JP3376231B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image formed by electrophotography or electrostatic printing.

[0002]

2. Description of the Related Art US Pat.
A large number of methods are known as described in JP-A-7,691 and JP-B-42-23910 and JP-B-43-24748. Generally, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with toner, and a toner image is transferred onto a transfer material such as paper, if necessary. After the transfer, the toner image is obtained by fixing with heating, pressure, heating pressure or solvent vapor.

In recent years, the copying machine is digitized and the toner is made finer, so that the copying machine becomes multifunctional, the image quality of the copy image is improved, and the drum heater is removed from the viewpoint of energy saving as an approach to environmental problems. Is traditionally
A drum heater was incorporated to prevent condensation in order to allow the photosensitive drum to function as expected even in high temperature and high humidity environments, but it is necessary to energize and consume power even at night when it is not used, so it is desirable to implement it as energy saving. It is rare. Further, it is desired to shorten the first copy time by improving the fixing method. However, a new problem arises due to the finer particles of the toner and the shortening of the first copy time for the purpose of improving the resolution and the sharpness of the image. In other words, by reducing the toner particle size, the surface area of the toner increases, and the charging characteristics of the toner are more easily affected by the environment, especially when left standing for a long time under high temperature and high humidity. However, the image density decreases after standing. Further, under low humidity, coating unevenness occurs on the sleeve due to excessive charging of the toner.

Further, in recent digital copying machines,
In a photographic image containing characters, the characters of the copied image are clear, and the photographic image is required to have density gradation that is faithful to the original. Generally, in copying a photographic image containing characters, if the line density is increased to make the characters clear, not only the density gradation of the photographic image is impaired, but also the image becomes very rough in the halftone portion. 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 image density is read and the density gradation is improved to some extent by digital conversion.
However, the present situation is still not enough. This is largely due to the developing characteristics of the developer. That is, the developing potential (difference between the photosensitive member potential and the developer carrying member) and the image density do not have a linear relationship, and as shown in FIG. On the other hand, when the electric potential is high, a convex curve is drawn. Therefore, in the halftone region, a slight change in the development potential causes a very large change in the image density. This makes it difficult to obtain a sufficiently satisfactory density gradation.

Usually, in order to copy a line image and maintain its sharpness, the maximum image density in a solid image portion which is not easily affected by the edge effect is 1.30 because it is affected by the edge effect.
Something is enough.

However, in a photographic image, the maximum density of the photograph itself is largely due to its surface glossiness, which is 1.9.
It is very high, from 0 to 2.00. Therefore, in copying a photographic image, even if the glossiness of the surface is suppressed, since the image area is large, the density is not increased by the edge effect. Therefore, the maximum image density in the solid image portion is 1.4 to 1. About 5 is necessary. Therefore, the developing potential and the image density are in a linear (linear) relationship, and the maximum image density is 1.4 to
Setting 1.5 becomes very important in copying a photo image with text.

Further, since the digital copying machine is a reversal developing system, the toner is developed by an electric field on the uncharged portion of the photoconductor or a portion of the same polarity at the time of development, and the surface of the photoconductor is electrostatically induced by the developer. It will be held by the generated charge.

Therefore, in order for the developer to be stably conveyed by the photoreceptor, it is necessary to increase the charge amount of the developer which causes electrostatic induction.

During transfer, the transfer material (transfer paper or the like) is charged to the opposite polarity to the photosensitive member. Therefore, when the current contributing to the transfer is increased, the transfer material and the photosensitive member are electrically adhered to each other. Problems such as sticking phenomenon and transferred toner are drawn back to the photoconductor again, that is, problems such as retransfer are likely to occur.

Therefore, the transfer current is inevitably weaker than in the conventional case. In that case, in order to prevent the transfer efficiency from being lowered by a weak electric field, the charge amount of the developer is increased and the distance between the toner and the photosensitive member is increased. It is necessary to increase formality.

That is, in the conventional developer, at the time of development, the developing rate is lowered and the image density is lowered due to the insufficient charge amount, and the toner having a higher charge amount is consumed.
Since the so-called selective development occurs, a large amount of the developer having a relatively low charge amount remains on the developing sleeve, the particle size of the toner in the developing device becomes coarse, and the image quality deteriorates due to durability.

In addition, at the time of transfer, the transfer rate decreases due to insufficient charge amount, the image density decreases and the charge amount decreases, and it becomes difficult for the charge to be restricted by the electric field, so that the developer scatters due to transfer and the image quality deteriorates. Occurs.

On the other hand, due to the high image quality, the toner has been becoming finer. However, if the toner is made into fine particles, the charging of the toner received from the sleeve tends to be non-uniform, and particularly in a low humidity environment, the toner on the sleeve is unevenly spotted or rippled due to excessive charging of the toner. become. When this state worsens, it eventually appears as an image defect.

In order to clear these various problems, it is important to control the charge amount of the toner as high and uniform as possible and to improve the releasability between the toner and the photoconductor. Further, as will be described later, it is possible to prevent a decrease in toner charge amount and a decrease in toner fluidity in a high-temperature and high-humidity environment that may occur due to the structure of a copying machine currently required, and to maintain a stable image for a long time. It is important to.

As a method for stabilizing the charge amount, JP-A-58-66951, JP-A-59-168458 to 59-168460, and JP-A-59-170.
A method using conductive zinc oxide and tin oxide is disclosed in Japanese Patent No. 847, etc. Further, Japanese Patent Application Laid-Open No. 60-3260 discloses a method of using two kinds of inorganic powders to remove paper powder, ozone deposits, etc. generated or attached to the surface of the photoconductor. In addition, JP-A-2-110475
In the publication, two kinds of inorganic fine powders are used for a toner using a metal-crosslinked styrene-acrylic resin to remove paper powder, ozone adducts, etc. generated or adhered to the surface of a photoconductor, and under high temperature and high humidity. A method for improving toner scattering, image deletion, and image density reduction is disclosed. However, with these methods, it is difficult to reduce the image density by making the toner finer and then shortening the first copy time, which is currently required in the configuration of the copying machine.

Further, Japanese Patent Laid-Open No. 61-236559,
Japanese Unexamined Patent Publication No. 63-2073 discloses a method of improving the chargeability of toner by using cerium oxide particles. However, although these methods certainly improve the charging property, when an organic photoconductor is used, the surface layer of the photoconductor is gradually scraped by continuous copying due to the abrasive effect of cerium oxide. It causes deterioration. That is, as the toner becomes finer, the toner is uniformly charged, and the developer does not reduce the toner charge even when left standing for a long time under high temperature and high humidity, and provides a stable image for a long time. Long-awaited.

[0017]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic image which solves all the above problems.

An object of the present invention is to provide a toner for developing an electrostatic charge image, which can obtain a high image density from the beginning even in a high temperature and high humidity environment.

An object of the present invention is to provide a toner for developing an electrostatic charge image which can obtain a high image density even after being left in a high temperature and high humidity environment.

An object of the present invention is to provide a toner for developing an electrostatic charge image, in which fog generation is suppressed under low humidity.

An object of the present invention is to provide an electrostatic charge image developing toner capable of uniformly coating a toner on a sleeve even under low humidity.

An object of the present invention is to provide an electrostatic charge image developing toner capable of uniformly coating a toner on a developer carrying member and efficiently and uniformly tribocharging toner particles.

