JP2003280246A - Toner and method for forming image - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner having excellent fixing property from a low tempera ture region to a high temperature region of the fixing temperature, preferable OHT transparency and preferable image density and suppression of fog. <P>SOLUTION: The toner comprises at least a binder resin containing a crosslinking agent component, a colorant, a compound (A) selected from the following group, and a compound (B) as a derivative of the compound (A). The total content A of the compound (A) and the compound (B) in the toner is 0.2 to 6 mass% and the content B of the crosslinking agent in the binder resin satisfies the relation of 0.1≤A/B≤70. The group of compounds for (A) includes abietic acid, dehydroabetic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, pulstric acid, sandaracopimaric acid, secodehydroabietic acid and agathic acid. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Many electrophotographic methods are known. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is formed. Is developed with toner, and a toner image is transferred to a transfer material such as paper by using a direct or indirect means as needed, and then fixed by heating, pressurization, heat pressurization, or solvent vapor, A fixed image is obtained. In addition, when there is a step of transferring a toner image, a step for removing the transfer residual toner on the photoconductor is usually provided, and the above steps are repeated (for example, refer to Patent Documents 1 to 3). .

Further, particularly in full-color image formation, an electrostatic latent image is generally developed by using magenta toner, cyan toner, yellow toner and black toner, and toner images of respective colors are superposed to form a multicolor image. The image is reproduced.

In recent years, the field of use of the image forming apparatus using the electrophotographic method as described above is not only a copying machine for simply copying an original document, but also a printer as an output of a computer or a personal copy for personal use. Moreover, it is rapidly developing into plain paper faxes and the like, and various demands are increasing. Further, the copying machines are also becoming more sophisticated by digitization.
In particular, miniaturization, speeding up, and colorization of the image forming apparatus portion are remarkable, and further, high reliability and high resolution are strongly demanded. For example, initially, 200 to 300 dpi
The resolution was (dot per inch) 400-1200d
pi and even 2400 dpi.

In response to the above demands, image forming apparatuses have been designed with simpler components by using highly functional members in various respects. As a result, the functionality required for the toner has become higher, and if the improvement in the performance of the toner cannot be achieved, a more excellent image forming apparatus cannot be established.

For example, in recent years, as a transfer device for electrostatically transferring a toner image on an electrostatic latent image bearing member or an intermediate transfer member onto a transfer material, it is possible to reduce the size of an image forming device and prevent ozone from being generated. From the viewpoint, a contact transfer device for performing a so-called contact transfer means in which a roller-shaped transfer member to which a voltage is applied from the outside is contacted with an electrostatic latent image carrier or an intermediate transfer member via the transfer material is used. The number of cases where it is used is increasing.

For such a contact transfer device, it is preferable to make the toner particles spherical, from the viewpoint of enhancing transferability and resistance to mechanical stress received from the device, but toner particles having high sphericity are used. It has been found that the toner has a small specific surface area of the toner particles, the dispersibility of the colorant inside the toner particles is poor, and the transferability and matching with a transfer device are greatly affected.

On the other hand, a fixing device for fixing a toner image generally includes a heating roller as a rotary heating member and a pressure roller as a rotary pressure member (hereinafter, both are collectively referred to as a fixing roller). A heat roller type heat fixing unit using is used, but when performing image formation at a higher speed, a large amount of heat energy is required instantaneously while applying a high pressing force. For this reason, an unfavorable situation occurs in which the fixing device becomes large and the preheating time at the time of startup is long. From these viewpoints, it is preferable that the toner used in the image forming apparatus as described above exhibits a high sharp melt property when heated. Further, since such a toner is excellent not only in fixing property but also in color mixing property during full-color image formation, it is possible to widen the color reproduction range of the obtained fixed image. In general, the excellent toner of (1) has a high affinity with the fixing roller, and therefore tends to cause an offset phenomenon of transferring to the surface of the fixing roller during fixing.

This offset phenomenon easily occurs when the fixing temperature is too high or too low. If the fixing temperature is too high, the viscosity of the toner will be too low, and the toner layer will tend to transfer to the surface of the fixing roller.If the fixing temperature is too low, the toner will not melt sufficiently and the toner will not be able to melt on the surface of the transfer material. It tends to transfer to the surface of the fixing roller.

Although the toner has a temperature range in which it can be suitably fixed, the temperature of the fixing roller surface is high in the actual image formation depending on the environmental temperature at the time of use and the use situation such as continuous printing of a large number of sheets. Since it changes, it is preferable that the temperature range in which the toner can be fixed is wide in order to meet various conditions.

Further, even if the toner is well fixed in a low temperature range, when the toner layer on the transfer material becomes thick, a diameter of 2 m called "image peeling" on the surface of the fixed image at the low temperature range side.
Fixing failure of about m may occur at several places. This development remarkably occurs particularly when a color image is formed by superposing a plurality of toners selected from yellow toner, magenta toner, cyan toner and black toner on the transfer material.

On the other hand, in order to prevent the toner from adhering to the surface of the fixing roller, for example, the surface material of the fixing roller is made of a material having excellent releasability from the toner, such as silicone rubber or fluorine resin. Further, for the purpose of preventing the offset phenomenon and the deterioration of the surface of the fixing roller, the surface of the fixing roller is coated with a thin film of an offset preventing liquid.

However, although the above method is extremely effective in preventing the offset phenomenon,
(1) Since a device for supplying an offset preventing liquid is required, the fixing device becomes complicated, which is an obstacle to designing a small and inexpensive image forming apparatus; (2)
The applied offset preventing liquid permeates into the fixing roller at the time of heating and induces peeling between the layers constituting the fixing roller, resulting in shortening the life of the fixing roller; (3) Obtained fixing Offset prevention liquid adheres to the image, resulting in a sticky feeling, and transparency is lost especially when a transparency film used in overhead projectors for presentations is used as the transfer material, so the desired color reproduction (4) The offset preventing liquid contaminates the inside of the image forming apparatus.

By the way, transfer materials used in the image forming apparatus as described above are also diversified. For example, as the type of paper used as a transfer material, not only the difference in basis weight but also the material and content of raw materials and fillers are different at present. Among these transfer materials, there are various transfer material qualities, such as those in which the constituent materials are easily detached and those which are easily adhered to the constituent members of the fixing device. The fixing device is greatly affected by these transfer materials, which makes it difficult to downsize and extend the life of the fixing device.

Further, the contaminants derived from the transfer material and the toner are agglomerated and adhere to each other on the fixing roller to cause a deterioration in the performance of the fixing device, or the adhered material is peeled off to deteriorate the quality of the fixed image. There was a problem such as dripping.

[0016] Specifically, recycled paper using recycled pulp obtained by deinking used paper has been widely used from the viewpoint of environmental protection and the like. However, recycled paper often contains various contaminants, and it is necessary to specify the content and composition of contaminants in recycled paper in order to enable use in the image forming apparatus as described above. (For example,
See Patent Documents 4 to 8).

Currently, in recycled paper used for general office work, etc., the mixing ratio of recycled pulp such as newspaper waste paper exceeds 70%, and it is expected that the mixing amount will increase more and more in the future.
It is feared that it may cause the above problems. Furthermore,
When a cleaning member for removing toner and other substances adhering to the surface of the heating roller and a separating member for preventing wrapping of the transfer material are provided, especially when recycled from medium-quality waste paper such as newspapers and magazines. It has been confirmed that the medium-quality pulp fibers contained in the paper powder detached from the paper may cause scratches and scrapes on the surface of the fixing roller, or significantly reduce the functions of the cleaning member and the separating member. The phenomenon as described above tends to become a serious problem when a fixing device in which the offset preventing liquid is applied to the fixing roller in a small amount or a fixing device in which the offset preventing liquid is not applied is used.

As described above, applying the offset preventing liquid to the surface of the fixing roller of the fixing device is very useful, but it has various problems.

Considering the recent demands for smaller and lighter image forming apparatuses and the quality of the obtained fixed image, it is preferable to remove even the auxiliary device for applying the offset preventing liquid.

Under such circumstances, technical development relating to heat and pressure fixing of toner is indispensable, and some measures have been proposed for these.

Conventionally, there are many methods of adding a wax component such as low molecular weight polyethylene or polypropylene to the toner from the idea of supplying the offset prevention liquid from the toner at the time of heating without using a device for supplying the offset prevention liquid. Proposed. However, in order to exert a sufficient effect, it is necessary to add a large amount of the above-mentioned wax component to the toner. In that case, filming on the photoconductor and contamination of the surface of the carrier and the toner carrier occur,
New problems such as image deterioration occur. Further, when the amount of the wax component added is small, it is necessary to provide a device for supplying a small amount of offset preventing liquid or an auxiliary cleaning member such as a winding type cleaning web or cleaning pad. Occurs. Especially in the formation of full-color images, when a transparency film is used as the transfer material, the transparency and haze (fogging value) of the fixed image may be increased due to the high crystallization of the wax component and the difference in the refractive index with the binder resin. The problem of aggravation remains unsolved.

Further, a technique of including a wax component in the toner has been proposed, but it is difficult to highly improve various properties required for the toner simply by including the wax component in the toner, The matching with the image forming apparatus using the heat and pressure fixing method is not sufficient (for example, see Patent Documents 9 to 21).

On the other hand, there is an attempt to improve the fixing property by improving the binder constituting the toner. For example, a toner to which rosin and a rosin-based derivative, which were originally used for toner as a pigment dispersion aid, are added for the purpose of improving fixability has been proposed.

There is also a proposal to use a polymer containing a rosin-based compound as a condensation component as a binder resin, and the presence of rosin and a rosin-based derivative in the toner can improve the fixing property to some extent. However, a fixing device with a small amount of offset prevention liquid applied,
Alternatively, when a fixing device to which the offset preventing liquid is not applied is used, there is room for improvement (for example, see Patent Documents 22 and 23).

Further, by controlling the addition amount of the crosslinking agent,
Although there is a proposal to improve the fixing property, no mention is made of a rosin compound or a combination with the rosin compound derivative (see, for example, Patent Documents 24 and 25).

By the way, in the art, in order to improve the color reproducibility of a color toner image,
It is known to use various pigments and dyes as colorants.

The magenta toner is important not only for reproducing red, which is highly visible to humans, when used together with the yellow toner, but is also excellent in developing the skin color of a human image having a complicated color tone. Sex is also required. Also,
Cyan toner has to achieve secondary color reproduction of blue, which is frequently used as a business color.

Conventionally, a magenta toner has been prepared by mixing a quinacridone colorant, a thioindigo colorant, a xanthene colorant, a monoazo colorant, a perylene colorant, a diketopyrrolopyrrole colorant, etc., alone or in combination. It is known to be used (for example, see Patent Documents 26 to 31).

However, these colorants do not meet all the conditions required for the magenta toner, and any one of the color tone of the toner, the light resistance, the charging property, and the matching with the image forming apparatus is used. There was room for improvement.

Further, due to the charging characteristics of the coloring agent used,
It is also necessary to take into consideration the problem that good negative chargeability cannot be obtained, and toner scatters from the developing device or the like during image formation, which adheres and contaminates inside the image forming device.

A technique has also been proposed in which a quinacridone organic pigment and a xanthene dye are used in combination (see, for example, Patent Document 32), and a quinacridone colorant and a methine colorant are used in combination (for example, refer to Patent Document 33). A method is disclosed in which a clear magenta-colored toner is obtained, the chargeability and light resistance of the toner are improved, and dyeing on a fixing roller such as a silicone rubber roller is prevented. Furthermore,
A toner using a mixed crystal quinacridone pigment has also been proposed (see, for example, Patent Document 34).

Further, a red pigment classified into CI Pigment Red 48 and a red pigment such as a quinacridone pigment having a b ^* value of -5 or less in the L ^* a ^* b ^* color system are 2 to 2% of all pigments. By using together in a mixing ratio of 30% by mass,
A toner of good magenta color can be obtained, the charging characteristics and light resistance of the toner can be improved, and further, the heat resistance to the fixing roller can be improved (for example, see Patent Document 35).

On the other hand, many colorants for yellow toner are known. For example, CISolvent Yellow
112, CISolvent Yellow160, CISolvent Yellow162
And benzidine yellow pigments, monoazo yellow pigments, and pigments such as CI Pigment Yellow 120, 151, 154, 156 (see, for example, Patent Documents 36 and 41).

However, although the yellow dye as described above is generally excellent in transparency, it is inferior in light resistance and causes a problem in storage stability of an image, and may cause a problem in combination with an image forming apparatus. .

On the other hand, the yellow pigment as described above is superior in light resistance to the yellow dye, but leaves room for improvement in the dispersed state in the toner particles, so that the image fog caused by the deterioration of the charging property is caused. There is a problem that occurs.

