JPH07175263A - Toner for developing electrostatic charge image, one-component developer and two-component developer - Google Patents

Abstract

PURPOSE:To obtain a toner, a one-component developer and a two-component developer excellent in low temp. fixability and anti-offsetting property, further excellent in environmental stability and so excellent in electrostatic charge stability, fixability, shelf life stability, developing characteristics and flowability as to prevent the charge-up phenomenon of the toner especially in an environment at a low temp. and humidity. CONSTITUTION:This toner contains at least a bonding resin and a colorant. The bonding resin contains polyester resin and at least a part of this polyester resin has been modified with a compd. having a 22-102C long chain alkyl group and terminal hydroxyl or carboxyl groups. The objective one-component developer and the objective two-component developer are obtd. using this toner.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in an image forming method such as an electrophotographic method, an electrostatic recording method and an electrostatic printing method, a one-component type developer having the toner and a toner. The present invention relates to a two-component developer having a toner and a carrier.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Publication (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,074)
Numerous methods are known, as described in US Pat. Generally, a photoconductive substance is used to form an electric latent image on the photoconductor by various means, and then the latent image is developed with toner to form a visible image, and if necessary, such as paper. After transferring the toner image to the transfer material, heat,
It is fixed by pressure to obtain a copy.

Further, various developing methods are known in which an electrostatic latent image is visualized using toner. For example, the magnetic brush method described in U.S. Pat. No. 2,874,063, the cascade developing method described in U.S. Pat. No. 2,618,552, and U.S. Pat. No. 2,22.
Many developing methods are known, such as the powder cloud method, the fur brush developing method, and the liquid developing method described in Japanese Patent No. 1,776.

Among these developing methods, a magnetic brush method, a cascade method, a liquid developing method and the like, which use a two-component developer mainly composed of toner and carrier, have been widely put into practical use. Further, a developer container that stores toner and magnetic particles for applying toner, a toner carrier that conveys toner to the latent image carrier, and a contact with the toner carrier upstream of the toner outlet of the developer container. And a magnet forming a magnetic brush of magnetic particles for toner application are formed to form a thin layer of toner on the toner carrier, and the gap between the toner carrier and the latent image carrier is smaller than the toner layer thickness. There is a method of setting a large value and developing the electrostatic latent image.

In these methods, it is necessary to substantially keep the toner in a uniformly mixed state with the carrier in the developing section, or in a uniform thin layer coating state on the toner carrier, and to achieve that state. The electrostatic attraction and the physical adhesive force are mainly dominant as the force to perform. That is,
It is necessary to precisely control the amount of electrostatic charge and the triboelectric charging ability of the toner.

However, it is quite difficult to uniformly control the charge amount of the toner, and to stabilize the charge amount even after repeating copying for a long period of time or under a special environment of high temperature and high humidity and low temperature and low humidity. It is accompanied by.

Various developing methods using a one-component developer consisting only of toner have been proposed which avoids the problems of the developing method using a two-component developer. Among them, a developing agent consisting of toner particles having magnetic properties is proposed. Many are excellent in the method used.

As the toner used in these developing methods, fine powders in which a dye or a pigment is dispersed in a natural or synthetic resin have been used. Further, it is known to use a developing fine powder to which a third substance is added for various purposes.

The developed toner image is fixed to a transfer material such as paper if necessary, and various methods and techniques have been developed for the step of fixing the toner image to the transfer material. The most common fixing method at present is a pressure heating method using a heating roller. The pressure heating method using this heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass under pressure while contacting the surface of the heating roller whose surface is formed of a material having releasability for toner. Is. According to this method, since the surface of the heating roller and the toner image on the sheet to be fixed are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and the fixing is performed quickly. be able to. However, in the pressure-bonding heating method using this heating roller, since the heating roller surface and the toner image are in contact with each other under pressure in a molten state, a part of the toner image adheres to and transfers to the fixing roller surface, and the next sheet to be fixed. In some cases, this re-transfers to cause a so-called offset phenomenon and stains the fixing target sheet. Therefore, development of a resin for toner having higher low-temperature fixability and high-temperature offset resistance is desired.

Further, in the future, since copying machines are moving toward higher speeds, the toner must satisfy the requirements for improved fixability on paper, high resolution and high speed development, and high durability. Is coming.

Therefore, JP-A-62-127748 and JP-A-62-127749 propose a developer comprising a toner containing a crosslinked polyester as a binder resin and a resin-coated carrier. However, this developer
In the evaluation of durability image development in a low humidity environment, there is a problem in that when the developer is mechanically stirred in the developing device, the chargeability of the toner becomes unstable.

In Japanese Patent Application Laid-Open No. 58-11953, the binder resin is made of a polyester resin containing 5% by weight or more of chloroform insoluble matter, and contains an offset preventive agent made of a non-polar substance and a polar substance. A toner for developing an electrostatic charge image, which is characterized by the above, has been proposed.

Japanese Unexamined Patent Publication No. 62-78569 proposes a toner using a polyester having a saturated or unsaturated aliphatic hydrocarbon group having 3 to 22 carbon atoms in its side chain.

However, in these toners, the poor compatibility between the polyester resin and the polyolefin wax tends to cause poor dispersion of the polyolefin wax during toner production, and free polyolefin may occur during pulverization. This causes problems such as occurrence of cleaning failure and deterioration of offset resistance in consideration of future expansion to high-speed copying machines. It is hard to say that a high-speed copying machine is sufficient in terms of fixability in a low temperature environment and developability in a low humidity environment.

JP-A-2-129653 and JP-A-3-46668 propose toners using a polyester obtained by treating a polyester resin with an acid or an alcohol as a binder resin.

These toners are certainly effective in improving the fixing property and stabilizing the triboelectric charge amount, but because the carbon number of the alkyl group of the monoalcohol used is as small as 10, the poor dispersion of the polyolefin wax occurs. More likely to occur,
Considering the future development to high-speed copying machines, the occurrence of cleaning defects and the deterioration of offset resistance become problems, and it cannot be said that the fixability in a low temperature environment and the developability in a low humidity environment are sufficient.

In the above-mentioned conventional technique, it is difficult to balance the fixing and the offset because the compatibility between the polyester and the polyolefin wax is poor, and when the process speed of the developer carrier is fast as in a high speed copying machine. ,
It is also difficult to control the toner charge amount, and in the future development of high-speed copying machines, it has not yet reached a sufficiently satisfactory level to further improve the fixing property, anti-offset property, and developability.

Further, in recent years, it has been desired to improve the image quality of copied images by digitizing copying machines and making toner particles finer. However, even if the resolution of the image and the sharpness of the image can be improved by making the toner fine particles, various problems occur. First of all, the fixing property of the halftone portion deteriorates due to the finer toner particles. The reason for this is that the toner transferred to the concave portions of the sheet to be fixed is less likely to be applied with the fixing pressure and the amount of heat applied is also small, and the toner transferred to the convex portions has a thin toner layer thickness, so that the amount of toner per toner particle is small. This is because the shearing force becomes large and the offset phenomenon easily occurs.

Further, when such a fine-particle size toner having a small particle size is applied to a high-speed copying machine, there is a case where fog or a decrease in density occurs due to excessive charging especially under low humidity.

In the multi-functionalization of a copying machine, for example, a part of an image is erased by exposure or the like, and then another image is inserted into the part to perform multiple multi-color copying, or the periphery of copy paper. In a function like
Fog occurs in the part of the image that should be removed in white.

In other words, when an image is erased by applying a potential opposite to the latent image potential with respect to the development reference potential with strong light such as an LED or a fuse lamp, there is a problem that the fog tends to occur at that portion. .

Further, although the resolution and the sharpness of the image can be improved by digitizing and reducing the particle size of the toner,
Various problems arise.

First, there is the above-mentioned problem of fog. By reducing the toner particle size, the surface area of the toner is increased, so that the width of the charge amount distribution is increased and fogging is likely to occur. Further, as the toner surface area increases, the charging characteristics of the toner become more susceptible to the environment. Further, when the toner particle size is further reduced, it is obvious that the dispersion state of the magnetic substance, the colorant and the release agent has a great influence on the charging property of the toner.

In recent digital copying machines, the characters in the copied image are clear in the photographic image containing the characters.
A photographic image is required to have density gradation that is faithful to the original. Generally, when the density of the character line is increased in order to make the character clear in the copy of the image with the character, not only the density gradation of the photographic image is impaired, but also the halftone portion becomes a very rough image. Furthermore, when the density of the character line is increased, the amount of toner adhered is large, so the toner is pressed against the photoconductor at the time of transfer and adheres to the photoconductor, causing the so-called hollow dot phenomenon in which the toner on the line escapes and The copy image is of high quality. On the other hand, if an attempt is made to improve the density gradation of the photographic image, the density of the character line will decrease and the sharpness will deteriorate.

In recent years, the density gradation has been improved to some extent by reading the image density and performing digital conversion. However, the present situation is still not enough.

[0026]

DISCLOSURE OF THE INVENTION The present invention provides a toner for developing an electrostatic image, which solves the above problems, a one-component developer containing the toner, and a two-component developer containing the toner and a carrier. The purpose is to do.

The present invention provides a toner for developing an electrostatic image which is excellent in low-temperature fixability and high-temperature offset resistance, a one-component developer containing the toner, and a two-component developer containing the toner and a carrier. With the goal.

The present invention provides an electrostatic charge developing toner capable of obtaining a high-density and high-quality copy image without impairing the fixability, fog, a one-component developer having the toner, the toner and the carrier. An object of the present invention is to provide a two-component developer having the same.

The present invention provides a toner for electrostatic charge development that gives good images even under low and high humidity without being affected by environmental changes, a one-component developer containing the toner, the toner and the carrier. An object of the present invention is to provide a two-component developer having

The present invention provides a stable and good image even in a high-speed machine and has a wide range of applicable models, a toner for electrostatic charge development, a one-component developer containing the toner, and a two-component toner containing the toner and a carrier. The purpose is to provide a system developer.

The present invention provides a toner for electrostatic charge development which has excellent durability, has a high image density even after continuous use for a long time, and is free of fog on a white background to obtain a copy image, and a one-component system developing toner containing the toner. An object of the present invention is to provide a two-component type developer having an agent, the toner and a carrier.

According to the present invention, in a photographic image with characters, the characters of the copied image are clear, and the photographic image has density gradation that is faithful to the original, a toner for electrostatic charge development, and a one-component system having the toner. It is an object to provide a developer and a two-component developer having the toner and the carrier.

The present invention provides a toner for developing an electrostatic image which has a high density of character lines and is less likely to cause voids during transfer, a one-component developer containing the toner, and a two-component developer containing the toner and a carrier. The purpose is to provide.

The present invention provides a toner for developing an electrostatic image which does not cause defective fusion of a photoreceptor and cleaning, a one-component developer containing the toner and a two-component developer containing the toner and a carrier. The purpose is to

The present invention provides a toner for developing an electrostatic charge image, which has a stable triboelectric charge amount between toner particles and between a toner and a toner carrier such as a sleeve and which can be controlled to a charge amount suitable for a developing system to be used. An object is to provide a one-component developer having a toner and a two-component developer having the toner and a carrier.

The present invention is capable of faithfully developing even a digital latent image, increasing the density difference between dots, and developing an electrostatic charge image developing toner in which the edges of dots are reproduced sharply. An object of the present invention is to provide a one-component developer containing the toner and a two-component developer containing the toner and a carrier.

The present invention is a toner for developing an electrostatic image having less fog and reversal fog even in an image forming process including post-charging, a one-component developer having the toner and a two-component developer having the toner and a carrier. The purpose is to provide.

The present invention relates to an electrostatic image developing toner having excellent storage stability which maintains initial properties even after long-term storage, a one-component developer containing the toner and a two-component system containing the toner and a carrier. The purpose is to provide a developer.

The present invention prevents the charge-up of the toner, which is an adverse effect when the toner particle size is reduced, and imparts a good image density to the toner for developing an electrostatic charge image, a one-component developer having the toner, and It is an object to provide a two-component developer having the toner and carrier.

[0040]

Means and Actions for Solving the Problems The present invention achieves the above object by the following constitutions.

The present invention provides an electrostatic image developing toner containing at least a binder resin and a colorant, wherein the binder resin has a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. The present invention relates to a toner for developing an electrostatic charge image, which comprises a polyester resin at least partially modified with a compound having

The present invention provides a one-component type developer having a toner containing at least a binder resin and a colorant, wherein the binder resin is a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. The present invention relates to a one-component developer containing a polyester resin at least a part of which is modified with a compound having a group.

The present invention provides a two-component developer having a toner and a carrier containing at least a binder resin and a colorant, wherein the binder resin is a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group at the terminal. Alternatively, the present invention relates to a two-component developer containing a polyester resin which is at least partially modified with a compound containing a carboxyl group.

In the present invention, the number of carbon atoms is 22 to 102.
A compound having a long-chain alkyl group and a terminal hydroxyl group or carboxyl group (hereinafter referred to as a modifying compound).
At least a part of the polyester resin is modified with, and the modification means a carboxyl group and / or a hydroxyl group in the main chain of the polyester resin and a carboxyl group and / or a hydroxyl group at the end of the main chain, and the above-mentioned modifying compound. The terminal hydroxyl group or carboxyl group has a state in which a long-chain alkyl group having 22 to 102 carbon atoms of the modifying compound is introduced into the structure of the polyester resin by an ester bond or a urethane bond.

Conventionally, US Pat. No. 4,883,736 and US Pat. No. 5,080,995 disclose a method in which an alcohol polymer wax is mixed with a developer. In these methods, when a large amount of alcohol polymer wax is used, the fixing temperature can be lowered, but the storage stability, developing characteristics, fluidity, etc. are deteriorated.

In the present invention, the compound for modifying the polyester resin is represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein x represents a number of 20 to 100). The alkyl alcohol shown by can be used.

The melting point of the alkyl alcohol represented by the above formula (1) is as low as 80 to 120 ° C., and the alkyl alcohol represented by the above formula (1) passes through the unreacted carboxyl group and hydroxyl group in the polyester main chain. It has the effect of lowering the fixing temperature by branching or bonding to the end of the polyester main chain.

Further, the compatibility between the binder resin and the polyolefin wax is improved, and the poor dispersion of the polyolefin wax in the binder resin is less likely to occur. Furthermore, if it is a long-chain alkyl group, sufficient releasability from the fixing roller can be obtained without using a polyolefin wax, and the offset resistance is improved.

Furthermore, in the conventional polyester resin, when the toner particle size was reduced, it was easy to become overcharged in a low humidity environment, but in the present invention, the polyester resin is represented by the above formula (1). By modifying with an alkyl alcohol, the property of being overcharged can be suppressed, and stable charging property can be obtained.

In the above formula (1), x is a number of 20 to 100, preferably 23 to 100, and more preferably 25 to 70. When x is smaller than 20, the effect of lowering the fixing temperature of the toner is small because it is short, and when used in a large amount in order to obtain the effect of lowering the fixing temperature, the storage stability deteriorates, and further, to the photoreceptor. The ability to impart slipperiness is reduced, and problems such as hollow defects at the time of transfer, fusing of the photoconductor, and poor cleaning are likely to occur. If x is larger than 100, the melting point becomes high, and similarly, the effect of lowering the fixing temperature becomes small.