The object of the present invention is to stabilize the concentration from the beginning,
An object of the present invention is to provide a toner for developing an electrostatic charge image, which can stably obtain an image having a uniform density without fog or unevenness for a long period of time even under a low humidity and a high humidity.

An object of the present invention is to provide an electrostatic charge image developing toner which has a high fluidity, a high resolution, a high sharpness and forms an image faithful to an original.

An object of the present invention is to provide a toner for developing an electrostatic charge image which is uniform and free of roughness in halftone images and solid images.

An object of the present invention is to provide an electrostatic charge image developing toner which can stably maintain high image quality and high image density even when many copies are made under various environments.

[0027]

The present invention provides a toner for developing an electrostatic charge image comprising toner particles containing at least a binder resin and a colorant and an inorganic fine powder, wherein the inorganic fine powder has the following formula (1): ) [M ¹ ] _a [Si] _b O _c (1) [In the formula, M ¹ is Sr, Mg, Zn, Co, Mn and Ce.
Represents a metal element selected from the group consisting of, a represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents 3
Indicates an integer of -9. Composite oxide represented by] (A), and the following formula _{^{(2) [M 2] d}} [Ti] e O f (2) wherein, M ² is Sr, Mg, Zn, Co, Mn and Ce
Represents a metal element selected from the group consisting of, d represents an integer of 1 to 9, e represents an integer of 1 to 9, and f represents 3
Indicates an integer of -9. ] A toner for developing an electrostatic charge image, comprising fine particles containing the complex oxide (B) represented by the above and treated with a silane coupling agent.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The toner has a distribution of charge amount in the same manner as a distribution of particle size. In the case of a one-component toner, this distribution state is affected by the distribution state of the materials constituting the toner, such as the magnetic substance and the colorant, and the particle size distribution of the toner. When the materials constituting the toner are uniformly dispersed, the charge amount distribution is mainly affected by the particle size distribution of the toner.

Generally, a toner having a small particle size has a large charge amount, and a toner having a large particle size has a small charge amount. In addition, the distribution width of a toner having a larger charge amount is wider, and that of a toner having a smaller charge amount is narrower.

As a method of stabilizing the charge amount, a method of attaching conductive powder to the toner as described above has been already disclosed. However, this method cannot sufficiently satisfy the points of maximum image density and deterioration of image quality in continuous copying.

The reason for this is considered as follows.

In the method in which the conductive powder is attached to the toner to reduce the charge amount, more conductive powder is attached to the toner having a small particle size, that is, the toner having the large charge amount. Although the fog in the white background portion is improved by this, the toner having a small particle size is easily developed selectively because the charge amount is reduced. When this is fixed, the area covering the fixing support is smaller than that of the toner having a large particle size.
Its maximum image density is low. Further, since the toner having a small particle size is selectively developed, the toner particle size in the developing device is coarsely shifted during continuous copying, causing image deterioration with respect to the initial image.

On the contrary to the method of reducing the charge amount of the toner, the method of contact friction charging the toner and the metal oxide in the developing device can certainly increase the charge amount of the toner and make it uniform. it can. Further, the drum heater conventionally provided in the main body of the copying machine not only prevents dew condensation on the drum, but also has an effect of suppressing moisture absorption of toner in the developing device to some extent. However, in the system where the drum heater is deleted, which is increasing in demand, it is not possible to shorten the first copy time, that is, the operation to increase the charge amount of the toner in the developing device by using the wait time. Becomes noticeable. This is because the fluidity of the toner decreases as the toner becomes finer particles, and particularly under high temperature and high humidity, the fluidity and the charging property further decrease due to the moisture absorption of the toner. More specifically, in the conventional copying machine configuration,
By having a drum heater inside the main body to prevent dew condensation on the photosensitive drum, the temperature inside the copying machine was raised and the inside of the copying machine was also dried. As a result, the damage of the toner in the developing device due to moisture absorption is weaker than the actual environmental humidity. Further, since the heat fixing roller is used for the fixing method, the time from the start of the first copy, that is, the time until the fixing roller is heated to the predetermined fixing temperature from the power-on is effectively used, and the toner is set in the developing device. It was possible to impart fluidity and chargeability to some extent by stirring. However, in recent years, energy conservation has progressed as an approach to environmental problems, and the drum heater has been removed by changing the main body configuration to prevent condensation even under high humidity, so the damage to the toner inside the developing device is more severe under the same environment as before. Will be things. Further, the fixing device is improved and the heat-up time is shortened, and the heat-up time is 0 in the surf fixing device. In such a fixing method, since the agitation described above cannot be performed, the fluidity and chargeability of the toner cannot be imparted, so that the copy image has a low density and is poorly fogged. Further, the transfer is not sufficiently performed on the transfer paper, and there is a problem that an image is scattered when the fixing device enters the fixing device. Also, without a drum heater, when the machine is not used at night, the humidity inside the machine becomes the same as the humidity outside the machine. When the situation of use in the high humidity environment is overlapped, the charge amount of the toner is affected by humidity and is lowered, which promotes the above-mentioned problems.

In Japanese Patent Application Laid-Open No. 5-333590,
The present inventors have proposed a toner containing a metal oxide powder. If the metal oxide powder, which has a certain size to the toner, adheres to the toner and is separated due to the shearing force received in the developing device, the number of times of contact with the toner increases and the toner charge amount increases. can do. However, the metal oxide reduces the fluidity of the toner. Therefore, as described above, especially when a system excluding the drum heater or a surf fixing device is used, a sufficiently satisfactory copy image cannot be obtained under high temperature and high humidity.

The inventors of the present invention have made earnest studies and found the following.

(A) The abrasive has the effect of removing the paper powder, ozone deposits, etc. that adhere to or are generated on the drum, and the effect increases as the amount of addition increases. Particularly, in a system having no drum heater, the growth of deposits and the like on the drum under high temperature and high humidity is remarkable, and image defects such as image deletion and fog occur during continuous image formation. In order to suppress these, it is necessary to remove the deposits formed on the drum. That is, a substance having a polishing effect is essential in the toner. Moreover, the amount added is increased compared to the conventional one in order to correspond to the removal of the drum heater. When using cerium oxide or the like as an abrasive, in continuous image formation, it works to scrape off the drum surface, so it is essential to increase the amount. For a system without a drum heater,
Conventional abrasives cannot be used.

(B) When a complex oxide containing a Ti element is used, it is effective for removing deposits on the drum, and does not damage the drum surface even in continuous image formation. However, since the toner fluidity is also lowered at the same time, there is a problem with the charging property especially under high temperature and high humidity, and it cannot be said that the structure of a copying machine required in recent years can be sufficiently dealt with.

The fluidizing agent (c) not only achieves the intended improvement in the fluidity of the toner, but also improves the developability. This also affects the charging characteristics of the toner because the fluidizing agents that are commonly used at present (fluoride, SiO ₂ , surface-treated SiO _2, etc.) have polarity. From the viewpoint of image density, it is generally considered advantageous that the added amount is large. However, if the amount of addition is excessive, the degree of adhesion to the toner varies, and it becomes difficult to maintain uniform charging between toner particles, resulting in fog. In other words, it cannot be dealt with by increasing the addition amount of the fluidizing agent.