In addition, the yellow pigment, which is excellent in light resistance and heat resistance, generally causes the transparency of the toner to extremely decrease,
The projected image of OHT tends to be dull.

CI Pigment Yell with excellent light resistance and heat resistance
Disazo compounds represented by ow180 have also been proposed, but toners using the above pigments are not said to have good transparency at all and are not designed in consideration of fixing property, so that full-color image formation is possible. The yellow toner for use needs further improvement (for example, Patent Documents 42 to 45).
reference).

In order to solve the above problems, there is also a proposal of an electrophotographic toner in which the transparency and tinting strength are improved by using a yellow pigment in which the yellow pigment is made into fine particles to improve the specific surface area of the yellow pigment. However, CI Pigmen
If the pigment classified as t Yellow 180 is miniaturized, the negative chargeability of the pigment itself is significantly reduced, and the toner using this pigment has a new charge shortage, especially under high temperature and high humidity. Occurs (for example, see Patent Document 46).

Further, since the above colorant has a strong self-aggregating property, it is difficult to disperse well in the binder resin constituting the toner. Therefore, there was a tendency that the OHT transparency was inferior.

Further, the present inventors have examined the fixing properties of the toners containing the above-mentioned colorants, and as a result, the temperature range in which fixing is possible tends to be narrowed and image peeling is likely to occur. I found that Regarding the toner containing the above-mentioned colorant, little consideration is given to the influence on the fixability, and particularly when recycled paper having a recycled pulp content of more than 70% is used as the transfer material, When multiple color toner layers formed on the transfer material have to be fixed at one time, when a color image is formed or a fixing device with a small amount of offset prevention liquid applied to the fixing roller, or an offset prevention liquid is applied. No consideration is given to the use of a non-fixing device or the adaptation to the contact developing system.

As described above, regarding the system design of the image forming apparatus using the heat and pressure fixing method, the comprehensive comprehensive response including the developing method including the colorant used in the toner is still insufficient. There is no such thing.

In particular, under the present circumstances, the magenta toner and the yellow toner, including their secondary colors, have not yet reached a sufficient level in terms of transparency and the like.

[0043]

[Patent Document 1] US Pat. No. 2,297,691

[Patent Document 2] Japanese Patent Publication No. 42-23910

[Patent Document 3] Japanese Patent Publication No. 43-24748

[Patent Document 4] Japanese Unexamined Patent Publication No. 3-28789

[Patent Document 5] Japanese Patent Laid-Open No. 4-65596

[Patent Document 6] JP-A-4-147152

[Patent Document 7] Japanese Patent Laid-Open No. 5-100465

[Patent Document 8] Japanese Patent Application Laid-Open No. 6-35221

[Patent Document 9] Japanese Patent Publication No. 52-3304

[Patent Document 10] Japanese Patent Publication No. 52-3305

[Patent Document 11] Japanese Patent Application Laid-Open No. 57-52574

[Patent Document 12] Japanese Patent Application Laid-Open No. 60-217366

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[Patent Document 14] Japanese Patent Laid-Open No. 60-252361

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[Patent Document 16] Japanese Patent Laid-Open No. 61-138259

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[Patent Document 18] Japanese Patent Laid-Open No. 62-14166

[Patent Document 19] Japanese Unexamined Patent Publication No. 1-109359

[Patent Document 20] Japanese Unexamined Patent Publication No. 2-79860

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[Patent Document 45] Japanese Unexamined Patent Publication No. 8-262799

[Patent Document 46] Japanese Patent Laid-Open No. 8-209017

[0044]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the problems of the prior art and an image forming method using the toner.

That is, an object of the present invention is to provide a toner having an excellent fixability from a low temperature region to a high temperature region at a fixing temperature and having a sufficiently wide latitude of the fixing temperature, and an image forming method using the toner. .

Another object of the present invention is to provide a toner which does not cause image peeling even in a low temperature range, and an image forming method using the toner.

A further object of the present invention is to provide a toner having good OHT transparency and an image forming method using the toner.

A further object of the present invention is a developing step in which an electrostatic latent image is developed by bringing a toner layer formed of toner carried on the surface of a toner carrier into contact with the surface of the image carrier. And a toner having a good image density and fogging suppression which can be applied in an image forming method having a fixing step using a heating and pressurizing means with a small amount of offset prevention liquid applied, and an image forming method using the toner. To provide.

[0049]

The present invention provides at least the following:
Binder resin containing cross-linking agent component, colorant, compound (A)
And a compound (B), wherein the compound (A) comprises abietic acid, dehydroabietic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastoric acid, and sandra coppi. A compound selected from the group consisting of malic acid, secodehydroabietic acid and agatoic acid, said compound (B)
Is a derivative of a compound included in the selected group of the compound (A), and the total content A (% by mass: based on the mass of the toner) of the compound (A) and the compound (B) in the toner is 0. 2 to 6% by mass, and when the content of the crosslinking agent component in the binder resin is B (% by mass: based on the mass of the toner), the relationship of 0.1 ≦ A / B ≦ 70 is satisfied. The present invention relates to a characteristic toner.

Furthermore, the present invention includes at least (a) a charging step of charging an image bearing member for bearing an electrostatic latent image;
(B) an exposure step of forming an electrostatic latent image on the charged image carrier by exposure; (c) developing the electrostatic latent image with toner carried on the surface of the toner carrier to form a toner image A developing step of: (d) a transfer 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 toner image on the transfer material. An image forming method, comprising: a fixing step of fixing the toner to a transfer material by heating and pressurizing means;
Binder resin containing cross-linking agent component, colorant, compound (A)
And a compound (B), wherein the compound (A) comprises abietic acid, dehydroabietic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastoric acid, and sandra coppi. A compound selected from the group consisting of malic acid, secodehydroabietic acid and agatoic acid, said compound (B)
Is a derivative of a compound included in the selected group of the compound (A), and the total content A (% by mass: based on the mass of the toner) of the compound (A) and the compound (B) in the toner is 0. 2 to 6% by mass, and when the content of the crosslinking agent component in the binder resin is B (% by mass: based on the mass of the toner), the relationship of 0.1 ≦ A / B ≦ 70 is satisfied. The present invention relates to a characteristic image forming method.

[0051]

DETAILED DESCRIPTION OF THE INVENTION As a result of earnest studies, the present inventors
Compound (A) in the toner (abietic acid, dehydroabietic acid, dihydroabietic acid, neoabietic acid,
(Pimaric acid, isopimaric acid, levopimaric acid, parastophosphoric acid, sandra copimaric acid, secodehydroabietic acid, agatoic acid) and their derivatives, the total content of the compound (B) and the content of the cross-linking agent As a result, the inventors have invented a toner having extremely good fixing characteristics and excellent in matching with an image forming apparatus.

First, the structural features and materials of the toner will be described.

Compound (A) contained in the toner of the present invention
Is a compound selected from the group consisting of abietic acid, dehydroabietic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastophosphoric acid, sandra copimaric acid, secodehydroabietic acid and agatoic acid. These compounds are usually contained in rosin in a large amount. Compound (A)
As the above, only one kind may be used, or two or more kinds may be used in combination.

Further, the compound (B) means a group from which the compound (A) is selected, that is, abietic acid, dehydroabietic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastoric acid. ,
It is a salt or ester of a compound selected from the group consisting of sand racco pimaric acid, secodehydroabietic acid and agato acid. As the compound (B), one type may be used alone, or two or more types may be used in combination. In the case of salt, K ⁺ , Na ⁺ , Ca ²⁺ , Ba ²⁺ , Al ^{3 +} , N
It is preferably any salt of H ₄ ⁺ , and in particular,
It is preferably a Ca ²⁺ salt. The main skeletons of the compound (A) and the compound (B) may be different from each other.

The toner of the present invention contains a binder resin containing a crosslinking agent, a colorant, a compound (A) and a compound (B), and the total content of the compound (A) and the compound (B) in the toner. The ratio A (% by mass: based on the mass of the toner) is 0.2 to 6% by mass, and when the content ratio of the crosslinking agent component in the binder resin is B (% by mass: based on the mass of the toner), it is 0. .1 ≦ A / B
≦ 70, preferably 1 ≦ A / B ≦ 50 is satisfied.

By satisfying the above relation, good fixing characteristics are obtained, and further, image density and image fog are improved.

The reason why the above effects are brought about is not always clear, but the present inventors have found that the compound (A)
Also, since the compound (B) has its unique cyclic structure and carboxyl group, when it is contained in the toner in a predetermined amount, it acts as a plasticizer, the toner has good fixability and offset resistance. I think it will be good. Specifically, since the fixability in the low temperature range and the high temperature range is improved, the latitude of the fixing temperature is widened, and even when the environment in which the image forming apparatus is used is different and the fixing temperature changes during a large number of continuous printouts. It is possible to respond sufficiently.

Further, the total content A (based on the mass of the toner) of the compound (A) and the compound (B) in the toner is 0.2 to 6.
%, Preferably 0.2 to 4% by mass, more preferably 0.2 to 3% by mass.

When the value of A is less than 0.2% by mass, the effect of the compound (A) and the compound (B) as a plasticizer does not work and image peeling easily occurs, and the value of A exceeds 6% by mass. When,
Due to the carboxyl group in the molecule, the chargeability of the toner is reduced, and when a large number of sheets are durable, the image density becomes low and image fog occurs.

Further, in the toner of the present invention, it is essential that a binder resin crosslinked by the crosslinking agent component is present in the toner. Compound (A) and compound (B) in the toner
0.1% A / B ≦, where A (mass%: toner mass basis) is the total content and B (mass%: toner mass basis) is the content of the crosslinking agent component in the binder resin. By satisfying 70, preferably 1 ≦ A / B ≦ 50, and more preferably 2 ≦ A / B ≦ 30, the toner fixability in both the low temperature region and the high temperature region is improved.

When the value of A / B is less than 0.1, the amount of the cross-linking agent becomes dominant, so that the toner becomes hard and the fixing property in the low temperature range is deteriorated. When the value exceeds 70, the effect of the compound (A) and the compound (B) as a plasticizer is too strong, so that the fixability in the high temperature range tends to be lowered.

As a method for quantifying the crosslinking agent contained in the binder resin of the present invention, a conventionally known measuring method can be used. As a specific example, a thermal decomposition gas chromatograph mass spectrometer is used to measure the crosslinking agent. It can be quantified by preparing a calibration curve of

Further, in the toner of the present invention, the content ratio of the compound (A) is X (mass%: based on the mass of the toner), and the compound (B) is
When the content rate of is Y (% by mass: based on the mass of the toner),
By controlling the content so as to satisfy the relationship of 0.25 ≦ X / Y ≦ 9, preferably 2 ≦ X / Y ≦ 7,
The dispersibility of the colorant in the toner is improved, and the transparency of the OHT becomes good.

As will be described later in detail, the compound (A) and the compound (B) may be introduced into the toner as a treatment agent for the colorant. In that case, the compound (A) present on the surface of the colorant. The content ratio of the compound (B) and the value of the abundance ratio X / Y can be determined by the following measuring methods.

The compound (A) is tetrahydrofuran (TH
The compound (B), which is soluble in F) and acetone and has a salt structure, is soluble in THF but insoluble in acetone. The THF-soluble component and the acetone-soluble component in the pigment may be obtained by utilizing this solubility. Specifically, pigment 0.
5 to 1.0 g was weighed (W1 g), put in a cylindrical filter paper (for example, Toyo Roshi Kaisha No. 86R), put on a Soxhlet extractor, extracted with 200 ml of THF as a solvent for 20 hours, and a soluble component extracted with THF. Is evaporated, dried in vacuum at 100 ° C. for 24 hours, and the amount of the THF-soluble component is weighed (W2 g). THF soluble matter (mass%)
Is calculated by 100 × (W2 / W1), and this ratio becomes the total content ratio of the compound (A) and the compound (B) in the pigment. Further, the content ratio of the compound (A) can be obtained by performing the same operation with respect to the THF-soluble component using acetone as a solvent, and by subtracting this ratio from the total ratio, The content ratio of the compound (B) can be determined. The ratio and content of the compound (A) and the compound (B) in the toner are
It can be adjusted by adjusting the throughput of both components with respect to the colorant.

When the compound (B) is an ester compound, the THF-soluble matter is extracted by the same method as described above, and the THF-soluble matter is analyzed from the calibration curve by gel permeation chromatography or liquid chromatography to obtain the compound (A). And the content of each of the compounds (B) can be determined.

