners (5B) to (5D) of the present invention and comparative toners (5a) and (5b) were prepared.

Table 1 shows the types and amounts of the phenol derivative condensate and the wax component in the respective toner production examples.
5

[0546]

[Table 15]

(Comparative Production Example 3 of Toner) The following materials were previously mixed, melt-kneaded with a twin-screw extruder, and the cooled kneaded material was coarsely pulverized with a hammer mill, and the coarsely pulverized material was finely pulverized with a jet mill. The obtained finely pulverized product was classified to obtain a classified powder (5c). 100 parts by mass of styrene-2-ethylhexyl acrylate-divinylbenzene resin (peak molecular weight = 20,000, Mw / Mn = 5.5, Tg = 60 ° C.) 7 parts by mass of carbon black used in Toner Production Example 22 -4 parts by mass of unsaturated polyester used in Toner Production Example 22-5 parts by mass of wax component used in Toner Production Example 22-3 parts by mass of phenol derivative (cyclic condensate: A1-6)

Using the classified powder (5c), a comparative toner 5c) and a toner 5c) were prepared in the same manner as in Production Example 22 of the toner.
A comparative developer (5c) was prepared.

The comparative toner (5c) contains a styrene monomer derived from a binder resin as a volatile component in an amount of 120%.
1 ppm, 2-ethylhexyl acrylate monomer
2 ppm remained. The wax component was finely dispersed.

The toners (5A) to (5D) of the present invention obtained in the above toner production examples and the comparative toner (5a)
Table 16 summarizes the properties of (5) to (5c).

[0551]

[Table 16]

(Toner Production Examples 26 to 29) The type and amount of the colorant and the phenol derivative condensate were changed, and the temperature, pressure reduction degree, processing time,
After obtaining polymer particles (5E) to (5H) in the same manner as in Production Example 22 of the toner except that the set temperature of the conical ribbon dryer, the stirring conditions, and the processing time were changed, the toner of the present invention was obtained. (5E) to (5H) were prepared.

The types and amounts of the colorant, the phenol derivative condensate and the wax component in the respective toner production examples, and the obtained toners (5E) to (5H) of the present invention
Are summarized in Table 17.

[0554]

[Table 17]

(Photoreceptor Production Example 1) Diameter 30 mm, length 2
A 54 mm aluminum cylinder was used as a substrate. On this substrate, layers having the following structures were sequentially laminated by dip coating to produce a photosensitive drum (1).

(1) Conductive coating layer: mainly composed of tin oxide and titanium oxide powder dispersed in a phenol resin. The thickness is 15 μm. (2) Undercoat layer: mainly composed of modified nylon and copolymerized nylon. The film thickness is 0.6 μm. (3) Charge generation layer: mainly composed of an azo pigment having absorption in a long wavelength region dispersed in butyral resin. Thickness 0.6
μm. (4) Charge transport layer: mainly composed of a hole-transporting triphenylamine compound dissolved in a polycarbonate resin (molecular weight 20,000 according to Ostwald viscosity method) at a mass ratio of 8:10, and further a polytetrafluoroethylene powder ( Particle size 0.2
μm) was added at 10% by mass based on the total solid content, and the mixture was uniformly dispersed. 25 μm thick.

[0557] The contact angle of water on the surface of the obtained photosensitive drum (1) was 95 degrees.

The contact angle was measured using pure water, and the apparatus used was a contact angle meter CA-DS, manufactured by Kyowa Interface Science Co., Ltd.

(Photoreceptor Production Example 2) A film thickness of 25 μm was prepared in the same manner as in Photoreceptor Production Example 1 except that polytetrafluoroethylene powder (particle diameter: 0.2 μm) was not added to the charge transport layer.
m of the charge transport layer was formed, and a photoreceptor drum (2) was produced.

The contact angle of the surface of the obtained photosensitive drum (2) with water was 79 degrees.

<Embodiment 29> An image forming apparatus of 600
dpi laser beam printer (Canon: LBP
-8 Mark IV) was prepared. Modified this device,
Twelve sheets were printed on LTR size paper at a process speed of 80 mm / s (variable toner carrier speed). As shown in FIG. 22, this device uses a charging roller 31 to which DC and AC components are applied, and uses a photosensitive drum 36 (30φ).
Is uniformly charged. At this time, the DC component is controlled to a constant voltage, and the AC component is controlled to a constant current. After the charging, an image portion is exposed by a laser beam 40 to form an electrostatic latent image, a toner image is formed as a visible image by the toner 30, and then the toner image is transferred to the transfer material 38 by the transfer roller 37 to which a voltage is applied. Have the process of transferring to

Next, the developing container 32 in the process cartridge was modified. A medium resistance rubber roller (16φ) made of silicone rubber in which resistance is adjusted by dispersing carbon black instead of an aluminum sleeve containing a magnet serving as a toner supply body is used as the toner carrier 34.
It came into contact with the photoconductor 36. The moving direction and the rotation peripheral speed of the surface of the toner carrier 34 are the same in the contact portion with the surface of the photoconductor drum, and are 1 to the rotation peripheral speed of the photoconductor drum.
Drive is performed so as to be 50%. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the photoconductor surface is 80 mm / s.

As a means for applying the toner to the toner carrier, an application roller 35 was provided at the developing portion, and was brought into contact with the toner carrier. At the contact portion, the toner was applied to the toner carrier by rotating the surface of the application roller 35 so that the moving direction was opposite to the direction of movement of the toner carrier. Furthermore, a resin-coated stainless steel blade 33 was attached to control the coat layer of the toner on the toner carrier. As the cleaning member 39, a blade made of urethane rubber is used.

As the photosensitive member, the photosensitive drum (1) manufactured in (Photosensitive member manufacturing example 1) was used, and process conditions were set so as to satisfy the following developing conditions. Photoconductor dark area potential -700V Photoconductor light area potential -150V Development bias -450V (DC component only)

The toner (5A) was used at room temperature and normal humidity (25 ° C.).
/ 60 RH%) environment, the character image with a print area ratio of 4% was continuously printed out for 100 sheets from the beginning, and image evaluation and image contamination due to charging failure were evaluated. Missing, image fog, dot reproducibility, and image ghost were all good. Further, no occurrence of cleaning failure was observed.

[0566] Further, after the image evaluation for the initial 100 sheets is completed,
Continuously under low temperature and low humidity (15 ℃ / 10RH%) environment
The image was printed out for 00 sheets, and the image evaluation was performed again. As a result, the same image quality as in the initial 100 sheets was obtained. Further, the observation of the toner layer thickness regulating blade, the photosensitive drum, and the cleaning blade revealed that the toner did not adhere and did not need to be replaced. Also, there was no problem with the fixing property.

(Evaluation Method) (1) Image Density 5 mm on a side of ordinary paper for copying machine (75 g / m ² )
Was printed out, and the relative density of the white background portion having a document density of 0.00 with respect to the printout image was measured using "Macbeth reflection densitometer RD918" (manufactured by Macbeth). A: 1.40 or more B: 1.35 or more and less than 1.40 C: 1.00 or more and less than 1.35 D: less than 1.00

(2) Image Scattering This is the evaluation of the scattering of fine lines related to the image quality of a graphical image. A 1-dot line image that is more easily scattered than a character image is converted to plain paper (75 g /
m ² ), the reproducibility of the line image when printed out and the scattering of toner to the periphery were visually evaluated. A: Almost no occurrence, showing good line reproducibility. B: Slight scattering is observed. C: Slight scattering is observed, but little influence on line reproducibility. D: Remarkable scattering is observed, line reproduction. Inferior

(3) Missing part of image The “surprise” character pattern shown in FIG.
8g / m ² ), the hollow portion of the character portion when printed out (the state shown in FIG. 16B) was visually evaluated. A: Almost no occurrence B: Slight hollowing out C: Some hollowing out D: Remarkable hollowing out

(4) Image Fogging The toner remaining on the photoreceptor at the time of forming a solid white image is taped off with a Mylar tape and peeled off, and the reflection density of the tape pasted on paper is measured using a Macbeth reflection densitometer RD.
918 ". Evaluation was performed using a numerical value obtained by subtracting the reflection density when the Mylar tape was directly pasted on paper from the obtained reflection density. The smaller the numerical value, the more the image fog is suppressed. A: less than 0.03 B: 0.03 or more and less than 0.07 C: 0.07 or more and less than 1.00 D: 1.00 or more

(5) Dot Reproducibility The electric field is easily closed by the latent image electric field, and it is difficult to reproduce
An image of an isolated dot pattern having a small diameter (X = 50 μm) as shown in (1) was printed out, and the dot reproducibility was evaluated. A: 2 or less defects in 100 B: 3 to 5 defects in 100 C: 6 to 10 defects in 100 D: 11 or more defects in 100

(6) Image Ghost After printing out a solid black band image X having a width a and a length 1 shown in FIG. 17A, a width b shown in FIG.
When a halftone image Y having a length of 1 is printed out in (> a), the grayscale difference appearing on the halftone image (FIG. 1)
7 (C), A, B, and C) were visually evaluated. A: No difference in contrast is observed at all. B: A slight difference in contrast is observed between B and C. C: A slight difference in contrast is observed between A, B and C. D: A noticeable difference in contrast is observed.

(7) Matching with Toner Layer Thickness Regulating Blade After the printout test, the state of fixation of the residual toner on the toner layer thickness regulating blade and the effect on the printout image were visually evaluated. A: No sticking occurred B: Contamination occurred, but almost no sticking C: Sticking, but little effect on image D: Lots of sticking, causing image unevenness

(8) Matching with Photoreceptor Drum After the printout test was completed, the state of scratches on the surface of the photoreceptor drum and adhesion of toner and the effect on the printout image were visually evaluated. A: No sticking occurred. B: Scratches occurred on the surface, but hardly any sticking. C: Sticking, but little effect on the image. D: Many sticking, vertical streak-like image defects. Arise

(9) Matching with Cleaning Blade After the printout test was completed, the scratch on the surface of the cleaning blade, the state of fixation of residual toner, and the effect on the printout image were visually evaluated. A: no sticking occurred B: scratches occurred on the surface, but hardly any sticking C: sticking but little effect on image D: many sticking, causing image defects

Table 18 shows the results of the evaluation.

