JPH09134030A - Toner for developing electrostatic charge image - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a toner excellent in stability to development in various environments and durability after use on many sheets. SOLUTION: This toner has toner particles contg. at least a bonding resin and a colorant and contains a multiple oxide represented by the formula [M]a [Si]b Oc [where M is a metallic element selected from among Sr, Mg, Zn, Co, Mn and Ce, (a) is an integer of 1-9, (b) is an integer of 1-9 and (c) is an integer of 3-9].

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 image formed by an electrophotographic method or an electrostatic printing method.

[0002]

2. Description of the Related Art US Pat.
Numerous methods are known as described in Japanese Patent Publication No. 7,691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748. Generally, a photoconductive substance is used to form an electrostatic latent image on a photoconductor by various means, and then the latent image is developed with toner, and a toner image is transferred to 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 digitalization of copiers and the use of finer toner particles have increased the number of functions of copiers, improved the quality of copied images, and improved the fixing method from the viewpoint of energy saving as an approach to environmental issues. Shortening of copy time is desired. 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. That is, by reducing the toner particle size, the surface area of the toner per unit weight increases, the charging characteristics of the toner are more easily affected by the environment, and especially when left for a long time under high temperature and high humidity It is easily affected, and image density is likely to decrease after being left.

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, density gradation has been improved to some extent by reading image density and converting it into digital data.
However, it 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 carrier potential) and the image density do not have a linear relationship, and as shown in FIG. Where the potential is high, an upwardly convex curve is drawn. Therefore, in the halftone region, a slight change in the developing potential causes a very large change in image density. This makes it difficult to obtain good density gradation. In FIG. 2, the solid line shows the case where the maximum image density is 1.4 or more, and the broken line shows the case where the density gradation is improved.

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.
A degree is sufficient.

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, even when the glossiness of the surface is suppressed in copying a photographic image, the image area is large, and 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 set to a primary (linear) relationship, and the maximum image density is set to 1.4 to
A value of 1.5 is very important in copying a photo image containing text.

To this end, it is important to control the charge amount of the toner as uniformly as possible. Further, it is important to prevent a decrease in the charge amount of the toner and a decrease in the fluidity of the toner in a high-temperature and high-humidity environment that may occur particularly in the structure of the copying machine currently required.

As a method for stabilizing the charge amount, JP-A-58-66951, JP-A-59-168458 to 59-168460, and JP-A-59-170.
No. 847 discloses a method using conductive zinc oxide and tin oxide. Further, Japanese Patent Application Laid-Open No. 60-32060 discloses a method of removing paper powder, ozone deposits and the like generated or adhered to the surface of a photoreceptor by using two kinds of inorganic powders. In addition, Japanese Patent Application Laid-Open No. Hei 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 and ozone adducts generated or adhered to the photoreceptor surface and to remove the toner under high temperature and high humidity. A method for improving toner scattering, image deletion, and image density reduction has been disclosed. Further, Japanese Patent Laid-Open Nos. 61-236559 and 63-2073 disclose methods for improving the chargeability of toner by using cerium oxide particles. However, although these methods can certainly improve the chargeability, when an organic photoreceptor is used, the surface layer of the photoreceptor is gradually removed by continuous copying due to the abrasive effect of cerium oxide, and the image is removed. It causes deterioration. That is, as the toner becomes finer,
There is a demand for a developer that charges the toner uniformly and that does not reduce the charge of the toner even when left standing for a long time under high temperature and high humidity.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for developing an electrostatic charge image which solves the above-mentioned 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, which has no fog in the non-image area or whose fog is suppressed.

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.

An object of the present invention is to provide an electrostatic charge image developing toner which is excellent in durability of a large number of sheets.

[0015]

The present invention provides a toner for developing an electrostatic charge image, which comprises toner particles containing at least a binder resin and a colorant, represented by the following formula (1) [M] _a [Si] _b O _c. (1) [In the formula, M represents a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn, and Ce, and a is 1
To 9 (preferably 1 to 3), and b is 1 to 9
(Preferably 1-2), and c represents an integer of 3-9 (preferably 3-7). And a particle (A) containing the composite oxide represented by the formula:

[0016]

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

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. Also, the distribution width of the toner is generally wider as the charge amount is larger, and narrower as the charge amount is small.