The method of obtaining the value of A from the toner is
The toner may be dissolved in a solvent such as THF and calculated from a calibration curve using gel permeation chromatography, gas chromatography, liquid chromatography or the like. In the examples, after weighing 0.5 to 1.0 g of the sample, a cylindrical filter paper (for example, No. 86 manufactured by Toyo Roshi Kaisha, Ltd. is used.
R) and apply it to a Soxhlet extractor, and use T as a solvent.
Extraction with HF 100-200ml for 20 hours, TH
The soluble component extracted by F was used as a measurement sample, and measurement was performed by gel permeation chromatography under the following conditions.

GPC measurement conditions Device: GPC-150 (Waters) Column: Shoredex KF-801, KF-802
KF-803, KF-804, KF-805, KF-8
06, KF-807 and KF-800P 8 stations (Showa Denko KK) Temperature: 40 ° C. Solvent: Tetrahydrofuran (THF) Flow rate: 1.0 ml / min Sample: 0.5-5 mg / ml sample 0.1 ml injection or more The molecular weight calibration curve prepared from the monodisperse polystyrene standard sample is used for the measurement of the molecular weight of the sample.

The value of Y was determined by the following method. The soluble component extracted with THF is evaporated, and then vacuum-dried at 100 ° C. for several hours to obtain a THF-soluble resin. The obtained THF-soluble resin was thoroughly washed with acetone to obtain an acetone-insoluble matter, and the obtained acetone-insoluble matter was again dissolved in THF and then similarly subjected to gel permeation chromatography, gas chromatography, liquid chromatography and the like. It may be calculated from a calibration curve.

The compounds (A) used in the present invention are listed below by structural formula. The order is from the top to dehydroabietic acid, abietic acid, dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastophosphoric acid, sandra trucipimaric acid, secodehydroabietic acid, and agatoic acid.

[0071]

[Chemical 2]

[0072]

[Chemical 3]

[0073]

[Chemical 4]

[0074]

[Chemical 5] (11) The binder resin used in the present invention is cross-linked with a cross-linking agent, and may be either one using the cross-linking effect by hydrogen bond or van der Waals force, or one using the cross-linking effect by covalent bond. However, a resin using a polyfunctional polymerizable vinyl monomer as the crosslinking agent component is preferable. Examples of the polyfunctional polymerizable vinyl monomer include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate. , Tripropylene glycol diacrylate, polypropylene glycol diacrylate, 2,2'-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate , Triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene Ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate,
Neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4
-(Methacryloxy-diethoxy) phenyl) propane, 2,2'-bis (4- (methacryloxy-polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene,
Examples include divinyl ether.

In the toner of the present invention, it is particularly preferable to use divinylbenzene as a crosslinking agent. In this case,
As described above, the plasticizing effect of the compound (A) and the compound (B) and the curing effect of the cross-linking agent are balanced, and the fixing property becomes better. The divinylbenzene used in the present invention may be any of o-form, m-form, p-form, or a mixture thereof.

The magenta colorant used when the toner of the present invention is a magenta toner includes color, light resistance, and
From the viewpoint of transparency, developability and fixability, the pigment composition represented by the following structural formula is more preferred.

[0077]

[Chemical 6]

Among the pigment compositions represented by the above structural formulas, from the viewpoint of light resistance and color, CIPigment Red5, CIPi
gment Red31, CIPigment Red146, CIPigment Red14
7, CI Pigment Red 150, CI Pigment Red 184, or C.
It is particularly preferred that it is selected from the group of I.Pigment Red 269 (each named according to the Color Index Fourth Edition).

The pigment composition as described above may be used alone or, if necessary, may be used in combination with other coloring agents. As the colorant that can be used in combination, conventionally known colorants can be used in combination, and examples thereof include a quinacridone colorant, a thioindigo colorant, a xanthene colorant, a perylene colorant, and a diketopyrrolopyrrole colorant.

The yellow colorant used when the toner of the present invention is a yellow toner is CI Pigment Yellow1.
7, CI Pigment Yellow 74, CI Pigment Yellow 93, C.
It is preferable to be selected from the group consisting of I.Pigment Yellow 155 and CI Pigment Yellow 180 (each according to the name described in the Color Index Fourth Edition), and one kind or a combination of two or more kinds may be used.

As the cyan colorant used when the toner of the present invention is used as a cyan toner, a copper phthalocyanine compound and its derivative, an anthraquinone compound, and a basic dye lake compound can be used. Specifically, CI Pigment
Blue1,7,15,15: 1,15: 2,15: 3,15: 4,60,62,66 (each with the name described in the Color Index Fourth Edition) can be particularly preferably used.

The toner of the present invention is referred to as black toner.
The black colorant used in the
A magnetic material and a magnetic material can be preferably used. Suitable for the present invention
The carbon black used for B is B from the viewpoint of coloring power.
ET specific surface area of 20-300m ²/ G, DBP oil absorption
30 to 200 ml / 100 g is preferable. Also, above
Toned to black using the yellow / magenta / cyan colorants
It is also available.

In the present invention, a resin having a polarity such as a polyester resin, a polycarbonate resin, a vinyl polymer having a polar group (hereinafter
(Referred to as “polar resin”) can be used together. By adding the polar resin to the toner, it is possible to prevent the compound (A) and the compound (B) in the toner from being unevenly distributed on the toner surface, and to suppress the influence on the charging property of the toner.

For example, in the case of directly producing a toner by the suspension polymerization method described later, when the polar resin as described above is added during the polymerization reaction from the dispersion step to the polymerization step, the polymerizable monomer composition which becomes the toner particles is added. It is possible to control the added polar resin so as to form a thin layer on the surface of the toner particle or to have a gradient from the surface of the toner particle toward the center, depending on the balance between the polarities of the substance and the aqueous dispersion medium.
Particularly, when a polar resin having an acid value of 1 to 20 mgKOH / g is used, it is possible to effectively prevent uneven distribution of the compound (A) and the compound (B) on the toner surface.

The amount of the polar resin added is 100
It is preferable to use 1 to 25 parts by weight with respect to parts by weight,
It is more preferably 2 to 15 parts by mass. If it is less than 1 part by mass, the state of existence of the polar resin in the toner particles tends to be non-uniform, and if it exceeds 25 parts by mass, the granulation property in the dispersion step tends to be poor, and it is formed on the surface of the toner particles. Since the polar resin has a large layer thickness, the fixability tends to be poor.

As the polyester resin usable in the present invention, those having a weight average molecular weight of 3,000 to 100,000 are suitable for obtaining a particularly excellent toner. If the molecular weight is lower than 3,000, the toner surface becomes soft and the blocking resistance may be lowered. On the other hand, when the molecular weight exceeds 100,000, the solubility of the polyester resin in the vinyl-based monomer becomes difficult, so that the production by the suspension polymerization method becomes difficult.

The following can be exemplified as the acid component and the alcohol component constituting the polyester resin.

As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol,
Diethylene glycol, triethylene glycol, 1,
5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-ethyl 1,3-hexanediol, hydrogenated bisphenol A, a bisphenol derivative represented by the following formula (a) and a formula (a) below. Examples include diols.

[0089]

[Chemical 7] (In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

[0090]

[Chemical 8]

Examples of the acid component include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof; alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid or azelaic acid or anhydrides thereof. Succinic acid having an alkyl group or alkenyl group having 6 to 18 carbon atoms as a substituent or an anhydride thereof; unsaturated dicarboxylic acid such as fumaric acid, maleic acid, citraconic acid, itaconic acid or an anhydride thereof.

Further, when the polyester resin or the polycarbonate resin is used as the polar resin, the charging property of the toner is improved, the image fog and the scattering of the toner are improved, and a high-quality image excellent in dot reproducibility is obtained. It will be easier to obtain. Further, it becomes possible to impart an appropriate mechanical strength to the toner particles, minimize the influence of toner deterioration received from the image forming apparatus, and durability against a large number of printouts and matching with the image forming apparatus described later. improves. Further, it is possible to minimize the influence of the toner manufacturing process such as the spheroidizing process of the toner and the drying process when the toner is directly manufactured by the polymerization method. Further, the polar resin can be used in combination of two or more kinds, and the chargeability of itself can be utilized.

The polar resin as described above is not limited to one kind of polymer, and for example, two or more kinds of reactive polyester resins can be used at the same time, or two or more kinds of vinyl polymers can be used. Further, completely different kinds of polymers such as non-reactive polyester resin, epoxy resin, polycarbonate resin, polyolefin, polyvinyl acetate, polyvinyl chloride, polyalkyl vinyl ether, polyalkyl vinyl ketone, polystyrene, poly (meth) Polymers such as acrylic ester, melamine formaldehyde resin, polyethylene terephthalate, nylon and polyurethane can be added to the binder resin as required.

In the toner of the present invention, a wax component may be contained. Specific examples of the wax component that can be used include paraffin wax, microcrystalline wax, petroleum wax such as petrolactam and derivatives thereof, Montan wax and its derivatives,
Examples include hydrocarbon waxes and their derivatives by the Fischer-Tropsch method, polyolefin waxes and their derivatives represented by polyethylene, natural waxes such as carnauba wax and candelilla wax, and their derivatives. The derivatives include oxides and vinyl monomers. Also included are block copolymers with and graft modified products. Also,
Alcohols such as higher aliphatic alcohols; aliphatic such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and its derivatives, vegetable wax, animal wax. These can be used alone or in combination.

Among these, when polyolefin, hydrocarbon wax by the Fischer-Tropsch method, petroleum wax, higher alcohol, or higher ester is used, the effect of improving the developability and transferability is further enhanced. An antioxidant may be added to these wax components within a range that does not affect the charging property of the toner. Moreover, these wax components are used as the binder resin 100.
It is preferable to use 1 to 30 parts by mass with respect to parts by mass.

The wax component used in the present invention has an endothermic main peak temperature (melting point) in the DSC curve measured according to "ASTM D3418-82" of 30 to 120 ° C, more preferably 40 to 90 ° C. Compounds in are preferred.

By using the wax component exhibiting the above-mentioned thermal characteristics, not only the good fixing property of the toner obtained but also the releasing effect by the wax component is efficiently exhibited, and a sufficient fixing area is secured. It is possible to eliminate the adverse effects on the developability, blocking resistance and image forming apparatus due to the conventionally known wax component. In particular, since the specific surface area of the toner decreases as the particle shape of the toner becomes spherical, controlling the thermal characteristics and dispersion state of the wax component becomes very effective.

For measuring the endothermic main peak temperature of the wax component, for example, "DSC-7" (manufactured by Perkin Elmer) is used. The melting points of iridium and zinc are used to correct the temperature of the device detection unit, and the heat of fusion of iridium is used to correct the amount of heat. At the time of measurement, a measurement sample placed in an aluminum pan and a control aluminum pan only (empty pan) were set to 20 to 180.
The endothermic main peak temperature can be determined from the DSC curve obtained when the temperature in the measurement region of ° C was increased at a temperature increase rate of 10 ° C / min. When measuring only the wax component, the temperature is raised and lowered under the same conditions as the measurement to remove the previous history, and then the measurement is started. Further, when measuring the wax component contained in the toner, the measurement is performed as it is without performing the operation of removing the previous history.

Further, the wax component used in the present invention has a number average molecular weight (Mn) in the molecular weight distribution measured by gel permeation chromatography (GPC).
Is 200 to 2000, and the weight average molecular weight (Mw) is 400.
It is preferable to use a material having a Mw / Mn of 3,000 or less and Mw / Mn of 3.0 or less. If the number average molecular weight of the wax component is less than 200 or the weight average molecular weight is less than 400, the ratio of the low molecular weight component increases, resulting in problems in the charging property of the toner and matching with the image forming apparatus. . When the number average molecular weight of the wax component exceeds 2000, or the weight average molecular weight is 3
When it exceeds 000, it becomes difficult to smooth the surface of the fixed image to an appropriate degree, which is not preferable from the viewpoint of a decrease in color mixing property. Further, when toner particles are obtained by a polymerization method, it is granulated in an aqueous dispersion medium. -Because of the polymerization, the wax component is mainly precipitated during granulation, which is not preferable.

In the present invention, the molecular weight distribution of the wax component is measured under the following conditions.

<GPC measurement conditions> Apparatus: GPC-150C (manufactured by Waters Co.) Column: GMH-HT (manufactured by Toso Co., Ltd.) Double temperature: 135 ° C. Solvent: o-dichlorobenzene (addition of 0.1% ionol) ) Flow rate: 1.0 ml / min Sample: A sample with a concentration of 0.15% by mass was measured under the condition of 0.4 ml injection or more, and the molecular weight calibration curve prepared with a monodisperse polystyrene standard sample was used to calculate the molecular weight of the sample. , Mark-Houwink viscosity equation was used to obtain polyethylene.