(D) The fluidity of the complex oxide itself can be improved by mixing the fluidizing agent into the complex oxide to be added before adding it to the toner. Further, by using this composite oxide, it is possible to prevent deterioration of toner fluidity under high temperature and high humidity. However, the charge imparting ability itself due to contact frictional electrification with the toner, which is the original purpose, is deteriorated, and problems such as a decrease in image density and fog occur. This is because, in addition to the contact triboelectric charging that originally occurs between the toner and the complex oxide, the transfer of charge between the fluidizing agent and the complex oxide occurs. Will be smaller than. As a result, the developability deteriorates, and the image density decreases and fog occurs. That is, addition of a fluidizing agent to the composite oxide cannot be applied.

Therefore, the present inventors provide a toner with an appropriate polishing effect, obtain a high charge amount by contact triboelectric charging with the toner without impairing the fluidity of the toner, and maintain a high transfer property. As a result of an examination based on the idea that they can continue to do so, they found the following.

In the method of increasing the charge amount by contacting the toner with the composite oxide, that is, the method of contact triboelectrifying the toner and the composite oxide in the developing device instead of adhering the composite oxide to the toner, By using the composite oxide (B) containing Ti, the toner has a polishing effect, and by using the composite oxide (A) containing Si, the fluidity of the toner is improved, and (A) and ( It has been found that by treating the inorganic fine powder composed of the complex oxide of B) with a silane coupling agent, high chargeability can be continuously imparted to the toner even in an environment of extremely high humidity.

Further, the toner of the present invention is capable of obtaining a high charge amount, and is generated during continuous image formation by removing deposits growing on the drum even under severe conditions of high temperature and high humidity. It has been found that high image density can be obtained while preventing image deletion and image quality deterioration.

Specifically, by mixing and using a compound oxide containing Si element and a compound oxide containing Ti element, the polishing effect of the toner and the fluidity of the toner are obtained. Improves. This is considered to be due to the fact that silica has excellent fluidity and is due to the polishing property of titanium, as silica is generally used as a fluidizing agent. Also,
The complex oxide containing Si has a high charge imparting ability even in the contact triboelectric charging with the toner and increases the toner charge amount. For this reason, even under high temperature and high humidity, it is possible to increase the charge amount while preventing the fluidity of the toner from decreasing and the number of contact with the toner being small. However, since the polishing effect of the above-mentioned compound oxide containing Si element is low, it is less effective for removing the deposits on the drum in the system without a drum heater, and this is compensated by the compound oxide containing Ti element. As a result, it has become clear that it is possible to cope with the need for a drum heater, which is a copying machine configuration required in recent years, and a reduction in the first copy time. Furthermore, by treating the above-mentioned inorganic fine powder containing two kinds of complex oxides with a silane coupling agent, high developability can be obtained for a long period of time even in an extremely harsh situation such as use in a high humidity environment without a drum heater. It was also found that it is possible to maintain the image quality.

From the above, even under a high temperature and high humidity condition, even for a copying machine structure having no drum heater inside the main body, a sufficient polishing effect can be obtained without being affected by deposits and the like growing on the photosensitive drum. And a composite oxide (B) which does not damage the drum surface and which has a higher charge imparting ability in contact triboelectric charging by imparting high fluidity to the toner. Inorganic fine powder is treated with a silane coupling agent to maintain high developability and image quality in all copier configurations (for example, copier configurations such as drum heaterless) and in all environments, especially in harsh high humidity environments. It is important to.

Further, the constitution of the developer preferable for achieving the object in the invention will be described in detail below.

In the composite oxide (A) used in the present invention, examples of M ¹ include magnesium, zinc, cobalt, manganese, strontium and cerium. In particular, strontium silicate (SrSiO ₃ ) is preferable as the composite oxide (A) because the effects of the present invention can be exhibited more effectively.

In the composite oxide (B) used in the present invention, examples of M ² include magnesium, zinc, cobalt, manganese, strontium and cerium. In particular, the composite oxide (B) is preferably strontium titanate (SrTiO ₃ ) because the effect of the present invention can be more exerted.

Further, in order to further exert the effect of the present invention, the molar ratio of the composite oxides (A) and (B) is (A).
/ (B) = 5/95 to 95/5 is preferable, and (A) / (B) = 20/80 to 80/20 is more preferable. If (A) / (B) is less than 5/95, problems such as fog and a decrease in image density after long-term storage may occur.
If it is larger than 5/5, a proper polishing property for removing the drum deposit cannot be obtained.

The inorganic fine powder before the treatment with the silane coupling agent used in the present invention is, for example, produced by a sintering method, mechanically pulverized, and then air-classified to have a desired particle size distribution. In order to further exert the effects of the present invention, it is preferable to mix the composite oxides (A) and (B) at the manufacturing stage in the sintering method.

The silane coupling agent used in the present invention has a general formula

[0051]

[Chemical 1] And, for example, typically dimethyldichlorosilane, trimethylchlorosilane, allyldimethylchlorosilane, hexamethyldisilazane, allylphenyldichlorosilane, benzyldimethylchlorosilane, vinyltriethoxysilane, γ-methacryloxypropyl. Examples thereof include trimethoxysilane, vinyltriacetoxysilane, divinylchlorosilane, dimethylvinylchlorosilane and the like. In addition, a silane compound substituted with a fluorine group or an amino group is also used.

The treatment of the above-mentioned inorganic fine powder with a silane coupling agent is a dry treatment of reacting the vaporized silane coupling agent with a cloud of the inorganic fine powder by stirring or dispersing the fine silicic acid powder in a solvent. The treatment can be performed by a generally known method such as a wet method in which a silane coupling agent is dropped.

The amount of the silane coupling agent used is
0.05 to 50 parts by weight, preferably 1 to 4 parts by weight based on 100 parts by weight of the inorganic fine powder containing the composite oxides (A) and (B).
It is preferable to use 0 part by weight. If it is less than 0.05 parts by weight, it is insufficient to improve the moisture resistance in a severe environment where the humidity exceeds 80%, and it is not sufficient from the viewpoint of maintaining the image density.
On the other hand, when the amount exceeds 50 parts by weight, aggregates are generated and the treatment becomes non-uniform, so that the fluidity of the toner is lowered and the image density is lowered under high temperature and high humidity.

Complex oxides (A) and (B) in the present invention
The fine particles obtained by treating the inorganic fine powder containing silane with a silane coupling agent have an amount of 0.05 to 100 parts by weight of the toner particles.
It is preferable to use 15 parts by weight, preferably 0.1 to 5.0 parts by weight.

That is, if less than 0.05 parts by weight,
Phenomenon such as deterioration of image density under high temperature and high humidity and deterioration of fog due to non-uniformity of toner coat property on sleeve under low temperature and low humidity occurs, and image density and image quality are maintained for a long period of time in all environments. However, the improvement in image characteristics, which is the object of the present invention, is not achieved. On the other hand, if the amount is more than 15 parts by weight, the charging of the toner itself from the sleeve is hindered and problems such as fog generation and density reduction occur.

The composite oxide (A) used in the present invention,
The inorganic fine powder containing (B) is treated with a silane coupling agent at the same time as or after being treated with a silane coupling agent in order to prevent roller electrification for ozone-less correspondence and prevention of voids in transfer or filming in a composite machine configuration using roller transfer. Treatment with oil is also one of the preferable forms.

The silicone oil is generally represented by the following formula.