<Example 30> The procedure of Example 29 was repeated, except for the following.

The surface of the toner carrier was moved in the same direction at the portion in contact with the surface of the photosensitive drum, and was driven so as to be 200% of the rotational peripheral speed of the photosensitive drum. The peripheral speed of the toner carrier is 160 mm / s,
The relative speed with respect to the photoreceptor surface is 80 mm / s.

Further, process conditions were set so as to satisfy the following developing conditions. Development bias -500V (DC component only)

[0580] A durability test was performed on 5000 sheets while replenishing the toner. As a result, the image density and the like were all good, no cleaning failure occurred, and an image quality equivalent to the initial level was obtained.
In addition, although the control blade, the photosensitive drum, and the cleaning blade were observed, they did not need to be replaced without sticking or the like. Table 18 shows the evaluation results.

<Examples 31 to 33> Evaluations were made in the same manner as in Example 29 except that toners (5B) to (5D) were used as toners. As shown in Table 18, generally good results were obtained.

<Comparative Example 10> A similar test was conducted as in Example 29, except that the comparative toner (5a) and the photosensitive drum (2) of Photoconductor Production Example 2 were used.

[0583] Process conditions were set so as to satisfy the following developing conditions. Development bias -350V (DC component only)

A cleaning failure occurred during a printout test in a low temperature and low humidity environment. When printing was continued up to 5000 sheets while cleaning the cleaning blade every time a cleaning failure occurred, white spots were generated in a part of the solid black image due to toner fusion at the photoconductor cycle.

When the photosensitive member was replaced, the white dots disappeared, but the image density did not recover to the initial level. The reproduction of the isolated dot of 50 μm was insufficient, and the scattering of the line image was conspicuous. The results are shown in Table 18.

<Comparative Examples 11 to 13> Evaluations were made in the same manner as in Example 29 except that comparative toners (5a) to (5c) were used as toners. As shown in Table 18, good results were not obtained because the phenol derivative condensate having a specific structure in the present invention was not used at a specific content ratio.

[0587]

[Table 18]

<Embodiment 34> In the electrophotographic apparatus used in Embodiment 29, the toner application roller 3 in the developing container 32
Example 5 is the same as Example 29 except that a sponge roller having a single layer structure is used and a bias voltage is applied from a bias applying means (not shown) to the toner applying roller 35. Image formation was performed in the same manner as in Example 29, and the evaluation was performed.

At the time of development, a DC bias of -300 V is applied to the developing roller 34 as a developing bias voltage.
To the toner application roller 35, only a DC component of -450 V was applied as an application bias voltage.

Evaluation was performed in the same manner as in Example 29. As a result, all were stable and good in image density and the like, and no poor cleaning occurred, and excellent image quality was obtained. The matching with the image forming apparatus was also good.

<Example 35> Toners (5E) to (5H)
Was used to form a full-color image using each of the developing units 54 to 57 of the image forming apparatus shown in FIG.

As shown in FIG. 23, after the first transfer step, the image forming apparatus is provided with a cleaning member in contact with the photoreceptor surface as first cleaning means for removing toner remaining on the photoreceptor surface. And a second cleaner for removing toner remaining on the surface of the intermediate transfer member after the second transfer step. As a cleaning unit, a cleaner having a cleaning member in contact with the surface of the intermediate transfer member is located downstream of the second transfer portion,
Is provided downstream of the transfer section.

As the developing devices 54 to 57, those having the structure of the developing device 8 shown in FIG. 23 were used.

Medium resistance rubber roller (16φ) made of silicone rubber with carbon black dispersed and resistance adjusted
Is a toner carrier 9 and is in contact with the photoconductor. The moving direction and the rotational peripheral speed of the surface of the toner carrier 9 are the same in the contact portion with the photoconductor surface, and the toner carrier 9 is driven to be 150% of the rotational speed of the photoconductor. That is, the peripheral speed of the toner carrier is 120 mm / s, and the relative speed with respect to the photoconductor surface is 80 mm / S.

As a means for applying the toner to the toner carrier, a single-layer sponge roller was provided as the application roller 12, and was brought into contact with the toner carrier. At the contact,
The toner was applied to the toner carrier by rotating the application roller so that the surface of the application roller moved in the direction opposite to the direction of movement of the toner carrier. Further, a resin-coated stainless steel blade 16 was attached for controlling the toner coat layer on the toner carrier.

As the photoreceptor, the photoreceptor drum (1) manufactured in (Photoreceptor Production Example 1) was used, and the following developing conditions and image forming conditions were set so as to satisfy the transfer member. Photoconductor dark area potential: -700 V Photoconductor light area potential: -150 V Development bias applied to the developing roller: -450 V (DC component only) Bias applied to the toner application roller: -300 V (DC component only) First transfer step Transfer bias applied to the intermediate transfer property at
300 V (DC component only) Transfer bias applied to the transfer roller in the second transfer step:
1000V (DC component only)

The toner image transferred onto the recording material under the above-mentioned image forming conditions was heat-fixed to the recording material by the following heat fixing device.

As the heat fixing device 70, a heat roll type fixing device having no oil application function was used. At this time, both the upper roller 68 and the lower roller 69 had a surface layer made of a fluororesin, and the diameter of the roller was 60 mm. The fixing temperature was set at 150 ° C., and the nip width was set at 7 mm.

Using the image forming apparatus having the above structure, 30
When a continuous image output test was performed on 00 sheets, a high-quality full-color image with high density and no image contamination was obtained.

The matching with the image forming apparatus was also good.

Example 36 A two-component developer was prepared by mixing a carrier with the toner (5E).
When an image was formed using the two-component developer at a process speed of 180 mm / sec in the image forming apparatus shown in (1), a high-density, high-quality image without image contamination was obtained. There was no problem with matching with the image forming apparatus.

The evaluation was performed in the same manner as in Example 29.

As a carrier of the above two-component developer, a ferrite carrier having a surface layer having an average particle diameter of 60 μm coated with a silicone resin was used, and the toner concentration was set to 6%.

The evaluation results are shown in Table 19.

<Embodiment 37> The embodiment 36 is similar to the embodiment 36 except that the photoconductor drum (2) of the photoconductor production example 2 is used as the photoconductor.
The evaluation was performed in the same manner as described above. As shown in Table 19, although slightly inferior to Example 36, generally good results were obtained.

<Examples 38 and 40> As toner, (5
Evaluation was performed in the same manner as in Example 36 except that F) to (5H) were used. As shown in Table 19, generally good results were obtained.

<Comparative Example 14> Evaluation was made in the same manner as in Example 36 except that the comparative toner (5c) was used as the toner. As shown in Table 19, good results could not be obtained because the phenol derivative condensate having a specific structure in the present invention was not used at a specific content ratio.

[0608]

[Table 19]

(Production Example 30 of Toner) 700 g of ion-exchanged water and 0,0 ml of a 2-liter four-necked flask equipped with a high-speed stirrer CLEARMIX (manufactured by M Technique Co., Ltd.)
800 g of a 1 mol / L-Na ₃ PO ₄ aqueous solution was charged, and the number of revolutions of the high-speed stirring device was set to 15000 rpm.
Warmed to ° C. Here, 1.0 mol / L-CaCl
₂ 70 parts by mass of an aqueous solution is added, and a minute poorly water-soluble dispersant C
An aqueous dispersion medium containing a ₃ (PO ₄ ) ₂ was prepared.

On the other hand, the dispersoids include:-61 parts by mass of styrene monomer-19 parts by mass of n-butyl acrylate monomer-0.1 parts by mass of divinylbenzene monomer-Carbon black (particle size = 35 nm, pH = 8.5) 5 parts by mass ・ 3 parts by mass of unsaturated polyester resin (condensed polymer of epoxidized bisphenol A and fumaric acid, peak molecular weight = 4500) ・ Ester wax (melting point = 70 ° C.) 10 parts by mass After dispersing for 3 hours using an attritor (manufactured by Mitsui Kinzoku Co., Ltd.), 4 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer was added to the aqueous dispersion medium.
The body composition is charged and the internal temperature is 70 ° C. _TwoAtmosphere, high speed
While maintaining the rotation speed of the stirrer at 15,000 rpm, 1
The mixture was stirred for 5 minutes to granulate the polymerizable monomer composition. That
After that, replace the stirring device with a paddle stirring blade,
While maintaining the same temperature while stirring at 80 rpm, a polymerizable vinyl
When the polymerization conversion of the styrene-based monomer has reached 50%, 20 parts by mass of a styrene monomer 2 parts by mass of a phenol derivative condensate mixture having the following content: 2 parts by mass of the cyclic condensate (A2-4): 50 parts by mass % Of the chain condensate (B2-4): 50% by mass.
Is absorbed into the granulated particles of the polymerizable monomer composition in progress.
Was. Thereafter, the reaction temperature was raised to 80 ° C., and the polymerization conversion rate was increased.
When it reached almost 100%, the polymerization reaction was completed.

After completion of the polymerization, the remaining monomers were distilled off under reduced pressure under heating, and then, after cooling, dilute hydrochloric acid was added to dissolve the poorly water-soluble dispersant. After repeating water washing several times,
Drying was performed using a conical ribbon dryer (manufactured by Okawara Seisakusho) to obtain polymer particles (6A).

The above polymer particles (6A) (100 parts by mass) and hydrophobic oil-treated silica fine powder (BET: 200 m ² /
g) 2 parts by mass were dry-mixed with a Henschel mixer (manufactured by Mitsui Kinzoku Co., Ltd.) to obtain the toner (6A) of the present invention.