Examples of the binder resin for the toner used in the present invention include styrene- (meth) acrylic copolymers, polyester resins, epoxy resins and styrene-butadiene copolymers which are generally used. When the toner particles are directly obtained by the polymerization method, as a monomer for forming the binder resin, for example, styrene; o- (m-, p
-) Styrene-based monomers such as methylstyrene and m- (p-) ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl acrylate, (meth)
Butyl acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, (Meth) acrylic acid ester-based monomers such as diethylaminoethyl (meth) acrylate; ene-based monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylic acid amide are preferably used.

These may be used alone or generally in the publication Polymer Handbook 2nd Edition III-P 139-19.
2 (manufactured by John Wiley & Sons) is used by appropriately mixing the monomers so that the theoretical glass transition temperature (Tg) is 40 to 75 ° C. When the theoretical glass transition temperature is lower than 40 ° C, problems tend to occur from the viewpoint of storage stability and durability stability of the toner, while when it exceeds 75 ° C, the fixing point of the toner is increased.

A charge control agent may be added to the present invention. As the charge control agent used in the present invention, a charge control agent having a particularly high charging speed and capable of stably maintaining a constant charge amount is preferable. Further, when the toner particles are produced by a direct polymerization method, a charge control agent which has no polymerization inhibitory property and does not have a solubilized product in an aqueous dispersion medium is preferable. Specific compounds include, as negative charge control agents, metal compounds of aromatic carboxylic acids such as salicylic acid, naphthoic acid, and dicarboxylic acid; polymeric compounds having a sulfonic acid or carboxylic acid group in the side chain; boron compound; urea Compounds; silicon compounds; calixarene. Examples of the positive charge control agent include a quaternary ammonium salt; a polymer type compound having the quaternary ammonium salt in its side chain; a guanidine compound; and an imidazole compound.

However, the addition of the charge control agent is not essential in the present invention. For example, when the two-component developing method is used, triboelectrification with a carrier is used, and when the non-magnetic one-component blade coating developing method is used, triboelectrification with a blade member or a sleeve member is positively performed. By utilizing it, it is not always necessary to include a charge control agent in the toner particles.

The addition of inorganic fine powder to the toner of the present invention is a preferred embodiment for improving the developability, transferability, charge stability, fluidity and durability. As the inorganic fine powder, known ones can be used, but it is preferable to select one from silica, alumina, titania or a complex oxide thereof. Of these, silica is preferable. Silica can be both dry silica called so-called fumed silica produced by vapor phase oxidation of silicon halide or alkoxide, and so-called wet silica produced from alkoxide, water glass, etc. Dry silica having less silanol groups inside the fine silica powder and less production residues such as Na ₂ O and SO ₃ ²⁻ is preferable. Further, in the case of dry silica, it is possible to obtain a composite fine powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride and titanium chloride together with the silicon halogen compound in the manufacturing process. They are also included.

The inorganic fine powder used in the present invention is BET.
The specific surface area by measuring nitrogen adsorption 30 m ² / g or more by law, in particular 50 to 400 m ² / g give good results in the range of, used 0.3 to 8 parts by mass with respect to 100 mass parts of the toner , Preferably 0.5 to 5 parts by mass.

By covering the surface of the toner with the inorganic fine powder whose BET specific surface area is controlled as described above, it is possible to suppress the charging failure due to the colorant existing on the surface of the toner.

Further, since the toner is imparted with an appropriate fluidity, the uniform charging property of the toner is synergistically improved, and the above-described excellent effect is maintained even if a large number of printouts are continuously repeated.

When the BET specific surface area is less than 30 m ² / g, it is difficult to impart appropriate fluidity to the toner. When the BET specific surface area exceeds 400 m ² / g, the inorganic fine powder is embedded in the surface of the toner particles during continuous printout, which may lower the fluidity of the toner.

The specific surface area was measured by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device "Autosorb 1" (manufactured by Yuasa Ionics) and calculating the specific surface area by the BET multipoint method.

Further, the addition amount of the inorganic fine powder is such that the toner particles 1
If it is less than 0.3 parts by mass with respect to 00 parts by mass, the effect of addition will not be exhibited, and if it exceeds 8 parts by mass, not only problems will occur in the charging property and fixing property of the toner, but also free particles Matching with the image forming apparatus is significantly deteriorated by the inorganic fine powder.

The inorganic fine powder used in the present invention is
Silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, other organic silicon compounds, organics for the purpose of hydrophobizing, controlling charging properties, etc. It is also possible and preferable to treat with a treating agent such as a titanium compound or in combination with various treating agents.

Further, in order to maintain a high charge amount of the toner, achieve a low consumption amount and a high transfer rate, the inorganic fine powder is preferably treated with at least silicone oil.

In the toner of the present invention, other additives, for example, a lubricant powder such as polyfluorinated ethylene powder, zinc stearate powder, and polyvinylidene fluoride powder; cerium oxide powder, Abrasives such as silicon carbide powder, strontium titanate powder;
Flowability-imparting agents such as titanium oxide powder and aluminum oxide powder; anti-caking agents or conductivity-imparting agents such as carbon black powder, zinc oxide powder, tin oxide powder, and organic fine particles and inorganic fine particles of opposite polarity. It can also be used in a small amount as a developability improver.

The toner of the present invention can be used as a one-component developer as it is or as a two-component developer by mixing with a carrier.

When used as a two-component developer, for example, iron is used as the magnetic carrier mixed with the toner.
An element selected from copper, zinc, nickel, cobalt, manganese, and chromium is used alone or in a ferrite state containing a plurality of types. The shape of the magnetic carrier may be spherical, flat, or indefinite, and further, those having a finely controlled surface state (for example, surface irregularity) may be used. Further, a resin-coated carrier whose surface is coated with a resin and a magnetic powder-dispersed resin carrier can also be preferably used. The carrier to be used preferably has a weight average particle diameter of 10 to 100 μm, more preferably 20 to 50 μm. The toner concentration in the developer when the carrier and toner are mixed to prepare a two-component developer is preferably 2 to 15% by mass.

Next, the method for producing the toner of the present invention will be described.

When the toner of the present invention is produced by the suspension polymerization method, the compound (A) and the compound (B) may be directly added to the polymerizable monomer for polymerization. When the toner is manufactured by a pulverization method, the toner may be added to the binder resin and melt-kneaded. Alternatively, in both the suspension polymerization method and the pulverization method, the compound (A) and the compound (B) may be treated with a colorant and introduced into the toner.

As the method for treating the colorant, (1) a dry mixing method in which the compound (A) and the compound (B) and the colorant are dry-mixed, and then a heat treatment such as melt-kneading is performed if necessary, (2 When the compound (B) is a salt, an alkaline aqueous solution of the compound (A) is added to the colorant synthesis solution at the time of producing the colorant, and then a lake metal salt such as calcium, barium, strontium, or manganese is added, A wet treatment method in which the surface of the colorant is coated with the compounds (A) and (B) by insolubilizing the compound (A) can be used. As the method (2), a method of adding an alkaline aqueous solution of the compound (A) to a mixed solution of the colorant and the lake metal salt may be used.

When a toner is produced by previously treating with a colorant, the abundance ratio (X / Y) of the compound (A) and the compound (B) in the toner is determined by the lake metal salt in the method (2). The value of X / Y can be easily controlled by changing the addition amount of.

In the method for producing the toner of the present invention, when the suspension polymerization method is used, as the dispersant added to the aqueous dispersion medium, known inorganic and organic dispersants can be used. Specifically, as the inorganic dispersant, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, magnesium carbonate, calcium carbonate, calcium hydroxide, magnesium hydroxide,
Examples thereof include aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and alumina. As the organic dispersant, for example, polyvinyl alcohol, gelatin, methyl cellulose, methyl hydroxypropyl cellulose, ethyl cellulose, sodium salt of carboxymethyl cellulose,
Starch can be used.

It is also possible to use commercially available nonionic, anionic and cationic surfactants. For example, sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and calcium oleate can be used.

In the method for producing a toner of the present invention, an inorganic sparingly water-soluble dispersant is preferable, and a sparingly water-soluble inorganic dispersant which is soluble in an acid may be used. Further, in the present invention, when a water-based dispersion medium is prepared using a poorly water-soluble inorganic dispersant, these dispersants are used in an amount of 0.2 to 2. It is preferable to use it in a ratio such that it is 0 parts by mass. Further, in the present invention, it is preferable to prepare the aqueous dispersion medium by using 100 to 3,000 parts by mass of water with respect to 100 parts by mass of the polymerizable monomer composition.

In the present invention, when an aqueous dispersion medium in which the poorly water-soluble inorganic dispersant as described above is dispersed is prepared, a commercially available dispersant may be used as it is, but a fine uniform particle size may be used. In order to obtain the dispersant particles having the above, the poorly water-soluble inorganic dispersant as described above may be prepared in a liquid medium such as water under high speed stirring. For example, when using tricalcium phosphate as a dispersant,
A preferable dispersant can be obtained by mixing an aqueous sodium phosphate solution and an aqueous calcium chloride solution under high-speed stirring to form fine particles of tricalcium phosphate.

When the toner of the present invention is produced by the suspension polymerization method, the polymerization initiator used is specifically
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,
Azo- or diazo-type polymerization initiators such as 1, -azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile; benzoyl Peroxide-based polymerization initiators such as peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide are used. The amount of these polymerization initiators used varies depending on the intended degree of polymerization, but is generally 5 to 20 parts by mass with respect to 100 parts by mass of the polymerizable vinyl-based monomer. Although the type of the polymerization initiator varies slightly depending on the polymerization method, it may be used alone or in combination with reference to the 10 hour half-life temperature.

In order to control the degree of polymerization, known crosslinking agents, chain transfer agents, polymerization inhibitors and the like may be further added to the polymerizable monomer composition. These additives can be added to the polymerizable monomer composition in advance, or can be appropriately added during the polymerization reaction, if necessary.

Next, the image forming method of the present invention will be described.

In the image forming method of the present invention, the "heating and pressing means" means that the toner image on the transfer material is heated and pressed and fixed to form a fixed image.
(I) A rotary heating member having at least a heating body, and a rotary pressing member forming a nip portion by being in pressure contact with the rotary heating member, and (ii) coating on a contact surface of the transfer material with the toner image. Consumption of offset prevention liquid is 0.025
It is set to not more than mg / cm ² (based on the unit area of the transfer material), and (iii) the toner image on the transfer material is heated and pressed at the nip portion.

The "rotary heating member" forming a part of the heating and fixing means is for applying heat for fixing the toner image on the transfer material, and will be described later in (i) Heat roller system. A cylindrical member used in the heating and pressurizing means of the above, and having a heating body for applying heat to the toner image therein;
i) A cylindrical heat-resistant member which is used in a film type heating and pressurizing means, has a heating body which is fixed and supported by a support for applying heat to a toner image, and moves while being pressed against the heating body. Endless film-like member; (iii) used for heating and pressurizing means of electromagnetic induction system, having a magnetic field generating means inside, and applying heat to the toner image by electromagnetic induction heat generation by the action of the magnetic field generating means. And a heat resistant endless film member having a cylindrical shape, which has a heat generating layer.

The "rotary pressing member" is a member that presses the rotating heating member to form a nip portion, and heats and presses the toner image on the transfer material while nipping and transferring the transfer material at the nip portion. Is.

In the image forming method of the present invention, the consumption amount of the offset preventing liquid applied to the contact surface of the transfer material with the toner image is 0.025 mg / cm ² or less (based on the unit area of the transfer material), More preferably, the offset prevention liquid is set in a state where it is not applied at all. This makes it possible to solve the problems caused by the offset preventing liquid as described above, and by using the toner of the present invention, the performance of the heating / pressurizing means as described above can be maintained for a long period of time, resulting in excellent fixing. It is possible to obtain an image.

For the measurement of the consumption amount of the offset preventing liquid, general office recycled paper (blending rate of recycled pulp ≧ 70%) corresponding to the maximum paper passing area of the heating / pressurizing means to be used was used, and the recycled paper was used. It is defined as a value (mg / cm ² ) obtained by dividing the mass (mg) of the offset preventing liquid consumed when 100 sheets of paper have been passed, by the total area (cm ² ) of the recycled paper used.

As the offset preventing liquid according to the present invention, a liquid that maintains a liquid state from −15 ° C. to nearly 300 ° C. and is excellent in releasability is used. Specific examples thereof include dimethyl silicone oil, modified silicone in which a part of the methyl group is replaced with other substituents, and a mixture of these and a small amount of a surfactant added.
Those of 000 mm ² / s (cSt) are preferably used.