Japanese Patent Laid-Open No. 3-466681 discloses a method of masking a polyester resin with a C ₁ -C ₁₀ monoalcohol. Although this method surely improves the environmental characteristics and the fixability, it is not sufficient for the problems such as the above-described phenomenon of void in transfer, fusion of the photoreceptor, and defective cleaning.

Alcohols used in the present invention include, for example, US Pat. No. 2,892,858 and US Pat. No. 27,814.
19, U.S. Pat. No. 2,787,626, U.S. Pat. No. 2,835,689, and British Patent No. 80.
It can be prepared by the method disclosed in the specification of 8055.

In the measurement of the molecular weight distribution of the alkyl alcohol of the general formula (1) by GPC, the value of the molecular weight distribution (weight average molecular weight: Mw) / (number average molecular weight: Mn) is preferably 1.0 to 4.0, More preferably 1.0 to
It is preferably 3.0. If the molecular weight distribution is larger than 4.0, the above-mentioned hollow defects at the time of transfer, photosensitive member fusion, cleaning failure, and charging characteristics and fluidity deteriorate.

Further, as a compound for modifying the polyester resin used in the present invention, when the polyester resin is a non-linear polyester resin described later, it has 2 carbon atoms.
Alkyl alcohols of 5 or more are preferred.

In the present invention, a part of the carboxyl group and hydroxyl group of the non-linear polyester resin is modified with a long-chain alkyl alcohol having 25 or more carbon atoms to give a long-chain alkyl group in the binder resin. The effects (1) to (3) are obtained. (1) The melt viscosity of the binder resin can be easily controlled and the fixability on paper can be improved. (2) The compatibility between the binder resin and the polyolefin wax is improved, the dispersibility of the polyolefin wax in the binder resin can be improved, and the offset resistance is sufficient even when applied to a high-speed copying machine. In addition, cleaning failure does not occur during durability. Furthermore, when a long-chain alkyl group having a carbon number of 30 or more is added to the binder resin, sufficient releasability from the fixing roller can be obtained without using a polyolefin wax, and the offset resistance can be improved. . (3) Since the acid value that affects the chargeability of the toner can be controlled, the charge amount does not excessively increase even in a low humidity environment, more stable chargeability can be obtained, and good developability can be obtained.

Further, as a compound for modifying the polyester resin used in the present invention, the following formula (2) CH ₃ (CH ₂ ) _n OH ... (2) (wherein, n represents a number from 21 to 101) .) And the following formula (3) having one epoxy group in the molecule.

[0057]

[Outside 7] (In the formula, R ′ represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group)). A reacted substance (hereinafter, referred to as substance α) can also be used.

The structure of the substance α obtained by reacting the alkyl alcohol represented by the above formula (2) with the compound represented by the above formula (3) is shown in the following formula (4).

[0059]

[Outside 8] (Where n is a number from 21 to 101, and m is 1 to 1)
R'represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ -CH _2- (R ₁ represents an ether group or an ester group). )

In the present invention, one epoxy group is included in the molecule.
The substance α obtained by reacting a compound of the above formula (3) with an alkyl alcohol of the above formula (2) has an alkyl chain length of the alkyl alcohol of the formula (2) and an epoxy group of 1 in the molecule.
The viscosity and plasticity can be controlled by the amount of the compound of formula (3) to be reacted.

In the above formula (2), when the number of n is less than 21, the viscosity control tends to be insufficient even if the alkyl alcohol is reacted with the compound represented by the above formula (3).

In the present invention, for example, a part of the carboxyl group in the main chain or at the end of the polyester resin is used as the substance α.
The effect of the following (4) to (6) is obtained by modifying the binder resin by adding the substance α to the binder resin. (4) It is easy to control the melt viscosity of the binder resin,
The fixability on paper can be improved. (5) The compatibility between the binder resin and the polyolefin wax is improved, and poor dispersion of the polyolefin wax in the binder resin is less likely to occur. Furthermore, if it is a long-chain alkyl group, sufficient releasability from the fixing roller can be obtained without using a polyolefin wax, and the offset resistance is improved. (6) Since the acid value that affects the chargeability of the toner can be controlled, the charge-up of the toner can be prevented in a low humidity environment, and stable chargeability can be obtained.

In particular, since the substance α has a higher reactivity with the polyester resin than the case where the alkyl alcohol represented by the general formula (1) alone is used, the substance α can surely react with the polyester resin. Is preferred.

In the present invention, the method of reacting the compound of formula (3) with the alkyl alcohol of formula (2) is not particularly limited, but examples include sodium hydroxide, sodium etoxide and potassium t. -A method of reacting under pressure at a temperature of 50 to 300 ° C using a base catalyst such as butoxide, metallic sodium, and metallic potassium.

As the alkyl alcohol of the formula (2),
The number of n is not particularly limited as long as it is an alkyl alcohol having 21 to 101, but n is preferably 23 to 101, and more preferably 26 to 71.

As the compound of the formula (3), those described below can be used.

Specific examples of the compound in which R'is hydrogen in the formula (3) are shown below.

[0068]

[Outside 9]

In the formula (3), R'is 1 to 2 carbon atoms.
Specific examples of the compound having 0 hydrocarbon group are shown below.

[0070]

[Outside 10]

Specific examples of the compound represented by the formula (3) in which R'is a group represented by R ₁ -CH _2- (R ₁ represents an ether group or an ester group) are shown below.

[0072]

[Outside 11]

In the present invention, the compound for modifying the polyester resin is represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 20 to 100). An alkyl monocarboxylic acid represented by can be used.

The alkyl monocarboxylic acid represented by the above formula (5) has a low melting point of 70 to 140 ° C., and the above formula (5)
The alkyl monocarboxylic acid shown in 1 has an effect of lowering the fixing temperature by branching through an unreacted hydroxyl group in the polyester main chain or by bonding to a hydroxyl group at the end of the polyester main chain.

Furthermore, since the alkyl monocarboxylic acid represented by the above formula (5) has an excellent releasing property, the high temperature offset resistance becomes good.

Furthermore, since a part of the unreacted hydroxyl groups in the terminal or main chain of the polyester resin reacts with the alkyl monocarboxylic acid represented by the above formula (5), the number of hydroxyl groups in the entire polyester resin is reduced, Good environmental stability.

JP-A-56-87051 discloses a method of carrying out a polymerization reaction in the presence of higher fatty acid or higher alcohol. In this method, the fatty acid or alcohol is merely dispersed in the binder resin, and if a large amount of fatty acid or alcohol is used, the fixability is improved, but the storage stability and environmental stability deteriorate. .

In the above formula (5), Y is a number of 20 to 100, preferably 23 to 100, more preferably 25 to 85, and further preferably 30 to 70. When Y is smaller than 20, the effect of lowering the fixing temperature when the toner is used is small because it is short, and when used in a large amount to obtain the effect of lowering the fixing temperature, the storage stability deteriorates. Further, the ability to impart slipperiness to the photoconductor is reduced, and problems such as hollow defects at the time of transfer, fusion of the photoconductor, and poor cleaning are likely to occur. When Y is larger than 100, the melting point becomes high and the effect of lowering the fixing temperature becomes small.

JP-A-2-173038 and JP-A-3
Japanese Patent Publication No. 46668 discloses a method of reacting a polyester resin with a monocarboxylic acid. The monocarboxylic acid used here has a Y value of less than 20, and when the transfer is performed, However, it is not sufficient for problems such as hollowing-out phenomenon, fusing of the photoreceptor and poor cleaning.

In the molecular weight distribution measurement of the alkyl monocarboxylic acid represented by the above formula (5) by GPC, the value of the molecular weight distribution (weight average molecular weight: Mw) / (number average molecular weight: Mn) is preferably 1.0 to 5. 0, more preferably 1.0
It is good that it is 3.0. If the molecular weight distribution is larger than 5.0, the above-mentioned hollowing phenomenon during transfer, photoreceptor fusion, cleaning failure, and charging property and fluidity are deteriorated.

The composition of the polyester resin used in the present invention is as follows.

The polyester resin used in the present invention is
45 to 55 mol% of all components are alcohol components,
It is preferable that 55 to 45 mol% is an acid component.

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, the following formula (I)

[0084]

[Outside 12] (In the formula, R represents an ethylene or propylene group, and x, y
Each represent an integer of 1 or more, and the average value of x + y represents 2 to 10. ) A bisphenol derivative represented by
Or the following formula (II)

[0085]

[Outside 13] And diols such as the diols represented by

Examples of the divalent carboxylic acid containing 50 mol% or more based on all acid components include phthalic acid, terephthalic acid, isophthalic acid, phthalic anhydride, diphenyl-P.P'-dicarboxylic acid and naphthalene-2,7-dicarboxylic acid. , Naphthalene-2,6-dicarboxylic acid, diphenylmethane-PP '
Benzenedicarboxylic acids such as dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid, 1,2-diphenoxyethane-P.P'-dicarboxylic acid or their anhydrides;
Alkyldicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, glital acid, cyclohexanedicarboxylic acid, triethylenedicarboxylic acid, malonic acid or anhydrides thereof, and further substituted with an alkyl group having 6 to 18 carbon atoms Succinic acid or its anhydride; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or their anhydrides.

The alcohol component of the polyester resin particularly preferred in the practice of the present invention is a bisphenol derivative represented by the above formula (I), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, and succinic acid. , N-dodecenylsuccinic acid or its anhydride, and dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride.

The glass transition temperature of the polyester resin obtained here is preferably 40 to 90 ° C., more preferably 45 to 85 ° C., and the number average molecular weight (Mn) is
It is preferably 1,500 to 50,000, more preferably 2,000 to 20,000, and has a weight average molecular weight (M
w) is preferably 3,000 to 100,000, more preferably 4,000 to 90,000.

Further, in the present invention, a non-linear polyester resin may be used as the polyester resin.

In the present invention, the non-linear polyester is a polyester having a so-called crosslinked structure or branched structure.

The non-linear polyester can be obtained by synthesizing a polycarboxylic acid having a valence of 3 or more and a polyol having a valence of 3 or more together with the above-mentioned divalent polycarboxylic acid and divalent polyol.

Examples of the trivalent or higher polycarboxylic acids include trimellitic acid, pyromellitic acid, cyclohexanetricarboxylic acids, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,
2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methylenecarboxylicxylpropane, 1,3-dicarboxyl-
2-Methyl-methylenecarboxylic propane, tetra (methylenecarboxylic) methane, 1,2,7,8-octanetetracarboxylic acid and their anhydrides can be used.

Examples of trihydric or higher polyols include sorbitol, 1,2,3,6-hexanetetol,
1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, sucrose,
1,2,4-mentatriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene are used. it can.

The glass transition temperature of the non-linear polyester resin is preferably 40 to 90 ° C, more preferably 45 to 8 ° C.
5 ° C., and the number average molecular weight (Mn) is preferably 1,500 to 100,000, more preferably 2,0.
100 to 40,000 and weight average molecular weight (Mw)
Is preferably 3,000 to 200,000, more preferably 4,000 to 180,000.

When only the carboxyl group of the polyester resin is modified with the alkyl alcohol represented by the formula (1) or the substance α represented by the formula (4), the acid value of the polyester resin is preferably 2 or more and 100 or less, more preferably It is preferably 5 or more and 80 or less, and the OH value is preferably 50 or less, more preferably 30 or less.

This is because when the acid value is less than 2, the modification ratio is low, and the effect of the present invention due to modification is small or almost nonexistent. When the acid value is greater than 100 or the OH value is 50.
This is because when the value is larger, the charging characteristics of the toner become more environmentally dependent.

For the same reason, when both the carboxyl group and the hydroxyl group of the polyester resin are modified with the alkyl alcohol represented by the formula (1) or the substance α represented by the formula (4), both the acid value and the OH value are Preferably 2 or more and 10
It is preferably 0 or less, more preferably 5 or more and 80 or less.

For the same reason, when only the hydroxyl group of the polyester resin is modified with the alkyl alcohol represented by the formula (1), the substance α represented by the formula (4) or the alkyl monocarboxylic acid represented by the formula (5), The OH value of the polyester resin is preferably 2 or more and 100 or less, more preferably 5 or more and 80 or less, and the acid value is preferably 50 or less, more preferably 30 or less.

In the present invention, the polyester resin has 22 to 1 carbon atoms such as an alkyl alcohol represented by the formula (1), a substance α represented by the formula (4) or an alkyl monocarboxylic acid.
Examples of the method of modifying with a compound (modifying compound) having a long-chain alkyl group of 02 and a hydroxyl group or a carboxyl group at the terminal include the following methods.

(I) When synthesizing a polyester resin, the above-mentioned modifying compound is charged together with a polyvalent acid and a polyhydric alcohol to obtain an organometallic salt of calcium phosphate, ferric chloride, zinc chloride, tin or titanium. A method for obtaining a modified polyester resin while using a catalyst such as tin oxide at a temperature of 160 to 270 ° C. under reduced pressure or azeotropically distilling with a solvent to remove water produced.

(Ii) After synthesizing the polyester resin, unreacted carboxyl groups and //
Alternatively, as a method for reacting the unreacted hydroxyl group with the above-mentioned modifying compound, 160 to 27 using the same catalyst as described above.
A method in which a polyester resin and the above-mentioned modifying compound are reacted to modify at a temperature of 0 ° C. under reduced pressure or while azeotropically distilling with a solvent to remove water produced.

(Iii) As a method of reacting with unreacted hydroxyl groups in the polyester resin, a method of reacting the polyester resin with the above-mentioned modifying compound at 60 to 200 ° C. using a solvent and diisocyanate to modify Can be mentioned.

As a method of modifying the polyester resin with the above-mentioned modifying compound, a method of reacting with an unreacted carboxyl group or an unreacted hydroxyl group in the polyester resin is mentioned. Among these methods, the polyester resin is synthesized. The most preferable method is to simultaneously denature it. This is because, when the polyester resin is synthesized, the modification reaction is promptly performed by simultaneously modifying the polyester resin, the molecular weight can be easily adjusted, and the modification rate can be increased. In the modified polyester resin obtained by this method, the polyester portion has a matrix (or domain), the alkyl chain portion of the modifying compound has a matrix-domain structure such as a domain (or matrix), and the domain is This is because the particles are very small and uniformly dispersed. In the method using diisocyanate, there is a case where alcohols react with each other, and it is preferable to modify by the former method.

In the present invention, the amount of modification of the polyester resin by the modifying compound is 0.1 to 100% by weight, more preferably 5 to 50% by weight, and further preferably 10 to 10% by weight based on the weight of the modified polyester resin. Thirty
It is preferable to be the weight%.

In the present invention, the modified amount of the polyester resin can be quantified by the following method.

Quantitative method of modified amount After dissolving the modified polyester resin in tetrahydrofuran or chloroform, the insoluble matter is filtered and removed, and the soluble matter is dried. The resin obtained here is referred to as resin A.

This resin A is subjected to DSC (for example, DSC-7 manufactured by Perkin Elmer Co., Ltd.) to measure an endothermic peak of a modifying component such as a modifying alkyl alcohol.