The toner (6A) has a circle-equivalent number average diameter of 5.5 μm, an average circularity in the circularity frequency distribution of 0.984, a circularity standard deviation of 0.029, and a circularity of less than 0.950. The number of toner particles was 9% by number, the molecular weight distribution by GPC was 13,000, the peak molecular weight was 13,000, and Mw / Mn
Was 25.

The total amount of the polymerizable monomer remaining in the toner (6A) was 60 ppm (styrene monomer: 60 ppm,
n-butyl acrylate monomer and divinylbenzene monomer: 0 ppm). Further, when the dispersion state of the wax component was observed with a TEM, it was found to be substantially spherical and dispersed in the binder resin as shown in the schematic diagram of FIG.

(Production Examples 31 to 33 of Toner and Production Examples 4 and 5 of Comparative Toner) The same procedures as in Production Example 3 were carried out except that the types and amounts of the phenol-derived condensate and the wax component were changed.
After obtaining polymer particles (6B) to (6D) in the same manner as in Example No. 0, toners (6B) to (6D) of the present invention and comparative toners (6a) and (6b) were prepared.

Table 2 shows the types and amounts of the phenol derivative condensate and the wax component in the respective toner production examples.
0.

[0618]

[Table 20]

(Comparative Production Example 6 of Toner) The following materials were previously mixed, melt-kneaded with a twin-screw extruder, and the cooled kneaded material was coarsely pulverized by a hammer mill, and the coarsely pulverized product was finely pulverized by a jet mill. The obtained finely pulverized product was classified to obtain a classified powder (6c).・ Styrene-n-butyl acrylate-divinylbenzene resin 100 parts by mass (peak molecular weight = 13,000, Mw / Mn = 3.5, Tg = 55 ° C.) 8 parts by mass of carbon black used in Toner Production Example 30 3 parts by mass of unsaturated polyester resin used in Toner Production Example 30 10 parts by mass of wax component used in Toner Production Example 30 2 parts by mass of phenol derivative (cyclic condensate: A1-6)

Using the classified powder (6c), a comparative toner (6c) and a comparative developer (6c) were prepared in the same manner as in Production Example 30 of the toner.

[0621] In the comparative toner (6c), 145 styrene monomers derived from the binder resin were used as volatile components.
ppm, and 8 ppm of n-butyl acrylate monomer remained. The wax component was finely dispersed.

The toners (6A) to (6D) of the present invention obtained in the above toner production examples and the comparative toner (6a)
Table 21 summarizes the properties of (6) to (6c).

[0623]

[Table 21]

(Toner Production Examples 34 to 37) The type and amount of the colorant and the phenol derivative condensate were changed, and the temperature, pressure reduction degree, treatment time,
Polymer particles (6E) to (6H) were obtained in the same manner as in Production Example 30 of the toner except that the set temperature, stirring conditions, and processing time of the conical ribbon dryer were changed, and then the toner of the present invention was obtained. (6E) to (6H) were prepared.

The types and amounts of the colorant, the phenol derivative condensate and the wax component in each of the toner production examples, and the obtained toners (6E) to (6H) of the present invention
Are summarized in Table 22.

[0626]

[Table 22]

Embodiment 41 A 600 dpi laser beam printer (manufactured by Canon: LBP-860) is prepared as an image forming apparatus shown in FIG.
It was modified to 94 mm / s.

The cleaning rubber blade in the process cartridge is removed, the charging method of the apparatus is set to contact charging in which the rubber roller is brought into contact, and the applied voltage is changed to a DC component (−
1400 V). As the process speed is increased, severe conditions are required for uniform charging of the photoconductor.

As the photoconductor, the photoconductor drum (1) manufactured in Photoconductor Manufacturing Example 1 was used.

Next, the developing portion of the process cartridge was modified. Medium resistance rubber roller (16φ, hardness ASKER C45 degree, resistance 10 ⁵ Ω ·) made of urethane foam instead of stainless steel sleeve as toner carrier
cm) to make contact with the photoreceptor. The direction of movement of the surface of the toner carrier is the same as the direction of movement of the surface of the photoconductor, and the toner carrier is driven to be 130% of the peripheral speed of the photoconductor.

As means for applying the toner to the toner carrier, an application roller was provided at the developing portion in contact with the toner carrier. Further, a stainless steel blade coated with a resin for controlling a toner coat layer was mounted on the toner carrier. The developing bias voltage applied to the toner carrier at the time of development was only DC component (-450 V).

The image forming apparatus was remodeled and the process conditions were set so as to be compatible with the process cartridge remodeling.

The photosensitive member charging potential was set to -800 V in the dark area potential.
And the bright portion potential was -150V. 7 for transfer material
5 g / m ² paper was used.

The toner (6A) was used at room temperature and normal humidity (25 ° C.).
/ 6 RH%), 100 characters of a character image with a print area ratio of 4% were continuously printed out from the initial stage, and the image evaluation and the image contamination due to poor charging were evaluated.
Image stain, transferability, image fog, and dot reproducibility were all good. Further, when the toner adhesion amount [mg] per unit surface area [cm ² ] of the charging roller was measured, it was very small at 0.01 mg / cm ² .

Further, after the image evaluation for the initial 100 sheets is completed,
Continuous 50 under high temperature and high humidity (30 ℃ / 80RH%) environment
The image was printed out for 00 sheets, and the image evaluation was performed again. As a result, the same image quality as in the initial 100 sheets was obtained. Also, both the photosensitive drum and the developing roller were observed, but it was not necessary to replace the photosensitive drum without fusing the toner. Also, there was no problem with the fixing property.

(Evaluation Method) (1) Image Density Evaluation was performed in the same manner as in Example 29.

(2) Image Stain The image stain when a halftone image composed of one dot line and one dot space was printed out was visually evaluated. A: Not generated B: Slight stains are observed C: Fine black spots are observed D: Periodic band-shaped stains and vertical stripe-shaped stains are observed

(3) Transferability The remaining transfer toner on the photoreceptor at the time of solid black image formation was taped off with a Mylar tape and peeled off, and the reflection density of the tape pasted on paper was measured using a Macbeth reflection densitometer RD.
918 ". Evaluation was performed using a numerical value obtained by subtracting the reflection density when the Mylar tape was directly pasted on paper from the obtained reflection density. The smaller the value, the better the transferability. A: Less than 0.03 B: 0.03 or more, less than 0.07 C: 0.07 or more, less than 0.10 D: 0.10 or more

(4) Image fog Evaluation was made in the same manner as in Example 29.

(5) Dot Reproducibility Evaluation was made in the same manner as in Example 29.

(6) Contamination of Charging Roller The mass of toner adhered on the charging roller per unit area was measured. The smaller the toner adhesion amount, the better. A: 0.20mg / cm ² less B: 0.20mg / cm ² or more, 0.35 mg / cm ² less than C: 0.35mg / cm ² or more, 0.55 mg / cm ² less than D: 0.55 mg / cm ² or more

(7) Matching with Developing Roller After completion of the printout test, the state of adhesion of the residual toner to the developing roller and the effect on the printout image were visually evaluated. A: No sticking occurred B: Contamination occurred, but almost no sticking C: Sticking, but little effect on image D: Lots of sticking, causing image unevenness

(8) Matching with Photosensitive Drum After completion of the printout test, the state of scratches on the surface of the photosensitive drum and adhesion of toner and the effect on the printout image were visually evaluated. A: No sticking occurred. B: Scratches occurred on the surface, but hardly any sticking. C: Sticking, but little effect on the image. D: Many sticking, vertical streak-like image defects. Arise

(9) Matching with Fixing Device After the printout test was completed, the scratches on the surface of the fixing roller, the state of fixation of the residual toner, and the effect on the printout image were visually evaluated. A: no sticking occurred B: scratches occurred on the surface, but hardly any sticking C: self-adhesion, but little effect on image D: many sticking, causing image defects

Table 23 shows the evaluation results.

<Example 42> Process speed was set to 120
mm / s, and evaluated in the same manner as in Example 41 except that the photoconductor drum (2) of Photoconductor Manufacturing Example 2 was used. As shown in Table 23, as shown in Table 23, the process speed was increased and the photoconductor drum was changed, which resulted in more severe conditions.
The results were generally good.

<Examples 43 to 45> Evaluations were made in the same manner as in Example 41 except that toners (6B) to (6D) were used as toners. The results are shown in Table 23.

<Comparative Example 15> Example 41 was repeated except that the comparative toner (6a) and the photosensitive drum (2) were used.
The evaluation was performed in the same manner as in As shown in Table 23, remarkable image stains were generated from the beginning, and 500
Since it was difficult to continuously print 0 sheets, the evaluation was unavoidably stopped halfway.

<Comparative Examples 16 to 18> Evaluations were made in the same manner as in Example 41 except that comparative toners (6a) to (6c) were used as toners. As shown in Table 23, good results could not be obtained because the phenol derivative condensate having a specific structure in the present invention was not used at a specific content ratio.

[0650]

[Table 23]

<Embodiment 46> In the image forming apparatus used in Embodiment 41, the toner application roller 3 in the developing container 32
5, image forming was performed in the same manner as in Example 41 except that a single-layer sponge roller was used and a bias voltage was applied from a bias applying unit (not shown) to the toner applying roller 35. And evaluation was performed. As a developing bias voltage applied to the developing roller 34 during this development, only a DC component was applied at −300 V, and to the toner application roller 35, only a DC component was applied at −480 V as an application bias voltage.

The evaluation results were stable and good in both image density and fogging suppression, and the adhesion of the toner to the charging roller was slight, and both development and cleaning were achieved. Got quality.

The matching with the image forming apparatus was also good.

<Example 47> Toner (6E) produced
To (6H) are the developing units 54 of the image forming apparatus shown in FIG.
To 57 were used to form a full-color image.