[0058]

[Chemical 2]

A preferred silicone oil is 25
A viscosity of about 10 to 1000 centistokes at 0 ° C. is used. A silicone oil having a too low molecular weight may generate a rare component due to heat treatment or the like, and if the molecular weight is too high, the viscosity becomes too high and the treatment operation becomes difficult. Preferred types of silicone oil include, for example, methyl silicone oil, dimethyl silicone oil, phenylmethyl silicone oil, chlorophenylmethyl silicone oil, alkyl-modified silicone oil, fatty acid-modified silicone oil, polyoxyalkyl-modified silicone oil, and the like.

In the present invention, the silicone oil may be a modified silicone oil having an organo group having at least one nitrogen atom in the side chain, for example, a silicone oil having at least a partial structure represented by the following formula. Can be used.

[0061]

[Chemical 3] (In the formula, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, R ₃ and R ₄ represent hydrogen, an alkyl group or an aryl group, and R ₅ represents The above-mentioned alkyl group, aryl group, alkylene group and phenylene group, which represent a nitrogen-containing heterocyclic group, may have an organo group having a nitrogen atom, or may have a substituent such as halogen.

As a method for treating silicone oil, a known technique is used. For example, the inorganic fine powder and the silicone oil may be directly mixed by using a mixer such as a Henschel mixer, or the inorganic fine powder may be sprayed with the silicone oil. It depends on the method. Alternatively, it may be produced by dissolving or dispersing silicone oil in a suitable solvent, mixing with inorganic fine powder, and then removing the solvent.

Examples of the binder resin used in the present invention include vinyl resins, polyester resins and epoxy resins. Among them, vinyl resins and polyester resins are more preferable in terms of charging property and fixing property.

Examples of vinyl resins include styrene and
o-methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene,
p-ethylstyrene, 2,4-dimethylstyrene, p-
n-butyl styrene, p-tert-butyl styrene,
Styrene and its derivatives such as pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene; ethylene, propylene, butylene, isobutylene and the like. Ethylenically unsaturated monoolefins; unsaturated polyenes such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride; vinyl ester acids such as vinyl acetate, vinyl propionate, vinyl benzoate Methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n methacrylate
-Octyl, dodecyl methacrylate, 2-methacrylic acid
Α-Methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate Acrylic acid esters such as propyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate;
Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole,
N-vinyl compounds such as N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; esters of α, β-unsaturated acids, diesters of dibasic acids. . These vinyl monomers are used alone or in combination of two or more.

Among these, a combination of monomers which is a styrene copolymer or a styrene-acrylic copolymer is preferable.

Further, it may be a polymer cross-linked with a cross-linking monomer as exemplified below, if necessary.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol acrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, and the above compounds The acrylates of the above are replaced by methacrylates; examples of the diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, and polyethylene glycol. # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and the acrylates of the above compounds are meta-acryed. Include those obtained by changing the over preparative; e.g. diacrylate compounds linked with a chain containing an aromatic group and an ether bond, polyoxyethylene (2)
-2,2-bis (4-hydroxyphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydroxyphenyl) propane diacrylate, and acrylates of the above compounds were replaced with methacrylate. Examples thereof include polyester type diacrylate compounds such as trade name MANDA (Nippon Kayaku Co., Ltd.). As the polyfunctional crosslinking agent, pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate,
Oligoester acrylates and those obtained by replacing the acrylates of the above compounds with methacrylates; triallyl cyanurate and triallyl trimellitate.

These cross-linking agents are used as the other monomer component 10
0.01 to 5 parts by weight (more preferably 0.03 to 3 parts by weight) can be used with respect to 0 parts by weight.

Among these crosslinkable monomers, those which are preferably used in the resin for toner from the viewpoints of fixability and anti-offset property are aromatic divinyl compounds (particularly divinylbenzene), chains containing an aromatic group and an ether bond. Examples of the diacrylate compounds bound by

In the present invention, a vinyl monomer homopolymer or copolymer, polyester, polyurethane,
Epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, etc. may be mixed with the above-mentioned binder resin, if necessary. it can.

When two or more kinds of resins are mixed and used as a binder resin, as a more preferable form, it is preferable to mix resins having different molecular weights in an appropriate ratio.

The glass transition temperature of this binder resin is 45-8.
0 ° C., preferably 55 to 70 ° C., number average molecular weight M
n 2,500 to 50,000, weight average molecular weight Mw1
It is preferably from 50,000 to 1,000,000.

The method for synthesizing the vinyl binder resin according to the present invention includes bulk polymerization, solution polymerization, suspension polymerization,
A polymerization method such as an emulsion polymerization method can be used. When using a carboxylic acid monomer or an acid anhydride monomer, it is preferable to use a bulk polymerization method or a solution polymerization method in view of the properties of the monomer.

The following method can be given as an example.
A vinyl copolymer can be obtained by a bulk polymerization method or a solution polymerization method using a monomer such as a dicarboxylic acid, a dicarboxylic acid anhydride, or a dicarboxylic acid monoester. In the solution polymerization method, the dicarboxylic acid and dicarboxylic acid monoester units can be partially dehydrated by devising the distillation conditions when the solvent is distilled off. Further, the vinyl-based copolymer obtained by the bulk polymerization method or the solution polymerization method is subjected to heat treatment, so that it can be further dehydrated. It is also possible to partially esterify the acid anhydride with a compound such as an alcohol.

On the contrary, the vinyl copolymer thus obtained can be partially hydrolyzed to form a dicarboxylic acid by ring-opening the acid anhydride group.

On the other hand, using a dicarboxylic acid monoester monomer, a vinyl-based copolymer obtained by a suspension polymerization method or an emulsion polymerization method is dehydrated from the anhydride by dehydration by heat treatment and ring opening by hydrolysis treatment. Obtainable. The vinyl copolymer obtained by the bulk polymerization method or the solution polymerization method is dissolved in a monomer, and then by a suspension polymerization method or an emulsion polymerization method, a method of obtaining a vinyl polymer or a copolymer is used, A part of the acid anhydride can be opened to obtain a dicarboxylic acid unit. Another resin may be mixed in the monomer during the polymerization, and the obtained resin can be subjected to an acid anhydride treatment by a heat treatment and an esterification treatment by a ring-opening alcohol treatment of the acid anhydride by a weak alkaline water treatment.

Since the dicarboxylic acid and dicarboxylic acid anhydride monomers have strong alternating polymerizability, the following method is preferable in order to obtain a vinyl copolymer in which functional groups such as anhydride and dicarboxylic acid are randomly dispersed. one of. This is a method in which a vinyl-based copolymer is obtained by a solution polymerization method using a dicarboxylic acid monoester monomer, the vinyl-based copolymer is dissolved in the monomer, and a binder resin is obtained by a suspension polymerization method. In this method, all or the dicarboxylic acid monoester portion can be dealcoholized and ring-closed and dehydrated depending on the treatment conditions when the solvent is distilled off after the solution polymerization to obtain an acid anhydride. During suspension polymerization, the acid anhydride group undergoes ring opening by hydrolysis to give a dicarboxylic acid.

In the acid anhydride formation in the polymer, the infrared absorption of carbonyl shifts to the higher wave number side than that of the acid or ester, so that the formation or disappearance of the acid anhydride can be confirmed.

In the binder resin thus obtained, the carboxyl group, the anhydride group and the dicarboxylic acid group are uniformly dispersed in the binder resin, so that the toner can be provided with a good charging property.