As a method for applying the offset preventing liquid to the fixing roller, a conventionally known method is used, and a method of applying the liquid by impregnating the applied felt, felt pad, felt roller, web, Pore Freon rod, etc. And a method of directly applying with an oil pan, a drawing roller, or the like.

Suitable heating and pressing means used in the image forming method of the present invention will be described with reference to the accompanying drawings.

In FIG. 2, a cylindrical heating roller having a heating element therein is used as a rotary heating member, and a cleaning member for removing toner remaining after fixing and a transfer material for preventing the transfer material from being wound around the surface of the heating roller. It is a schematic diagram of an example of a heating and pressing unit of a heat roller type in which a separating member is not provided.

A rotary heating member comprising a cylindrical heating roller 11 having a heating body such as the heater 11a therein,
With the cylindrical pressure roller 12 as the rotary pressure member,
When pressed, they form nip portions, and each of them rotates in the direction of the arrow during operation.

The transfer material P as a material to be heated carrying the unfixed toner T as a toner image is conveyed from the right side (upstream side) of the drawing by the conveying belt 13 and the heating roller 11
The transfer material P is nipped and conveyed at the nip portion between the pressure roller 12 and the pressure roller 12, and is heated and pressed to form a fixed image on the transfer material P and is discharged to the left side (downstream side) in the drawing.

In the heating / pressurizing means according to the present invention, the separating claw 1 for separating the transfer material P from the heating roller 11 or the pressing roller 12 as shown in FIGS. 3 (a) and 3 (b).
It does not have 4a or 14b.

Further, as shown in FIG. 3 (a), the brush-like fibers are formed into a cylindrical shape for the purpose of applying the offset preventing liquid while removing the residual toner remaining on the surface of the heating roller 11. A cleaning roller 15 implanted, a felt-like oil pad 16 impregnated with an offset prevention liquid, and a cleaning roller 17 impregnated with an offset prevention liquid as shown in FIG. 3B are provided. In this case, the consumption amount of the offset preventing liquid for the transfer material is 0 to 0.025 mg / cm ^2.
Is set to be within the range.

Conventionally, the offset preventing liquid also serves to protect the surface of the heating roller and the pressure roller.
When the consumption amount of the offset preventing liquid is set in the above range, the coating amount is small, so that scratches and abrasions generated on the surfaces of the heating roller 11 and the pressure roller 12 due to long-term use, and further due to them Releasability is likely to deteriorate. In the heating / pressurizing means in such a state, the phenomenon of winding of the transfer material around the heating roller or the pressure roller is likely to occur, and when the separating claw as described above is excluded, the winding phenomenon is more likely to occur. By using the toner of the present invention, it is possible to reduce the load on the heating and pressing means as described above and obtain an excellent fixed image for a long period of time.

For the heating roller 11 used in the heating and pressing means according to the present invention, for example, an aluminum pipe having a thickness of about 2 to 5 mm is used as a core metal, and the outer peripheral surface has a thickness of 20 mm.
For example, a silicone rubber having a thickness of 0 to 500 μm, or one coated with fluororubber is used.

The pressure roller 12 may be, for example, a cored bar made of SUS pipe having a diameter of 10 mm and coated with silicone rubber on its outer peripheral surface to a thickness of about 3 mm.

A tubular heating heater such as a halogen lamp is used as the heater 11a provided inside the heating roller 11, and heat is generated by applying a predetermined voltage, and the heating roller 11 is heated by the radiant heat. . At this time, the heating roller 11 and the pressure roller 12 that is in pressure contact with the heating roller 11 are heated relatively gently, but since they generally have a large heat capacity, they are often heated for a long time. 1
2 is susceptible to thermal deterioration. In particular, when recycled paper is used or when the amount of offset prevention liquid applied is small, the heating roller 11 and the pressure roller 12 are likely to be scratched or chipped, so that thermal deterioration is promoted and the roller surface is separated. It causes problems due to the deterioration of moldability. However, by using the toner of the present invention, the load on the heating and pressing means as described above is reduced, and it becomes possible to obtain an excellent fixed image for a long period of time.

FIG. 4A shows a cylindrical heat-resistant endless film which has a heating body fixedly supported by a support and is driven and moved while being pressed against the heating body as a rotary heating member. FIG. 4B is an exploded perspective view of an example of a film-type heating and pressing unit that heats and presses a toner image through a film, and FIG. 4B is an enlarged cross-sectional view of a main part of the heating and pressing unit.

A rotary heating member comprising a cylindrical heat-resistant endless film 32 having a heating body 31 fixedly supported by a support, and a cylindrical pressing member as a rotary pressing member via the heat-resistant endless film 32. The pressure roller 33 is pressed against each other to form a nip portion, and at the time of operation, it rotates in the direction of the arrow to bring a transfer material as a heated object carrying a toner image into close contact with the heat-resistant endless film 32 to heat the heating element. It is pressed against 31 and moved together with the heat resistant endless film 32.

Fixed-supported low heat capacity linear heating element 31
Is a heater substrate 31a and a heating resistor 3 (heating element)
1b, a surface protective layer 31c, a temperature measuring element 31d, and the like. The heater substrate 31a is preferably a member exhibiting heat resistance, insulation, low heat capacity and high heat conductivity, and is, for example, an alumina substrate having a thickness of 1 mm, a width of 10 mm and a length of 240 mm.

The heating element 31b is formed, for example, on the lower surface of the heater substrate 31a (on the side facing the film 32) along the longitudinal direction, along the length, for example, Ag-Pd (silver palladium), Ta ₂ N,
An electrical resistance material such as RuO ₂ having a thickness of about 10 μm and a width of 1 to 3
mm linear or strip-shaped by screen printing or the like, and a heat-resistant glass as a surface protective layer 31c on the surface of about 1
It is coated with 0 μm.

The temperature detecting element 31d is, for example, the upper surface of the heater substrate 31a (side surface opposite to the surface on which the heating element 31b is provided).
Is a resistance temperature detector having a low heat capacity, such as a Pt film, which is provided by coating by screen printing or the like in the substantially central portion of the above. A thermistor having a low heat capacity may be used instead.

The heating element 31 heats the heating element 31b over substantially the entire length by energizing the heating element 31b at a predetermined timing with an image formation start signal.

Energization is 100 VAC, and the temperature measuring element 31
The power supply is controlled by controlling the phase angle of the power supply by a power supply control circuit (not shown) including a triac according to the detected temperature of c.

In the heating element 31, since the heater substrate 31a, the heating element 31b and the surface protection layer 31c have small heat capacities,
The heat-resistant endless film 32 is used because the surface of the heating element 31 rapidly rises to a desired fixing temperature due to energization of the heating element 31b or is rapidly cooled to around room temperature when not in use.
The thermal shock given to the pressure roller 33 as a rotary pressure member is large and has releasability. However, by using the toner of the present invention, the load on the heating and pressure means as described above is reduced, It is possible to obtain an excellent fixed image for a long period of time.

The cylindrical heat-resistant endless film 32 located between the rotary heating member and the rotary pressing member has a thickness of 2 from the viewpoint of heat resistance, strength assurance, durability and low heat capacity.
A heat-resistant sheet having a single layer or a composite layer having a thickness of 0 to 100 μm is preferable, and examples thereof include polyimide, polyether imide (PEI), and polyether sulfone (P).
ES), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin (PFA), polyether ether ketone (PEEK), polyparabanic acid (PPA),
Alternatively, a composite layer film, for example, a polyimide film having a thickness of 20 μm, at least on the toner image contact surface side, is a fluororesin such as tetrafluoroethylene resin (PTFE), PAF, FEP, or a silicone resin, and further carbon black or graphite. It is preferable that the release coating layer having a conductive material such as a conductive whisker added thereto has a thickness of 10 μm.

Also, the pressure roller 3 which is a rotary pressure member.
Since 3 also functions as a drive roller for moving and driving the heat-resistant endless film 32 as described above, it not only has excellent releasability for toner and the like, but also has adhesiveness with the heat-resistant endless film 32. Preferably, for example, a rubber elastic body such as silicone rubber is used. As described above, the thermal shock applied to the pressure roller 33 is large, and the surface deterioration of the pressure roller 33 due to long-term use affects the driving function itself of the heating and pressure means as described above, but the toner of the present invention is used. As a result, it is possible to reduce the load on the heating and pressing means as described above and obtain an excellent fixed image for a long period of time.

FIG. 5 shows an electromagnetic induction type heating having a rotary heating member having a cylindrical heat-resistant endless film having a magnetic field generating means inside and a heat generating layer for electromagnetically generating heat by the action of the magnetic field generating means. It is a schematic diagram of an example of a pressurizing means.

Inside the exciting coil 40, the exciting coil 40
The heat-resistant endless film 4 while supporting the coil core material (magnetic material) 42 around which the
7 has a magnetic field generating means composed of a slide plate 43 for guiding the traveling of 7, and a rotary heating member composed of a cylindrical heat resistant endless film 47 that is driven to move while being pressed against the magnetic field generating means, and a heat resistant endless film 47. And a cylindrical pressure roller 48 as a rotary pressure member to form a nip portion N by pressure contact with each other, and at the time of operation, rotate in the direction of the arrow to transfer the toner image T as a material to be heated, which is a transfer material. The heat-resistant endless film 47 was adhered to the heat-resistant endless film 47 and pressed against the magnetic field generating means.
Together with the drive.

At this time, the magnetic field generated by the magnetic field generating means is 10 to 500 kHz from an exciting circuit (not shown).
The magnetic flux H indicated by the arrow is repeatedly generated and extinguished around the exciting coil 40 by applying an alternating current having a frequency of. In the conductive layer (induction magnetic material) 47b in the heat-resistant endless film 47 moving in this fluctuating magnetic field, eddy current A as indicated by an arrow is generated by electromagnetic induction so as to reduce the change in the magnetic field. . This eddy current is converted into Joule heat by the skin resistance of the conductive layer, and as a result, the conductive layer in the heat resistant endless film 47 becomes a heat generating layer. Since heat is generated directly near the surface layer of the heat-resistant endless film 47 in this manner, rapid heating that does not depend on the thermal conductivity and heat capacity of the film base layer and the thickness of the heat-resistant endless film can be realized.

The transfer material P as a heated body carrying the toner image T adheres to the heat-resistant endless film 47 and passes through the nip portion N, whereby a fixed image can be obtained on the transfer material P.

The cylindrical heat-resistant endless film 47 used in the heating and pressing means according to the present invention preferably comprises at least three layers of a film base layer 47a, a conductive layer 47b, and a surface layer 47c. Thickness 1
A heat resistant resin such as polyimide having a thickness of 0 to 100 μm is used as a film base layer 47a, and a conductive layer 47b is formed on the outer peripheral surface of the base layer 47a (the pressure contact surface side of the body to be heated), for example, Ni, Cu, Cr.
And the like with a thickness of 1 to 100 μm by a process such as plating. Further, on the free surface of the conductive layer 47b, a surface layer 47c is formed by coating a heat-resistant resin having a good toner releasing property, such as PFA or PTFE, or by coating it alone. Further, the film base layer 47a may have a role of a conductive layer to form a two-layer structure.

The coil core member 42 is made of, for example, ferrite permalloy having a high magnetic permeability and a low residual magnetic flux density. Use a coil core material 42 with a low residual magnetic flux density.
Since it is possible to suppress the overcurrent generated in the core member itself, the coil core member 42 does not generate heat and the efficiency is improved. Further, by using a material having a high magnetic permeability, the coil core material 42 serves as a path for the magnetic flux H, and magnetic flux leakage to the outside can be suppressed as much as possible.

The exciting coil 40 is formed by bundling a plurality of thin copper wires, each of which is insulation-coated, as a conductive wire (electric wire) (bundled wire), and is wound a plurality of times. Alternatively, a sheet coil substrate may be used in which the excitation coil pattern is multilayer-printed on a substrate plane of a non-magnetic material such as glass-containing epoxy resin (general-purpose electric substrate) or ceramic.

The sliding plate 43 is made of a heat-resistant resin such as liquid crystal polymer or phenol, and is made of a heat-resistant endless film 47.
In order to reduce the frictional resistance with the heat resistant endless film 47, for example, a resin coat such as PFA or PTFE, or a glass coat having a high slidability is applied to the surface opposite to.

The pressure roller 48 is formed by winding silicone rubber, fluororubber or the like around the cored bar. The pressure roller 48 is arranged in pressure contact with the lower surface of the slide plate 43 through a heat-resistant endless film 47 with a predetermined pressing force F by bearing means and urging means (both not shown). Heat-resistant endless film 4 between
The nip portion N is formed while sandwiching 7 in between.