[0655] As shown in FIG. 23, the image forming apparatus includes a cleaner having a first cleaning member for cleaning and removing the toner present on the surface of the photosensitive drum after the transfer step, between the transfer section and the development section. And a cleaning means for removing toner remaining on the surface of the intermediate transfer member after the second transfer step is provided with a cleaning member in contact with the surface of the intermediate transfer member. It is provided on the further downstream side and on the upstream side of the first transfer portion.

As the developing devices 54 to 57, those having the structure of the developing device 8 shown in FIG. 24 were used. After the first transfer, the toner remaining on the surface of the photoreceptor drum is charged with a charging bias by a charging unit so that the charging polarity of the toner is adjusted to a negative polarity.
At the time of development, only the toner present in the non-image area in the developing section is collected in the developing device.

In the developing unit 8, a medium-resistance rubber roller (16φ) made of silicone rubber in which carbon black was dispersed and the resistance of which was adjusted was used as the toner carrier 9, and was brought into contact with the photosensitive member. The moving direction and the rotational peripheral speed of the surface of the toner carrier 9 are the same in the contact portion with the photoconductor surface, and the toner carrier 9 is driven to be 150% of the rotational speed of the photoconductor.
That is, the peripheral speed of the toner carrier is 120 mm / s,
The relative speed with respect to the photoreceptor surface is 80 mm / s.

As means for applying toner to the toner carrier, a sponge roller having a single layer structure was provided as an application roller 12, and was brought into contact with the toner carrier. At the contact,
The toner was applied onto the toner carrier by rotating the application roller 12 such that the moving direction of the surface of the applying roller 12 moved in the opposite direction to the moving direction of the toner carrier. Further, a resin-coated stainless steel blade 16 was attached for controlling the toner coat layer on the toner carrier.

[0659] The photosensitive drum (1) produced in (Photoreceptor Production Example 1) was used, and image forming conditions were set so as to satisfy the following developing conditions and transfer conditions. Photoconductor dark area potential: -700V Photoconductor light area potential: -150V Development bias applied to the developing roller: -450V (DC component only) Bias applied to the toner application roller: -300V (DC component only) In the first transfer step Transfer bias applied to the intermediate transfer member:
350 V (only DC component) Transfer bias applied to the transfer roller in the second transfer step:
1100V (only DC component)

The toner image transferred onto the recording material under the above-described image forming conditions was heat-fixed to the recording material by the following heat fixing device.

As the heat fixing device 70, a heat roll type fixing device having no oil application function was used. At this time, both the upper roller 68 and the lower roller 69 had a surface layer made of a fluororesin, and the diameter of the roller was 60 mm. The fixing temperature was set at 150 ° C., and the nip width was set at 7 mm.

Using the image forming apparatus having the above configuration, 20
When a continuous image output test was performed on 00 sheets, a high-quality full-color image with high density and no image contamination was obtained.

Also, the toner adhesion mass on the charging roller was as small as 0.35 mg / cm ² , and the matching with other image forming apparatuses was good.

Example 48 A two-component developer was prepared by mixing a carrier with the toner (E), and the image forming apparatus shown in FIGS. 20 and 21 was processed at a process speed using the two-component developer. When an image was formed at 180 mm / sec, a high-quality image with high density and no image contamination was obtained. Also, there was no problem in matching with the image forming apparatus.

The evaluation was performed in the same manner as in Example 40.

As a carrier of the above two-component developer, a ferrite carrier having a surface layer having an average particle diameter of 60 μm coated with a silicone resin was used, and the toner concentration was set to 7%.

[0667] Table 24 shows the evaluation results.

Example 49 Example 48 was repeated except that the photoconductor drum (2) of Photoconductor Production Example 2 was used as the photoconductor.
The evaluation was performed in the same manner as in As shown in Table 24, although generally slightly inferior to Example 48, good results were obtained.

<Examples 49 to 52> As toner, (6
Evaluation was performed in the same manner as in Example 48 except that E) to (6H) were used. As shown in Table 24, although generally slightly inferior to Example 48, good results were obtained.

<Comparative Example 19> Evaluation was made in the same manner as in Example 48 except that Comparative Toner (6c) was used as the toner. As shown in Table 24, as shown in Table 24, the toner was significantly contaminated by the charging member, resulting in a remarkable image defect due to charging failure.

[0671]

[Table 24]

[0672]

The toner of the present invention 1 is excellent in low-temperature fixability and high-temperature offset resistance, and has a good charge amount of the toner.
Excellent image density) and transferability. Furthermore, a high quality transparency image excellent in the transparency of the fixed image of the OHP film can be provided.

The toner of the present invention 2 is excellent in electrophotographic properties, gives a high-definition image, is excellent in charge stability, and has little contamination to a developer holding member, a photoreceptor, a fixing device and the like. Further, the toner is excellent in fixability and storage stability.

The toner of the third invention uses a composite oxide containing at least Fe and Mn and having a surface treated with an organic compound as a coloring agent. Since this coloring agent is excellent in coloring power and dispersibility, even if the toner of the present invention 3 is used for either a one-component developer or a two-component developer, it has a high image density and no fog under high temperature and high humidity. High-resolution image quality is stably obtained, and excellent durability without toner scattering or the like is exhibited.

According to the present invention 4, even under severe conditions such as high temperature and high humidity, image quality is not impaired, fusion to a photosensitive member does not occur, and the surface of a toner carrier such as a carrier or a sleeve is formed. A highly durable toner that is resistant to contamination is provided.

According to the fifth aspect of the invention, the charging characteristics are improved by allowing the phenol derivative condensate having a specific structure to be present in the toner at a specific content ratio.

In particular, since the charge controllability of the toner in a low-temperature and low-humidity environment is improved, when used in the one-component contact developing system, high-quality image reproduction is possible, and the developed toner on the photoreceptor is improved. By appropriately controlling the charge amount, it is possible to prevent a decrease in cleaning performance due to excessive charging of the toner remaining after transfer. Further, the present invention can be applied to an image forming method having a high process speed at a low cost without adding an auxiliary member to the developing and cleaning process.

According to the present invention 6, since the charge controllability is improved by allowing the phenol derivative condensate having a specific structure to be present in the toner at a specific content ratio, a high quality image can be obtained.

Further, in the case of using the developing and cleaning method, the charge polarity control and the charge amount control of the transfer residual toner on the photoreceptor by the charging member are more reliably and uniformly performed, and the transfer residual in the developing process is performed. More stable recoverability and developability of the toner can be obtained. Further, the present invention can be applied to an image forming method having a high process speed at a low cost without adding an auxiliary member to the developing and cleaning process.

[Brief description of the drawings]

FIG. 1 is a schematic explanatory view of an apparatus for measuring a triboelectric charge amount of a toner.

FIG. 2 is a schematic view of a cross section of a toner particle in which a release agent is included in an outer shell resin.

FIG. 3 is a schematic diagram of a developing device to which the toner of the present invention can be applied.

FIG. 4 is a schematic diagram for explaining a full-color or multi-color image forming method.

FIG. 5 is a schematic diagram for explaining another image forming method.

FIG. 6 is a schematic diagram for explaining another image forming method.

FIG. 7 is a schematic diagram illustrating an example of a developing device.

FIG. 8 is a schematic diagram illustrating an example of another developing device.

FIG. 9 is a schematic diagram of a color image output apparatus using an intermediate transfer belt used in an embodiment of the present invention.

FIG. 10 is an exploded perspective view of a main part of the fixing device used in the embodiment of the present invention.

FIG. 11 is an enlarged cross-sectional view of a main part showing a film state when the fixing device used in the embodiment of the present invention is not driven.

FIG. 12 is an explanatory diagram of a small-diameter isolated dot pattern for checking development characteristics of toner.

FIG. 13 is a schematic view of a process of an electrophotographic apparatus preferably used in the image forming method of the present invention.

FIG. 14 is a schematic view illustrating an example of a cross section of a toner particle including a wax component.

FIG. 15 is a diagram schematically illustrating an image forming method using a contact one-component developing device, which is used as an example of an embodiment of the image forming method of the present invention.

FIG. 16 is an explanatory diagram of missing images.

FIG. 17 is an explanatory diagram of an image ghost.

FIG. 18 is a schematic diagram of a full-color image forming apparatus.

FIG. 19 is a schematic view illustrating an example of a developing device.

FIG. 20 is a schematic diagram of an image forming apparatus used in an embodiment of the present invention.

FIG. 21 is a schematic diagram of an image forming apparatus used in an embodiment of the present invention.

FIG. 22 is a schematic diagram of an image forming apparatus used in an embodiment of the present invention.

FIG. 23 is a schematic view of a full-color image forming apparatus.

FIG. 24 is a schematic view illustrating an example of a developing device.