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,
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, and (a)
A bisphenol derivative represented by the formula;

[0083]

[Chemical 4]

Further, diols represented by the formula (b):

[0085]

[Chemical 5] And diols such as glycerin, sorbit, sorbitan, and the like.

As the divalent carboxylic acid containing 50 mol% or more in all the acid components, benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides; succinic acid, adipic acid, sebacine Acids, alkyl dicarboxylic acids such as azelaic acid or anhydrides thereof, and succinic acid substituted by an alkyl group having 6 to 18 carbon atoms or anhydrides thereof; fumaric acid, maleic acid, citraconic acid, itaconic acid, or the like. Examples thereof include saturated dicarboxylic acids and anhydrides thereof, and examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and anhydrides thereof.

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 (a), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, and succinic acid. , N-dodecenyl succinic acid or its anhydride, dicarboxylic acids such as fumaric acid, maleic acid and maleic anhydride; trimellitic acid or its tricarboxylic acid anhydride.

This is because the polyester resin obtained from these acids and alcohols has good fixability as a heat roller fixing toner and excellent offset resistance.

The acid value is 90 or less, preferably 50.
Hereinafter, the OH value is preferably 50 or less, and more preferably 30 or less. This is because when the number of terminal groups of the molecular chain is increased, the toner depends on the environment for the charging characteristics of the toner.

Further, the glass transition temperature of the polyester resin obtained here is 50 to 75 ° C, preferably 55 to 65 ° C.
C., and number average molecular weight Mn 1,500 to 50,000
Preferably 2,000-20,000, weight average molecular weight Mw 6,000-100,000, preferably 10,000.
It is preferably 0 to 90,000.

In the toner for developing an electrostatic charge image of the present invention, a charge control agent can be used, if necessary, in order to further stabilize the chargeability thereof. The charge control agent is the binder resin 100.
0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight
It is preferred to use parts by weight.

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

To control the toner to be negatively charged,
For example, organic metal complexes and chelate compounds are effective. Examples thereof include monoazo metal complexes, aromatic hydroxycarboxylic acids, metal complexes, and aromatic dicarboxylic acid-based metal complexes. In addition, aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters,
Examples thereof include phenol derivatives of bisphenol.

The following substances are used to control the toner to have a positive chargeability.

Modified products of nigrosine and fatty acid metal salts and the like; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate,
And onium salts such as phosphonium salts and the like, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid) , Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxide such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin borate. Such as diorgano tin borate; guanidine compound, imidazole compound. These can be used alone or in combination of two or more.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxides such as magnetite, maghemite and ferrite, and iron oxides containing other metal oxides; Fe, Co and Ni. Like metals, or these metals and Al, Co, Cu, P
b, Mg, Ni, Sn, Zn, Sb, Be, Bi, C
Examples thereof include alloys with metals such as d, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

Conventionally, as a magnetic material, ferrosoferric oxide (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 gadolinium oxide (Gd ₃ Fe ₅ —O ₁₂ ), iron oxide copper (CuF)
e ₂ O ₄ ), lead iron oxide (PbFe ₁₂ —O ₁₉ ), iron nickel oxide (NiFe ₂ O ₄ ), iron neodymium oxide (NdFe)
₂ O ₃ ), iron oxide barium (BaFe ₁₂ O ₁₉ ), iron oxide magnesium (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), lanthanum iron oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known, but according to the present invention, the above magnetic materials are used alone or in combination of two or more kinds. Particularly suitable magnetic materials for the purposes of the invention are fine powders of ferric tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic characteristics under application of 795.8 kA / m are coercive force of 1.6 to 12.0 kA / m and saturation magnetization of 50 to 200 A.
m ² / kg (preferably 50 to 100 Am ² / kg) and residual magnetization of ^{2 to 20} Am ² / kg are desirable.

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.

Colorants that can be used in the toner of the present invention include any suitable pigment or dye.

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. It is preferable to use the pigment in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the binder resin. Similarly, a dye is used as a colorant. For example, there are anthraquinone dyes, xanthene dyes, and methine dyes, and it is preferable to use 0.1 to 20 parts by weight, preferably 0.3 to 10 parts by weight of dye per 100 parts by weight of the binder resin.

In the present invention, one or more releasing agents may be contained in the toner particles, if desired.

Examples of the releasing agent used in the present invention include the following. Aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, paraffin wax, and oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax, or block copolymers thereof; carnauba Examples thereof include waxes containing a fatty acid ester as a main component such as wax, sazol wax, and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid ester such as deoxidized carnauba wax.
Further, saturated linear fatty acids such as palmitic acid, stearic acid, and montanic acid, unsaturated fatty acids such as brassic acid, eleostearic acid, and vinalinaric acid, stearyl alcohol, aralkyl alcohol, behenyl alcohol, carnaubayl alcohol, ceryl. Alcohol, saturated alcohols such as melysyl alcohol, long-chain alkyl alcohols, 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 amide, and other saturated fatty acid bisamides, ethylenebis Oleic acid amide, hexamethylenebisoleic acid amide,
Unsaturated fatty acid amides such as N, N'-dioleyl adipamide, N, N'-dioleyl sebacic acid amide, m-xylene bisstearic acid amide, N, N'-
Aromatic bisamides such as distearylisophthalic acid amide, fatty acid metal salts (commonly called metal soap) such as calcium stearate, calcium laurate, zinc stearate, magnesium stearate, and aliphatic hydrocarbon wax Waxes grafted with vinyl monomers such as styrene and acrylic acid, partial esterification products of fatty acids and polyhydric alcohols such as behenic acid monoglyceride,
Examples thereof include a hydroxyl group-containing methyl ester compound obtained by hydrogenation of vegetable oils and the like.

The amount of the releasing agent used in the present invention is 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the binder resin.

Further, 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 externally adding it to the toner particles by comparing the fluidity before and after the addition. For example, vinylidene fluoride fine powder, fluororesin powder such as polytetrafluoroethylene fine powder, wet process silica,
There are finely powdered silica such as dry process silica, and treated silica obtained by subjecting the silica to a surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil or the like.

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, it is also possible to obtain a fine composite powder of silica and another metal oxide by using another metal halogen compound such as aluminum chloride or titanium chloride together with a silicon halogen compound. Also includes. The particle size is preferably in the range of 0.001 to 2 μm as an average primary particle size, and particularly preferably, silica fine powder in the range of 0.002 to 0.2 μm is used. .

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

[0111]   AEROSIL (Japan Aerosil Co., Ltd.) 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     (WACKER-CHEMIE GMBH company) N20E                                                       T30                                                       T40   D-C Fine Silica (Dow Corning Co.)   Francol (Fransil)

Furthermore, 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
For example, there is dimethylpolysiloxane having siloxane units and each terminal unit having a hydroxyl group bonded to Si. These are used alone or as a mixture of two or more.

The fluidizing agent used in the present invention has a specific surface area of 30 m ² / g or more, preferably 50 m ² / g or more by nitrogen adsorption measured by the BET method, which gives good results. Fluidizing agent 0.01 per 100 parts by weight of toner
-8 parts by weight, preferably 0.1-4 parts by weight.

Next, a method for measuring various physical property data measured in the following examples will be described below.

[0117]   (1) X-ray diffraction measurement   Device used: X-ray diffractometer CN2013 (Rigaku Denki Co., Ltd.)           : Powder sample molding machine PX-700

The sample to be measured is compression-pressed using the above-mentioned molding apparatus. Set the molded sample in the X-ray diffractometer,
Measure under the following conditions. The structure is determined from the peak intensity of the obtained X-ray diffraction pattern and the 2θ angle.