As a method of stabilizing the charge amount, there is a method of adhering conductive powder to the toner as described above, but this method can sufficiently satisfy the points of maximum image density and deterioration of image quality in continuous copying. Absent.

The following points can be considered as the reason for this.

In the method in which the conductive powder is attached to the toner particles to reduce the charge amount, more conductive powder is attached to the toner having a small particle size per unit weight, that is, the toner having a large charge amount. By this, the fog in the white background portion is improved, but the toner having a small particle diameter is selectively developed and consumed because the charge amount is reduced. When a toner having a small particle size is fixed, the area covering a fixing support such as a transfer paper is smaller than that of a toner having a large particle size, so that the maximum image density is low. Further, since the toner having a small particle diameter is selectively developed, the toner particle size in the developing device is shifted to be coarse in continuous copying, and the initial image is deteriorated.

On the contrary to the method of reducing the charge amount of the toner, in the method of frictionally charging the toner and the metal oxide in the developing device, the charge amount of the toner is surely increased and is made uniform. You can However, if the first copy time required by the main body is shortened, it becomes difficult to start up the charging of the toner in the developing device during a short wait time, and it can be said that it is sufficient especially under high temperature and high humidity. Absent. This is because the fluidity of the toner decreases as the toner becomes finer, and especially under high temperature and high humidity, the fluidity and the chargeability further decrease due to the moisture absorption of the toner. In the conventional copying machine configuration, since the heat fixing roller is used as the fixing method, the time from power-on until the fixing roller rises to the predetermined fixing temperature from the start of the first copy is effectively used for development. By stirring the toner in the container, it was possible to impart fluidity and chargeability to some extent.
However, in recent years, the improvement of the fixing device has been advanced, and the heat-up time has been shortened. In such a fixing method, since the agitation described above cannot be performed sufficiently, the fluidity and chargeability of the toner cannot be imparted, and therefore, the copy image has a low density and an image in which fogging occurs is likely to be formed.

In Japanese Patent Laid-Open No. 5-333590,
The present inventors have proposed a toner containing a metal oxide powder. When the metal oxide powder having a certain size with respect to the toner adheres to the toner, due to the shearing force received in the developing device, the number of contact with the toner increases because the metal oxide powder separates from the toner, and the charge amount of the toner increases. can do. However, metal oxides reduce the fluidity of the toner. Therefore, as described above, especially when a surf fixing device is used, there is room for further improvement in the copy image under high temperature and high humidity.

The present inventors have paid attention to the following points.

The fluidizing agent (a) not only achieves the intended improvement of the fluidity of the toner, but also improves the developability thereof. This also affects the charging characteristics of the toner because the fluidity improvers 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 that a larger amount of addition is advantageous. However, if the amount of addition is excessive, the degree of adhesion to the surface of the toner particles varies, and it becomes difficult to maintain uniform charging between the toner particles, resulting in fogging. Therefore, it cannot be satisfactorily dealt with only by increasing the addition amount of the fluidity improver.

(B) By mixing the added composite oxide particles with the fluidity improver before mixing with the toner particles, the fluidity of the composite oxide particles themselves can be improved. Further, by using the composite oxide particles, it is possible to prevent the fluidity of the toner from being deteriorated under high temperature and high humidity. However, the charge imparting ability itself due to contact frictional charging with the toner, which is the original purpose, is lowered, and problems such as image density reduction and fog are likely to occur. This is because in addition to the contact triboelectric charging that originally occurs between the toner and the complex oxide particles, the transfer of charge between the fluidity improver and the complex oxide particles occurs, and the charge amount of the toner as a whole is not sufficient. It becomes smaller than the system of addition. As a result, the developability is lowered, and the image density and fog are likely to occur. That is, the addition of the fluidity improver to the composite oxide particles alone cannot be sufficient.

Therefore, the present inventors are based on the idea that a high charge amount can be obtained by contact triboelectric charging between toner particles and complex oxide particles without impairing the fluidity of the toner.
As a result of the examination, the following was found.

In the method of contact triboelectrically charging the toner particles and the complex oxide particles in the developing device, the complex oxide containing Si is used to improve the fluidity of the toner and obtain a high charge amount. Therefore, it was found that a high image density can be obtained even under severe high temperature and high humidity.