The measuring method is ASTM D3418-82.
Carry out according to. The DSC curve used in the present invention has a temperature rate of 10 ° C./min after the temperature is raised once and a previous history is taken.
The temperature is lowered and raised in the range of 0 to 200 ° C. for measurement. By this method, the value ΔH _A (J / g) is obtained by dividing the height of the measured endothermic peak of the modified component by the weight of the measurement sample.

Next, the unmodified polyester resin and the modified component are weighed and uniformly mixed in an unreacted state. Five or more kinds of samples with different mixing ratios are prepared, and ΔH (J / g) is obtained by the same method as described above to prepare a calibration curve showing the relationship between ΔH and the amount of the denaturing component.

From this calibration curve, the amount of modification by the modifying component of the modified polyester resin corresponding to ΔH _A is determined. By this method, the amount of modification by the modifying component in the toner can be similarly measured.

When the amount of modification of the polyester resin by the modifying compound is less than the above range, the effect of modification is small, and the offset resistance and fixing property such as image stains and cleaning wave stains are liable to be lowered. When the amount is larger than the range, the alcohol portion tends to lower the charging property and the acid portion tends to lower the environmental stability.

In the present invention, the above-mentioned (i) to (ii)
When modifying the polyester resin with the modifying compound by the method i), not all of the compounding compound added is modified with respect to the polyester resin. Therefore, the polyester resin is modified with the modifying amount described above. In order to do so, it is preferable to modify the polyester resin with the following compounding amounts.

In the case of the method of charging the above-mentioned modifying compound together with the polyvalent acid and the polyhydric alcohol of (i) and simultaneously modifying them when synthesizing the polyester resin, the polyvalent acid and the polyhydric acid are used. The modifying compound is preferably used in an amount of 0.1 to 150 parts by weight, more preferably 5 to 100 parts by weight, still more preferably 10 to 60 parts by weight, based on 100 parts by weight of the total amount of alcohol.

In the case of the method of modifying the unreacted carboxyl group or unreacted hydroxyl group in the polyester resin after synthesizing the above-mentioned (ii) or (iii) polyester resin, 100 weight% of the polyester resin is used. The modifying compound is preferably 0.1 to 15 parts by weight.
It is preferable to use 0 part by weight, more preferably 5 to 100 parts by weight, and further preferably 10 to 60 parts by weight.

In the present invention, at least a part of the polyester resin is modified with the above-mentioned modifying compound. Therefore, even if only alcohol-modified polyester is used as the binder resin, a polyester resin having a different composition is blended. You can use it. However, when blended and used, the content of the modifying compound in the binder resin is preferably 0.1 based on the weight of the binder resin.
-100% by weight, more preferably 1-50% by weight, even more preferably 5-30% by weight, still more preferably 1
It is preferably 0 to 30% by weight.

In the present invention, the Tg of the modified polyester resin is preferably 25 to 75 ° C, more preferably 30 to 70 ° C.

In the case of a linear polyester, the further modified polyester resin has a number average molecular weight (Mn) of
It is preferably 2,000 to 51,000, more preferably 2,500 to 25,000, and has a weight average molecular weight (M
w) is preferably 3,500 to 105,000, more preferably 4,000 to 90,000. In the case of a non-linear polyester, the number average molecular weight (M
n) is preferably 2,000 to 102,000, more preferably 2,500 to 50,000, and the weight average molecular weight (Mw) is preferably 3,500 to 210,0.
00, more preferably 4,000 to 180,000.

In the present invention, the further modified polyester resin has an acid value of preferably 1 to 60, more preferably 5 to 45, and an OH value of 1 to 60, more preferably 11 to 40. It is good because it can exert the effect of kicking more.

The toner of the present invention has a weight average particle diameter (D ₄ ).
Is preferably 3 to 20 μm, more preferably 4 to 10 μm.
It is preferable that the thickness is μm in that an image with high resolution can be obtained.

The electrostatic charge developing toner of the present invention may optionally contain a negative or positive charge control agent in order to further stabilize its chargeability. The charge control agent is used in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin.

Charge control agents known in the art today include the following.

For controlling the toner to be negatively charged, organic metal complexes and chelate compounds are effective, for example, monoazo metal complexes, acetylacetone metal complexes,
Examples thereof include aromatic hydroxycarboxylic acid and aromatic dicarboxylic acid-based metal complexes. Other examples include aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters and phenol derivatives such as bisphenol.

For controlling the toner to be positively charged, for example, a modified product of nigrosine and a fatty acid metal salt; tributylbenzylammonium-1-hydroxy-4-
Naphtosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof and lake pigments thereof; triphenylmethane dyes and lake pigments (lakers) As phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.); metal salts of higher fatty acids;
Dibutyltin oxide, dioctyltin oxide,
Diorganotin oxides such as dicyclohexyltin oxide; and diorganotinborates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, which may be used alone or in combination with 2
A combination of more than one type can be used. Among these, charge control agents such as nigrosine and quaternary ammonium salts are particularly preferably used.

The electrostatic charge developing toner of the present invention may be either magnetic toner or non-magnetic toner.
When used as a magnetic toner, it is preferable to use the following magnetic materials for reasons such as charging property, fluidity, and uniformity of copy density.

When the toner of the present invention is used as a magnetic toner, the magnetic material used as a colorant includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co, Metals such as Ni, or these metals and Al, Co, C
u, Pb, Mg, Ni, Sn, Zn, Sb, Be, B
Alloys with metals such as i, Cd, Ca, Mn, Se, Ti, W, V, and mixtures thereof.

Conventionally, as a magnetic material, iron tetroxide (F) has been used.
e ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc iron oxide (ZnFe ₂ O ₄ ), yttrium iron oxide (Y ₃ Fe)
₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron cadmium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (C
uFe ₂ O _4), oxidation Tetsunamari (PbFe ₁₂ -O _19), iron oxide nickel (NiFe ₂ O _4), iron oxide, neodymium (Nd
Fe ₂ O _3), barium iron oxide (BaFe ₁₂ O _19), iron oxide magnesium (MgFe ₂ O _4), manganese iron oxide (MnFe ₂ O _4), iron oxide, lanthanum (LaFeO
₃ ), iron powder (Fe), cobalt powder (Co), and nickel powder (Ni) are known. According to the present invention, the above magnetic materials are used alone or in combination of two or more kinds. be able to. Particularly suitable magnetic materials for the purposes of the invention are fine powders of ferric tetroxide or γ-iron sesquioxide.

The average particle size of these ferromagnetic materials is preferably 0.1 to 2 μm, more preferably 0.1 to 0.5 μm, and the magnetic properties at 10 K oersted application are coercive force,
It is preferably 20 to 200 oersteds, more preferably 20 to 150 oersteds, and the saturation magnetization is preferably 50 to 200 emu / g, and more preferably 50 to 10 emu / g.
0 emu / g and the residual magnetization is preferably 2 to 25 e
Mu / g, more preferably 2 to 20 emu / g is preferable.

The magnetic material 1 was added to 100 parts by weight of the binder resin.
It is recommended to use 0 to 200 parts by weight, preferably 20 to 150 parts by weight.

When the toner of the present invention is used as a non-magnetic toner, any suitable pigment or dye can be used as a colorant.

Examples of the pigment include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue and indanthrene blue. These pigments are added to 100 parts by weight of resin. It is preferable to use 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight. Dyes can be used for the same purpose. Examples include azo dyes, anthraquinone dyes, xanthene dyes, methine dyes,
These dyes are added in an amount of 0.1-20 per 100 parts by weight of resin.
It is preferred to use parts by weight, preferably 0.3 to 10 parts by weight.

In the present invention, one kind or two kinds may be used as needed.
One or more release agents can be included in the toner.

The releasing agent used in the present invention includes the following. Low molecular weight polyethylene, low molecular weight polypropylene, aliphatic hydrocarbon wax such as microcrystalline wax, paraffin wax, oxide of aliphatic hydrocarbon wax such as oxidized polyethylene wax, block copolymers thereof; carnauba wax,
Examples thereof include waxes containing a fatty acid ester as a main component such as montanic acid ester wax; and those obtained by partially or entirely deoxidizing fatty acid ester such as deoxidized carnauba wax. In addition, palmitic acid, stearic acid,
Saturated straight-chain fatty acids such as montanic acid; unsaturated fatty acids such as blancinic acid, eleostearic acid, and vinalinaric acid; saturated alcohols such as stearin alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl alcohol, and melicyl alcohol. Polyhydric alcohols such as sorbitol; Fatty acid amides such as linoleic acid amide, oleic acid amide, and lauric acid amide; Methylenebisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid Saturated fatty acid bisamides such as amides; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N'-
Unsaturated fatty acid amides such as dioleyl adipamide, N, N'-dioleyl sebacic acid amide; aromatic bisamides such as m-xylene bisstearic acid amide, N, N'-distearyl isophthalic acid amide; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate (generally referred to as metallic soap); grafted onto aliphatic hydrocarbon wax using vinyl monomers such as styrene and acrylic acid Examples of the waxes include partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenation of vegetable oils and fats.

The releasing agent particularly preferably used in the present invention includes an aliphatic hydrocarbon wax. For example, a low molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or Ziegler catalyst under low pressure, an alkylene polymer obtained by thermally decomposing a high molecular weight alkylene polymer, a synthesis gas composed of carbon monoxide and hydrogen, and an Arge process. Waxes such as synthetic hydrocarbons obtained from the distillation residue of hydrocarbons obtained by or by hydrogenating these are preferable. Further, the one in which the hydrocarbon wax is fractionated by the use of press sweating method, solvent method, vacuum distillation or fractional crystallization method is more preferably used. The hydrocarbon as a base is one synthesized by the reaction of carbon monoxide and hydrogen using a metal oxide catalyst (often two or more multi-component system), for example, the gintol method,
Hydrocarbons (using a fluidized catalyst bed) or Arge's method (using a fixed catalyst bed) where a large amount of waxy hydrocarbons can be obtained, and hydrocarbons with carbon numbers up to several hundred and alkylene such as ethylene are Ziegler The hydrocarbon polymerized by the catalyst is preferable because it is a straight chain hydrocarbon which has a small number of branches, is small, and has a long saturation. A wax synthesized by a method that does not rely on the polymerization of alkylene is particularly preferable because of its molecular weight distribution.

In the molecular weight distribution of the above releasing agent, the molecular weight is 40
In the region of 0 to 2400, preferably 450 to 2000,
Particularly preferably, the peak exists in the region of 500 to 1600. By having such a molecular weight distribution, it is possible to give the toner favorable thermal characteristics.

The amount of the releasing agent used in the present invention is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin. These release agents are usually contained in the binder resin by a method of dissolving the resin in a solvent, raising the temperature of the resin solution, and adding and mixing while stirring, or a method of mixing at the time of kneading.

As the fluidizing agent used in the present invention, any fluidizing agent can be used as long as the fluidity can be increased by adding it to the colorant-containing resin particles as compared with before and after the addition. , For example, fine powder silica such as vinylidene fluoride fine powder, polytetrafluoroethylene fine powder and the like, fine powder silica such as wet process silica and dry process silica, silane coupling agent for these silicas, silane coupling having a functional group Silica, treated with a surface treating agent such as a silicone coupling agent, a silicone oil, a modified silicone oil, a silicone varnish and a modified silicone varnish.

A preferable fluidizing agent is a fine powder produced by vapor phase oxidation of a silicon halogen compound,
It is so-called dry process silica or fumed silica and is produced by a conventionally known technique. For example, the thermal decomposition oxidation reaction of silicon tetrachloride gas in oxyhydrogen flame is utilized, and the basic reaction formula is as follows.

SiCl ₄ + 2H ₂ + O ₂ → SiO ₂ + 4HCl In this manufacturing process, by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound, a fine composite powder of silica and another metal oxide is used. It is also possible to obtain and include them. The particle size is 0.00 as the average primary particle size.
It is preferably in the range of 1 to 2 μm, and particularly preferably, fine silica powder in the range of 0.002 to 0.2 μm is used.

Examples of commercially available silica fine powders produced by vapor phase oxidation of a silicon halogen compound used in the present invention include those commercially available under the following trade names.

AEROSIL (Japan Aerosil Co.) 130 200 300 380 TT600 MOX170 MOX80 COK84 Ca-O-SiL (CABOT Co.) M-5 MS-7 MS-75 HS-5 EH-5 Wacker HDK N 20 V15 (WACK) -CHEMIE GMBH) N20E T30 T40 D-C Fine Silica (Dow Corning Co.) Francol (Fransil)

Further, it is more preferable to use a treated silica fine powder obtained by subjecting the silica fine powder produced by vapor-phase oxidation of the silicon halogen compound to a hydrophobic treatment. Among the treated silica fine powders, those obtained by treating the silica fine powder so that the degree of hydrophobicity measured by the methanol titration test is in the range of 30 to 80 are particularly preferable.

As a method of hydrophobizing, it is imparted by chemically treating with an organic silicon compound or the like which reacts with or physically adsorbs on silica fine powder. As a preferred method, silica fine powder produced by vapor phase oxidation of a silicon halogen compound is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyl. Dimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxy Silane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 12 per molecule
There are dimethylpolysiloxanes each having one siloxane unit and each having a hydroxyl group bonded to Si in a terminally located unit, and these are used in one kind or in a mixture of two or more kinds.

The fluidizing agent used in the present invention preferably has a specific surface area by nitrogen adsorption measured by the BET method of 30 m.
Those having a flow rate of ² / g or more, more preferably 50 m ² / g or more give good results, and these fluidizing agents are preferably 0.01 to 8 parts by weight, and more preferably 0, to 100 parts by weight of the toner. It is preferable to use 1 to 4 parts by weight.

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

When the toner according to the present invention is used in a two-component type developer, the carrier used so as to sufficiently exert its effect plays an important role. As the carrier used in the present invention, for example, surface-oxidized or unoxidized iron,
Metals such as nickel, copper, zinc, cobalt, manganese, chromium and rare earths, alloys thereof, or magnetic powders such as oxides and ferrite and glass beads can be used. There are no particular restrictions on the method of manufacturing the carrier.

A system in which the surface of the carrier is coated with a fixing substance such as a resin is particularly preferable in the J / B developing method.
As the method, any conventionally known method such as a method of dissolving or suspending a fixing material coating material such as a resin in a solvent and applying it and adhering it to a carrier, or a method of simply mixing with a powder can be applied.

The substance adhered to the surface of the carrier varies depending on the toner material. For example, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, polyvinylidene fluoride, silicone resin, polyester resin,
Ditertiary butyl salicylic acid metal complex, styrene resin, acrylic resin, polyamide, polyvinyl butyral, nigrosine, amino acrylate resin, basic dye and its lake, silica fine powder, alumina fine powder may be used alone or in combination. Appropriate, but not necessarily limited to this.

The treatment amount of the above-mentioned compound may be appropriately determined so that the carrier satisfies the above-mentioned conditions, but generally, the total amount is preferably 0.1 to 30% by weight, more preferably 0% by weight based on the carrier of the present invention. 0.5 to 20% by weight is preferable. The average particle size of these carriers is preferably 10 to 100 μm.
m, more preferably 20 to 70 μm.