[0119]   Target, Filter Cu, Ni   Voltage, Current 32.5kV, 15mA   Counter Sc   Time Constant 1sec   Divergence Slit 1 °   Receiving Slit 0.15mm   Scatter Slit 1 °   Angle Range 60-20 °

[0120]   (2) Method for quantifying complex oxide in toner   Device used: X-ray fluorescence analyzer 3080 (Rigaku Denki Co., Ltd.)           : Sample press molding machine

Preparation of calibration curve The magnetic oxide (X) was mixed with a complex oxide for quantitative determination in a coffee mill at the following ratios (% by weight).
Create a sample for the calibration curve.

0%, 0.5%, 1.0%, 2.0%,
3.0%, 5.0%, 10.0%

Sample 7 was prepared using a sample press molding machine.
Press molding the points. The K _α peak angle (a) of [M] in the composite oxide is determined from the 2θ table. The calibration curve sample is put into the X-ray fluorescence analyzer, and the sample chamber is decompressed and evacuated.

Under the following conditions, the X-ray intensity of each sample is obtained and a calibration curve is prepared.

[Measurement conditions] Measurement potential, voltage 50kV-50mA 2θ angle a Crystal plate LiF Measurement time 60 seconds

After forming a sample by the same method as the quantitative determination of the complex oxide in the toner, the X-ray intensity is obtained under the same measurement conditions, and the addition amount is calculated from the calibration curve.

(3) Measurement of particle size distribution The particle size distribution can be measured by various methods, but in the present invention, it was measured using a Coulter counter multisizer.

That is, a Coulter counter Multisizer II (manufactured by Coulter) was used as a measuring device, and an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution and a CX-1 personal computer (manufactured by Canon) were connected. Then, as the electrolytic solution, a 1% NaCl aqueous solution is prepared by using special grade or primary grade sodium chloride. As a measuring method, a surfactant, preferably 0.1 to 5 ml of alkylbenzene sulfonate is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2
Add ~ 20 mg. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment for about 1 to 3 minutes with an ultrasonic disperser, and a 100 μm aperture is used when measuring the toner particle size as an aperture by the Multisizer II type Coulter Counter. 13μ when measuring the particle size of inorganic fine powder
Measurement is performed using the m aperture. The volume and number of the toner and the inorganic fine powder were measured, and the volume distribution and the number distribution were calculated. Then, the weight-based weight average diameter obtained from the volume distribution according to the present invention is obtained.

(4) Measurement of acid value in vinyl resin The qualitative and quantitative determination of the functional group in the binder resin is carried out by infrared absorption spectrum, acid value measurement according to JIS K-0707, and hydrolysis acid value measurement (total acid value measurement). ) Is applied as an example.

For example, in the infrared absorption, 1780 cm ^-1
The presence of the acid anhydride is confirmed because an absorption peak derived from the carbonyl of the anhydride in the vicinity appears.

In the present invention, the peak of the infrared absorption spectrum refers to a peak clearly confirmed as a peak after 16 times integration by FT-IR with a resolution of 4 cm ^-1 . F
As a model of T-IR, for example, FT-IR1600
(Manufactured by Perkin Elmer).

Acid value measurement according to JIS K-0070 (hereinafter referred to as J
IS acid value), the acid anhydride is about 50% of the theoretical value (the acid anhydride has an acid value as a dicarboxylic acid).
Is measured.

On the other hand, in the measurement of the total acid value (a), a value substantially in accordance with the theoretical value is measured. Therefore, the difference between the total acid value (a) and the JIS acid value is about 50% of the theoretical value, and the acid anhydride is measured as a dibasic acid. Therefore, the total acid value derived from the acid anhydride per 1 g ( b) is required.

[0134] Total acid value (b) = [total acid value (a) -JIS acid value] x 2

Further, for example, when a maleic acid monoester is used as an acid component and a vinyl copolymer composition used as a binder resin is prepared by a solution polymerization method or a suspension polymerization method, the solution polymerization method is used. The total acid value (b) was measured by measuring the total acid value (a) of the JIS acid value of the produced vinyl-based copolymer, and the total acid value (b) and the vinyl used in the solution polymerization method. The amount of acid anhydride generated in the polymerization step and the solvent removal step from the composition ratio of the system monomer (for example,
Mol%) is calculated. Furthermore, the vinyl copolymer prepared by the solution polymerization method is dissolved in a monomer such as styrene and butyl acrylate to prepare a monomer composition, and the prepared monomer composition is suspension polymerized. At that time, a part of the acid anhydride group is opened. Based on JIS acid value, total acid value (a), monomer composition ratio of vinyl copolymer composition obtained by suspension polymerization method and addition amount of vinyl copolymer prepared by solution polymerization method, binding The amount of the dicarboxylic acid group, acid anhydride group and dicarboxylic acid monoester group present in the vinyl copolymer composition used as the resin can be calculated.

The total acid value (a) of the binder resin is determined as follows. 30 g of dioxane with 2 g of sample resin
And 10 ml of pyridine, 20 mg of dimethylaminopyridine and 3.5 ml of water are added thereto, and the mixture is heated under reflux for 4 hours with stirring. After cooling, 1/10 N KOH
The acid value obtained by neutralization titration with a solution of phenolphthalein in a THF solution is taken as the total acid value (a). Under the condition of measuring the total acid value (a), the acid anhydride group is hydrolyzed to a dicarboxylic acid, but the acrylic acid ester group, the methacrylic acid ester group and the dicarboxylic acid monoester group are not hydrolyzed.

The 1/10 N KOH.THF solution is prepared as follows. 1.5 g of KOH is dissolved in about 3 ml of water, and 200 ml of THF and 30 ml of water are added and stirred. If the solution is separated after standing, use a small amount of methanol,
If the solution is cloudy, add a small amount of water to make a homogeneous clear solution. Standardize the measured value of the KOH / THF solution with a 1/10 N HCl standard solution.

The total acid value (a) in the binder resin is 2 to 100.
Although it is mgKOH / g, the acid value according to JIS K-0070 of the vinyl-based copolymer containing the acid component in the binder resin is 1
It is preferably less than 00. JIS K-0070
When the acid value is 100 or more, a carboxyl group,
Since the density of functional groups such as acid anhydride groups is high, it becomes difficult to obtain a good charge balance, and when diluted and used, problems due to the dispersibility thereof tend to occur.

(5) Method for Measuring Acid Value of Polyester Resin The acid value is defined as the number of milligrams of potash of potassium necessary to neutralize the carboxyl groups contained in 1 g of the resin. Therefore, the acid value indicates the number of terminal groups. The measuring method is as follows.

200 to 300 ml of 2 to 10 g of sample
Weigh in an Erlenmeyer flask and methanol: toluene = 3
The resin is dissolved by adding about 50 ml of a mixed solvent of 0:70.
A small amount of acetone may be added if the solubility is poor. N / 1 pre-standardized using a mixed indicator of 0.1% bromthymol blue and phenol red
Titrate with 0-potassium-alcohol solution, and calculate the acid value from the consumption of the alcohol potash by the following calculation.

[0141] Acid value = KOH (number of ml) × N × 56.1 / sample weight (However, N is a factor of N / 10KOH)

(6) Glass transition temperature Tg In the present invention, the measurement is carried out using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by Perkin Elmer).