By containing the Si element in the composite oxide particles, the fluidity of the toner is improved as compared with the system containing other elements. It is considered that this is because the Si element has characteristics of excellent fluidity, as silica is generally used as a fluidizing agent. Further, the Si-containing composite oxide has a high charge imparting ability even in the contact triboelectric charging with the toner,
Increase the toner charge amount. For this reason, even under high temperature and high humidity, it is possible to obtain a charge amount that sufficiently satisfies the developability even with a small number of contact with toner particles, while preventing deterioration of the toner fluidity.

From the above, in order to obtain sufficient developability even under high temperature and high humidity, and especially to obtain a high image density even after standing, it is necessary to prevent the fluidity of the toner from being deteriorated due to water absorption and the contact friction. It is important to use the composite oxide composed of formula (1), which has a higher charge imparting ability in charging. An example of a graph of the relationship between the developing potential of the toner of the present invention and the image density is shown by a dashed line in FIG.

Further, in the present invention, a more preferable constitution of the toner will be described in detail below.

The complex oxide used in the present invention includes:
Examples of [M] in the formula (1) include magnesium, zinc, cobalt, manganese, strontium and cerium. Especially silicate strontium [Sr] _a [Si] _b O _c) is preferably from be more effective in the present invention. More specifically, SrSiO ₃ , Sr ₃ SiO ₅ ,
Examples thereof include Sr ₂ SiO ₄ , SrSiO ₅ and Sr ₃ Si ₂ O ₇ , and among them, SrSiO ₃ is preferable.

Further, in order to further exert the effect of the present invention, the ratio of the metal element and Si in the formula (1) is a / b =
1/9 to 9.0 are preferable, and more preferably a / b =
0.5 to 3.0.

The particles containing the complex oxide are preferably produced by, for example, a sintering method, mechanically crushed, and then subjected to air classification to use particles having a desired particle size distribution.

The particles containing the complex oxide in the present invention are
It is preferable to use 0.05 to 15 parts by weight, preferably 0.1 to 5.0 parts by weight, relative to 100 parts by weight of the toner particles.
The particles including the composite oxide have a weight average particle diameter of 0.5 to 5 μm.
It is preferably m and smaller than the weight average particle diameter of the toner particles.

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

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

Of these, a combination of monomers that forms a styrene copolymer or a styrene-acrylic copolymer is preferable.

Further, it may be a polymer or copolymer 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 Diacrylate compounds linked by an alkyl chain containing an ether bond, for example, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, and methacrylate 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 methacrylates. And polyester-type diacrylate compounds, for example, trade name MANDA (Nippon Kayaku). Examples of polyfunctional crosslinking agents include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylol methanetetraacrylate,
Oligoester acrylates and those obtained by replacing the acrylates of the above compounds with methacrylates; triallyl cyanurate, triallyl trimellitate;

These cross-linking agents are based on other monomer components 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 binder resin from the viewpoints of fixing property 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 homopolymer or copolymer of vinyl monomers, polyester, polyurethane, epoxy resin, polyvinyl butyral, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, An aromatic petroleum resin or the like can be used by mixing it with the binder resin described above, if necessary.

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

The glass transition temperature of the binder resin is preferably 4
5 to 80 ° C., more preferably 55 to 70 ° C., the number average molecular weight (Mn) is 2,500 to 50,000, and the weight average molecular weight (Mw) is 10,000 to 1,000,000.
It is preferred that

As a method for synthesizing the binder resin composed of a vinyl polymer or a copolymer, a polymerization method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method or an emulsion polymerization method can be used. When a carboxylic acid monomer or an acid anhydride monomer is used, it is preferable to use a bulk polymerization method or a solution polymerization method in view of the nature 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 dicarboxylic acid, dicarboxylic anhydride or dicarboxylic acid monoester. In the solution polymerization method, it is possible to partially dehydrate the dicarboxylic acid or dicarboxylic acid monoester unit by devising the conditions for distilling off the solvent when distilling off the solvent. Furthermore, the vinyl copolymer obtained by the bulk polymerization method or the solution polymerization method can be further dehydrated by heat treatment. It is also possible to partially esterify the acid anhydride with a compound such as an alcohol.