In a particularly preferred embodiment, Cu-Zn-
It is a ternary ferrite of Fe, and its surface is a combination of resins such as fluorine resin and styrene resin, for example, polyvinylidene fluoride and styrene-methyl methacrylate resin, polytetrafluoroethylene and styrene-methyl methacrylate resin, Fluorine-based copolymer and styrene-based copolymer, etc., 90:10 to 20:80, preferably 7
A mixture having a ratio of 0:30 to 30:70,
0.01 to 5% by weight, preferably 0.1 to 1% by weight, and a coated ferrite carrier having the above-mentioned average particle diameter of 250% by weight and 400% mesh-on carrier particles of 70% by weight or more. To be As the fluorine-based copolymer, vinylidene fluoride-
Tetrafluoroethylene copolymer (10:90 to 90:
10) is exemplified, and the styrene-based copolymer is styrene-2-ethylhexyl acrylate (20:80 to 8).
0:20), styrene-2-ethylhexyl acrylate-methyl methacrylate (20-60: 5-30: 10).
50) is exemplified. The above-mentioned coated ferrite carrier has a sharp particle size distribution, and it is possible to obtain a preferable triboelectrification property for the toner of the present invention and to improve electrophotographic properties.

When a two-component developer is prepared by mixing with the toner according to the present invention, the mixing ratio is preferably 2 to 15% by weight, more preferably 4 to 13% by weight as the toner concentration in the developer. This usually gives good results. If the toner density is less than 2% by weight, the image density is low,
If the content exceeds 10% by weight, fog and scattering in the machine will increase and the useful life of the developer will be shortened.

To prepare the toner for developing an electrostatic image of the present invention, a binder resin, a magnetic material, a release agent, a colorant, a charge control agent or other additives are mixed with a mixer such as a Henschel mixer or a ball mill. Mix well, melt, knead and knead using a heat kneader such as a heating roll, kneader or extruder to make the resins compatible with each other, cool and solidify the melt-kneaded product, then crush the solidified product and crush it. The toner of the present invention can be obtained by classifying the materials.

Further, if necessary, the fluidizing agent and the toner can be sufficiently mixed with a mixer such as a Henschel mixer, and the additive can be added to the surface of the toner particles to obtain a toner for developing an electrostatic image.

The method for measuring the properties of the binder resin according to the present invention is as follows. The examples described below are also based on these methods.

(1) Method for measuring acid value / OH value 2 to 10 g of a sample is weighed in an Erlenmeyer flask of 200 to 300 ml, and about 50 ml of a mixed solvent of methanol: toluene = 30: 70 is added to dissolve the sample. If the solubility seems to be poor, a small amount of acetone may be added. 0.1
% Bromthymol blue and phenol red mixed indicators were used to pre-standardize N / 10 caustic potash ~
Titration is performed with an alcohol solution, and the acid value is calculated from the consumption amount of the alcohol potash according to the following calculation formula (1).

Acid value = KOH (ml number) × N × 56.1 / Sample weight (1) (wherein, N represents a factor of N / 10 KOH). Acetylation is carried out by heating with acetic acid, the saponification value of the acetylated product produced is measured, and then the hydroxyl value is determined according to the following calculation formula (2).

[0157]

[Outside 14] (In the formula, A represents the saponification value after acetylation, and B represents the saponification value before acetylation.)

(2) Glass transition temperature Tg Differential thermal analysis analyzer (DSC analyzer), DSC-7
(Perkin Elmer).

A measurement sample is 5 to 20 mg, preferably 10
Precisely weigh mg.

This was placed in an aluminum pan, and an empty aluminum pan was used as a reference, and the measurement temperature range was 30 to 20.
The measurement is performed at a temperature rising rate of 10 ° C / min between 0 ° C and normal temperature and normal humidity.

During this temperature rising process, the endothermic peak of the main peak in the temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection between the line at the midpoint of the baseline before and after the appearance of the endothermic peak and the differential heat curve is taken as the glass transition temperature Tg in the present invention.

(3) Measurement of molecular weight (polyester resin) The molecular weight of the chromatogram by GPC (gel permeation chromatography) is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was flowed through the column at this temperature at a flow rate of 1 ml / min to obtain a sample concentration of 0.05 to 0.6 wt. Inject 50 to 200 μl of a THF sample solution of the resin adjusted to 100% for measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of a calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As a standard polystyrene sample for preparing a calibration curve, for example, Pressure Chemical
Co. Made or manufactured by Toyo Soda Kogyo Co., Ltd. has a molecular weight of 6 ×
10 ² , 2.1 × 10 ³ , 4 × 10 ³ , 1.75 × 10
⁴ , 5.1 × 10 ⁴ , 1.1 × 10 ⁵ , 3.9 × 10
^{5, 8.6 × 10 5, 2} × 10 6, used as a 4.48 × 10 ^6, it is appropriate to use at least about 10 standard polystyrene samples. In addition, the detector is RI
A (refractive index) detector is used.

As the column, 10 ³ to 2 × 10
^In order to accurately measure the molecular weight region of ⁶ , it is preferable to combine a plurality of commercially available polystyrene gel columns.
.mu.-styragel 500, 10
Combination of ³ , 10 ⁴ , 10 ⁵ and sho made by Showa Denko KK
dex KF-80M and KF-801, 803, 80
4, 805 combination, AK-802, 803, 804,
Combination of 805 or TSKgel made by Toyo Soda
G1000H, G2000H, G2500H, G300
0H, G4000H, G5000H, G6000H, G
A combination of 7000H and GMH is preferable.

(4) Measurement of molecular weight distribution (denaturing compound) (GPC measurement conditions) Device: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 series (Tosoh Corp.) Temperature: 135 ° C. Solvent: o-dichlorobenzene (Addition of 0.1% ionol) Flow rate: 1.0 ml / min Sample: 0.45 ml of 0.15% sample was injected under the above conditions, and the molecular weight of the sample was calculated using a monodisperse polystyrene standard sample. Use a calibration curve. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

(5) Measurement of particle size distribution As a measuring device, COULTER MULTISIZE
PC (980) and interface (made by Nikkaki) that outputs the number distribution and volume distribution to R II (made by Coulter)
1 A personal computer (manufactured by NEC) was used. The electrolyte is 1% N using first-grade sodium chloride.
Prepare an aCl aqueous solution. As a measuring method, a surfactant as a dispersant in 100 to 150 ml of the electrolytic aqueous solution,
Preferably the alkylbenzene sulfonate is 0.1 to
Add 5 ml, and further add 2 to 20 mg of the measurement sample. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and then the COULTER MULTISIZER I
According to I, the particle size distribution of particles of 2 to 40 μm is measured based on the number using an aperture of 100 μm as an aperture, the volume distribution and the number distribution of particles of 2 to 40 μm are calculated, and the weight-based weight average determined from the volume distribution. The particle size (D4: the median value of each channel is used as the representative value of the channel) was determined.

[0168]

EXAMPLES The present invention will be described below with reference to production examples and examples.

(Production of modified polyester resin (1)) Bisphenol derivative 360 represented by the following formula (I)
Parts by weight

[0170]

[Outside 15] (R is a propylene group) 100 parts by weight of terephthalic acid 75 parts by weight of dodecenylsuccinic acid 135 parts by weight of alkyl alcohol represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (x = 48, Mw / Mn = 1.2) Stannous oxide 0.5 parts by weight The above raw materials were charged in a 5 liter 4-necked flask, and a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer, and a stirrer were installed. Then, while introducing nitrogen into the flask, a modification reaction is carried out simultaneously with the condensation polymerization reaction at 220 ° C., and Mn = 600
0, Mw = 12000, Tg = 57 ° C., acid value 20, OH
A modified polyester resin (1) having a valence of 18 was obtained.

The modified amount of the modified polyester resin (1) with alkyl alcohol was 17% by weight based on the weight of the modified polyester resin.

Various physical properties of the obtained modified polyester resin (1) are shown in Table 1.

(Modified polyester resin (2)-(10)
Production of Modified Polyester Resin (1) The modified polyester resin (2)-(10) having the physical properties shown in Table 1 by changing the composition and molecular weight of the alkyl alcohol and the polyester resin used in the production of the modified polyester resin (1). Got

[0174]

[Table 1] (Production of Polyester Resin (A)) Bisphenol Derivative Represented by Formula (1)

[0175]

[Outside 16] (R is an ethylene group and x + y = 2.2)
17 mol% (R is a propylene group and x + y = 2.2) 34 mol% terephthalic acid 17 mol% succinic acid 20 mol% trimellitic acid 12 mol% 100 parts by weight of the above raw materials and 0.1 part by weight of stannous oxide A 5-liter 4-necked flask was charged with a reflux condenser, a water separator, a nitrogen gas introduction pipe, a thermometer, and a stirrer.
A condensation polymerization reaction was carried out at 220 ° C. while introducing nitrogen into the flask, and Mn = 3800, Mw = 9200, Tg = 6.
Polyester resin (A) with 2 ° C, acid value 10 and OH value 20
Got

(Production of Polyester Resin (B)) Bisphenol derivative 360 represented by the following formula (I)
Parts by weight

[0177]

[Outside 17] (Where R is a propylene group) 100 parts by weight of terephthalic acid 75 parts by weight of dodecenylsuccinic acid 0.5 parts by weight of stannous oxide 0.5 parts by weight of the above materials are charged into a 5 liter 4-necked flask, a reflux condenser, a water separator, and a nitrogen gas is introduced. Attaching a tube, a thermometer, and a stirrer, the condensation polymerization reaction was carried out at 220 ° C. while introducing nitrogen into the flask, and Mn = 5000, Mw = 1200
A polyester resin (B) having 0, Tg = 70 ° C., an acid value of 35 and an OH value of 25 was obtained.

Example 1 Modified polyester resin (1) 100 parts by weight Magnetic iron oxide 80 parts by weight (average particle size 0.15 μm, Hc = 115 oersted,
σs = 80 emu / g, σr = 11 emu / g) Monoazo complex (negative charge control agent) 2 parts by weight After premixing the above materials with a Henschel mixer, 130
Melt kneading was carried out at 2 ° C by a twin-screw kneading extruder. After the kneaded product is allowed to cool, it is roughly crushed with a cutter mill, crushed with a fine crusher using a jet stream, and further classified with an air classifier to obtain a black fine powder having a weight average particle diameter of 8.0 μm. (Magnetic toner) was obtained.

To 100 parts by weight of the obtained black fine powder, 0.6 parts by weight of hydrophobic dry silica (BET150 m ² / g) was externally added by a Henschel mixer to obtain a magnetic toner, which was used for one-component development. I used it as an agent.

Using the obtained one-component type developer, an unfixed image was obtained with a Canon copying machine NP-6060, and NP-
A fixing test was conducted by changing the temperature with a fixing machine having the same structure as 6060.

As a result, the fixable temperature range is 130 to 24.
It was 0 ° C.

Further, using a one-component type developer, the photosensitive drum of the Canon laser copying machine NP9330 is converted into an OPC photosensitive drum, and a latent image is formed with a laser after charging with a negative corona, and a reversal development is carried out. The image was evaluated with the modified machine.

As a result, there was no fog in the white background and no voids in the transfer, the maximum image density was 1.45, and the density gradation was good even in a photographic image containing characters. In terms of the relationship between the developing potential and the image density, almost satisfactory linearity was obtained.

Further, a copy test of 20,000 sheets was conducted. As a result, the copied image had good image quality with almost no change from the initial image described above, and good results were obtained in terms of fixing property. Further, neither fusion of the toner to the photosensitive member nor cleaning failure occurred at all.

Furthermore, under low temperature and low humidity (5 ° C., 10% R
H) and under a high temperature and high humidity condition (30 ° C., 80% RH), a copy test was conducted, and good results were obtained as in the initial stage. A long-term storage test (one week storage) under high temperature and high humidity was performed, and good results were obtained without a decrease in concentration.

Furthermore, the storage stability was examined by leaving it at 50 ° C. for 1 week, and it was found to have good fluidity without causing blocking.

In the above developing device, the photosensitive drum is charged by the contact charging roller instead of the corona charging, and the toner image is transferred to the recording material by the contact transfer roller instead of the corona transfer. The stain and the void during transfer were evaluated. The evaluation results are shown in Table 3.

Examples 2 to 8 A one-component type developer was prepared in the same manner as in Example 1 except that the prescription for preparing the magnetic toner was changed as shown in Table 2. The image formation was evaluated in the same manner. The evaluation results are shown in Table 3.

[0189]

[Table 2]

[0190]

[Table 3]

Comparative Examples 1 to 4 A one-component type developer was prepared in the same manner as in Example 1 except that the formulation for preparing the magnetic toner was changed as shown in Table 4. The image formation was evaluated in the same manner. The evaluation results are shown in Table 5.

[0192]

[Table 4]

[0193]

[Table 5]

(Production of modified polyester resin (11)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 21.5 mgKOH / g.

Then, a linear alkyl alcohol C ₄₀ H ₈₁ O
520 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (11).

The acid value of the modified polyester resin (11) is 1
0.3 mgKOH / g, hydroxyl value is 20.7 mgKOH
/ G, the glass transition point (Tg) was 59.3 ° C.

The modified amount of the modified polyester resin (11) with alkyl alcohol was 14% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (12)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight Dodecenyl succinic anhydride 399 parts by weight Terephthalic acid 464.8 parts by weight Trimellitic acid 147 parts by weight The above raw materials are placed in a 4-neck flask, and a stirrer, condenser, thermometer, and gas inlet pipe are set, and the mantle heater is installed. I put it in. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 23.5 mgKOH / g.

Then, a linear alkyl alcohol C ₇₅ H ₁₅₁
1068 parts by weight of OH was added, and the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (12).

The acid value of the modified polyester resin (12) is 1
2.5mgKOH / g, hydroxyl value is 15.7mgKOH
/ G, Tg was 58.6 ℃.

The modified amount of the modified polyester resin (12) with alkyl alcohol was 18% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (13)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 860
Parts by weight neopentyl glycol 52.5 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials are put into a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and put into a mantle heater. It was After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 19.7 mgKOH / g.

Then, a straight-chain alkyl alcohol C ₃₅ H ₇₁ O
390 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (13).

The acid value of the modified polyester resin (13) is 1
1.5mgKOH / g, hydroxyl value is 20.7mgKOH
/ G, Tg was 60.2 ℃.

The modified amount of the modified polyester resin (13) with alkyl alcohol was 11% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (14)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight adipic acid 73 parts by weight terephthalic acid 581 parts by weight trimellitic acid 210 parts by weight The above raw materials were placed in a four-necked flask, and a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 18.9 mgKOH / g.

Then, a linear alkyl alcohol C ₇₀ H ₁₄₁
770 parts by weight of OH was added, and the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (14).

The acid value of the modified polyester resin (14) is 1
0.7mgKOH / g, hydroxyl value is 13.2mgKOH
/ G, Tg was 58.7 ℃.