FIG. 25 is an explanatory diagram of a method for measuring the electric resistance of the developing roller.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/083 G03G 15/06 101 2H077 9/097 15/08 112 2H134 15/02 101 501A 2H200 15/06 101 501C 15/08 112 501Z 501 504B 15/09 Z 15/16 103 504 15/20 101 507 9/08 325 15/09 331 15/16 103 384 15/20 101 346 21/10 301 302 15/08 507L 507D 21/00 326 15/08 507A 507X 507B (72) Inventor Yoshihiro Nakagawa 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Keiji Kawamoto 3-30 Shimomaruko, Ota-ku, Tokyo No.2 Canon Inc. (72) Inventor Akira Hashimoto Ota, Tokyo 3-30-2 Shimomaruko Canon Inc. (72) The inventor Takeshi Takiguchi 3-30-2 Shimomaruko 3-chome, Ota-ku, Tokyo Inside the Canon Inc. (72) Masanori Ito 3-chome Shimomaruko, Ota-ku, Tokyo No. 30-2 within Canon Inc. (72) Motoki Hisagi, the inventor 3--30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Manabu Ono, 3-30-2, Shimomaruko, Ota-ku, Tokyo No. Inside Canon Inc. (72) Inventor Satoshi Handa 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term inside Canon Inc. (reference) 2H005 AA01 AA02 AA03 AA06 AA13 AB06 AB07 CA04 CA14 CA17 CA22 CA26 CA30 DA02 EA03 EA05 EA06 EA07 EA10 2H031 AC02 AC08 AC14 AC19 AC31 AC33 AD09 AD15 BA02 BA03 BA05 BA09 CA01 CA10 FA01 2H033 AA02 AA09 BA58 BE03 2H068 AA06 BB31 2H073 AA07 BA03 BA11 BA13 BA21 BA23 BA43 CA02 AD03 AD23 AD02 AD03 AD24 AD31 AD35 DB08 EA03 EA12 EA13 EA14 EA15 FA01 FA19 FA22 GA 13 2H134 GA01 GB02 HD00 HF13 JA11 KG03 KG07 KH04 KJ02 2H200 FA01 FA08 GA23 GA28 GA44 GA47 GA49 GA50 GA56 HA02 HA12 HA29 HB03 HB12 HB14 HB22 HB45 HB46 HB47 HB48 JA02 JA23 JA25 JA26 JA27 JA28 J15 J01 J01 J03 MAB MC01 MC02 NA02 NA06 NA09 PA02 PA08

Claims (133)