In the nip portion N, the magnetic field generated by the magnetic field generating means is concentrated, so that the vicinity of the surface layer of the heat-resistant endless film 47 rapidly heats directly due to electromagnetic induction heat generation. As a result, a large thermal shock is given to the surface of the heat-resistant endless film 47 and the pressure roller 48, and the releasability of the toner and the like and the heat-resistant endless film 47 are provided.
However, by using the toner of the present invention, it is possible to reduce the load on the heating and pressing means as described above and obtain an excellent fixed image for a long period of time.

[0166]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.

Pigment Treatment Example 1 In a four-necked container, 5000 parts by weight of a 2.5 × 10 ⁻³ mol / liter CaCl ₂ aqueous solution (adjusted to pH = 4.7) was added to a red pigment [CIPigment Red150, described above. In the formula of the monoazo colorant, R ₁ = -NH ₂ , R ₂ = -OCH ₃ , R ₃
= -H, were R ₄ = -CONC ₆ H _5] a is 100 parts by mass dispersion. While stirring at 200 rpm under the condition of 25 ° C,
20.5 parts by mass of a 5% by mass aqueous solution (pH = 10) of the compound represented by the formula (1) (dehydroabietic acid) was added dropwise. Then, the temperature was raised to 100 ° C. and the mixture was stirred for 20 hours. The obtained treated pigment dispersion liquid was cooled to 25 ° C., filtered, dried at 50 ° C. for 20 hours and then pulverized with a hammer mill to obtain a treated pigment (1).

The treated pigment (1) was prepared from dehydroabietic acid (compound (A)) from THF-soluble components and acetone-soluble components.
And Ca salt of dehydroabietic acid (compound (B))
Is contained in the pigment in a total amount of 10% by mass, and the value of X / Y is 4.
It was 0.

Treatment Example 2 of Pigment In Treatment Example 1 of Pigment, a compound represented by the formula (1) was prepared by using a CaCl ₂ aqueous solution (adjusted to pH = 4.7) of 1.5 × 10 ⁻³ mol / liter. Was carried out in the same manner as in Pigment Treatment Example 1 except that the amount of the 5% by mass aqueous solution of 3 was added to 39.0 parts by mass. The obtained treated pigment is designated as treated pigment (2).

The treated pigment (2) was prepared from dehydroabietic acid (compound (A)) from THF-soluble components and acetone-soluble components.
And Ca salt of dehydroabietic acid (compound (B))
Is contained in the pigment in a total amount of 19% by mass, and the value of X / Y is 6.
It was 7.

Pigment Treatment Example 3 In the pigment treatment example 1, a compound represented by the formula (1) was prepared by using a 5.0 × 10 ⁻² mol / liter CaCl ₂ aqueous solution (adjusted to pH = 4.7). Was carried out in the same manner as in Treatment Example 1 of the pigment, except that the amount of the 5% by mass aqueous solution of the above was dropped to 116.9 parts by mass. The obtained treated pigment is designated as treated pigment (3).

The treated pigment (3) was prepared from dehydroabietic acid (compound (A)) from THF-soluble components and acetone-soluble components.
And Ca salt of dehydroabietic acid (compound (B))
Is contained in the pigment in a total amount of 57% by mass, and the value of X / Y is 0.
It was 2.

Treatment Example 4 of Pigment In Treatment Example 1 of Pigment, a compound represented by the formula (1) was prepared by using 1.0 × 10 ⁻³ mol / liter of CaCl ₂ aqueous solution (adjusted to pH = 4.7). Was carried out in the same manner as in Treatment Example 1 of the pigment, except that the amount of the 5% by weight aqueous solution of 4 was added to 41.0 parts by weight. The obtained treated pigment is designated as treated pigment (4).

The treated pigment (4) was treated with dehydroabietic acid (compound (A)) from THF-soluble components and acetone-soluble components.
And Ca salt of dehydroabietic acid (compound (B))
Is contained in the pigment in a total amount of 20% by mass, and the value of X / Y is 1
It was 0.0.

Pigment Treatment Example 5 Pigment Treatment Example 1 except that in the Pigment Treatment Example 1, the compound represented by Formula (1) is replaced with the compound represented by Formula (2) (abietic acid). I went in the same way. The obtained treated pigment is designated as treated pigment (5).

The treated pigment (5) contained abietic acid (compound (A)) and Ca salt of abietic acid (compound (B)) in total amount of 10 in the pigment from THF-soluble and acetone-soluble components.
It was contained in a mass% and the X / Y value was 4.0.

Pigment Treatment Example 6 In Pigment Treatment Example 1, the compound represented by formula (1) was replaced with the compound represented by formula (2) (abietic acid), and the magenta pigment was replaced with a cyan pigment (CI Pigment Blue 15: The same procedure as in Pigment Treatment Example 1 was carried out except that the procedure (3) was replaced. The obtained treated pigment is designated as treated pigment (6).

In the treated pigment (6), the abietic acid (compound (A)) and the Ca salt of abietic acid (compound (B)) were dissolved in the pigment in a total amount of 10 from the THF-soluble content and the acetone-soluble content.
It was contained in a mass% and the X / Y value was 4.0.

Production Example of Ca Salt of Dehydroabietic Acid In a four-necked container, 1000 parts by mass of 0.1 mol / liter CaCl ₂ aqueous solution (adjusted to pH = 4.7) was stirred at 200 rpm under the condition of 25 ° C. Then, 100 parts by mass of a 5% by mass aqueous solution (pH = 10) of the compound represented by the formula (1) was added dropwise. The precipitated white crystalline product was filtered and washed thoroughly with acetone to remove dehydroabietic acid having no salt structure. Washed crystals at 50 ℃, 20
After drying for an hour, a Ca salt of dehydroabietic acid was obtained.

Production Example of Ba Salt of Dehydroabietic Acid In a four-necked container, 1000 parts by mass of 0.1 mol / liter BaCl ₂ aqueous solution (adjusted to pH = 4.7) was stirred at 200 rpm under the condition of 25 ° C. Then, 100 parts by mass of a 5% by mass aqueous solution (pH = 10) of the compound represented by the formula (1) was added dropwise. The precipitated white crystalline product was filtered and washed thoroughly with acetone to remove dehydroabietic acid having no salt structure. Washed crystals at 50 ℃, 20
After drying for an hour, Ba salt of dehydroabietic acid was obtained.

Production Example of Ca Salt of Abietic Acid In a four-necked container, 1000 parts by mass of 0.1 mol / liter CaCl ₂ aqueous solution (adjusted to pH = 4.7) was stirred at 200 rpm under the condition of 25 ° C. 100 parts by mass of a 5% by mass aqueous solution (pH = 10) of the compound represented by the formula (2) was added dropwise. The precipitated white crystals were filtered and washed sufficiently with acetone to remove abietic acid having no salt structure. The washed crystal product was dried at 50 ° C. for 20 hours to obtain a Ca salt of abietic acid.

Production Example of Ethyl Ester of Abietic Acid A mixture of 100 parts by mass of absolute ethanol, 20 parts by mass of abietic acid and 10 parts by mass of concentrated sulfuric acid was placed in a four-necked container, and 3
Reflux for a period of time. Then, cool to room temperature and add water to 3
00 parts by mass was added, and sodium carbonate was further added to adjust the pH in the container to 10. Next, the oily substance is extracted three times using diethyl ether, and the diethyl ether layer is washed with water and dried. After distilling off diethyl ether, the residue was distilled under reduced pressure to obtain ethyl ester of abietic acid.

(Toner Production Example 1) 360 parts by mass of ion-exchanged water and 0.1 mol / liter of Na were placed in a four-necked container.
430 parts by mass of a ₃ PO ₄ aqueous solution was added, and the mixture was maintained at 60 ° C. while stirring at 15,000 rpm using a high speed stirring device CLEAR MIXER. After 10 parts by mass of 1N hydrochloric acid was added thereto, 34 parts by mass of 1.0 mol / liter-CaCl ₂ aqueous solution was gradually added, and an aqueous system containing a fine sparingly water-soluble dispersion stabilizer Ca ₃ (PO ₄ ) ₂ was added. A dispersion medium was prepared.
At this time, the pH in the aqueous medium was 5.3.

On the other hand, as a dispersoid, styrene monomer 83 parts by mass n-butyl acrylate 17 parts by mass divinylbenzene 0.11 parts by mass Treated pigment (1) 5 parts by mass Polyester resin (Mw = 25,000, acid value 15 mgKOH / g ) 5 parts by mass dialkyl salicylic acid 0.03 parts by mass Ester wax (Mn = 1,000, Mw / Mn = 1.9, melting point 60 ° C.) 3 parts of a mixture of 15 parts by mass using an attritor (Mitsui Kinzoku Co., Ltd.) 3 After being dispersed for 3 hours, 3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added to prepare a polymerizable monomer composition.

Next, the polymerizable monomer is added to the aqueous dispersion medium.
The body composition is added and the internal temperature is 60 ° C. _TwoFast in the atmosphere
While maintaining the rotation speed of the stirring device at 15000 rpm, 4
After stirring for a minute, the polymerizable monomer composition was granulated. That
After that, change the stirring device to one equipped with paddle stirring blades, and
Polymerization for 5 hours while maintaining the same temperature while stirring at 00 rpm
I went.

After the completion of the polymerization, sodium hydrogen carbonate was added to the aqueous medium to readjust the pH to 11, and the internal temperature was adjusted to 80 ° C. for 3 minutes.
Distillation was performed under a reduced pressure of 50 mmHg for 5 hours, and after cooling, dilute hydrochloric acid was added to adjust the pH of the aqueous dispersion medium to 1.2 to dissolve the hardly water-soluble dispersant. Further, after solid-liquid separation by pressure filtration, washing was performed with 18,000 parts by mass of water. Then, it was dried at 45 ° C. for 4 hours using a fluidized bed dryer (Okawara Seisakusho) to obtain magenta toner particles having a weight average diameter of 7.1 μm.

Next, 100 parts by mass of the above polymer particles, 0.7 parts by mass of hydrophobized titanium oxide having an average major axis of 30 nm and hydrophobized silica fine particles (specific surface area 120
m ^{2 /} g) 0.7 part by mass was dry mixed. The obtained toner is designated as Toner (A).

A and A / B in the obtained toner (A)
The values of X and Y are shown in Table 1.

(Production Example 2 of Toner) In Production Example 1 of Toner, 0.4 part by mass of ethylene glycol diacrylate was added in place of divinylbenzene, and the treated pigment (2) was replaced with the treated pigment (1). A toner was produced in the same manner as in Toner Production Example 1 except that 6.15 parts by mass was added. The obtained toner is designated as Toner (B).

A and A / B in the obtained toner (B)
The values of X and Y are shown in Table 1.

(Production Example 3 of Toner) In Production Example 1 of Toner, 5 parts by mass of untreated yellow pigment CIPigment Yellow 93 is used in place of the treated pigment (1), and the addition amount of divinylbenzene is 0.0033 parts by mass. And then
Preparation Example 1 of Toner except that 0.15 parts by mass of the compound of formula (2) (abietic acid) and 0.15 parts by mass of the ethyl ester of abietic acid are added to the polymerizable monomer composition. It was manufactured in the same manner. The obtained toner is designated as Toner (C).

A, A / B in the obtained toner (C)
The values of X and Y are shown in Table 1.

(Production Example 4 of Toner) In Production Example 1 of Toner, 3 parts by mass of untreated red pigment CI Pigment Red 150 was used in place of the treated pigment (1), and the above formula was added to the polymerizable monomer composition. 2 parts by mass of the compound of (1) (dehydroabietic acid) and 5 parts of Ba salt of dehydroabietic acid
A toner was produced in the same manner as in Toner Production Example 1, except that the addition of parts by mass was added. The obtained toner is designated as Toner (D).

A, A / B in the obtained toner (D)
The values of X and Y are shown in Table 1.

(Manufacturing Example 5 of Toner) In the manufacturing example 1 of toner, the treated pigment (3) is replaced by 1 instead of the treated pigment (1).
Toner Production Example 1 with the exception of adding 0.5 part by mass
It was manufactured in the same manner as. The obtained toner is used as toner (E)
And

A and A / B in the obtained toner (E)
The values of X and Y are shown in Table 1.

(Production Example 6 of Toner) Production Example 1 of Toner is the same as Production Example 1 of Toner except that 5.6 parts by mass of the treated pigment (4) is added instead of the treated pigment (1).
It was manufactured in the same manner as. The obtained toner is used as toner (F)
And

A and A / B in the obtained toner (F)
The values of X and Y are shown in Table 1.