The 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 of 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.

(7) Measurement of toner charge amount (FIG. 2) Conductor of 500 mesh (which can be appropriately changed to a size where magnetic particles do not pass) on the bottom after weighing the developer sampled from the developer carrier of the developing device A measurement sample is put in a metal measuring container 2 having a permeable screen 3 and a metal lid 4 is placed on it. At this time, weigh the entire measuring container 2 W ₁ (g)
And Next, in the suction device 1 (at least the portion in contact with the measurement container 2 is an insulator), suction is performed from the suction port 7 to adjust the air volume control valve 6 to adjust the pressure of the vacuum gauge 5 to 250 mmAq. In this state, suction is sufficiently performed (for about 2 minutes) to remove the toner by suction. The potential of the electrometer 9 at this time is V (volt). Here, 8 is a condenser, and the capacity is C
(ΜF). The weight of the entire measuring container after suction is weighed and is W ₂ (g). This triboelectric charge amount T (mC / k
g) is calculated by the following formula.

T (mC / kg) = (C × V) / (W ₁ −W ₂ ).

[0149]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples. This does not limit the invention in any way.

(Production Example 1 of Complex Oxide: Silane Coupling Fine Particles Containing Strontium Silicate and Strontium Titanate) Strontium Carbonate 1500
g, 180 g of silicon oxide, and 560 g of titanium oxide were wet mixed in a ball mill for 8 hours, filtered and dried, and the mixture was molded at a pressure of 5 kg / cm ² at 8 ° C. at 1300 ° C.
I calcined for an hour. This is mechanically pulverized to have a weight average diameter of 2.
Strontium silicate (SrSiO ₃ ) and strontium titanate (SrTi) having a diameter of 2 μm and a number average diameter of 1.1 μm
O ₃₎ and to obtain inorganic fine powder (M-0) having a. next,
100 parts by weight of this inorganic fine powder is dispersed in methanol,
10 parts by weight of γ-aminopropyltriethoxysilane was added dropwise thereto, and the mixture was stirred for 2 hours, filtered, and dried at 130 ° C. for 6 hours.
It was dried for an hour and crushed to obtain fine particles (M-1). Further, X-ray diffraction was carried out on the obtained (M-0), and from the peak pattern of FIG.
It was confirmed that 1, b = 1, c = 3, d = 1, e = 1 and f = 3.

Further, quantitative analysis of Si and Ti was carried out by fluorescent X-ray analysis to confirm the ratio.

(Production Examples 2 to 8 of Composite Oxide: Silane-Coupling Fine Particles Containing Strontium Silicate and Strontium Titanate) In Production Example 1 of composite oxide, the molar ratio of strontium silicate to strontium titanate was 3/97, 6/94, 20/80, 70/3
The mixing amount was adjusted so that it became 0, 80/20, 94/6, 97/3, and the weight average diameter of 1.8 to
An inorganic fine powder containing strontium silicate and strontium titanate having a number average diameter of 2.3 μm and a number average diameter of 0.9 to 1.2 μm was obtained, and subjected to the same silane coupling treatment as in Production Example 1 to obtain fine particles (M-2 to M). -8) was obtained.

(Production Examples 9 to 14 of Composite Oxide) The addition amount of the silane coupling agent in Production Example 1 of the composite oxide was 0.03 parts by weight and 0.5 parts by weight based on 100 parts by weight of the inorganic fine powder.
Parts by weight, 1.2 parts by weight, 30 parts by weight, 48 parts by weight, 55
Fine particles (M-9 to
M-14) was obtained.

(Comparative Production Example of Composite Oxide 1: Strontium Titanate Treated by Silane Coupling) 600 g of strontium carbonate and 320 g of titanium oxide were wet mixed in a ball mill for 8 hours, filtered and dried, and 5 kg of this mixture was added. It was molded at a pressure of / cm ² and calcined at 1100 ° C. for 8 hours. This was mechanically pulverized to obtain strontium titanate fine powder (M-15) having a weight average diameter of 1.9 μm and a number average diameter of 1.1 μm, which was subjected to the silane coupling treatment in the same manner as in Production Example 1.

(Comparative Production Example 2 of Composite Oxide: Strontium Titanate Titanium Silicate Containing Silane Coupling) Silane Coupling Treated Strontium Titanate Fine Powder Produced in the Same manner as Comparative Production Example 1 of Composite Metal Oxide 475g and commercial reagent silicon oxide (oil absorption 236ml
/ 100 g, apparent specific gravity 0.18 g / ml) 25 g were mixed in a coffee mill, and silane coupling treated strontium titanate fine powder (M-1) containing 5% by weight of silicon oxide.
6) was obtained.

(Comparative Production Example 3 of Complex Oxide: Cerium Oxide Treated with Silane Coupling) 1500 g of cerium carbonate was burned in the presence of oxygen at 1300 ° C. for 10 hours. This was mechanically pulverized and subjected to the same silane coupling treatment as in Production Example 1 to obtain a weight average diameter of 2.0 μm and a number average diameter of 1.1.
A cerium oxide fine powder (M-17) having a size of μm was obtained.

[Example 1] Binder resin (polyester resin) 100 parts by weight (Tg 60 ° C, acid value 20 mgKOH / g, hydroxyl value 30 mgKOH / g, molecular weight: Mp7000, Mn3000, Mw55000) Magnetic iron oxide 90 parts by weight (average) particle size 0.15 [mu] m, 795.8 kA / m characteristic at magnetic field Hc = 9.2kA / m, σs = 83Am 2 /kg,σr=11.5Am 2 / kg) monoazo metal complex (negative charge control agent) 1 Parts by weight polyethylene 3 parts by weight

After the above materials were mixed by a Henschel mixer, melt kneading was carried out at 130 ° C. by a twin-screw kneading extruder, the kneaded product was cooled, coarsely pulverized by a cutter mill, and finely pulverized by a jet stream. The toner was pulverized and further classified using an air classifier to obtain magnetic toner particles (X) having a weight average diameter of 6.5 μm.

To 100 parts by weight of the magnetic toner particles (X), 1 part of hydrophobic silica (specific surface area of 200 m ² / g) was added.
The magnetic toner for evaluation (X-
1).

(Evaluation-1) 1 kg of toner at the stage of coarse crushing with a cutter mill after melt kneading in the process of producing the magnetic toner particles (X) produced in Example 1 was passed through a 60 mesh (opening diameter 250 μm) pass, 100 Mesh (opening diameter 150
µm) Sieve on, carrier for tribo measurement (C)
Was produced.

A composite oxide was prepared in the production example (M-1).
After weighing 0.50 g of each of (M-17) in 50 ml of polybin, the mixture is left to stand in an open system for 24 hours in a room temperature and humidity room (23.5 ° C., 60%). Carrier (C)
After adding 9.50 g of each of the above to each of the polybins, the mixture was sealed and shaken and mixed for 2 minutes (about 120 times).

The charge amount of the measurement sample produced by the above operation is measured by the same method as the toner charge amount measurement (the charge imparting ability to the toner is preferably larger on the plus side). The results are shown in Table 3.

Further, the following items were evaluated using the evaluation toner (X-1).