On the contrary, the thus obtained vinyl-based copolymer 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 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, the entire or dicarboxylic acid monoester moiety can be de-alcoholized and ring-closed and dehydrated depending on the processing conditions when the solvent is distilled off after the solution polymerization, and an acid anhydride can be obtained. 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 a higher wave number side than that in the case of acid or ester, so that the production 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 good chargeability.

The following polyester resins are also preferable as the binder resin.

Polyester resin is 45 to 55 in all components.
mol% is alcohol component, 55-45 mol%
Is the 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 (B)
A bisphenol derivative represented by the formula:

[0055]

Embedded image Further, diols represented by the formula (C):

[0056]

Embedded image And polyhydric alcohols such as glycerin, sorbit, and sorbitan.

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 further succinic acid substituted with an alkyl group or an alkenyl group having 6 to 18 carbon atoms or anhydrides thereof; fumaric acid, maleic acid, citraconic acid, itaconic acid Examples of such unsaturated dicarboxylic acids or their anhydrides include tricarboxylic or higher carboxylic acids such as trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and their anhydrides.

The alcohol component of the particularly preferred polyester resin is a bisphenol derivative represented by the above formula (B), and the acid component is phthalic acid, terephthalic acid, isophthalic acid or its anhydride, succinic acid, n-dodecenylsuccinic acid. Or dicarboxylic acids such as anhydrides thereof, fumaric acid, maleic acid and maleic anhydride; trimellitic acid or tricarboxylic acid anhydrides thereof.

This is because the heat roller fixing toner using the polyester resin obtained from the acid component and the alcohol component as a binder resin has good fixability and excellent offset resistance.

The acid value of the polyester resin is preferably 90.
The OH number is preferably 50 or less, more preferably 50 or less, and more preferably 30 or less. This is because as the number of terminal groups of the molecular chain increases, the environmental dependence of the charging characteristics of the toner increases.

The glass transition temperature of the polyester resin is preferably 50 to 75 ° C., more preferably 55 to 65 ° C., and the number average molecular weight (Mn) is preferably 1,50.
0-50,000, more preferably 2,000-20,
And the weight average molecular weight (Mw) is preferably 6,000 to 100,000, more preferably 10.0.
It is preferably from 00 to 90,000.

In the toner for developing an electrostatic charge image of the present invention, a charge control agent may be used, if necessary, in order to further stabilize its chargeability. The charge control agent is a 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.

Examples of the charge control agent include the following.

An organometallic complex or a chelate compound is effective as a negative charge control agent for controlling the toner negatively. Examples thereof include a monoazo metal complex, a metal complex of an aromatic hydroxycarboxylic acid, and a metal complex of an aromatic dicarboxylic acid. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides or esters thereof, and phenol derivatives of bisphenol. In the case of negatively chargeable toner particles, the effect of adding the composite oxide particles is more remarkable.

Examples of the positive charge control agent for controlling the toner to have a positive charge include nigrosine and a nigrosine derivative organic quaternary ammonium salt.

When the toner of the present invention is used as a magnetic toner, the magnetic material contained in the magnetic toner includes iron oxide such as magnetite, maghemite, and ferrite, and magnetic iron oxide 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
Examples thereof include alloys with metals such as i, Cd, Ca, Mn, Se, Ti, W and V, and mixtures thereof.

Conventionally, as a magnetic material, ferrosoferric oxide (F
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 ), barium iron oxide (BaFe ₁₂ O ₁₉ ), iron magnesium oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnF
e ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ), iron powder (F
e), cobalt powder (Co), nickel powder (Ni) and the like are known. The above magnetic materials are used alone or in combination of two or more. Particularly preferred magnetic materials for the purposes of the present invention are fine powders of iron tetroxide or γ-iron sesquioxide.

These ferromagnetic materials have an average particle size of 0.05 to
At 2 μm, the magnetic properties under application of 795.8 kA / m show coercive force of 1.6 to 12.0 kA / m, 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 preferable.

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

Non-magnetic colorants that can be used in the toner of the present invention include any suitable pigments or dyes.