[Claims] 1. A toner obtained by polymerizing a polymerizable monomer composition comprising at least a polymerizable monomer, a colorant, a polar resin, an ester-based wax and a crosslinking agent represented by the following formula, 135 ° C./Load 68.6N (7k
The melt index (MI) value in g) is 10 to
A toner characterized by being 100 g / 10 min. Embedded image [In the formula, R ₁ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₂ represents a linear or branched alkylene group having 2 to 6 carbon atoms, and n represents 0 to 20. ] 2. In a GPC chromatogram of a THF-soluble component of the toner, the main peak molecular weight Mp is 50.
And the weight average molecular weight Mw is 500
2. The method according to claim 1, wherein the number is from 100 to 1,000,000.
The toner according to 1. 3. An average circularity of 0.95 to 1.00 in a scattergram of circular equivalent diameter-circularity based on the number of toners measured by a flow-type particle image measuring apparatus. Item 3. The toner according to Item 1 or 2. 4. The amount of the crosslinking agent added to the polymerizable monomer 100
The toner according to any one of claims 1 to 3, wherein the amount is 0.01 to 5 parts by mass with respect to parts by mass. 5. The polar resin having an acid value of 1 to 35 (mgK
OH / g). The toner according to claim 1, wherein 6. The toner according to claim 1, wherein the polar resin is a polyester resin. 7. The method for producing a toner according to claim 1, wherein the polymerizable monomer composition is obtained by polymerization in an aqueous medium containing a dispersant. Of producing toner. 8. The method according to claim 7, wherein the pH of the aqueous medium is adjusted to 4.5 to 8.5. 9. A toner comprising at least one kind of a binder resin, a colorant, and a wax component. Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
Having a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ ; In the scattergram of the circular equivalent-circularity based on the number of toners measured by the flow type particle image measuring device for the toner, the circle-equivalent number average diameter D1 (μm) of the dry toner
Is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
A toner less than 0. 10. The toner according to claim 9, wherein the wax component is a compound having at least one long-chain ester group having 10 to 60 carbon atoms. 11. The toner according to claim 9, comprising at least one charge control agent represented by the following general formula (I). Embedded image 12. An acid value (AV ₁ ) of a component that determines T ₁ ,
The hydroxyl value (OHV ₁ ), the acid value (AV ₂₄ ) of the soluble component extracted after 24 hours of reflux, and the hydroxyl value (OHV ₂₄ ) are expressed by the following relational expressions: | AV ₂₄ −AV ₁ | ≦ 5 (mgKOH / ( extractable content per _{1g)) │OHV 24 -OHV 1 │} ≦ 5 (mgKOH / ( solubles 1
The toner according to any one of claims 9 to 11, wherein each of (g) is satisfied. 13. The toner according to claim 9, wherein 95% by number or more of toner particles having a continuous layer with a thickness of 10 to 200 nm on the outer periphery are present. 14. The toner according to claim 1, wherein the toner has an average circularity of 0.970 or more.
The toner according to any one of claims 9 to 13, wherein the circularity standard deviation is less than 0.035 at 0.995. 15. In a scattergram of circularity-circularity based on the number of toners measured by the flow-type particle image measuring device, toner particles having a circularity of less than 0.950 are 15% by number or less. The toner according to any one of claims 9 to 14, wherein: 16. The toner according to claim 9, wherein a surface layer is formed by a seed polymerization method. 17. at least one binder resin, a colorant,
A polymerizable monomer having at least one or more polymerizable monomers and a polymerization initiator as essential components in microparticles containing a wax component and at least one or more charge control agents represented by the following general formula (I): A method for producing a toner, comprising forming a surface layer by adding a body composition and performing seed polymerization. Embedded image 18. The fine particles are produced by a suspension polymerization method or an emulsion polymerization method, and the polymerization conversion is 30 to 95%.
2. The method according to claim 1, wherein the seed polymerization is performed when
8. The method for producing a toner according to item 7. 19. The method according to claim 1, wherein the polymerizable monomer composition in the production method contains a charge control agent as an essential component.
19. The method for producing a toner according to 7 or 18. 20. At least a charging step of externally applying a voltage to a charging member to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier. A forming step, a developing step of developing the electrostatic image with toner to form a toner image on the electrostatic latent image carrier, and a transfer step of transferring the toner image on the electrostatic latent image carrier to a transfer material, A fixing step of heating and fixing the toner image on the transfer material, wherein the toner is a dry toner comprising at least one kind of a binder resin, a colorant, and a wax component; Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
Having a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ ; In the scattergram of the circular equivalent-circularity based on the number of toners measured by the flow type particle image measuring device for the toner, the circle-equivalent number average diameter D1 (μm) of the dry toner
Is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
An image forming method characterized by being less than 0. 21. In a scattergram of circle-based circularity-circularity based on the number of toners measured by a flow type particle image measuring device, the circle-equivalent number average diameter D1 (μm) of the toner is 2 to 10 μm, and , Average circularity is 0.920 ~
The image forming method according to claim 20, wherein the circularity standard deviation is less than 0.040 at 0.995. 22. The toner has an average circularity of 0.970 or more.
22. The image forming method according to claim 20, wherein the circularity standard deviation is less than 0.035 at 0.995. 23. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring apparatus, the toner has 15% by number or less of toner particles having a circularity of less than 0.950. The image forming method according to any one of claims 20 to 22, wherein: 24. In the developing step, the moving speed of the toner carrier surface in the developing area is 1.05 to 3.0 times the moving speed of the electrostatic latent image carrier. The image forming method according to any one of claims 20 to 23, wherein the surface roughness Ra (μm) is 1.5 or less. 25. The image forming method according to claim 20, wherein a ferromagnetic metal blade is arranged at a minute interval so as to face the toner carrier. 26. The image forming method according to claim 20, wherein a blade made of an elastic material is brought into contact with said toner carrier. 27. The image according to claim 20, wherein said electrostatic latent image carrier and said toner carrier have a certain interval, and are developed while applying an alternating electric field. Forming method. 28. The charging step includes: applying a voltage to the charging member from outside by bringing the charging member into contact with the electrostatic latent image carrier;
21. The electrostatic latent image carrier is charged.
28. The image forming method according to any one of the above items. 29. In a transfer step of electrostatically transferring a toner image on an electrostatic latent image carrier to a transfer material using a transfer device, the electrostatic latent image carrier and the transfer device are interposed via the transfer material. The image forming method according to any one of claims 20 to 28, wherein the image forming method is abutted. 30. The heat fixing step in which a toner image is heat-fixed to a recording material by a heat fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 30. The image forming method according to any one of the above items. 31. A heating and fixing step in which a toner image is formed on a recording material by a fixedly supported heating member and a pressing member which is in pressure contact with the heating member and closely adheres to the heating member via a film. 31. The image forming method according to claim 20, wherein the image is fixed by heating. 32. An untransferred residual toner on the electrostatic latent image carrier after the transfer is cleaned and collected, and the collected toner is supplied to a developing unit and held again in the developing unit. 32. The image forming method according to claim 20, further comprising a toner reuse mechanism for developing an electrostatic latent image on the carrier. 33. At least a charging step of externally applying a voltage to a charging member to charge an electrostatic latent image carrier, and a latent image forming an electrostatic latent image on the charged electrostatic latent image carrier Forming a toner image on the electrostatic latent image carrier by developing the electrostatic charge image with toner, and a first process of transferring the toner image on the electrostatic latent image carrier to the intermediate transfer body A transfer step, and a second step of transferring the toner image on the intermediate transfer body to a transfer material.
And a fixing step of heating and fixing the toner image on the transfer material, wherein the toner is a dry toner comprising at least one binder resin, a colorant, and a wax component, . Under chloroform reflux, the glass transition temperature (T ₁ ) of the soluble component extracted from the toner during the time t from the start of reflux measured by a differential scanning calorimeter, and the soluble component extracted 24 hours after reflux. The glass transition temperature (T ₂₄ ) measured by a differential scanning calorimeter satisfies the following relationship: 40 ≦ T ₂₄ ≦ 70 (° C.) 5 <T ₁ −T ₂₄ <75 (° C.) 100 <T ₁ + T ₂₄ <180 (° C) 15 ≦ t ≦ 60 (min). Of the components to determine the T _1, the main component of the resin component is a polymer of a vinyl monomer. In the molecular weight distribution of the toner obtained by gel permeation chromatography (GPC) of the tetrahydrofuran (THF) soluble portion, the molecular weight in terms of polystyrene was 3
Having a peak molecular weight in the range of × 10 ^{3 to} 5 × 10 ⁵ , and the circle of the dry toner in the circle equivalent diameter-circularity scattergram based on the number of toners measured by the flow type particle image measuring device of the toner. The equivalent number average diameter D1 (μm) is 2
And the average circularity of the toner is 0.1 to 10 μm.
An image forming method wherein the circularity standard deviation is 920 to 0.995 and is less than 0.040. 34. In a scattergram of circle-based diameter-circularity based on the number of toners measured by a flow-type particle image measuring device, the circle-equivalent number average diameter D1 (μm) of the toner is 2 to 10 μm, , Average circularity is 0.920 ~
The image forming method according to claim 33, wherein the circularity standard deviation is less than 0.040 at 0.995. 35. The toner has an average circularity of 0.970 or more.
35. The image forming method according to claim 33, wherein the circularity standard deviation is less than 0.035 at 0.995. 36. In the scattergram of the circle-equivalent diameter-circularity based on the number of toners measured by the flow type particle image measuring device, the toner has 15% by number or less of toner particles having a circularity of less than 0.950. The image forming method according to any one of claims 33 to 35, wherein: 37. In the developing step, the moving speed of the toner carrier surface in the developing area is 1.05 to 3.0 times the moving speed of the electrostatic latent image carrier. 37. The image forming method according to claim 33, wherein the surface roughness Ra (μm) is 1.5 or less. 38. The image forming method according to claim 33, wherein a ferromagnetic metal blade is disposed at a minute interval so as to face the toner carrier. 39. The image forming method according to claim 33, wherein a blade made of an elastic body is brought into contact with the toner carrier. 40. The image according to claim 33, wherein the electrostatic latent image carrier and the toner carrier have a certain interval, and are developed while applying an alternating electric field. Forming method. 41. The charging step includes: bringing a charging member into contact with the electrostatic latent image carrier, applying a voltage to the charging member from outside,
34. The electrostatic latent image carrier is charged.
40. The image forming method according to any one of the above items. 42. In a transfer step of electrostatically transferring a toner image on an electrostatic latent image carrier to a transfer material using a transfer device, the electrostatic latent image carrier and the transfer device are interposed via the transfer material. The image forming method according to any one of claims 33 to 41, wherein the image forming apparatus is in contact with the image forming apparatus. 43. The heating and fixing step, wherein a toner image is heat-fixed to a recording material by a heating and fixing device which does not supply an offset preventing liquid or does not have a fixing device cleaner. 43. The image forming method according to any one of the above items. 44. The toner image is formed on a recording material by the heating and fixing step, in which a heating member fixed and supported and a pressing member which is in pressure contact with the heating member and closely adheres to the heating member via a film. The image forming method according to any one of claims 33 to 43, wherein heating and fixing are performed. 45. An untransferred residual toner on an electrostatic latent image carrier after transfer is collected by cleaning, and the collected toner is supplied to a developing unit and held again by the developing unit. The image forming method according to any one of claims 33 to 44, further comprising a toner reuse mechanism for developing the electrostatic latent image on the carrier. 46. A toner comprising at least a binder resin, a colorant and a release agent, wherein at least a part of the binder resin has a cross-linked structure by a cross-linking agent, and the cross-linking agent has the following general formula [a]: 4] (Wherein at least one of R _{1 to} R ₅ and at least one of R _{6 to} R ₁₀ are a substituent having a vinyl group, and the others are each independently a hydrogen atom, a halogen atom, C ₁
Saturated / unsaturated alkyl group having -C _20, alkoxy groups, aromatic hydrocarbon group, a hydroxyl group, a carboxyl group, 1
It is selected from the group consisting of a tertiary amino group, a nitro group, a sulfone group, a sulfamide group, a cyano group, an alkyl carboxylate, and an acyl group. A) a biphenyl compound represented by the formula: 47. The toner according to claim 47, wherein the toner is a polymerized toner obtained by polymerizing a polymerizable monomer composition comprising at least a polymerizable monomer, a colorant, a release agent, and a crosslinking agent. 47. The toner according to claim 46. 48. The toner according to claim 46, wherein the release agent is an ester wax having a melting point of 40 to 100 ° C. 49. The method for producing a toner according to claim 46, wherein the polymerizable monomer composition is contained in an aqueous dispersion medium containing a sparingly water-soluble salt compound as a dispersion stabilizer. A process for producing a toner. 50. The aqueous dispersion medium has a pH of 4.5 to 8.5.