The modified amount of the modified polyester resin (14) with alkyl alcohol was 20% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (15)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight straight chain alkyl alcohol C ₄₀ H ₈₁ OH 460 parts by weight The above raw materials are put in a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction pipe are set. I put it in the mantle heater. After purging the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 7 hours, cooled to room temperature and taken out to obtain a modified polyester resin (15).

The acid value of the modified polyester resin (15) is 1
2.7 mgKOH / g, hydroxyl value is 19.3 mgKOH
/ G, Tg was 58.8 ℃.

The modified amount of the modified polyester resin (15) with alkyl alcohol was 12% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (16)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 19.8 mgKOH / g.

Then, a linear alkyl alcohol C ₁₅ H ₃₁ O
180 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a polyester resin (16).

The acid value of the modified polyester resin (16) is 1
0.9mgKOH / g, hydroxyl value is 17.8mgKOH
/ G, Tg was 59.7 ℃.

The amount of the modified polyester resin (16) modified with alkyl alcohol was 6.0% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (17)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 21.7 mgKOH / g.

Then, a linear alkyl alcohol C ₁₀ H ₂₁ O
140 parts by weight of H was added, and the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (17).

The acid value of the modified polyester resin (17) is 1
2.7 mgKOH / g, hydroxyl value is 18.1 mgKOH
/ G, Tg was 58.5 ℃.

The modified amount of the modified polyester resin (17) with alkyl alcohol was 5.0% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (18)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 21.5 mgKOH / g.

Then, a linear alkyl alcohol C ₄₀ H ₁₈ O
230 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (18).

The acid value of the modified polyester resin (18) is 1
4.0mgKOH / g, hydroxyl value is 20.7mgKOH
/ G, the glass transition point (Tg) was 62.0 ° C.

The modified amount of the modified polyester resin (18) with alkyl alcohol was 8.0% by weight based on the weight of the modified polyester resin.

(Production of polyester resin (C)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight Dodecenyl succinic anhydride 399 parts by weight Terephthalic acid 464.8 parts by weight Trimellitic acid 147 parts by weight The above raw materials are placed in a 4-neck flask, and a stirrer, condenser, thermometer, and gas inlet pipe are set, and the mantle heater is installed. I put it in. After purging the inside of the reaction vessel with nitrogen gas, the content was heated to 210 ° C. and reacted for 7 hours, cooled to room temperature and taken out to obtain a modified polyester resin 18.

The acid value of the resin is 16.7 mgKOH / g,
Hydroxyl value is 15.2mgKOH / g, Tg is 59.3 ° C
Met.

From the above modified polyester resin (11) to
Table 6 shows the formulation and physical properties of (18) and the polyester resin (C).

[0228]

[Table 6]

Example 9 Modified polyester resin (11) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polypropylene 3 parts by weight After thoroughly mixing the above materials with a blender, the temperature was set to 120 ° C. The mixture was kneaded with the twin screw kneading extruder. The obtained kneaded product is cooled, coarsely pulverized by a cutter mill, and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained is classified to have a volume average particle diameter of 8.26 μm. To obtain a black fine powder (magnetic toner). To 100 parts by weight of the obtained black fine powder, 0.5 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner. Used as a system developer. This one-component type developer was applied to a commercially available copying machine Canon NP-9800, and it was stored at room temperature and low humidity (23.5 ° C,
Images were printed under the environmental conditions of 5% RH). Table 7 shows the image output test results. As is clear from Table 7, both the initial image and the 100,000-sheet durability image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

The charge amount of the toner layer per unit area on the sleeve was determined by using the so-called suction type Faraday cage method. In this suction type Faraday cage method, the outer cylinder is pressed against the toner carrier to suck all toner on a certain area on the carrier, and at the same time, the toner is accumulated in the inner cylinder electrostatically shielded from the outside. This is a method in which the charge amount of the toner layer on the toner carrier can be determined by measuring the charge amount.

The fixing property and the offset property were evaluated by the following procedure.

The fixing property is as follows.
% RH), the evaluation machine is left overnight, and the evaluation machine and the fixing device inside the evaluation machine take 200 continuous copy images from the state where they are completely acclimated in a low temperature and low humidity environment, and the 200th copy image is taken. Used for evaluation of fixability. To evaluate the fixing property, the image was rubbed with a sillbon paper 10 times in a reciprocating manner under a load of about 100 g, and the peeling of the image was evaluated by the reduction rate (%) of the reflection density.

Therefore, the larger the value of the reduction rate of the reflection density after rubbing (the reduction rate of the image density) is, the more the rate of peeling of the image due to the rubbing is, and the fixing property of the toner is poor. The offset resistance was evaluated by removing the cleaning mechanism of the fixing roller and evaluating the number of copies to stain the image or the roller.

Further, since the toner once taken in the cleaning wave may be transferred to the upper roller due to the dirt of the cleaning wave during continuous copying, the copy may be contaminated. After returning the cleaning mechanism of the fixing roller to the normal state, raising the set temperature of the fixing device by 5 ° C. and taking 200 copies of the image continuously, take each copy of the image at intervals of 30 seconds for up to 3 minutes,
It was investigated whether image contamination occurred, and the state of stain on the cleaning wave of the fixing roller was evaluated.

Example 10 A black powder having a volume average particle size of 8.34 μm was prepared in the same manner as in Example 9 except that the modified polyester resin (12) used in Example 9 was replaced with the modified polyester resin (12). Fine powder (magnetic toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 part by weight of T specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. This one-component developer was applied to a commercially available copying machine Canon NP-6060, and the same evaluation as in Example 9 was performed. As is clear from Table 7, both the initial image and the 100,000-sheet durability image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 11 Modified Polyester Resin (13) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polyethylene 3 parts by weight Using the above materials, the volume was changed in the same manner as in Example 9. A black fine powder (magnetic toner) having an average particle size of 8.42 μm was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.5 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer.

This one-component type developer was applied to a commercially available copying machine, NP-6060 manufactured by Canon Inc., under normal temperature and low humidity (23.5).
Image formation was performed under the environmental conditions of ℃, 5% RH). Table 7 shows the image output test results. As is clear from Table 7, both the initial image and the 100,000-sheet endurance image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

Example 12 Modified polyester resin (14) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polyethylene 3 parts by weight Using the above materials, the volume was changed by the same method as in Example 9. A black fine powder (magnetic toner) having an average particle size of 8.27 μm was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.5 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer.

This one-component type developer was applied to a commercially available copying machine, NP-6060 manufactured by Canon Inc., under normal temperature and low humidity (23.5%).
Image formation was performed under the environmental conditions of ℃, 5% RH). Table 7 shows the image output test results. As is clear from Table 7, both the initial image and the 100,000-sheet durability image have high image density, are clear and have high quality, and neither defective cleaning nor drum fusion occurs. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

Example 13 Modified Polyester Resin (12) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight By the same method as in Example 9 using the above materials, the volume average particle size was 7.97 μm. To obtain a black fine powder (magnetic toner). 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.5 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer.

This one-component type developer was applied to a commercially available copying machine, NP-6060 manufactured by Canon Inc., at room temperature and low humidity (23.5%).
Image formation was performed under the environmental conditions of ℃, 5% RH). Table 7 shows the image output test results. As is clear from Table 7, both the initial image and the 100,000-sheet durable image had high image density and were clear and of high quality. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 14 Modified polyester resin (14) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight By the same method as in Example 9 using the above materials, the volume average particle diameter was 8.31 μm. To obtain a black fine powder (magnetic toner). 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.5 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer.

This one-component type developer was applied to a commercially available copying machine, NP-6060 manufactured by Canon Inc., under normal temperature and low humidity (23.5).
Image formation was performed under the environmental conditions of ℃, 5% RH). Table 7 shows the image output test results. As is clear from Table 7, both the initial image and the 100,000-sheet durable image had high image density and were clear and of high quality. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 15 In the same manner as in Example 9 except that the modified polyester resin (11) used in Example 9 was replaced with the modified polyester resin (15), the volume average particle diameter was 8.41 μm. A black fine powder (magnetic toner) was obtained. Black fine powder 1 obtained
Negatively charged hydrophobic dry colloidal silica (B
0.5 part by weight of an ET specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. This one-component developer was applied to a commercially available copying machine Canon NP-6060, and the same evaluation as in Example 9 was performed. As is clear from Table 7, both the initial image and the 100,000-sheet durability image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 16 In the same manner as in Example 9 except that the modified polyester resin (18) was used in place of the modified polyester resin (11) used in Example 9, a volume average particle diameter of 8.41 μm was obtained. A black fine powder (magnetic toner) was obtained. Black fine powder 1 obtained
Negatively charged hydrophobic dry colloidal silica (B
0.5 part by weight of an ET specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. This one-component developer was applied to a commercially available copying machine Canon NP-6060, and the same evaluation as in Example 9 was performed. As is clear from Table 7, the results show that the fixability, the number of sheets at which image stain started to occur, and the stains on the cleaning wave were slightly lowered as compared with Example 9, but there was no problem in practical use. Met.

Comparative Example 5 Black color having a volume average particle diameter of 8.19 μm was prepared in the same manner as in Example 9 except that the modified polyester resin (16) used in Example 9 was replaced with the modified polyester resin (16). Fine powder (magnetic toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 parts by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 9 was performed.

The initial image was good, but 13 during durability.
The image density begins to drop from around 5,000 sheets and reaches 15,000.
It became 1.21 at the time of one piece. The toner charge amount on the sleeve at the time of running 15,000 sheets was -18.9 µc / g. During cleaning, defective cleaning and drum fusion occurred from around 10,000 sheets. The evaluation results are shown in Table 7.

Comparative Example 6 A black powder having a volume average particle diameter of 8.31 μm was prepared in the same manner as in Example 9 except that the modified polyester resin (17) used in Example 9 was replaced with the modified polyester resin (17). Fine powder (magnetic toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 parts by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer, and then the same evaluation as in Example 9 was performed.

The initial image was good, but 80
The image density started to decrease from around 00 sheets and became 1.16 at 10000 sheets. The toner charge amount on the sleeve at the time of running 10,000 sheets was -19.8 μc / g. During cleaning, defective cleaning and drum fusion occurred from around 8500 sheets. The evaluation results are shown in Table 7.

Comparative Example 7 Black fine powder having a volume average particle size of 8.27 μm was prepared in the same manner as in Example 9 except that the modified polyester resin (11) used in Example 9 was replaced with the polyester resin (C). A body (magnetic toner) was obtained. 0.5 parts by weight of negatively charged hydrophobic dry colloidal silica (BET specific surface area of 300 m ² / g) was added to 100 parts by weight of the obtained black fine powder and mixed with a Henschel mixer, and then the same evaluation as in Example 9 was performed. went.

The initial image was good, but 30 during durability.
The image density started to decrease from around 00 sheets and became 1.11. The toner charge amount on the sleeve at the time of running 10,000 sheets was −20.7 μc / g. During cleaning, defective cleaning and drum fusion occurred from around 5,000 sheets. The evaluation results are shown in Table 7.

[0252]

[Table 7]

(Production of Modified Polyester Resin (19)) bisphenol A ethylene oxide adduct 474 parts by weight bisphenol A propylene oxide adduct 120
4 parts by weight terephthalic acid 581 parts by weight trimellitic acid 210 parts by weight dodecenyl succinic anhydride 133 parts by weight The above raw materials are put into a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and put into a mantle heater. It was After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 210 ° C. and reacted for 5 hours. The acid value at this time was 25.6 mgKOH / g.

Then, a linear alkyl alcohol C ₄₀ H ₈₁ O
580 parts by weight of H was added, the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (19).

The acid value of the modified polyester resin (19) is 1
3.4 mgKOH / g, hydroxyl value is 18.6 mgKOH
/ G, Tg was 65.1 ° C.

The modified amount of the modified polyester resin (19) with alkyl alcohol was 16% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (20)) bisphenol A ethylene oxide adduct 474 parts by weight bisphenol A propylene oxide adduct 120
4 parts by weight Dodecenyl succinic anhydride 266 parts by weight Terephthalic acid 415 parts by weight Trimellitic acid 294 parts by weight Adipic acid 14.6 parts by weight The above raw materials are put in a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction pipe are set. Then put it in the mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 21.4 mgKOH / g.

Then, a linear alkyl alcohol C ₇₅ H ₁₅₁
960 parts by weight of OH was added, and the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (20).

The acid value of the modified polyester resin (20) is 1
1.4 mgKOH / g, hydroxyl value is 14.6 mgKOH
/ G, Tg was 64.5 ℃.

The modified amount of the modified polyester resin (20) with alkyl alcohol was 23% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (21)) Bisphenol A Ethylene Oxide Adduct 316 parts by Weight Bisphenol A Propylene Oxide Adduct 120
4 parts by weight neopentyl glycol 52.5 parts by weight terephthalic acid 664 parts by weight trimellitic acid 210 parts by weight The above raw materials are put into a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and the mantle heater is set. I put it in. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 23.4 mgKOH / g.

Then, a straight-chain alkyl alcohol C ₃₅ H ₇₁ O
460 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (21).

The acid value of the modified polyester resin (21) is 1
0.3 mgKOH / g, hydroxyl value is 15.2 mgKOH
/ G, Tg was 64.8 ℃.

The modified amount of the modified polyester resin (21) with alkyl alcohol was 14% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (22)) Bisphenol A ethylene oxide adduct 474 parts by weight Bisphenol A propylene oxide adduct 120
4 parts by weight adipic acid 109.5 parts by weight terephthalic acid 622.5 parts by weight trimellitic acid 105 parts by weight The above raw materials are put in a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and the mantle heater is placed inside. I put it in. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 210 ° C. and reacted for 5 hours. The acid value at this time was 19.4 mgKOH / g.

Then, a linear alkyl alcohol C ₇₀ H ₁₄₁
800 parts by weight of OH was added, and the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (22).

The acid value of the modified polyester resin (22) is 1
1.4mgKOH / g, hydroxyl value is 12.6mgKOH
/ G, Tg was 65.4 ℃.

The modified amount of the modified polyester resin (22) with alkyl alcohol was 20% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (23)) Bisphenol A ethylene oxide adduct 316 parts by weight Bisphenol A propylene oxide adduct 120
4 parts by weight Neopentyl glycol 52.5 parts by weight Terephthalic acid 664 parts by weight Trimellitic acid 210 parts by weight Linear alkyl alcohol C ₃₅ H ₇₁ OH 410 parts by weight The above raw materials are put into a 4-neck flask, and a stirrer, a condenser, and a thermometer. Then, the gas introduction tube was set and placed in the mantle heater. After purging the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours, cooled to room temperature and taken out to obtain a modified polyester resin (23).

The acid value of the modified polyester resin (23) is 1
3.5 mgKOH / g, hydroxyl value is 18.2 mgKOH
/ G, Tg was 63.8 ℃.

The modified amount of the modified polyester resin (23) with alkyl alcohol was 13% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (24)) Bisphenol A ethylene oxide adduct 474 parts by weight Bisphenol A propylene oxide adduct 120
4 parts by weight terephthalic acid 581 parts by weight trimellitic acid 210 parts by weight dodecenyl succinic anhydride 133 parts by weight The above raw materials are put into a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and put into a mantle heater. It was After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 210 ° C. and reacted for 5 hours. The acid value at this time was 25.6 mgKOH / g.