Examples of pigments 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 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight of the pigment based on 100 parts by weight of the binder resin. Similarly, a dye is used as a coloring agent. 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 the dye based on 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 include the following. Aliphatic hydrocarbon-based waxes such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, and paraffin wax; and aliphatic hydrocarbon-based waxes such as oxidized polyethylene wax, or block copolymers thereof; Examples of the wax include waxes mainly containing a fatty acid ester such as wax, sasol wax and montanic acid ester wax, and those obtained by partially or entirely deoxidizing fatty acid esters 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. Alcohols, saturated alcohols such as melicyl 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, ethylenebisca Saturated fatty acid bisamides such as purine amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide, ethylenebisoleic acid amide,
Unsaturated fatty acid amides such as hexamethylene bisoleic acid amide, 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 (generally 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,
Further, a partial esterification product of a fatty acid such as behenic acid monoglyceride and a polyhydric alcohol, and a methyl ester compound having a hydroxyl group obtained by hydrogenation of vegetable oils and the like can be mentioned.

The amount of the release agent 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 releasing 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. it can. The toner particles have a weight average particle size of
The thickness is preferably 3 to 12 μm, more preferably 3 to 9 μm.

A fluidity improver may be used in the toner of the present invention. As the fluidity improver, it is possible to use a fluidity improver capable of increasing the fluidity by externally adding it to the toner particles as compared with before and after addition. For example, fluororesin powders such as vinylidene fluoride fine powder and polytetrafluoroethylene fine powder, fine powder silica such as wet-process silica, dry-process silica, etc .; these silicas as silane coupling agents, titanium coupling agents, silicone oils, etc. And the like, surface-treated silica.

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

SiCl ₄ + 2H ₂ + O ₂ → SiO
₂ + 4 HCl

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 included as silica. The average particle diameter of the particles is preferably in the range of 0.001 to 2 μm, and particularly preferably 0.002 to 0.2.
It is preferable to use silica fine powder in the range of μm.

Commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include, for example, those commercially available under the following trade names.

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 ER15 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. It is particularly preferable that the treated silica fine powder is obtained by treating the silica fine powder such that the degree of hydrophobicity measured by a methanol titration test shows a value in the range of 30 to 80.

As a method for 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 halide is treated with an organosilicon compound.

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane and benzyldimethyl. Chlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, ρ-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane , Dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-
Divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane and 2 to 1 per molecule
Examples thereof include dimethylpolysiloxane having two siloxane units and having a hydroxyl group bonded to Si for each unit located at the terminal. These are used alone or as a mixture of two or more.

The fluidity-improving agent has a specific surface area of 30 m ² / g or more, preferably 5 as measured by the BET method by nitrogen adsorption.
Those with 0 m ² / g or more give good results. It is preferable to use 0.01 to 8 parts by weight, preferably 0.1 to 4 parts by weight of a fluidity improver based on 100 parts by weight of the toner particles.

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

(1) Measurement of X-ray diffraction Apparatus used: X-ray diffraction apparatus CN2013 (Rigaku Denki Co., Ltd.): Powder sample molding machine PX-700 (manufactured by Thermonics Co., Ltd.)

The sample to be measured is compression-pressed using the above 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.

Target, Filter Cu, Ni Voltage, Current 32.5 kV, 15 mA Counter Sc Time Constant 1 sec Diversity Slit 1 ° Receiving Slit 0.15 mm Scatter 20 ° Slit 20 ° Slit 1 °

(2) Method for quantifying complex oxide in toner Used device: X-ray fluorescence analyzer 3080 (Rigaku Denki Co., Ltd.): Sample press molding machine MAEKAWA Testing Machine (MFG Co. LTD)

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 using a sample press molding machine
Press forming points. 2θ composite oxide from the table to determine the K _alpha peak angle (a) of [M]. 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 50 kV-50 mA 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.

A Coulter counter, Multisizer II type (manufactured by Coulter, Inc.) 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, As the electrolyte, a 1% NaCl aqueous solution is prepared using special grade or primary grade sodium chloride. As a measuring method, 0.1 to 5 ml of a surfactant (preferably alkylbenzene sulfonate) as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 measuring samples are further added.
Add mg. The electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser for about 1 to 3 minutes, and as an aperture by the Multisizer II type Coulter Counter,
When measuring the toner particle size, a 100 μm aperture is used, and when measuring the inorganic fine powder particle size, a 13 μm aperture is used. 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 is obtained.