50. The method according to claim 49, wherein the polymerizable monomer composition is polymerized after the adjustment. 51. A toner having toner particles containing at least a binder resin and a colorant, wherein a complex oxide having at least a surface treated with an organic compound is used as the colorant, and the complex oxide is formed of at least Fe. And Mn, and the content of Mn in the composite oxide is 2 to 55 with respect to the total amount of Fe in the composite oxide.
Atomic%. 52. The content of Mn in the composite oxide is 3 to 50 at% based on the total amount of Fe in the composite oxide.
52. The toner according to claim 51, wherein: 53. The toner according to claim 51, wherein the surface treatment of the composite oxide is performed using at least a silicon-containing compound. 54. The toner according to claim 53, wherein the silicon-containing compound contains at least a silane coupling agent. 55. The composite oxide having an average diameter of 0.01 to
The thickness is 0.13 µm.
4. The toner according to any one of 4. 56. A nitrogen adsorption specific surface area (B
ET specific surface area) The toner according to any one of claims 51 to 55, characterized in that a 6~80m ² / g. 57. The composite oxide according to claim 51, wherein the surface treatment is performed by a wet method.
The toner according to any one of the above. 58. The toner according to claim 51, wherein the weight average particle diameter is 1 to 9 μm. 59. The toner according to claim 51, wherein a part or the whole of the toner is formed by a polymerization method. 60. At least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image on the charged image carrier by image exposure; (C) development of the electrostatic latent image is achieved by a toner layer formed of toner carried on the surface of the toner carrier carrying the electrostatic latent image, whereby development of the electrostatic latent image is achieved; A developing step of forming an image; (d) applying the toner image formed on the surface of the image carrier through an intermediate transfer member;
Or (e) a cleaning step of cleaning and removing toner remaining on the surface of the image carrier after the transfer process, and using a cleaned image carrier. A toner used in an image forming method in which the steps (a) to (e) are repeated, wherein the toner contains at least a binder resin, a colorant, a wax component, and a phenol derivative condensate. The phenol derivative condensate in the following general formula <
A> a mixture of a cyclic condensate represented by A>, a chain condensate represented by general formula <B>, and a low molecular weight condensate represented by general formula <C>, and their respective content ratios are represented by general formula <A> Cyclic condensate represented by the formula: 5 to 95% by mass Chain condensate represented by the general formula <B>: 5 to 95% by mass Low molecular weight condensate represented by the general formula <C>: 0 to 5% by mass A toner characterized in that: Embedded image [Wherein, R _{1 to} R ₁₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic acid ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X1 and Y1 are integers of 0 to 8, and the sum of X1 and Y1 is 3 to 12. ] [Wherein, R _{21 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X2 and Y2 are integers of 0 to 8, and the sum of X2 and Y2 is 3 to 12. ] [In the formula, R _{41 to} R ₅₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X3 and Y3 are integers of 0 to 2, and the sum of X3 and Y3 is 1 to 2. ] 61. A circle-equivalent diameter-circularity scattergram based on the number of toners measured by a flow type particle image measuring device, wherein the circle-equivalent number average diameter D1 (μm) of the toner is 2 to 10 μm, and The average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
61. The toner of claim 60, wherein the value is less than zero. 62. The toner has an average circularity of 0.950 or more.
62. The toner of claim 61, wherein the circularity standard deviation is less than 0.035 at 0.995. 63. The toner has an average circularity of 0.970 or more.
0.990, circularity standard deviation is 0.015 or more and 0.0
62. The toner of claim 61, wherein the toner is less than 35. 64. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring device, the number of toner particles having a circularity less than 0.950 is 15% by number or less. The toner according to any one of claims 60 to 63, wherein: 65. A transmission electron microscope (TEM) of the toner.
In the observation of the tomographic plane of the toner particles by using (1), 0.9 ≦ R / D4 with respect to the circle-based weight average diameter D4 (μm) based on the weight of the toner measured by the flow type particle image measuring device.
Twenty tomographic planes of toner particles exhibiting a major diameter R (μm) satisfying the relationship of ≦ 1.1 are selected, and (2) a phase separation structure caused by a wax component present in the selected tomographic planes of the toner particles; The longest major axis r was measured, and (3) the arithmetic mean value of the obtained r / R (r / R)
_The wax component is substantially spherical and / or in the binder resin such that _st satisfies 0.05 ≦ (r / R) _st ≦ 0.95.
65. The toner according to any one of claims 60 to 64, wherein the toner is dispersed in a spindle-shaped island shape. 66. An arithmetic mean value of the r / R (r / R) _st
Wherein the wax component is substantially dispersed in the binder resin in a spherical and / or spindle-shaped island shape so as to satisfy 0.25 ≦ (r / R) _st ≦ 0.90. The toner according to claim 65. 67. The toner according to claim 60, wherein the residual amount of the polymerizable vinyl monomer in the toner is 200 ppm or less. 68. at least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image on the charged image carrier by image exposure; (C) development of the electrostatic latent image is achieved by a toner layer formed of toner carried on the surface of the toner carrier carrying the electrostatic latent image, whereby development of the electrostatic latent image is achieved; A developing step of forming an image; (d) applying the toner image formed on the surface of the image carrier through an intermediate transfer member;
Or (e) a cleaning step of cleaning and removing toner remaining on the surface of the image carrier after the transfer process, and using a cleaned image carrier. In the image forming method in which the steps (a) to (e) are repeated, the toner is a toner containing at least a binder resin, a colorant, a wax component, and a phenol derivative condensate, and the phenol in the toner is The derivative condensate is a mixture of a cyclic condensate represented by the following general formula <A>, a chain condensate represented by the general formula <B>, and a low molecular weight condensate represented by the general formula <C>. Cyclic condensate represented by the general formula <A>: 5 to 95% by mass Chain condensate represented by the general formula <B>: 5 to 95% by mass Low molecular weight condensation represented by the general formula <C> Object: 0-5 % By mass. Embedded image [Wherein, R _{1 to} R ₁₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, and a phenyl group. X1 and Y1 are integers of 0 to 8, and the sum of X1 and Y1 is 3 to 12. ] [Wherein, R _{21 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X2 and Y2 are integers of 0 to 8, and the sum of X2 and Y2 is 3 to 12. ] [In the formula, R _{41 to} R ₅₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X3 and Y3 are integers of 0 to 2, and the sum of X3 and Y3 is 1 to 2. ] 69. In a scattergram equivalent to circle number-circularity based on the number of toners measured by a flow-type particle image measuring device, the circle-equivalent number average diameter D1 (μm) of the toner is 2 to 10 μm, and The average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
The image forming method according to claim 68, wherein the value is less than 0. 70. The toner has an average circularity of 0.950 or more.
70. The image forming method according to claim 69, wherein the circularity standard deviation is less than 0.035 at 0.995. 71. The toner has an average circularity of 0.970 or more.
0.990, circularity standard deviation is 0.015 or more and 0.0
70. The image forming method according to claim 69, wherein the number is less than 35. 72. In the scattergram of the circle equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring device, 15% by number or less of toner particles having a circularity less than 0.950. The image forming method according to any one of claims 68 to 71, wherein: 73. A transmission electron microscope (TEM) of the toner.
In the observation of the tomographic plane of the toner particles by using (1), 0.9 ≦ R / D4 with respect to the circle-based weight average diameter D4 (μm) based on the weight of the toner measured by the flow type particle image measuring device.
Twenty tomographic planes of toner particles exhibiting a major diameter R (μm) satisfying the relationship of ≦ 1.1 are selected, and (2) a phase separation structure caused by a wax component present in the selected tomographic planes of the toner particles; The longest major axis r was measured, and (3) the arithmetic mean value of the obtained r / R (r / R)
_The wax component is substantially spherical and / or in the binder resin such that _st satisfies 0.05 ≦ (r / R) _st ≦ 0.95.
73. The image forming method according to any one of claims 68 to 72, wherein the image is dispersed in a spindle-shaped island shape. 74. An arithmetic mean value of the r / R (r / R) _st
Wherein the wax component is substantially dispersed in the binder resin in a spherical and / or spindle-shaped island shape so as to satisfy 0.25 ≦ (r / R) _st ≦ 0.90. An image forming method according to claim 73. 75. The image forming method according to claim 68, wherein the residual amount of the polymerizable vinyl monomer in the toner is 200 ppm or less. 76. The image bearing member according to claim 68, wherein the image bearing member is made of an electrophotographic photoreceptor, and the surface of the photoreceptor has a contact angle with water of 85 ° or more. The image forming method as described in the above. 77. The image forming method according to claim 76, wherein a surface layer in which a compound powder containing a fluorine atom is dispersed in a resin is formed on the surface of the photoreceptor. 78. A compound powder containing a fluorine atom,
The image forming method according to claim 77, comprising a fluororesin powder. 79. The developing device has a developing device for holding the toner and a toner carrier for carrying and transporting the toner held in the developing device, and a surface of the toner carrier. 79. The development of the electrostatic latent image is achieved by bringing a toner layer formed by toner carried on the surface of the image carrier into contact with the toner layer. Image forming method. 80. In a developing step, a toner layer having a regulated toner layer thickness is formed on the surface of the toner carrier by bringing a toner layer thickness regulating member into contact with the toner carried on the toner carrier. 80. The image forming method according to claim 79, wherein the method is performed. 81. The method according to claim 79, wherein, in the developing step, the moving direction of the surface of the toner carrier in the developing area is set to the same direction as the moving direction of the surface of the image carrier. Image forming method. 82. In the developing step, the moving speed of the surface of the toner carrier in the developing area is set to be 1.05 to 3.0 times the moving speed of the surface of the image carrier. The image forming method according to claim 81, wherein 83. The toner holding device according to claim 79, wherein the toner held in the developing device is supplied to the toner carrier by a toner supply member for supplying the toner to the toner carrier. The image forming method according to any one of the above. 84. The toner supply member is a toner application roller that contacts the surface of the toner carrier, and the direction of movement of the surface of the toner application roller is set to be opposite to the direction of movement of the surface of the toner carrier. 84. The image forming method according to claim 83, wherein: 85. A developing bias voltage is applied to said toner carrier when developing said electrostatic latent image, and an application bias voltage is applied to said toner applying roller when supplying toner to said toner carrier. The image forming method according to claim 84, wherein: 86. An application bias voltage applied to the toner application roller is set to be higher in absolute value than a development bias voltage applied to the toner carrier, and the toner application roller is provided on a surface of the toner carrier. Supplies toner to
The image forming method according to claim 85, wherein the toner remaining on the surface of the toner carrier after development is removed. 87. The light potential of the electrostatic latent image on the image carrier has an absolute value of 0 to 250 V, and the dark portion potential has an absolute value of 30 V.
0 to 1000 V, and an application bias voltage applied to the toner application roller has an absolute value of 100 to 900 V,
The developing bias voltage applied to the toner carrier has an absolute value of 100 to 900 V, the coating bias voltage is set to be higher than the developing bias voltage by 10 to 400 V in absolute value, and the toner applying roller is The image forming method according to claim 85, wherein the toner is supplied to the surface of the toner carrier, and the toner remaining on the surface of the toner carrier after development is removed. 88. A developing device for holding a two-component developer having the toner and the carrier, and a developer for carrying and transporting the two-component developer held in the developing device. A magnetic brush of a two-component developer carried on the surface of the developer carrier, the magnetic brush of the two-component developer being brought into contact with the surface of the image carrier, so that the toner of the two-component developer is used. The image forming method according to any one of claims 68 to 80, wherein development of the electrostatic latent image is achieved. 89. The image forming method according to claim 88, wherein a developing bias voltage is applied to said developer carrier when said electrostatic latent image is developed. 90. In the transfer step, a transfer member to which a voltage is applied from the outside is brought into contact with the image carrier through the transfer material, whereby the toner image formed on the image carrier is removed. 7. Transferring to a transfer material.
The image forming method according to any one of Items 8 to 89. 91. In the transfer step, a recording material is used as the transfer material, and the toner image formed on the surface of the image carrier is transferred to the recording material, and the toner image transferred to the recording material is used. 90. The image forming method according to claim 68, wherein the image is fixed on the recording material. 92. In the transfer step, a first transfer is performed in which an intermediate transfer member is used as the transfer material, and the toner image formed on the image carrier is transferred to the intermediate transfer member. 69. A second transfer for transferring the toner image transferred to the transfer member to a recording material, and the toner image transferred to the recording material is fixed to the recording material.
90. The image forming method according to any one of the above items. 93. The image bearing member according to claim 68, wherein in the charging step, the image bearing member is charged by bringing a charging member to which an external voltage is applied into contact with the image bearing member. The image forming method according to any one of the above. 94. The image forming apparatus according to claim 68, wherein in the charging step, the image carrier is charged by bringing a charging member to which an external voltage is applied into contact with the image carrier. The image forming method according to any one of the above. 95. In the charging step, a DC voltage is externally applied to the charging member.