Then, a linear alkyl alcohol C ₄₀ H ₈₁ O
235 parts by weight of H was added, the mixture was reacted for 3 hours, cooled to room temperature and taken out to obtain a modified polyester resin (24).

The acid value of the modified polyester resin (24) is 1
7.0 mgKOH / g, hydroxyl value is 18.6 mgKOH
/ G, Tg was 67 ℃.

The modified amount of the modified polyester resin (24) with alkyl alcohol was 8% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (25)) Bisphenol A ethylene oxide adduct 474 parts by weight Bisphenol A propylene oxide adduct 120
4 parts by weight terephthalic acid 581 parts by weight trimellitic acid 210 parts by weight dodecenyl succinic anhydride 133 parts by weight The above raw materials are put into a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and put into a mantle heater. It was After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 24.6 mgKOH / g.

Then, a linear alkyl alcohol C ₁₅ H ₃₁ O
230 parts by weight of H was added and reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (25).

The acid value of the modified polyester resin (25) is 1
3.1 mgKOH / g, hydroxyl value is 15.4 mgKOH
/ G, Tg was 64.7 ℃.

The modified amount of the modified polyester resin (25) with alkyl alcohol was 8% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (26)) Bisphenol A Ethylene Oxide Adduct 474 parts by weight Bisphenol A Propylene Oxide Adduct 120
4 parts by weight terephthalic acid 581 parts by weight trimellitic acid 210 parts by weight dodecenyl succinic anhydride 133 parts by weight The above raw materials are put into a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction pipe are set, and put into a mantle heater. It was After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours. The acid value at this time was 25.1 mgKOH / g.

Then, a linear alkyl alcohol C ₁₀ H ₂₁ O
160 parts by weight of H was added, the mixture was reacted for 2 hours, cooled to room temperature and taken out to obtain a modified polyester resin (26).

The acid value of the modified polyester resin (26) is 1
2.3 mgKOH / g, hydroxyl value is 13.7 mgKOH
/ G, Tg was 65.4 ℃.

The modified amount of the modified polyester resin (26) with alkyl alcohol was 5% by weight based on the weight of the modified polyester resin.

(Production of polyester resin (D)) Bisphenol A ethylene oxide adduct 474 parts by weight Bisphenol A propylene oxide adduct 120
4 parts by weight Dodecenyl succinic anhydride 399 parts by weight Terephthalic acid 464.8 parts by weight Trimellitic acid 147 parts by weight Put the above raw material in a 4-neck flask, set a stirrer, a condenser, a thermometer, and a gas introduction pipe, and set in a mantle heater. I put it in. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 210 ° C. and reacted for 6 hours, cooled to room temperature and taken out to obtain a modified polyester resin (D).

The acid value of the polyester resin (D) is 19.2.
mgKOH / g, hydroxyl value is 17.6 mgKOH / g,
Tg was 65.3 ° C.

Table 8 shows the formulation and physical properties of the modified polyester resins (19) to (26) and the polyester resin (D).

[0287]

[Table 8]

Example 17 Modified polyester resin (19) 100 parts by weight Carbon black Mogall L (manufactured by Cabot) 5
Parts by weight Negatively charge control agent 2 parts by weight Low molecular weight polypropylene 3 parts by weight The above materials were well mixed in a blender and then kneaded by a twin-screw kneading extruder set at 120 ° C. The obtained kneaded product is cooled, coarsely pulverized by a cutter mill, and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained is classified to have a volume average particle diameter of 8.31 μm. To obtain a black fine powder (toner). 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 30
0.5 part by weight of 0 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer. This two-component developer was applied to a commercially available copying machine Canon NP-5060, and images were printed under ambient conditions of room temperature and low humidity (23.5 ° C., 5% RH). The image output test results are shown in Table 9. As is clear from Table 9, both the initial image and the 100,000-sheet durability image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

The toner layer on the sleeve was evaluated for charge amount, fixing property and anti-offset property in the same manner as in Example 9.

Example 18 A black powder having a volume average particle diameter of 8.24 μm was prepared in the same manner as in Example 17, except that the modified polyester resin (20) used in Example 17 was replaced with the modified polyester resin (20). A fine powder (toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 part by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. Obtained toner and fluorine-coated carrier (300/350 mesh)
And were mixed to obtain a two-component developer. This two-component developer was applied to a commercially available copying machine Canon NP-5060, and the same evaluation as in Example 17 was performed. As is clear from Table 9, both the initial image and the 100,000-sheet durable image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred.
The amount of electrostatic charge on the sleeve and the amount of toner coat on the sleeve are initial,
It was stable even after running 100,000 sheets.

Example 19 Modified polyester resin (21) 100 parts by weight Carbon black # 30 (manufactured by Orient Chemical Co.) 5 parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polyethylene 3 parts by weight Example 17 Using the above materials A black fine powder (toner) having a volume average particle diameter of 8.34 μm was obtained by the same method as described above.
100 parts by weight of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
0.5 part by weight was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer.

This two-component developer was applied to a commercially available copying machine, NP-5060 manufactured by Canon, and was used at room temperature and low humidity (23.5%).
Image formation was performed under the environmental conditions of ℃, 5% RH). The image output test results are shown in Table 9. As is clear from Table 9, both the initial image and the 100,000-sheet durability image had high image density, were clear, and had high quality, and neither defective cleaning nor drum fusion occurred. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

Example 20 Modified polyester resin (22) 100 parts by weight Carbon black Mogall L (manufactured by Cabot) 5
Parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polyethylene 3 parts by weight By using the above materials and in the same manner as in Example 17, a black fine powder (toner) having a volume average particle diameter of 8.15 μm was obtained.
100 parts by weight of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
0.5 part by weight was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer.

This two-component type developer was applied to a commercially available copying machine, NP-5060 manufactured by Canon, under normal temperature and low humidity (23.5).
Image formation was performed under the environmental conditions of ℃, 5% RH). The image output test results are shown in Table 9. As is clear from Table 9, both the initial image and the 100,000-sheet durability image have high image density, are clear and have high quality, and neither defective cleaning nor drum fusion occurs. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

Example 21 Modified polyester resin (20) 100 parts by weight Carbon black # 30 (manufactured by Orient Chemical Co.) 5 parts by weight Negatively charged charge control agent 2 parts by weight Using the above materials, the volume was changed by the same method as in Example 17. A black fine powder (toner) having an average particle size of 8.22 μm was obtained.
100 parts by weight of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
0.5 part by weight was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer.

This two-component developer was applied to a commercially available copying machine, NP-5060 manufactured by Canon Inc., under normal temperature and low humidity (23.5).
Image formation was performed under the environmental conditions of ℃, 5% RH). The image output test results are shown in Table 9. As is clear from Table 9, both the initial image and the 100,000-sheet durable image had high image density and were clear and of high quality. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 22 Modified polyester resin (22) 100 parts by weight Carbon black Mogall L (manufactured by Cabot) 5
Parts by weight 2 parts by weight of negatively chargeable charge control agent Using the above materials, a black fine powder (toner) having a volume average particle diameter of 8.37 μm was obtained in the same manner as in Example 17.
100 parts by weight of the obtained black fine powder was added to negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g).
0.5 part by weight was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer.

This two-component developer was applied to a commercially available copying machine, NP-5060 manufactured by Canon Inc., under normal temperature and low humidity (23.5).
Image formation was performed under the environmental conditions of ℃, 5% RH). The image output test results are shown in Table 9. As is clear from Table 9, both the initial image and the 100,000-sheet durable image had high image density and were clear and of high quality. Charge on the sleeve,
The toner coat amount on the sleeve was stable at the initial stage and after 100,000 sheets were used.

Example 23 By the same method as in Example 17, except that the modified polyester resin (23) used in Example 17 is replaced with the modified polyester resin (23), the volume average particle diameter is 8.28 μm.
m black fine powder (toner) was obtained. To 100 parts by weight of the obtained black fine powder, 0.5 part by weight of negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. Obtained toner and fluorine-coated carrier (300/350 m
esh) was mixed to obtain a two-component developer. This two-component developer was applied to a commercially available copying machine Canon NP-5060, and the same evaluation as in Example 17 was performed. As is clear from Table 9, the result shows that the initial image is 100,000.
The image durability was high, the image was clear and the quality was high, and neither cleaning failure nor drum fusion occurred. The charge amount on the sleeve and the toner coat amount on the sleeve were stable at the initial stage and after 100,000 sheets were used.

Example 24 A black powder having a volume average particle diameter of 8.28 μm was obtained in the same manner as in Example 17, except that the modified polyester resin (26) used in Example 17 was replaced with the modified polyester resin (26). A fine powder (toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 part by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. Obtained toner and fluorine-coated carrier (300/350 mesh)
And were mixed to obtain a two-component developer. This two-component developer was applied to a commercially available copying machine Canon NP-5060, and the same evaluation as in Example 17 was performed. As is clear from Table 9, the results show that the fixability, the number of sheets that start to have image stains, and the stains on the cleaning wave are slightly reduced as compared with Example 17, but there is no practical problem. It was a level.

Comparative Example 8 A black powder having a volume average particle diameter of 8.24 μm was prepared in the same manner as in Example 17, except that the modified polyester resin (24) was used in place of the modified polyester resin (19) used in Example 17. A fine powder (toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 part by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. Obtained toner and fluorine-coated carrier (300/350 mesh)
And were mixed to obtain a two-component developer. The same evaluation as in Example 17 was carried out using this two-component developer.

The initial image was good, but 80
The image density started to decrease from around 00 sheets and became 1.19 after 10000 sheets. The toner charge amount on the sleeve at the time of running 10,000 sheets was −20.5 μc / g. During cleaning, defective cleaning and drum fusion occurred from around 8500 sheets. The evaluation results are shown in Table 9.

Comparative Example 9 A black powder having a volume average particle diameter of 8.29 μm was prepared in the same manner as in Example 17, except that the modified polyester resin (25) used in Example 17 was replaced with the modified polyester resin (25). A fine powder (toner) was obtained. Obtained black fine powder 10
Negatively charged hydrophobic hydrophobic colloidal silica (BE)
0.5 part by weight of T specific surface area of 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. Obtained toner and fluorine-coated carrier (300/350 mesh)
And were mixed to obtain a two-component developer. The same evaluation as in Example 17 was carried out using this two-component developer.

The initial image was good, but 65 during the durability test.
The image density started to decrease from around 00 sheets and became 1.17 at 8000 sheets. The toner charge amount on the sleeve at the time of durability 8000 sheets was −21.4 μc / g. From around 7,000 sheets during running, defective cleaning and drum fusion occurred. The evaluation results are shown in Table 9.

Comparative Example 10 Example 17 is repeated except that the modified polyester resin (19) used in Example 17 is replaced with the polyester resin (D).
A black fine powder (toner) having a volume average particle diameter of 8.32 μm was obtained in the same manner as in (1). To 100 parts by weight of the obtained black fine powder, 0.5 part by weight of negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. The obtained toner was mixed with a fluorine-coated carrier (300/350 mesh) to give a two-component developer. The same evaluation as in Example 17 was carried out using this two-component developer.

The initial image was good, but 40% during durability.
The image density started to decrease from around 00 sheets and became 1.15 at 5000 sheets. The toner charge amount on the sleeve at the time of running 5000 sheets was −20.8 μc / g. From around 4000 sheets during running, defective cleaning and drum fusion occurred. The evaluation results are shown in Table 9.

[0307]

[Table 9]

(Production of Modifying Compound A) CH ₃ (CH ₂ ) ₅₀ OH 732 parts by weight Propylene oxide 290 parts by weight The above materials were added in the presence of sodium ethoxide at a pressure of 1.
The reaction was carried out under the conditions of 72 × 10 ⁵ Pa and a temperature of 140 ° C. After a reaction time of 20 minutes, the reaction product was taken out. This was designated as modifying compound A.

(Production of Modifying Compound B) CH ₃ (CH ₂ ) ₅₅ OH 802 parts by weight Ethylene oxide 264 parts by weight The above materials were added in the presence of sodium ethoxide at a pressure of 1.
The reaction was carried out under the conditions of 38 × 10 ⁵ Pa and a temperature of 170 ° C. After a reaction time of 40 minutes, the reaction product was taken out. This was designated as a modifying compound B.

(Production of modifying compound C) CH ₃ (CH ₂ ) ₃₅ OH 522 parts by weight n-butyl glycidyl ether 300 parts by weight The above materials were added under pressure of 2.41 in the presence of sodium hydroxide.
The reaction was performed under the conditions of × 10 ⁵ Pa and temperature of 160 ° C. After a reaction time of 60 minutes, the reaction product was taken out. This was designated as a modifying compound C.

(Production of Modifying Compound D) CH ₃ (CH ₂ ) ₇₀ OH 1012 parts by weight Phenylglycidyl ether 450 parts by weight The above materials were added under pressure of 2.07 in the presence of sodium hydroxide.
The reaction was carried out under the conditions of × 10 ⁵ Pa and temperature of 170 ° C. The reaction product was taken out after a reaction time of 30 minutes. This was designated as a modifying compound D.

(Production of Modifying Compound E) CH ₃ (CH ₂ ) ₁₇ OH 270 parts by weight n-butyl glycidyl ether 195 parts by weight The above materials were added in the presence of sodium ethoxide at a pressure of 2.
The reaction was carried out under the conditions of 07 × 10 ⁵ Pa and temperature of 150 ° C. The reaction product was taken out after a reaction time of 30 minutes. This was designated as a modifying compound E.

(Production of modified polyester resin (27)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After replacing the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 4 hours.

Then, 500 parts by weight of the modifying compound A was added, and the mixture was reacted for 1.5 hours, cooled to room temperature and taken out to obtain a modified polyester resin (27).

The acid value of the modified polyester resin (27) is 1
6.8mgKOH / g, hydroxyl value is 16.1mgKOH
/ G, the glass transition point (Tg) was 59.3 ° C.

The amount of the modified polyester resin (27) modified with the modifying compound A was 15% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (28))
The modified polyester resin (28) was prepared in the same manner as in the modified polyester resin (27) except that 400 parts by weight of the modifying compound B was used instead of the modifying compound A used in the modified polyester resin (27). Manufactured.

The modified polyester resin (28) thus obtained had an acid value of 17.4 mgKOH / g and a hydroxyl value of 15.3 m.
The gKOH / g and glass transition point (Tg) were 58.7 ° C.

The amount of the modified polyester resin (28) modified with the modifying compound B was 12% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (29))
A modified polyester resin (29) was produced in the same manner as in the modified polyester resin (27) except that 450 parts by weight of the modifying compound C was used instead of the modifying compound A used in the production of the modified polyester resin (27). Manufactured.

The modified polyester resin (29) thus obtained had an acid value of 18.4 mgKOH / g and a hydroxyl value of 16.3 m.
The gKOH / g and glass transition point (Tg) were 59.4 ° C.

The modified amount of the modified polyester resin (29) with the modifying compound C was 14% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (30))
The modified polyester resin (30) was prepared in the same manner as in the modified polyester resin (27) except that 400 parts by weight of the modifying compound D was used instead of the modifying compound A used in the modified polyester resin (27). Manufactured.