(4) Measurement of Acid Value in Vinyl Resin The qualitative and quantitative determination of the functional group in the binder resin was 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 by the appearance of an absorption peak derived from the carbonyl of the anhydride nearby.

In the present invention, the peak of the infrared absorption spectrum refers to a peak clearly confirmed after being integrated 16 times by FT-IR having 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
The acid anhydride is about 50% of the theoretical value (the acid anhydride has an acid value as dicarboxylic acid).
Is measured.

On the other hand, in the measurement of the total acid value (A), a value substantially according to the theoretical value is measured. Therefore, the total acid value (A) and J
Since the difference from the IS acid value is about 50% of the theoretical value and the acid anhydride is measured as a dibasic acid, the total acid value (B) derived from the acid anhydride per 1 g is obtained.

Total acid value (B) = [total acid value (A) -JIS acid value] × 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 vinyl copolymer produced, 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 the JIS acid value, total acid value (A), monomer composition ratio of the vinyl-based copolymer composition obtained by the suspension polymerization method and the addition amount of the vinyl-based copolymer prepared by the solution polymerization method, the 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 THF solution using phenolphthalein as an indicator is defined 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.

A 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. The measured value of the KOH / THF solution is standardized with a 1 / 10N HCl standard solution.

The total acid value (A) of the binder resin is 2 to 100 m.
gKOH / g, the acid value of the vinyl copolymer containing the acid component in the binder resin is 10 according to JIS K-0070.
Preferably it is less than zero. When the acid value according to JIS K-0070 is 100 or more, the density of functional groups such as a carboxyl group and an acid anhydride group is high, and it becomes difficult to obtain a good charge balance. Problems tend to occur.

(5) Method for Measuring Acid Value of Polyester Resin The acid value is defined as the number of milligrams of potassium caustic needed 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
Weighed in an Erlenmeyer flask, and methanol: toluene = 3
About 50 ml of a 0:70 mixed solvent is added to dissolve the resin.
If solubility is poor, a small amount of acetone may be added. Using a mixed indicator of 0.1% bromthymol blue and phenol red, a standardized N / 1
The titration is performed using a potassium hydroxide solution to an alcoholic solution, and the acid value is determined by the following calculation from the consumption amount of the alcoholic potassium solution.

Acid value = KOH (number of ml) × N × 56.1 / Sample weight (where N is a factor of N / 10 KOH)

(6) Glass transition temperature Tg The Tg of the binder resin is measured using a differential thermal analysis measuring device (DSC measuring device), DSC-7 (manufactured by Perkin Elmer Co., Ltd.).

The measurement sample is 5 to 20 mg, preferably 10
Weigh the mg precisely.

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

In this heating process, an endothermic peak of a main peak in a temperature range of 40 to 100 ° C. is obtained.

At this time, the intersection point 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.

[0117]

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

(Production Example of Composite Oxide 1: Strontium Silicate) 1500 g of strontium carbonate and 600 g of silicon oxide
g was wet mixed in a ball mill for 8 hours, filtered and dried, and the mixture was molded under a pressure of 5 kg / cm ² to give 13
It was calcined at 00 ° C. for 8 hours. This was mechanically pulverized to obtain a strontium silicate fine powder (M-1) having a weight average diameter of 2.0 μm and a number average diameter of 1.0 μm. Further, X-ray diffraction was performed on the obtained (M-1), and from the peak pattern of FIG. 1, the produced composite oxide was SrSiO ₃ (a =
1, b = 1, c = 3) and Sr ₂ SiO ₄ (a = 2, b =
1, c = 4) was confirmed.

(Comparative Production Example 1 of Complex Oxide: Strontium Titanate) After 600 g of strontium carbonate and 320 g of titanium oxide were wet mixed in a ball mill for 8 hours,
After filtering and drying, the mixture was molded under a pressure of 5 kg / cm ² and calcined at 1100 ° C. for 8 hours. This was mechanically pulverized to obtain a strontium titanate fine powder (M-2) having a weight average diameter of 1.9 μm and a number average diameter of 1.1 μm.