3. The image forming method according to 1., 96. The image forming apparatus according to claim 94, wherein in the charging step, a DC voltage and an AC voltage that is less than twice the discharge start voltage in applying the DC voltage are externally applied to the charging member. Method. 97. at least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image on the charged image carrier by image exposure; (C) developing the electrostatic latent image with a toner included in a developing device to form a toner image; (d) transferring the toner image formed on the surface of the image carrier through an intermediate transfer member A transfer step of transferring to a transfer material without or with intermediary, and a developing and cleaning method in which the developing device also serves in the developing step to collect toner remaining on the surface of the image carrier after the transfer step. A toner used in an image forming method using the toner, wherein the toner contains at least a binder resin, a colorant, a wax component, and a phenol derivative condensate, and the phenol derivative condensate in the toner has the following general formula: Expression <
A> a mixture of a cyclic condensate represented by A>, a chain condensate represented by general formula <B>, and a low molecular weight condensate represented by general formula <C>, and their respective content ratios are represented by general formula <A> Cyclic condensate represented by the formula: 5 to 95% by mass Chain condensate represented by the general formula <B>: 5 to 95% by mass Low molecular weight condensate represented by the general formula <C>: 0 to 5% by mass A toner characterized in that: Embedded image [Wherein, R _{1 to} R ₁₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X1 and Y1 are integers of 0 to 8, and the sum of X1 and Y1 is 3 to 12. ] [Wherein, R _{21 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X2 and Y2 are integers of 0 to 8, and the sum of X2 and Y2 is 3 to 12. ] [In the formula, R _{41 to} R ₅₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X3 and Y3 are integers of 0 to 2, and the sum of X3 and Y3 is 1 to 2. ] 98. In a scattergram of the circle equivalent diameter-circularity based on the number of toners measured by a flow type particle image measuring apparatus, the circle equivalent number average diameter D1 (μm) of the toner is 2 to 10 μm, and The average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.0
The toner according to claim 97, wherein the number is less than 40. 99. The toner has an average circularity of 0.950 or more.
99. The toner of claim 98, wherein the circularity standard deviation is less than 0.035 at 0.995. 100. The toner has an average circularity of 0.970.
０．９0.990, and the circularity standard deviation is 0.015 or more.
The toner according to claim 98, wherein the number is less than 035. 101. In the scattergram of circle equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring device, 15% or less of toner particles having a circularity less than 0.950 are not more than 15%. The toner according to any one of claims 97 to 100, wherein: 102. A transmission electron microscope (TE) of the toner
In the observation of the tomographic plane of the toner particles using M), (1)
With respect to the weight average diameter D4 (μm) of the toner based on the weight of the toner measured by the flow type particle image measuring device, 0.9 ≦ R /
Twenty tomographic planes of the toner particles exhibiting a major diameter R (μm) satisfying the relationship of D4 ≦ 1.1 are selected at (20). (2) Among the phase separation structures caused by the wax component present in the tomographic planes of the selected toner particles. , The major axis r of the largest one is measured, and (3) the arithmetic mean value of the obtained r / R (r / R
R) _st is, to satisfy _{0.05 ≦ (r / R) st} ≦ 0.95, substantially be dispersed in spherical and / or islands of spindle in the wax component in the binder resin The toner according to any one of claims 97 to 101, wherein: 103. An arithmetic mean value of the r / R (r / R)
_The wax component is substantially dispersed in the binder resin in a spherical and / or spindle-shaped island shape so that _st satisfies 0.25 ≦ (r / R) _st ≦ 0.90. 103. The toner according to claim 102. 104. The toner according to claim 97, wherein the residual amount of the polymerizable vinyl monomer in the toner is 200 ppm or less. 105. at least (a) a charging step of charging an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image on the charged image carrier by image exposure; (C) developing the electrostatic latent image with a toner included in a developing device to form a toner image; (d) transferring the toner image formed on the surface of the image carrier through an intermediate transfer member A transfer step of transferring to a transfer material without or with intermediary, and a developing and cleaning method in which the developing device also serves in the developing step to collect toner remaining on the surface of the image carrier after the transfer step. Wherein the toner comprises at least a binder resin, a colorant, a wax component, and a phenol derivative condensate, wherein the phenol derivative condensate in the toner has the following general formula: <
A> a mixture of a cyclic condensate represented by A>, a chain condensate represented by general formula <B>, and a low molecular weight condensate represented by general formula <C>, each having a content ratio of general formula <A> Cyclic condensate represented by the formula: 5 to 95% by mass Chain condensate represented by the general formula <B>: 5 to 95% by mass Low molecular weight condensate represented by the general formula <C>: 0 to 5% by mass An image forming method comprising: Embedded image [Wherein, R _{1 to} R ₁₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X1 and Y1 are integers of 0 to 8, and the sum of X1 and Y1 is 3 to 12. ] [Wherein, R _{21 to} R ₃₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X2 and Y2 are integers of 0 to 8, and the sum of X2 and Y2 is 3 to 12. ] [In the formula, R _{41 to} R ₅₅ represent a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, a sulfonic ester group, a carboxy ester group, an amino group, an amide group, a nitro group, a silyl group, or a phenyl group. X3 and Y3 are integers of 0 to 2, and the sum of X3 and Y3 is 1 to 2. ] 106. In a scattergram of circle-based circularity-circularity based on the number of toners measured by a flow-type particle image measuring apparatus, a circle-equivalent number average diameter D1 (μm) of the toners
Is 2 to 10 μm, the average circularity of the toner is 0.920 to 0.995, and the circularity standard deviation is 0.04.
The image forming method according to claim 105, wherein the value is less than 0. 107. The toner has an average circularity of 0.950.
107. The image forming method according to claim 106, wherein the circularity standard deviation is less than 0.035. 108. The toner has an average circularity of 0.970.
０．９0.990, and the circularity standard deviation is 0.015 or more.
107. The image forming method according to claim 106, wherein the number is less than 035. 109. In a scattergram of circular equivalent diameter-circularity based on the number of toners measured by the flow-type particle image measuring device, 15% by number or less of toner particles having a circularity less than 0.950 is less than 15%. An image forming method according to any one of claims 105 to 108. 110. A transmission electron microscope (TE) of the toner
In the observation of the tomographic plane of the toner particles using M), (1)
With respect to the weight average diameter D4 (μm) of the toner based on the weight of the toner measured by the flow type particle image measuring device, 0.9 ≦ R /
Twenty tomographic planes of the toner particles exhibiting a major diameter R (μm) satisfying the relationship of D4 ≦ 1.1 are selected at (20). (2) Among the phase separation structures caused by the wax component present in the tomographic planes of the selected toner particles. , The major axis r of the largest one is measured, and (3) the arithmetic mean value of the obtained r / R (r / R
R) _st is, to satisfy _{0.05 ≦ (r / R) st} ≦ 0.95, substantially be dispersed in spherical and / or islands of spindle in the wax component in the binder resin The image forming method according to claim 105, wherein: 111. An arithmetic mean value of the r / R (r / R)
_The wax component is substantially dispersed in the binder resin in a spherical and / or spindle-shaped island shape so that _st satisfies 0.25 ≦ (r / R) _st ≦ 0.90. The image forming method according to claim 110. 112. The image forming method according to claim 105, wherein the residual amount of the polymerizable vinyl monomer in the toner is 200 ppm or less. 113. The image bearing member according to claim 105, wherein the image bearing member comprises an electrophotographic photosensitive member, and the surface of the photosensitive member has a contact angle with water of 85 ° or more. The image forming method as described in the above. 114. The image forming method according to claim 113, wherein a surface layer in which a compound powder containing a fluorine atom is dispersed in a resin is formed on the surface of the photoreceptor. 115. The compound powder containing a fluorine atom comprises a fluorine resin powder.
15. The image forming method according to 14. The developing device has a developing device for holding the toner and a toner carrier for carrying and transporting the toner held in the developing device, and a surface of the toner carrier. The toner layer formed by the toner carried on the surface of the image carrier,
The image forming method according to any one of claims 105 to 115, wherein the development of the electrostatic latent image is achieved. 117. In a developing step, a toner layer having a regulated toner layer thickness is formed on the surface of the toner carrier by bringing a toner layer thickness regulating member into contact with the toner carried on the toner carrier. The image forming method according to claim 116, wherein the method is performed. 118. The developing device according to claim 116, wherein the moving direction of the surface of the toner carrier in the developing area is set to the same direction as the moving direction of the surface of the image carrier. Image forming method. 119. In the developing step, the moving speed of the surface of the toner carrier in the developing area is set to be 1.05 to 3.0 times the moving speed of the surface of the image carrier. The image forming method according to claim 118, wherein: 120. The toner holding device according to claim 116, wherein the toner held in the developing device is supplied to the toner carrier by a toner supply member for supplying the toner to the toner carrier. The image forming method according to any one of the above. 121. The toner supply member is a toner application roller that is in contact with the surface of the toner carrier, and the direction of movement of the surface of the toner application roller is set to be opposite to the direction of movement of the surface of the toner carrier. The image forming method according to claim 120, wherein the method is performed. 122. A developing bias voltage is applied to the toner carrier during development of the electrostatic latent image, and an application bias voltage is applied to the toner applying roller when supplying toner to the toner carrier. The image forming method according to claim 121, wherein the method is performed. 123. An application bias voltage applied to the toner application roller is set to be larger in absolute value than a development bias voltage applied to the toner carrier, and the toner application roller is provided on a surface of the toner carrier. 126. The image forming method according to claim 122, wherein the toner is supplied to the toner carrier, and the toner remaining on the surface of the toner carrier after development is removed. 124. The bright portion potential of the electrostatic latent image on the image carrier has an absolute value of 0 to 250 V, and the dark portion potential has an absolute value of 3 V.
The application bias voltage applied to the toner application roller has an absolute value of 100 to 900 V, and the development bias voltage applied to the toner carrier has an absolute value of 100 to 900 V. The coating bias voltage is
The developing bias voltage is set to be larger than the developing bias voltage by 10 to 400 V in absolute value, and the toner application roller supplies the toner to the surface of the toner carrier, and removes the toner remaining on the surface of the toner carrier after the development. The image forming method according to claim 122, wherein the image is peeled. 125. A developing device for holding a two-component developer having the toner and the carrier, and a developer for carrying and transporting the two-component developer held in the developing device. A magnetic brush of a two-component developer carried on the surface of the developer carrier, the magnetic brush of the two-component developer being brought into contact with the surface of the image carrier, so that the toner of the two-component developer is used. The image forming method according to any one of claims 105 to 117, wherein the development of the electrostatic latent image is achieved. 126. The image forming method according to claim 125, wherein a developing bias voltage is applied to said developer carrier when said electrostatic latent image is developed. 127. In the transfer step, a transfer member to which a voltage is applied from the outside is brought into contact with the image carrier through the transfer material, so that the toner image formed on the image carrier is removed. The image forming method according to any one of claims 105 to 126, wherein the image is transferred onto a transfer material. 128. In the transfer step, a recording material is used as the transfer material, and the toner image formed on the surface of the image carrier is transferred to the recording material, and the toner image transferred to the recording material is used. 130. The image forming method according to claim 105, wherein the image is fixed on the recording material. 129. In the transfer step, a first transfer is performed in which an intermediate transfer member is used as the transfer material and the toner image formed on the image carrier is transferred to the intermediate transfer member.
A second transfer for transferring the toner image transferred to the intermediate transfer member to a recording material is performed, and the toner image transferred to the recording material is fixed to the recording material. Item 1
125. The image forming method according to any one of Items 05 to 127. 130. The image carrier according to claim 105, wherein in the charging step, the image carrier is charged by bringing a charging member to which a voltage is applied from the outside into contact with the image carrier. The image forming method according to any one of the above. 131. In the charging step, a DC voltage is externally applied to the charging member.
30. The image forming method according to 30. 132. The image forming apparatus according to claim 130, wherein in the charging step, a DC voltage and an AC voltage that is less than twice the discharge start voltage in applying the DC voltage are externally applied to the charging member. Method. 133. A transfer section in the transfer step, a charging section in the charging step, and a developing section in the developing step, the transfer section, the charging section, and the developing section in the moving direction of the image carrier. It is arranged in the order of the developing unit, and between the transfer unit and the charging unit and between the charging unit and the developing unit, both contact the surface of the image carrier and contact the surface of the image carrier. 133. The image forming method according to claim 105, wherein the image forming method does not include a cleaning member for collecting the remaining toner.