The modified polyester resin (30) thus obtained had an acid value of 15.7 mgKOH / g and a hydroxyl value of 14.3 m.
The gKOH / g and the glass transition point (Tg) were 60.2 ° C.

The amount of the modified polyester resin (30) modified with the modifying compound D was 12% by weight based on the weight of the modified polyester resin.

(Production of Modified Polyester Resin (31))
The modified polyester resin (31) was prepared in the same manner as in the modified polyester resin (27) except that 400 parts by weight of the modifying compound E was used instead of the modifying compound A used in the modified polyester resin (27). Manufactured.

The modified polyester resin (31) thus obtained had an acid value of 17.1 mgKOH / g and a hydroxyl value of 15.8 m.
The gKOH / g and glass transition point (Tg) were 59.7 ° C.

The amount of modification of the modified polyester resin (31) with the modifying compound E was 12% by weight based on the weight of the modified polyester resin.

(Production of modified polyester resin (32)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight Compound A for modification 350 parts by weight The above raw materials are placed in a 4-neck flask, and a stirrer, a condenser, a thermometer, and a gas introduction tube are set and placed in a mantle heater. It was After purging the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 5 hours to obtain a modified polyester resin (32). The modified polyester resin (32) thus obtained had an acid value of 16.4 mgKOH / g, a hydroxyl value of 15.7 mgKOH / g, and a glass transition point (Tg) of 5.
It was 9.7 ° C.

The amount of modification of the modified polyester resin (32) with the modifying compound A was 11% by weight based on the weight of the modified polyester resin.

(Production of polyester resin (E)) Bisphenol A ethylene oxide adduct 632 parts by weight Bisphenol A propylene oxide adduct 103
2 parts by weight terephthalic acid 581 parts by weight trimellitic acid 315 parts by weight The above raw materials were placed in a four-necked flask, a stirrer, a condenser, a thermometer, and a gas introduction tube were set and placed in a mantle heater. After purging the inside of the reaction vessel with nitrogen gas, the content was heated to 200 ° C. and reacted for 4 hours to obtain a polyester resin (E). The acid value of the obtained polyester resin is 2
5.4mgKOH / g, hydroxyl value is 20.7mgKOH
/ G, the glass transition point (Tg) was 61.5 ° C.

Example 25 Modified polyester resin (27) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charged charge control agent 2 parts by weight Low molecular weight polypropylene 3 parts by weight After thoroughly mixing the above materials with a blender, set to 110 ° C. The mixture was kneaded by the twin-screw kneading extruder. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained was classified to obtain a volume average particle diameter of 8.17 μm. To obtain a black fine powder (magnetic toner). To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner. Used as a system developer.

This one-component type developer was applied to a commercially available copying machine, NP-6060 manufactured by Canon, under normal temperature and low humidity (23.5%).
Image formation was performed under the environmental conditions of ℃, 5% RH). Table 10 shows the image output test results. As is clear from Table 10, both the initial image and the 30,000-sheet durability image were high in image density and were good images. The amount of electrostatic charge on the sleeve was stable at the initial stage even after 30,000 sheets had been durable, and neither cleaning failure nor drum fusion occurred during image formation durability. Further, both fixability and offset resistance were good.

The charge amount of the toner layer per unit area on the sleeve was determined by using the so-called suction type Faraday cage method. In this suction type Faraday cage method, the outer cylinder is pressed against the toner carrier to suck all toner on a certain area on the carrier, and at the same time, the toner is accumulated in the inner cylinder electrostatically shielded from the outside. This is a method in which the amount of charge per unit area on the toner carrier can be determined by measuring the amount of charge.

In the present invention, the fixing property and the offset resistance are evaluated by the following procedures.

The fixing property is as follows.
% RH), the evaluation machine is left overnight, and the evaluation machine and the fixing device inside the evaluation machine take 200 continuous copy images from the state where they are completely acclimated in a low temperature and low humidity environment, and the 200th copy image is taken. Used for evaluation of fixability. The fixing property was evaluated by rubbing the image with sillbon paper 10 times in a reciprocating manner under a load of about 100 kg, and peeling of the image was evaluated by a reduction rate (%) of reflection density.

Therefore, the larger the value of the reduction rate of the reflection density after rubbing (the reduction rate of the image density) is, the more the peeling rate of the image due to the rubbing is, and the fixing property of the toner is poor.

The offset resistance was evaluated based on whether or not the toner once taken in the cleaning wave was transferred to the upper fixing roller and contaminates the copy when continuous copying was performed. As an evaluation method, under a low temperature and low humidity environment (15
After taking 200 copies of the image continuously at 30 ° C and 10% RH), take one copy of the copy at intervals of 30 seconds for up to 3 minutes,
It was investigated whether image contamination would occur. Here, the offset resistance of the toner was evaluated as good (∘) when image contamination did not occur.

Further, the state of dirt on the cleaning wave of the fixing roller was evaluated.

Example 26 A black fine powder having a volume average particle size of 8.04 μm was obtained in the same manner as in Example 25 except that the modified polyester resin (28) used in Example 25 was replaced with the modified polyester resin (28). (Magnetic toner) was obtained. Black fine powder 1 obtained
Negatively charged hydrophobic dry colloidal silica (B
0.6 parts by weight of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The obtained one-component developer was applied to a commercially available copying machine Canon NP-6060, and Example 2 was used.
The same evaluation as 5 was performed. As is clear from Table 10, the results showed that the initial image and the 30,000-sheet durability image were both high in image density and good. The amount of electrostatic charge on the sleeve was stable at the initial stage even after 30,000 sheets had been durable, and neither cleaning failure nor drum fusion occurred during image formation durability. Further, both fixability and offset resistance were good.

Example 27 A black fine powder having a volume average particle size of 6.07 μm was obtained in the same manner as in Example 25 except that the modified polyester resin (29) used in Example 25 was replaced with the modified polyester resin (29). (Magnetic toner) was obtained. Black fine powder 1 obtained
Negatively charged hydrophobic dry colloidal silica (B
0.6 parts by weight of ET specific surface area 300 m ² / g) and mixed with a Henschel mixer to obtain a magnetic toner, which is used as a one-component developer, and the obtained one-component developer is used as a commercial copying machine Canon. Example 25 applied to NP-6060 manufactured by
The same evaluation as was done. As is clear from Table 10, the results showed that the initial image and the 30,000-sheet durability image were both high in image density and good. The amount of electrostatic charge on the sleeve was stable at the initial stage even after 30,000 sheets had been durable, and neither cleaning failure nor drum fusion occurred during image formation durability. Further, both fixability and offset resistance were good.

Example 28 A black fine powder having a volume average particle diameter of 6.28 μm was obtained in the same manner as in Example 25 except that the modified polyester resin (30) used in Example 25 was replaced with the modified polyester resin (30). (Magnetic toner) was obtained. Black fine powder 1 obtained
Negatively charged hydrophobic dry colloidal silica (B
0.6 parts by weight of ET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The obtained one-component developer was applied to a commercially available copying machine Canon NP-6060, and Example 2 was used.
The same evaluation as 5 was performed. As is clear from Table 10, the results showed that the initial image and the 30,000-sheet durability image were both high in image density and good. The amount of electrostatic charge on the sleeve was stable at the initial stage even after 30,000 sheets had been durable, and neither cleaning failure nor drum fusion occurred during image formation durability. Further, both fixability and offset resistance were good.

Example 29 Modified polyester resin (32) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charge control agent 2 parts by weight Low molecular weight polyethylene 3 parts by weight By the same method as in Example 25 using the above materials, A black fine powder (magnetic toner) having a volume average particle diameter of 5.94 μm was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.6 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The same evaluation as in Example 25 was performed using the obtained one-component developer. As is clear from Table 10, the results showed that the initial image and the 30,000-sheet durability image were both high in image density and good. Initial charge on sleeve is 3
It is stable even after 50,000 copies have been made.
There was no cleaning failure or drum fusion. Further, both fixability and offset resistance were good.

Example 30 Modified polyester resin (27) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively-charged charge control agent 2 parts by weight By the same method as in Example 25 using the above materials, the volume average particle size of 6. 21 μm black fine powder (magnetic toner) was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.6 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The obtained one-component type developer was applied to a commercially available copying machine Canon NP-6060, and the same evaluation as in Example 25 was performed. As a result, as is clear from Table 10, the image density is high in both the initial image and the 30,000-sheet durability image,
It was a good image. The amount of electrification on the sleeve is 30,
It was stable even after 000 sheets were durable, and neither cleaning failure nor drum fusion occurred during image formation durability. further,
Both fixability and offset resistance were good.

Comparative Example 11 Polyester Resin (E) 100 parts by weight Magnetic iron oxide 90 parts by weight Negatively charge control agent 2 parts by weight Low molecular weight polypropylene 3 parts by weight By the same method as in Example 25 using the above materials, the volume was increased. A black fine powder (magnetic toner) having an average particle size of 8.04 μm was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² /
g) 0.6 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The same evaluation as in Example 25 was performed using the obtained one-component developer. Although the initial image was good, the image density decreased as the image output durability was advanced, and the image density became 1.11 at 7,500 sheets, so the durability was stopped at 7,500 sheets. The toner charge amount on the sleeve at 7,500 sheets during running was −21.4 μC / g. During image development durability, defective cleaning occurred from around 7,300 sheets. Further, the fixability is at a low level of 25.1% in the image density reduction rate, and the offset resistance is the image density due to wave stains. The evaluation results are shown in Table 10.

Comparative Example 12 A black fine powder (magnetic toner) having a volume average particle diameter of 6.34 μm was obtained in the same manner as in Comparative Example 11 using the same material as in Comparative Example 11. To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner. Used as a system developer. Example 2 using the obtained one-component developer
The same evaluation as 5 was performed. The initial image was good,
Image density decreases as image development progresses,
Since the image density was 1.07 at 4,500 sheets,
Durability was stopped at 4,500 sheets. The charge amount of toner on the sleeve at 4,500 sheets during running was −20.7 μC / g. During image development durability, defective cleaning occurred around 4,100 sheets, and drum fusion occurred around 4,300 sheets. Further, as for the fixability, the image density reduction rate is 24.7.
%, Which is a low level, and the offset resistance was caused by image contamination due to wave stains. The evaluation results are shown in Table 10.

Comparative Example 13 Instead of the polyester resin (E) used in Comparative Example 11,
A black fine powder (magnetic toner) having a volume average particle size of 8.17 μm was obtained by the same method except that the modified polyester was used as the resin 31. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 3
(00 m ² / g) 0.6 part by weight was added and mixed with a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer. The same evaluation as in Comparative Example 11 was performed using the obtained one-component developer. The initial image was good, but the image density decreased as the image development durability increased, and 7,000
Since the image density was 1.09 at the time of one sheet, it was 7,000
Durability was stopped at the time of sheet. The toner charge amount on the sleeve at the time of 7,000 sheets during running was −20.4 μC / g. During image development durability, defective cleaning occurred from around 6,700 sheets. Further, the fixability is such that the image density reduction rate is 23.7.
%, Which is a low level, and the offset resistance was caused by image contamination due to wave stains. The evaluation results are shown in Table 10.

Comparative Example 14 A black fine powder (magnetic toner) having a volume average particle size of 6.04 μm was obtained in the same manner as in Comparative Example 13 using the same material as in Comparative Example 13. To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of a negatively chargeable hydrophobic dry colloidal silica (BET specific surface area of 300 m ² / g) was added, mixed with a Henschel mixer, and then evaluated in the same manner as in Comparative Example 13. went. Although the initial image was good, the image density decreased as the image output durability was increased, and the image density became 1.12 at 4,000 sheets, so the durability was stopped at 4,000 sheets. The toner charge amount on the sleeve at the time of 4,000 sheets during running was −20.3 μC / g. During image development durability, cleaning failure occurred from around 3,700 sheets.
Drum fusion occurred from around 900 sheets. Further, the fixability was a poor level of image density reduction rate of 22.4%, and the anti-offset property caused image contamination due to wave stain. The evaluation results are shown in Table 10.

[0349]

[Table 10]

(Production of modified polyester resin (33)) Bisphenol derivative represented by the following formula (1): 36
0 parts by weight

[0351]

[Outside 18] (R is a propylene group) -Terephthalic acid: 100 parts by weight-Adipic acid: 55 parts by weight-Alkyl monocarboxylic acid represented by the following formula (5): 1
00 parts by weight CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (Y = 48, Mw / Mn = 2.0) -Polyethylene: 20 parts by weight-Stannous oxide: 0.5 parts by weight A 5-liter 4-necked flask was charged, equipped with a reflux condenser, a water separator, a nitrogen gas inlet tube, a thermometer and a stirrer, and the condensation polymerization reaction was carried out at 220 ° C. while introducing nitrogen into the flask. 6,000, Mw = 11,
000, Tg = 59 ° C modified polyester resin (33)
Got

The modified amount of the modified polyester resin (33) with the alkyl monocarboxylic acid was 14% by weight based on the weight of the modified polyester resin. Table 11 shows various physical properties of the modified polyester resin (33) obtained.

(Modified polyester resin (34)-(4
0) Production) Modified polyester resin (34) having the physical properties shown in Table 11 by changing the composition and molecular weight of the alkyl monocarboxylic acid and polyester resin used in the production of modified polyester resin (33) as shown in Table 11. -(4
0) was obtained.

(Production of modified polyester resin (41)) Bisphenol derivative represented by the following formula (I): 36
0 parts by weight

[0355]

[Outside 19] (R is a propylene group) -terephthalic acid: 100 parts by weight-fumaric acid: 40 parts by weight-stannous oxide: 0.5 parts by weight Similar to the production of the modified polyester resin (33) using the above raw materials By reacting in the same manner using a device, Mn
= 5,000, Mw = 10,000, Tg = 65 ° C, acid value 20, OH value 35, polyester resin (F) was obtained.

Polyester resin (F): 100 parts by weight Monocarboxylic acid represented by the following formula (5): 30 parts by weight CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (x = 48, Mw /Mn=2.0) Stannous oxide: 0.5 parts by weight The above raw materials were charged in the same apparatus as used in the production of the polyester resin (F) described above, and 200 were introduced while introducing nitrogen into the flask. A denaturation reaction is carried out at ℃
A modified polyester resin (41) having 0, Mw = 12,000 and Tg = 58 ° C. was obtained.

The modified amount of the modified polyester resin (41) with the alkyl monocarboxylic acid was 20% by weight based on the weight of the modified polyester resin. Table 11 shows various physical properties of the modified polyester resin (41).

(Production of Modified Polyester Resin (42)) A bisphenol derivative represented by the following formula (I): 36
0 parts by weight (where R is a propylene group)

[0359]

[Outside 20] (In the formula, R represents an ethylene or propylene group, and x, y
Each represent an integer of 1 or more, and the average value of x + y represents 2 to 10. ) -Terephthalic acid: 80 parts by weight-trimellitic acid: 70 parts by weight-stannous oxide: 0.5 parts by weight-alkyl monocarboxylic acid represented by the following formula (5): 1
00 parts by weight CH ₃ (CH ₂ ) _Y CH ₂ COOH ... (5) (x = 48, Mw / Mn = 2.0) Stannous oxide: 0.5 parts by weight The above raw materials were put into a 5 liter 4-neck flask. Charge, reflux condenser, water separator, nitrogen gas inlet tube, thermometer and stirrer were attached, while introducing nitrogen into the flask, condensation polymerization reaction was carried out at 220 ° C., Mn = 6500, Mw = 1150.
A modified polyester resin (42) having 0 and Tg = 59 ° C. was obtained.