(Comparative Production Example 2 of Composite Oxide: Mixed Powder of Silicon Oxide and Strontium Titanate) A weight average particle diameter of the composite metal oxide produced in the same manner as in Comparative Production Example 1 was 1.
475 g of strontium titanate fine powder having a particle size of 9 μm and a number average particle size of 1.1 μm, and silicon oxide of a commercially available reagent (oil absorption 23
6ml / 100g, apparent specific gravity 0.18g / ml) 25
g in a coffee mill, 5% by weight of silicon oxide fine powder
Strontium titanate fine powder (M-
3) 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 ( the average particle diameter of 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 part by weight Low molecular weight polyethylene (release agent) 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, and the kneaded product was cooled, coarsely pulverized by a cutter mill, and finely pulverized by a jet stream. The powder was pulverized and further classified using an air classifier to obtain negatively chargeable triboelectric 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 200 m ² / g) was added.
0 parts by weight and 3.0 parts by weight of the composite oxide (M-1) were externally added and mixed with a Henschel mixer, and the magnetic toner for evaluation (X-
1).

Using this toner, the following items were evaluated using a digital copying machine GP-55 modified by Canon (a heat roller for fixing was changed to a surf fixing sheet).

(Evaluation-1) 400 g of the toner (X-1) for evaluation was put in a developing device and kept in a room temperature and normal humidity chamber (23 ° C., 60%).
Overnight (over 12 hours). After 1000 images have been printed, the image density is measured. The developer is taken out and left overnight (12 hours) in a high-temperature and high-humidity room (30 ° C., 80%).
After returning the developing device to the room temperature and normal humidity chamber, 20 images are immediately output and the image density is measured in the same manner as the previous day. The last day image density and the first sheet image density are compared. The evaluation level is confirmed by the difference between the density of the 1000th sheet (last day before) and the density after standing. (Smaller value is better)

◎: Density difference 0.02 or less ○: Density difference 0.03 to 0.05 ○ △: Density difference 0.06 to 0.10 Δ: Density difference 0.11 to 0.15 ×: Density difference 0 .16 to 0.20 XX: density difference of 0.21 or more

(Evaluation-2) 400 g of the evaluation toner (X-1) is put in a developing device and left overnight (12 hours or more) in a low temperature and low humidity chamber (15 ° C., 5%). An external drive device is used to rotate the developer carrier gear. The state of toner application on the surface of the developer carrier is visually observed for 10 minutes from the start of rotation. The evaluation levels are shown below.

⊚: The surface state of the carrier is extremely uniform.

◯: The surface state of the carrier is uniform, but a ripple pattern can be seen in a very small part.

B: A ripple pattern is visible on a part of the surface of the carrier.

Δ: A ripple pattern is visible on the entire surface of the carrier.

X: Ripples on the surface of the carrier grow, and some irregularities are clearly visible.

XX: Concavities and convexities on the surface of the carrier spread over the entire surface and can be clearly seen.

(Evaluation-3) 400 g of the evaluation toner (X-1) is put in a developing device and left in a low temperature and low humidity chamber (15 ° C., 5%) overnight (12 hours or more). 2000 images are printed using the density evaluation chart. The fog in the solid white image before and after this is measured. The evaluation levels are shown below.

REFLECTM Reflection Measuring Device for Fog Measurement
The reflectance of the white image and the unused paper is measured by ETER (Tokyo Electric Co., Ltd.), and the difference between the two is regarded as fog. [Reflectance of unused paper]-[Reflectance of solid white] = Fog%

◎: Fog 0.1% or less ○: Fog 0.1 to 0.5% ○ △: Fog 0.5 to 1.0% △: Fog 1.0 to 1.5% ×: Fog 1. 5-2.0% XX: Fog 2.0% or more

The same evaluations as in Example 1 were carried out for the following Examples 2-8 and Comparative Examples 1-5. The results are shown in Tables 1 and 2.

Example 2 Using the magnetic toner particles (X), the addition amount of the composite oxide (M-1) to be added was 0.03.
An evaluation toner (X-2) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 3 Using the magnetic toner particles (X), the addition amount of the complex oxide (M-1) to be added was 0.05.
An evaluation toner (X-3) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 4 Using the magnetic toner particles (X), the added amount of the composite oxide (M-1) added was 0.10.
An evaluation toner (X-4) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 5 In the same manner as in Example 1 except that the amount of the composite oxide (M-1) added was changed to 5.0 parts by weight using the magnetic toner particles (X). The evaluation toner (X-5) was used.