(Evaluation-2) The evaluation toner (X-1) is left overnight (12 hours or more) in a high temperature and high humidity chamber (35 ° C., 85%). Using a Canon copier NP6060 modified machine (without drum heater), 250,000 images are output, and image deletion and drum scraping are evaluated. The evaluation level of image deletion was determined by measuring the area of the image missing portion. (The smaller the value, the better)

◎: Area on image 0 cm ² ○: Area on image 0.01 to 0.25 cm ² ○ △: Area on image 0.26 to 2.0 cm ² △: Area on image 2.1 to 5.0 cm ² ×: image on area 5.1~10.0cm ² ××: image on an area 10.1 cm ² or more

[0166] ◎: Abrasion amount of drum 0-5.0Å ○: Drum abrasion amount 5.1 to 10.0Å ○ △: Abrasion amount of drum 10.1 to 15.0Å △: Drum abrasion amount 15.1 to 20.0Å ×: Abrasion amount of drum 20.1 to 25.0Å XX: Abrasion amount of drum 25.1 Å or more

(Evaluation-3) 150 g of the evaluation toner (X-1) was put in a developing device and kept in a room temperature and normal humidity chamber (23 ° C., 60%).
Let stand overnight (12 hours or more). Canon Copier N
Using a modified P6030 machine (without drum heater, changing the fixing heat roll to a surf-fixing sheet, reversal developing machine), 1000 images were printed, and then the image density was measured. Remove the developing device and put it in a high temperature and high humidity room (30 ° C, 80%) overnight (12
Leave for hours). After returning the developing device to the room temperature and normal humidity chamber, 20 sheets of images are immediately output and the image density is measured in the same manner as the previous day. The last day image density is compared with the first image density. The evaluation level is confirmed by the difference between the density of the 1000th sheet (last day before) and the density after standing. (The smaller the value, the better)

[0168] ◎: Concentration difference 0.02 or less ◯: Concentration difference 0.03 to 0.05 ○ △: density difference 0.06 to 0.10. Δ: Concentration difference 0.11 to 0.15 ×: Concentration difference 0.16 to 0.20 XX: density difference of 0.21 or more

(Evaluation-4) The toner (X-1) for evaluation is G
400g was put in a P55 developing unit, and a low temperature and low humidity chamber (15 ° C,
50%) overnight (12 hours or more). The developer carrier gear is rotated using an external drive device. Visually check the toner application state on the surface of the developer carrier from the start of rotation to 10
Observe for minutes. The evaluation level is shown below.

⊚: The surface state of the carrier is extremely uniform. ◯: The surface state of the carrier is uniform, but a ripple pattern is seen in a very small part. B: A ripple pattern is seen on a part of the surface of the carrier. Δ: A ripple pattern is visible on the entire surface of the carrier. X: Ripples grow on the surface of the carrier, and some irregularities are clearly visible. XX: Concavities and convexities on the surface of the carrier are spread over the entire surface and can be clearly seen.

(Evaluation-5) 150 g of the toner (X-1) for evaluation was put in a developing device and placed in a low temperature and low humidity chamber (15 ° C., 50%).
Let stand overnight (12 hours or more). Canon Copier N
Using a modified P6030 machine (without a drum heater, the fixing heat roll was changed to a surf fixing sheet, a reversal developing machine), 1,000 images were printed. The fog in the solid white image before and after this is measured. The evaluation level is shown below.

REFLECTM Reflection Measuring Machine for Fog Measurement
The reflectance of the white image and the unused paper are measured with ETER (Tokyo Electric Co., Ltd.), and the difference between the two is taken as the fog. Unused paper reflectance-solid white reflectance = fog%

[0173] ◎: Fog 0.1% or less ○: Fog 0.1 to 0.5% ○ △: Fog 0.5-1.0% △: Fog 1.0 to 1.5% ×: Fog 1.5 to 2.0% XX: Fog 2.0% or more

The following Examples 2 to 20 and Comparative Examples 1 to 5 were also evaluated in the same manner as in Example 1, and the results shown in Tables 1 to 3 were obtained.

[Examples 2 to 7] Using the magnetic toner particles (X), the addition amount of the composite oxide (M-1) to be added was set to 0.
03, 0.06, 0.10, 5.0, 14.5, 15.
In the same manner as in Example 1 except that the amount was changed to 5 parts by weight,
The evaluation toners (X-2 to X-7) were used.

[Examples 8 to 20] Magnetic toner particles (X)
By using (M-2) to (M-1)
Evaluation toners (X-8 to X-20) were obtained in the same manner as in Example 1 except that the toner was changed to 4).

[Comparative Example 1] Hydrophobic silica (specific surface area 200 m ² / g) to be added by using the magnetic toner particles (X).
A toner for evaluation (Y-1) was obtained in the same manner as in Example 1 except that the addition amount of was changed to 5.0 parts by weight and the complex oxide to be added was changed to (M-15).

[Comparative Example 2] Evaluation was carried out in the same manner as in Example 1 except that the amount of the composite oxide added (M-1) was changed to 0 using the magnetic toner particles (X). The toner (Y-2) was used.

[Comparative Examples 3 to 5] Using the magnetic toner particles (X), the composite oxide to be added (M-15, M-16,
The toners for evaluation (Y-3, Y-4, Y-5) were obtained in the same manner as in Example 1 except that the toner was changed to M-17).

[0180]

[Table 1]

[0181]

[Table 2]

[0182]

[Table 3]

[0183]

[Table 4]

[0184]

The toner for developing an electrostatic charge image of the present invention is excellent in development stability in various environments, uniform coatability on a developing sleeve, and durability for multiple sheets.

[Brief description of drawings]

FIG. 1 is a view showing an X-ray diffraction pattern of an inorganic fine powder containing strontium silicate and strontium titanate obtained in Production Example 1.

FIG. 2 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of toner or fine particles.

FIG. 3 is a graph showing the relationship between developing potential and copy image density.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Iwaichi Endo 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-8-328295 (JP, A) JP-A 4-214568 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (4)

(57) [Claims] 1. An electrostatic charge image developing toner comprising toner particles containing at least a binder resin and a colorant and an inorganic fine powder, wherein the inorganic fine powder is represented by the following formula (1) [M ¹ ] _a [Si ] _b O _c (1) wherein, M ¹ is Sr, Mg, Zn, Co, Mn and Ce
Represents a metal element selected from the group consisting of, a represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents 3
Indicates an integer of -9. Composite oxide represented by] (A), and the following formula _{^{(2) [M 2] d}} [Ti] e O f (2) wherein, M ² is Sr, Mg, Zn, Co, Mn and Ce
Represents a metal element selected from the group consisting of, d represents an integer of 1 to 9, e represents an integer of 1 to 9, and f represents 3
Indicates an integer of -9. ] A toner for developing an electrostatic charge image, comprising fine particles containing a complex oxide (B) represented by the following and treated with a silane coupling agent. 2. The silane coupling treatment fine particles containing the complex oxide (A) and the complex oxide (B) are added in an amount of 0.05 to 15 parts by weight with respect to 100 parts by weight of the toner particles. The toner for developing an electrostatic image as described above. 3. The static particles according to claim 1, wherein the composite oxide (A) and the composite oxide (B) are contained in the inorganic fine powder in a molar ratio of 5/95 to 95/5. Toner for charge image development. 4. The silane coupling agent is contained in an amount of 0.05 to 50 parts by weight based on 100 parts by weight of the inorganic fine powder containing the composite oxide (A) and the composite oxide (B). The toner for developing an electrostatic image as described in 1.