(Production Example 7 of Toner) In Production Example 1 of Toner, 3 parts by mass of untreated cyan pigment CI Pigment Blue 15: 3 was used in place of the treated pigment (1) in a polymerizable monomer composition. A toner was produced in the same manner as in Toner Production Example 1 except that 2 parts by weight of the compound of formula (2) (abietic acid) and 5 parts by weight of Ca salt of abietic acid were added. The obtained toner is designated as Toner (G).

A, A / B in the obtained toner (G)
The values of X and Y are shown in Table 1.

(Production Example 8 of Toner) In Production Example 1 of Toner, carbon black not treated (BET specific surface area 65 m ² / g, DBP in place of the treated pigment (1) was used.
8 parts by mass of oil absorption 42 ml / 100 g), and the compound of the formula (2) (abietic acid) in the polymerizable monomer composition.
2 parts by mass and 5 parts by mass of Ca salt of abietic acid were added, and the toner was manufactured in the same manner as in the toner manufacturing example 1. The obtained toner is designated as Toner (H).

A, A / B in the obtained toner (H)
The values of X and Y are shown in Table 1.

(Manufacturing Example 9 of Toner) A toner manufacturing example 1 is manufactured in the same manner as in toner manufacturing example 1 except that the treated pigment (5) is added in place of the treated pigment (1). . The obtained toner is designated as Toner (I).

A and A / B in the obtained toner (I)
The values of X and Y are shown in Table 1.

(Toner Production Example 10) Toner Production Example 1
In the same manner as in Toner Production Example 1 except that the treated pigment (6) was added in place of the treated pigment (1). The obtained toner is designated as Toner (J).

A, A / B in the obtained toner (J)
The values of X and Y are shown in Table 1.

(Production Example 1 of Comparative Toner) In Production Example 1 of Toner, 4.5 parts by mass of untreated red pigment CI Pigment Red 150 was added in place of the treated pigment (1), and the above formula (1) was used. The toner was manufactured in the same manner as in the toner manufacturing example 1 except that 0.04 parts by mass of the compound () and 0.01 part by mass of the Ca salt of dehydroabietic acid were added. The obtained toner is designated as toner (a).

A and A / B in the obtained toner (a)
The values of X and Y are shown in Table 1.

(Production Example 2 of Comparative Toner) In Production Example 1 of Toner, 4.5 parts by mass of untreated red pigment CI Pigment Red 150 was added in place of the treated pigment (1), and divinylbenzene (purity: 55 mass%) to 0.3
Manufactured in the same manner as in Toner Production Example 1 except that 8 parts by mass of the compound of formula (1) (dehydroabietic acid) and 2 parts by mass of Ca salt of dehydroabietic acid were added. The obtained toner is designated as toner (b).

A and A / B in the obtained toner (b)
The values of X and Y are shown in Table 1.

(Production Example 3 of Comparative Toner) In Production Example 1 of Toner, 4.5 parts by mass of untreated red pigment CI Pigment Red 150 was added in place of the treated pigment (1), and divinylbenzene (purity: 55 parts by mass), 0.4 parts by mass of the compound of formula (1) (dehydroabietic acid), and 0.1 parts of Ca salt of dehydroabietic acid.
A toner was produced in the same manner as in Toner Production Example 1, except that the addition of parts by mass was added. The obtained toner is designated as toner (c).

A, A / B in the obtained toner (c)
The values of X and Y are shown in Table 1.

(Production Example 4 of Comparative Toner) In Production Example 1 of Toner, 4.5 parts by mass of untreated red pigment CI Pigment Red 150 was added in place of the treated pigment (1) to prepare divinylbenzene (purity 55 % By weight) and 0.01 part by weight of the compound of formula (1) (dehydroabietic acid) and 0.1 part by weight of Ca salt of dehydroabietic acid. Manufacturing Example 1
It was manufactured in the same manner as. The obtained toner is used as toner (d)
And

A, A / B in the obtained toner (d)
The values of X and Y are shown in Table 1.

[0215]

[Table 1]

Example 1 Toner (A) is used as a developer,
Image evaluation was performed on the developer using an image forming apparatus as shown in FIG. The image forming apparatus will be described below.

FIG. 1 is a schematic view of a modified 1200 dpi laser beam printer (Canon: LBP-840) utilizing an electrophotographic process of a non-magnetic one-component contact developing system. In this example, an apparatus obtained by modifying the following (a) to (g) was used. (A) Changed the process speed to 65 mm / s. (B) The charging method was contact charging in which the rubber roller was brought into contact with the image bearing member (photosensitive member) to perform charging, and the applied voltage was only the DC component (-1200 V). (C) A medium resistance rubber roller (diameter 16 m) made of silicone rubber in which carbon black is dispersed as a toner carrier.
m, hardness ASKER-C 45 degrees, resistance 10 ⁵ Ω · cm)
Changed to contact the photoconductor. (D) The rotational peripheral speed of the toner carrier is in the same direction at the contact portion with the photosensitive member, and is 14 with respect to the rotational peripheral speed of the photosensitive member.
It was driven so as to be 0%. (E) As a means for applying toner to the toner carrier, an application roller made of urethane foam rubber was provided in the developing device and brought into contact with the toner carrier. For the application roller,
A voltage of about -550V was applied. (F) To control the coat layer of the toner on the toner carrier,
A resin-coated stainless steel blade was used. (G) The applied voltage at the time of development was only the DC component (-450V).

In the modified apparatus, the image bearing member is charged by using a roller charger (only direct current is applied), and then an electrostatic latent image is formed by exposing the image portion with a laser beam, and the toner is After that, a visible image is formed, and then a toner image is transferred onto a transfer material by a roller to which a voltage of +700 V is applied.

As for the charging potential of the photoconductor, the dark potential is -580V.
And the light portion potential was set to -150V.

In the fixing device, the heat roller type heating and pressing means shown in FIG. 2 is used, which is not provided with a separating claw or an offset preventing liquid applying mechanism.

The heating roller was treated with a primer of a cylindrical core made of aluminum, and then 50 μm thick through an elastic layer of dimethyl silicone rubber and a primer layer.
Using a PFA tube provided with a surface layer,
On the other hand, the pressure roller is provided with an elastic layer of dimethyl silicone rubber after priming a SUS core metal,
Further, a PFA tube having a thickness of 50 μm provided with a surface layer via a primer layer was used.

Further, a halogen heater is arranged as a pressurizing member inside the cylindrical core metal of the heating roller, and the pressing roller is 245 N (25 kgf) with respect to the heating roller.
The nip portion having a width of 5 mm was formed by abutting with the contact pressure.

As for the evaluation method, image peeling in the initial stage, fixing property in low temperature region and high temperature region, and OHT transparency were evaluated, and further up to 10,000 sheets for those having an acceptable level (C rank or higher) in each item. Printout evaluation was performed, and matching with the photosensitive drum, image density, and fog were evaluated. The printout evaluation was performed on an A4 size paper with an image pattern printed with an area ratio of 4%.

As a result, image peeling, fixability and OHT transparency were good, and good results were obtained for each item even when the printout of 10,000 sheets was evaluated. The evaluation results are shown in Table 2.

The evaluation method is as follows, and Examples 2 to 6 and Comparative Examples 1 to 4 described later also follow this evaluation method.

Image peeling When a solid image (size: 2 cm × 5 cm, toner amount: 0.8 mg / cm ² ) is printed out on a slightly thick transfer paper (basis weight: 105 g / m ² , A4 size paper) The evaluation was made by the number of image peelings that occurred on the image. A: not generated B: 1 to 5 places C: 6 to 10 places D: 11 places or more (or image peeling with a diameter of 2 mm or more occurs) Fixability in low temperature range Transfer paper (grammage 75 g / m ² , A solid image (toner application amount: 0.6 mg / cm ² ) on A4 size paper was evaluated by changing the fixing temperature (130 to 175 ° C.). In addition,
The fixing temperature is a value measured on the surface of the fixing roller using a non-contact thermometer. A: No offset above 130 ° C B: No offset above 150 ° C, offset below 150 ° C C: No offset above 170 ° C, offset below 170 ° C D: High offset above 170 ° C Fixability in the area A solid image (toner loading: 0.6 mg / cm ² ) on a transfer paper (grammage 75 g / m ² , A4 size paper) can be fixed by changing the fixing temperature (175 to 220 ° C.). evaluated. In addition,
The fixing temperature is a value measured on the surface of the fixing roller using a non-contact thermometer. A: 220 ° C. or lower does not offset, B: 200 ° C. or lower does not offset, and when 200 ° C. is exceeded, offset occurs C: 180 ° C. Offset does not occur below, and offset occurs when the temperature exceeds 180 ° C D: Offset occurs even when 180 ° C or less.

OHT Transparency Transparency film (OHT) transparency was evaluated by forming a solid image on the OHT with a toner amount of 0.6 mg / cm ² and using the obtained OHT image as an overhead projector (OHP). The evaluation was performed by evaluating the projection image obtained when the image was projected. A: The obtained image is not offset, has excellent transparency, has no uneven brightness, and has excellent color reproducibility. B: There is no problem, though there is some uneven brightness. C: There is light and dark unevenness and color reproduction is poor, but a usable level. D: The transparency is remarkably inferior and almost no color is reproduced.

[0228] Matching with the photoconductor drum Initially, after the print-out test of 5,000 and 10,000 sheets,
The state of scratches on the surface of the photosensitive drum and the adhesion of toner and the influence on the printout image were visually evaluated. A: No sticking has occurred B: Scratch has occurred on the surface, but there is almost no sticking C: There is sticking, but there is little effect on the image D: Many sticking, causing image defects Initial image density After the printout test of 5,000 and 10,000 sheets,
The image density of the solid portion was evaluated. The image density was measured by using a "Macbeth reflection densitometer RD918" (manufactured by Macbeth Co., Ltd.) to measure the relative density of a white background portion having a document density of 0.00 to a printout image. 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 Image fog "REFLECTOMETER MODEL TC-6DS" (manufactured by Tokyo Denshoku Co., Ltd.) Using, the reflectance of the non-image part of the printout image (%)
To measure. The obtained reflectance was evaluated using a numerical value (%) subtracted from the reflectance (%) of an unused printout paper (standard paper) measured in the same manner. The smaller the value, the more the image fogging is suppressed. In addition,
Image fogging was evaluated after the initial printout test of 5,000 and 10,000 sheets. A: Less than 0.5 B: 0.5 or more, less than 1.0 C: 1.0 or more, less than 5.0 D: 5.0 or more <Example 2> Printout of toner (B) by the above evaluation method The test was conducted. As a result, image peeling, fixability and OHT transparency were slightly inferior to those of Example 1, but generally good results were obtained. The evaluation results are shown in Table 2.

Example 3 A printout test was conducted on Toner (C) by the above evaluation method. As a result, image peeling and fixing property were slightly inferior to those of Example 1, but generally good results were obtained. The evaluation results are shown in Table 2.

Example 4 A printout test was conducted on the toner (D) by the above evaluation method. As a result, the fixing property and the like were slightly inferior to those of Example 1, but generally good results were obtained. The evaluation results are shown in Table 2.

<Example 5> A printout test was conducted on the toner (E) by the above-described evaluation method. As a result, the OHT transparency was slightly inferior to that of Example 1, but was at a level without a problem. The evaluation results are shown in Table 2.

<Example 6> A printout test was conducted on the toner (F) by the above evaluation method. As a result, the OHT transparency was inferior to that of Example 1, but it was at a level without a problem. The evaluation results are shown in Table 2.

<Comparative Example 1> A printout test was conducted on the toner (a) by the above evaluation method. As a result, the peeling of the image remarkably deteriorated, so the evaluation was stopped.
The evaluation results are shown in Table 2.

Comparative Example 2 A printout test was conducted on the toner (b) by the above evaluation method. As a result, the matching with the photoconductor drum, the image density and the fog at the end of 5,000 sheets and 10,000 sheets were significantly deteriorated. The evaluation results are shown in Table 2.

<Comparative Example 3> A printout test was conducted on the toner (c) by the above-described evaluation method. As a result, image peeling and fixability in the low temperature range were significantly deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 2.

<Comparative Example 4> A printout test was conducted on the toner (d) by the above-described evaluation method. As a result, the fixability in the high temperature range was remarkably deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 2.

<Embodiment 7> A roller impregnated with dimethyl silicone oil is brought into contact with the heating roller of the pressurizing and heating means used in Embodiment 4 as a mechanism for applying an offset preventing liquid, and the toner image on the transfer material is transferred. The consumption amount of the offset preventing liquid applied to the contact surface with 0.015 to 0.
Evaluations were made in the same manner as in Example 4 except that the amount was set to 020 mg / cm ² .