The modified amount of the modified polyester resin (42) with the alkyl monocarboxylic acid was 14% by weight based on the weight of the modified polyester resin. Table 11 shows various physical properties of the modified polyester resin (42) thus obtained.

[0361]

[Table 11]

(Production of Polyester Resin (G)) Bisphenol Derivative Represented by the Following Formula (1)

[0363]

[Outside 21] (R is an ethylene group and x + y = 2.2)
17 mol% (R is a propylene group and x + y = 2.2) 34 mol% terephthalic acid 15 mol% fumaric acid 22 mol% trimellitic acid 12 mol% 100 parts by weight of the above raw materials and 0.1 part by weight of stannous oxide A 5 liter 4-necked flask was charged, equipped with a reflux condenser, a nitrogen gas introducing pipe, a thermometer and a stirrer. While introducing nitrogen gas into the flask, a condensation polymerization reaction was carried out at 220 ° C. and Mn = 3,800. , Mw = 16,000, Tg = 6
A polyester resin (G) having an acid value of 9 and an OH value of 18 was obtained at 2 ° C.

Example 31 Modified polyester resin (33) 100 parts by weight Magnetic iron oxide 80 parts by weight (average particle size 0.15 μm, Hc115 oersted, σ
s80 emu / g, σr11 emu / g) Monoazo complex (negative charge control agent) 2 parts by weight After premixing the above materials with a Henschel mixer, 130
Melt kneading was carried out at 2 ° C by a biaxial kneader. After the kneaded product is allowed to cool, it is roughly crushed by a cutter mill, then crushed by a fine crusher using a jet stream, and further classified by an air classifier to obtain a black fine powder having a weight average particle diameter of 8.0 μm. (Magnetic toner) was obtained. To 100 parts by weight of this black fine powder, 0.6 part by weight of hydrophobic silica (BET 150 m ² / g) was externally added by a Henschel mixer to obtain a magnetic toner, which was used as a one-component developer.

Using the obtained one-component type developer, an unfixed image was obtained with a Canon copying machine NP-6060, and NP-
A fixing test was conducted by changing the temperature with a fixing machine having the same structure as 6060. As a result, the fixable area is 130-
It was 240 ° C.

Further, using a one-component type developer, the photosensitive drum of Canon laser copying machine NP-9330 is OPC'ed.
After conversion to a photosensitive drum and charging with a negative corona, a latent image was formed with a laser, and the image was evaluated by a modified machine modified to a method of reversal development. As a result, there was no fog in the white background and no voids in the transfer, and the density gradation was good even in a photographic image containing characters. In the relationship between the development potential and the image density, almost satisfactory linearity was obtained.

Further, a copy test of 20,000 sheets was conducted. As a result, the copy image was of high image quality with almost no change from the initial image described above, and good results were also obtained in terms of fixability. Further, neither fusion of the toner to the photosensitive member nor cleaning failure occurred at all.

Furthermore, under low temperature and low humidity (5 ° C., 10% R
H) and under a high temperature and high humidity condition (30 ° C., 80% RH), a copy test was conducted, and good results were obtained as in the initial stage. A long-term storage test (one week storage) under high temperature and high humidity was performed, and good results were obtained without a decrease in concentration.

Further, it was allowed to stand at 50 ° C. for 1 week and its storage stability was examined. As a result, no blocking occurred and it had good fluidity.

In the above developing apparatus, the contact charging roller is used instead of corona charging to charge the photosensitive drum, and the contact transfer roller is used instead of corona transfer to transfer the toner image to the recording material to stain the contact transfer roller. Also, the dropout of transfer was evaluated. The evaluation results are shown in Table 13.

Examples 32 to 38 and Comparative Examples 15 to 1
7 Example 3 except that the formulation for preparing the magnetic toner was changed as shown in Table 12.
A one-component developer was prepared in the same manner as in No. 1 and evaluated in the same manner. The evaluation results are shown in Table 13.

[0372]

[Table 12]

[0373]

[Table 13]

[0374]

EFFECT OF THE INVENTION In the toner for developing an electrostatic image and the one-component developer and two-component developer using the toner of the present invention, the polyester resin used as the binder resin has 2 carbon atoms.
At least a part of which is modified with a compound having a long chain alkyl group of 2 to 102 and a hydroxyl group or a carboxyl group at the terminal, so that a long chain alkyl group having 22 to 102 carbon atoms is introduced into the structure of the polyester resin. Therefore, it is excellent in low-temperature fixability and anti-offset property, and is also excellent in environmental stability, and it is possible to prevent the charge-up phenomenon of the toner especially in a low temperature and low humidity environment.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (31) Priority claim number Japanese Patent Application No. 5-293838 (32) Priority date Hei 5 (1993) November 1 (33) Priority claim country Japan (JP) (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Yuji Mikura, 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (52)

[Claims] 1. A toner for developing an electrostatic charge image containing at least a binder resin and a colorant, wherein the binder resin has a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. A toner for developing an electrostatic charge image, which comprises a polyester resin which is at least partially modified with a compound. 2. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein x represents a number of 20 to 100). The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with alcohol. 3. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein x represents a number of 23 to 100). The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with alcohol. 4. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein, n represents a number from 21 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with a substance α which is reacted with a compound. 5. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein, n represents a number of 23 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with a substance α which is reacted with a compound. 6. The alkyl resin represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 20 to 100). The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with a monocarboxylic acid. 7. The alkyl resin represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 25 to 80). The toner for developing an electrostatic charge image according to claim 1, comprising a polyester resin at least a part of which is modified with a monocarboxylic acid. 8. The binder resin comprises (i) a polyol, (ii) a polycarboxylic acid, and (iii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group or a carboxyl group at the end when a polyester resin is synthesized. The toner for developing an electrostatic image according to claim 1, further comprising a polyester resin modified by the polycondensation and ester reaction using a compound having a group. 9. The binder resin comprises, after synthesizing a polyester resin, (i) at least one of an unreacted carboxyl group and an unreacted hydroxyl group in the polyester resin,
(Ii) A polyester resin modified by the compound prepared by subjecting a long-chain alkyl group having 22 to 102 carbon atoms to a compound having a hydroxyl group or a carboxyl group at the terminal, which is modified by the compound. The toner for developing an electrostatic charge image according to claim 1. 10. The binder resin comprises, after synthesizing a polyester resin, (i) only unreacted hydroxyl groups in the polyester resin, (ii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group at the terminal. The toner for developing an electrostatic charge image according to claim 1, further comprising a polyester resin modified by the reaction of the compound having the above with urethane using diisocyanate. 11. The amount of modification of the polyester resin with a compound having a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 0.1 to 10 based on the weight of the modified polyester resin. 100
The toner for developing an electrostatic charge image according to claim 1, characterized in that the toner is wt%. 12. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 5 to 50 weight based on the weight of the modified polyester resin. %
The toner for developing an electrostatic charge image according to claim 1, wherein 13. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 10 to 30 weight based on the weight of the modified polyester resin. %, The toner for developing an electrostatic charge image according to claim 1. 14. The modified polyester resin is 2
The toner for developing an electrostatic charge image according to claim 1, having a glass transition temperature (Tg) of 5 to 75 ° C. 15. The modified polyester resin is 3
The toner for developing an electrostatic charge image according to claim 1, having a glass transition temperature (Tg) of 0 to 70 ° C. 16. The electrostatic image developing toner according to claim 1, wherein the toner is a magnetic toner containing a magnetic material as the colorant. 17. The toner is a magnetic toner containing a magnetic material as the colorant, and the binder resin is a long-chain alkyl alcohol having 25 or more carbon atoms and is at least one of non-linear polyester resins. The toner for developing an electrostatic charge image according to claim 1, characterized in that the toner contains a modified polyester resin. 18. The electrostatic charge image developing toner according to claim 1, wherein the toner is a non-magnetic toner containing a dye and / or a pigment as the colorant. 19. A one-component developer having a toner containing at least a binder resin and a colorant, wherein the binder resin has a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. A one-component developer comprising a polyester resin at least a part of which is modified with a compound having 20. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein x represents a number of 20 to 100). The one-component developer according to claim 19, comprising a polyester resin at least a part of which is modified with alcohol. 21. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein, x represents a number of 23 to 100). The one-component developer according to claim 19, comprising a polyester resin at least a part of which is modified with alcohol. 22. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein, n is a number from 21 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) 20. The one-component type developer according to claim 19, which has a polyester resin at least a part of which is modified with a substance α reacted with a compound. 23. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein, n represents a number from 23 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) 20. The one-component type developer according to claim 19, which has a polyester resin at least a part of which is modified with a substance α reacted with a compound. 24. The alkyl resin represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 20 to 100). 20. A polyester resin having at least a part thereof modified with a monocarboxylic acid.
The one-component developer described. 25. The binder resin is an alkyl represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 25 to 80). 20. The one-component developer according to claim 19, comprising a polyester resin which is at least partially modified with a monocarboxylic acid. 26. The binder resin comprises (i) a polyol, (ii) a polycarboxylic acid, and (iii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group or a carboxyl group at the end when a polyester resin is synthesized. 20. The one-component type developer according to claim 19, which contains a polyester resin modified by the polycondensation and ester reaction using a compound having a group. 27. The binder resin comprises, after synthesizing a polyester resin, (i) at least one of an unreacted carboxyl group and an unreacted hydroxyl group in the polyester resin, and (ii) a long chain having 22 to 102 carbon atoms. 20. A one-component system comprising a polyester resin modified by the ester reaction of a chain alkyl group and a compound having a hydroxyl group or a carboxyl group at the terminal, the polyester resin modified by the compound. Developer. 28. The binder resin comprises, after synthesizing a polyester resin, (i) only an unreacted hydroxyl group in the polyester resin, (ii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group at the terminal. 20. The one-component type developer according to claim 19, further comprising a polyester resin modified by the reaction of the compound having the above with urethane using diisocyanate. 29. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 0.1 to 10 based on the weight of the modified polyester resin. 100
20. The one-component developer according to claim 19, wherein the one-component developer is in weight%. 30. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 5 to 50 weight based on the weight of the modified polyester resin. %
20. The one-component developer according to claim 19, wherein 31. The amount of modification of the polyester resin with a compound having a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 10 to 30 weight based on the weight of the modified polyester resin. 20. The one-component developer according to claim 19, which is%. 32. The modified polyester resin is 2
The one-component developer according to claim 19, which has a glass transition temperature (Tg) of 5 to 75 ° C. 33. The modified polyester resin is 3
The one-component developer according to claim 19, which has a glass transition temperature (Tg) of 0 to 70 ° C. 34. The one-component developer according to claim 19, wherein the toner is a magnetic toner containing a magnetic material as the colorant. 35. The toner is a magnetic toner containing a magnetic material as the colorant, and the binder resin is a long-chain alkyl alcohol having 25 or more carbon atoms and is at least one of non-linear polyester resins. 20. The one-component type developer according to claim 19, wherein the part contains a modified polyester resin. 36. A two-component developer having a toner and a carrier containing at least a binder resin and a colorant, wherein the binder resin is a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal. A two-component developer comprising a polyester resin at least a part of which is modified with a compound containing a group. 37. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein x represents a number of 20 to 100). The two-component developer according to claim 36, comprising a polyester resin at least a part of which is modified with alcohol. 38. The binder resin is an alkyl represented by the following formula (1) CH ₃ (CH ₂ ) _x CH ₂ OH (1) (wherein, x represents a number of 23 to 100). The two-component developer according to claim 36, comprising a polyester resin at least a part of which is modified with alcohol. 39. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein, n represents a number from 21 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) 37. The two-component developer according to claim 36, which has a polyester resin at least a part of which is modified with a substance α reacted with a compound. 40. The binder resin is an alkyl alcohol represented by the following formula (2) CH ₃ (CH ₂ ) _n OH (2) (wherein n represents a number from 23 to 101). , The following formula (3) having one epoxy group in the molecule: (In the formula, R ′ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₁ —CH ₂ — (R ₁ represents an ether group or an ester group).) 37. The two-component developer according to claim 36, which has a polyester resin at least a part of which is modified with a substance α reacted with a compound. 41. The binder resin is an alkyl represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 20 to 100). 37. A polyester resin having at least a portion modified with a monocarboxylic acid.
The two-component developer described. 42. The alkyl resin represented by the following formula (5) CH ₃ (CH ₂ ) _Y CH ₂ COOH (5) (wherein Y represents a number of 25 to 80). 37. The two-component developer according to claim 36, comprising a polyester resin which is at least partially modified with a monocarboxylic acid. 43. The binder resin comprises (i) a polyol, (ii) a polycarboxylic acid, and (iii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group or a carboxyl group at the terminal when a polyester resin is synthesized. 37. The two-component type developer according to claim 36, which contains a polyester resin modified by the polycondensation and esterification reaction using a compound having a group with the compound. 44. The binder resin comprises, after synthesizing a polyester resin, (i) at least one of an unreacted carboxyl group and an unreacted hydroxyl group in the polyester resin, and (ii) a long chain having 22 to 102 carbon atoms. 37. A two-component system according to claim 36, which contains a polyester resin modified by the ester reaction of a chain alkyl group and a compound having a hydroxyl group or a carboxyl group at the terminal, the polyester resin being modified by the compound. Developer. 45. The binder resin comprises, after synthesizing a polyester resin, (i) only an unreacted hydroxyl group in the polyester resin, (ii) a long-chain alkyl group having 22 to 102 carbon atoms, and a hydroxyl group at the terminal. 37. The two-component type developer according to claim 36, further comprising a polyester resin modified by the urethane reaction of the compound having the above with a compound using diisocyanate. 46. The amount of modification of the polyester resin with a compound having a long chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 0.1 to 10 based on the weight of the modified polyester resin. 100
37. The two-component developer according to claim 36, wherein the two-component developer is in weight%. 47. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 5 to 50% by weight based on the weight of the modified polyester resin. %
37. The two-component developer according to claim 36, wherein 48. The amount of modification of the polyester resin with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at the terminal is 10 to 30 weight based on the weight of the modified polyester resin. 37. The two-component developer according to claim 36, wherein the two-component developer is%. 49. The modified polyester resin is 2
The two-component developer according to claim 36, having a glass transition temperature (Tg) of 5 to 75 ° C. 50. The modified polyester resin is 3
The two-component developer according to claim 36, having a glass transition temperature (Tg) of 0 to 70 ° C. 51. The two-component developer according to claim 36, wherein the toner is a non-magnetic toner containing a dye and / or a pigment as the colorant. 52. The binder resin according to claim 36, wherein the binder resin contains a polyester resin in which at least a part of the non-linear polyester resin is modified with a long-chain alkyl alcohol having 25 or more carbon atoms. Component developer.