Example 6 Using the magnetic toner particles (X), the amount of the composite oxide (M-1) added was 10.0.
An evaluation toner (X-6) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 7 Using the magnetic toner particles (X), the addition amount of the complex oxide (M-1) to be added was 15.0.
An evaluation toner (X-7) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Example 8 Using the magnetic toner particles (X), the addition amount of the complex oxide (M-1) to be added was 15.5.
An evaluation toner (X-8) was prepared in the same manner as in Example 1 except that the amount was changed to parts by weight.

Comparative Example 1 Using the magnetic toner particles (X), the amount of hydrophobic silica (specific surface area 200 m ² / g) added was changed to 5.0 parts by weight without using a complex oxide. A toner for evaluation (Y-
1).

[Comparative Example 2] A toner for evaluation was prepared 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). (Y
-2).

Comparative Examples 3 to 4 For evaluation, in the same manner as in Example 1 except that the magnetic toner particles (X) were used and the added complex oxide was changed to (M-2, M-3). Toner (Y
-3, Y-4).

[0148]

[Table 1]

[0149]

[Table 2]

[0150]

The toner for developing an electrostatic charge image of the present invention is excellent in development stability in various environments and durability of a large number of sheets.

[Brief description of the drawings]

FIG. 1 is a diagram showing an X-ray diffraction pattern of strontium silicate.

FIG. 2 is a graph showing the relationship between development potential and copy image density.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI Technical indication location G03G 9/08 351 361 375 (72) Inventor Tadashi Michigami 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (17)

[Claims] 1. A toner for developing an electrostatic charge image, comprising toner particles containing at least a binder resin and a colorant, comprising the following formula (1) [M] _a [Si] _b O _c (1) [wherein M Is a metal element selected from the group consisting of Sr, Mg, Zn, Co, Mn and Ce, and a is 1
Represents an integer of 1 to 9, b represents an integer of 1 to 9, and c represents 3 to
Indicates an integer of 9. ] The toner for developing an electrostatic image, comprising particles (A) containing the composite oxide represented by the following formula: 2. The electrostatic image developing toner according to claim 1, wherein 0.05 to 15 parts by weight of the particles (A) containing a complex oxide are externally added to 100 parts by weight of the toner particles. 3. The electrostatic image developing toner according to claim 1, wherein M is Sr. 4. The electrostatic image developing toner according to claim 1, wherein the composite oxide (A) is strontium silicate (SrSiO ₃ ). 5. The composite oxide (A) has a / b value of 1 /
The toner for developing an electrostatic charge image according to any one of claims 1 to 4, which has a toner density of 9 to 9.0. 6. The composite oxide (A) has an a / b value of 0.
The toner for developing an electrostatic charge image according to claim 5, which is 5 to 3.0. 7. The electrostatic image developing toner according to claim 1, wherein the particles containing the composite oxide (A) are produced by a sintering method. 8. The static particles according to claim 1, wherein the particles containing the composite oxide (A) are externally added in an amount of 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the toner particles. Toner for charge image development. 9. The toner for developing an electrostatic charge image according to claim 1, wherein the binder resin is a styrene-acrylic copolymer or a styrene-methacrylic copolymer. 10. The toner for developing an electrostatic charge image according to claim 1, wherein the binder resin is a polyester resin. 11. The coloring agent according to claim 1, which is a magnetic material.
0. The toner for developing an electrostatic image according to any one of 0 to 0. 12. The toner for developing an electrostatic charge image according to claim 1, wherein the toner particles contain a negative charge control agent. 13. The toner for developing an electrostatic charge image according to claim 1, wherein the toner particles contain a positive charge control agent. 14. The toner for developing an electrostatic charge image according to claim 1, wherein silica fine powder is further externally added to the toner particles. 15. The toner particles have a weight average particle size larger than that of the particles containing the composite oxide.
5. The toner for developing an electrostatic image according to any one of 4. 16. The toner particles have a weight average particle diameter of 3 to 1.
The toner for developing an electrostatic charge image according to claim 1, which has a thickness of 2 μm. 17. The toner particles have a weight average particle diameter of 3-9.
The toner for developing an electrostatic charge image according to claim 16, which has a thickness of μm.