As a result, although the obtained image had a slight gloss, the fixing property in a high temperature region was slightly improved. The evaluation results are shown in Table 2.

[0239]

[Table 2]

<Embodiment 8> In the image forming apparatus for evaluation of Embodiment 1, the film type pressurizing and heating means shown in FIG. 4 is not provided with a separating claw or an offset preventing liquid application mechanism as a fixing device. Was used.

As the heat-resistant endless film, a 60 μm-thick polyimide film having a low-resistance release layer in which a conductive substance is dispersed in PTFE is used on the contact surface with the transfer material, and the pressure roller is made of SUS. The core metal of No. 1 was subjected to a primer treatment, and thereafter, an elastic layer of a foam of dimethyl silicone rubber, an elastic layer of dimethyl silicone rubber and a surface layer of PTFE having a thickness of 20 μm were provided with a primer layer interposed therebetween.

Inside the heat-resistant endless film, a heating resistor is screen-printed on the heater substrate as a heating element, and a low heat capacity linear heating element provided with a heat-resistant surface protective layer is arranged to provide heat resistance. A contact pressure of 96 N (10 kgf) was applied to the heating body and the pressure roller via the endless film, and the nip portion having a width of 5 mm was formed.

Image evaluation (only in the initial stage) was performed on the toner (A) using this heating and pressing means, and image peeling, fixability in a low temperature region and a high temperature region, and OHT transparency were evaluated. As a result, the results were generally good. Table 3 shows the evaluation results
Shown in.

The evaluation method was the same as in Example 1.
The same procedure was performed for Examples 9 and 10 and Comparative Examples 5 and 6.

Example 9 Evaluation was performed in the same manner as in Example 8 except that Toner (C) was used as the evaluation toner. As a result, the results were generally good. The evaluation results are shown in Table 3.

<Example 10> Evaluation was performed in the same manner as in Example 8 except that Toner (D) was used as the evaluation toner. As a result, the results were generally good. The evaluation results are shown in Table 3.

<Comparative Example 5> Evaluation was performed in the same manner as in Example 8 except that Toner (a) was used as the evaluation toner. As a result, the peeling of the image remarkably deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 3.

<Comparative Example 6> Evaluation was performed in the same manner as in Example 8 except that Toner (c) was used as the evaluation toner. As a result, image peeling and fixability in the low temperature range were significantly deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 3.

[0249]

[Table 3]

<Embodiment 11> In the image forming apparatus for evaluation of Embodiment 1, the heating and pressurizing means of the electromagnetic induction system shown in FIG. 5 in which the separating claw and the coating mechanism for the offset preventing liquid are not provided is used. I was there.

The heat-resistant endless film has a thickness of 50.
A three-layer structure in which a cylindrical nickel film material of μm is used as a resistance layer for electromagnetic induction heat generation, and the outer peripheral surface is covered with an elastic layer made of dimethyl silicone rubber and a release layer made of PFA is used. The roller is provided with an elastic layer of a dimethyl silicone rubber foam after the SUS core metal is subjected to a primer treatment, and further provided with an elastic layer of the dimethyl silicone rubber and a surface layer of a PFA tube having a thickness of 50 μm through the primer layer. Was used.

Further, a magnetic field generating means is provided inside the cylindrical heat-resistant endless film, and two magnetic field generating means and a pressure roller are provided through the heat-resistant endless film.
A contact pressure of 45 N (25 kgf) was applied so that a nip portion having a width of 6 mm was formed.

Image evaluation (only in the initial stage) was performed on the toner (A) using this heating and pressurizing means, and image peeling, fixability in low and high temperature regions, and OHT transparency were evaluated. As a result, generally good results were obtained. The evaluation results are shown in Table 4.

The evaluation method was the same as in Example 1.
Moreover, it carried out similarly about Examples 12 and 13, and Comparative Examples 7 and 8.

<Example 12> Evaluation was performed in the same manner as in Example 11 except that Toner (C) was used as the evaluation toner. As a result, the results were generally good. The evaluation results are shown in Table 4.

<Example 13> Evaluation was performed in the same manner as in Example 11 except that Toner (D) was used as the evaluation toner. As a result, the results were generally good. The evaluation results are shown in Table 4.

<Comparative Example 7> Evaluation was performed in the same manner as in Example 11 except that Toner (a) was used as the evaluation toner. As a result, the peeling of the image remarkably deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 4.

<Comparative Example 8> Evaluation was performed in the same manner as in Example 11 except that Toner (c) was used as the evaluation toner. As a result, image peeling and fixability in the low temperature range were significantly deteriorated, so the evaluation was stopped. The evaluation results are shown in Table 4.

<Examples 14 to 17> Evaluations were performed in the same manner as in Example 11 except that Toners (G) to (J) were used as the evaluation toners. As a result, the results were generally good. The evaluation results are shown in Table 4.

[0260]

[Table 4]

[0261]

As described above, according to the present invention,
By specifying the contents of the rosin compound, the rosin compound derivative, and the cross-linking agent present in the toner, it is possible to provide a toner in which image peeling does not occur and the latitude of the fixing temperature is sufficiently wide. Further, the OHT transparency is good, and a toner having a stable image density and free from fog even when a printout of a large number of sheets is evaluated is provided.

[Brief description of drawings]

FIG. 1 is a schematic explanatory diagram of an image forming apparatus used in an embodiment of the present invention.

FIG. 2 is a schematic explanatory view of a heat roller type heating and pressing means used in an example of the present invention.

FIG. 3 is a heating and pressurizing means using a heating roller system having a separating claw, which is equipped with a brush-shaped cleaning roller (a) and a cleaning roller impregnated with an offset preventing liquid. It is a schematic explanatory drawing which shows (b).

FIG. 4 is an explanatory diagram showing an exploded perspective view (a) and an enlarged cross section (b) of a main part of a heating and pressing means using a film system used in an embodiment of the present invention.

FIG. 5 is a schematic explanatory view of an electromagnetic induction type heating / pressurizing means used in an embodiment of the present invention.

[Explanation of symbols] 11 Rotating heating member (heating roller) 11a Heating body (heater) 12 Rotating pressure member (pressure roller) 13 Conveyor belt 30 stay 31 heating body 31a heater substrate 31b heating element 31c Surface protection layer 31d Temperature measuring element 32 Endless film 33 Pressure roller 34 coil spring 35 Film edge control flange 36 power supply connector 37 Breaking member 38 Entrance guide 39 Exit guide (separation guide) 40 excitation coil 42 Coil core material (magnetic material) 47 Endless film N Nip T toner image P transfer material

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masanori Ito             Kyano, 3-30-2 Shimomaruko, Ota-ku, Tokyo             Within the corporation (72) Inventor Emi Tosaka             Kyano, 3-30-2 Shimomaruko, Ota-ku, Tokyo             Within the corporation F-term (reference) 2H005 AA01 AA06 AA21 CA03 CA17                       CA21 CA25 CA30 CB03 CB18                       DA06 DA10 EA07                 2H033 AA02 AA09 AA11 AA32 BA31                       BB01 BB05 BB18 BB29 BE03                       BE06 CA02

Claims (17)

[Claims] 1. A toner containing at least a binder resin containing a crosslinking agent component, a colorant, a compound (A) and a compound (B), wherein the compound (A) is abietic acid or dehydroabietic acid. , Dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastophosphoric acid, sandra trucipimaric acid, secodehydroabietic acid, and agatoic acid, wherein the compound (B) is The compound (A) is a derivative of a compound contained in the selected group, and the total content A (% by mass: based on the mass of the toner) of the compound (A) and the compound (B) in the toner is 0.2. Is 6% by mass, and the content of the crosslinking agent component in the binder resin is B (% by mass:
The toner is characterized by satisfying the following relationship: 0.1 ≦ A / B ≦ 70 (based on toner mass). 2. The content X of the compound (A) (% by mass: based on the mass of the toner) and the content Y of the compound (B) (% by mass: based on the mass of the toner) are 0.25 ≦ X. The toner according to claim 1, wherein the relationship of / Y≤9 is satisfied. 3. A compound in which the compound (B) has a salt structure.
And K⁺, Na ⁺, Ca²⁺, Ba²⁺, Al³⁺
And NH_Four ⁺Form a cation and salt selected from the group consisting of
3. The toner according to claim 1 or 2, characterized in that
Na. 4. The toner according to claim 1, wherein the compound (B) is an ester compound. 5. The toner according to claim 1, wherein the crosslinking agent is divinylbenzene. 6. The toner according to claim 1, wherein the colorant is a magenta colorant and is a monoazo colorant represented by the following structural formula. [Chemical 1] 7. The CIPigment Red is a monoazo colorant.
5, CIPigment Red31, CIPigment Red 146, CIPig
ment Red 147, CI Pigment Red 150, CI Pigment Red
7. The toner according to claim 6, wherein the toner is a compound selected from the group consisting of 184 and CI Pigment Red 269 (each having a name described in Color Index Fourth Edition). 8. The colorant is a yellow colorant, CI
Pigment Yellow 17, CI Pigment Yellow 74, CI Pigm
ent Yellow 93, CI Pigment Yellow 155 and CI Pigme
6. The toner according to claim 1, wherein the toner is a compound selected from the group consisting of nt Yellow 180 (each of which has a name described in Color Index Fourth Edition). 9. The colorant is a cyan colorant, and CIPi
gment Blue1,7,15,15: 1,15: 2,15: 3,15: 4,60,62,66
The toner according to any one of claims 1 to 5, wherein the toner is a compound selected from the group consisting of (according to names described in Color Index Fourth Edition). 10. The toner according to claim 1, wherein the colorant is a black colorant, which is carbon black or a magnetic material. 11. A charging step of charging at least (a) an image carrier for carrying an electrostatic latent image; (b) an exposure step of forming an electrostatic latent image by exposing the charged image carrier.
(C) a developing step of developing the electrostatic latent image with toner carried on the surface of the toner carrier to form a toner image; (d) intermediate transfer of the toner image formed on the surface of the image carrier. An image forming method comprising: a transfer step of transferring to a transfer material with or without a body; and (e) a fixing step of fixing the toner image on the transfer material to the transfer material by a heating and pressing means, The toner is a toner containing at least a binder resin containing a crosslinking agent component, a colorant, a compound (A) and a compound (B), wherein the compound (A) is abietic acid, dehydroabietic acid, It is a compound selected from the group consisting of dihydroabietic acid, neoabietic acid, pimaric acid, isopimaric acid, levopimaric acid, parastophosphoric acid, sandrasucco pimaric acid, secodehydroabietic acid and agato acid. , The compound (B) is a derivative of the compound contained in the group Compound (A) is selected, the compounds in the toner (A)
And the total content A (% by mass: based on the mass of the toner) of the compound (B) is 0.2 to 6% by mass, and the content of the crosslinking agent component in the binder resin is B (% by mass: the mass of the toner). The image forming method is characterized by satisfying the following relationship: 0.1 ≦ A / B ≦ 70. 12. The heating / pressurizing means includes (i) a rotary heating member having at least a heating body, and a rotary pressing member forming a nip portion in pressure contact with the rotary heating member, (ii)
The consumption amount of the offset prevention liquid applied to the contact surface of the transfer material with the toner image is set to 0.025 mg / cm ² or less (based on the unit surface area of the transfer material), and (ii)
12. The image forming method according to claim 11, wherein i) the toner image on the transfer material is heated and pressed in the nip portion. 13. A cylindrical heating roller having a heating element therein is used as a rotary heating member, and a cleaning member for removing toner remaining after fixing and a separating member for preventing winding of a transfer material are provided on the surface of the heating roller. The image forming method according to claim 12, wherein a heat roller type heating / pressurizing unit which is not provided is used. 14. A rotary heating member having a heating element fixedly supported on a support and having a cylindrical heat-resistant endless film which moves while being pressed against the heating element.
13. A film type pressurizing and heating means for pressurizing through the endless film is used.
The image forming method described in 1 .. 15. An electromagnetic induction system in which a heating body made of a cylindrical heat-resistant endless film having a magnetic field generating means therein and having a heating layer for electromagnetically generating heat by the action of the magnetic field generating means is used as a rotary heating member. The image forming method according to claim 12, wherein a heating and pressing unit is used. 16. The electrostatic latent image is developed by contacting a toner layer formed of toner carried on the surface of the toner carrier with the surface of the image carrier in the developing step. The image forming method according to claim 11. 17. The image forming method according to claim 11, wherein the toner is the toner according to any one of claims 2 to 10.