JP2002082475A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner capable of maintaining good flowability and stable electrostatic chargeability, and excellent in printing durability for a large number of sheets. SOLUTION: In the toner containing at least toner particles and inorganic fine particles, the average primary major axial length of the inorganic fine particles ranges from 10 to 100 nm and the inorganic fine particles are surface treated with at least a charge controlling agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an electrophotographic method or an electrostatic printing method, and more particularly, to a color toner capable of maintaining image quality by stable charging even in long-term image output. About.

[0002]

2. Description of the Related Art Conventionally, many methods have been known as electrophotography. In general, an electric latent image is formed on a photoreceptor by various means using a photoconductive substance, The latent image is developed using toner, and if necessary, a toner image is transferred to a transfer material such as paper, and then fixed by heating or solvent vapor to obtain a copy. In this case, the residual toner on the photoreceptor that has not been transferred onto the transfer material is generally removed by a cleaning mechanism including a regulating blade or a fur brush.

A developing method for visualizing an electric latent image using toner is described in, for example, a powder cloud method described in US Pat. No. 2,221,776 and US Pat. No. 2,618,552. No. 2,872
No. 4,063, a magnetic brush method, and a method using a conductive magnetic toner described in US Pat. No. 3,909,258, and a developer carrying member (developing sleeve) and a photoconductive member. Japanese Patent Application Laid-Open No. Sho 62-639 in which a bias electric field consisting of an AC component and a direct component is applied between layers to perform development.
There is a so-called J / B development method disclosed in Japanese Patent Publication No. 70-70.

A large number of developing methods are known for such an electrophotographic method. In particular, a magnetic brush method, a cascade method, and the like using a two-component developer mainly composed of a toner and a carrier are widely used. . Each of these methods is an excellent method for obtaining a good image relatively stably, and is often constituted by a full-color toner or the like which is required to have a clear and faithful color reproducibility to a document. There are inherent disadvantages associated with the two-component developer, such as toner spent on the surface and fluctuations in charging characteristics due to fluctuations in the mixing ratio of toner and carrier.

In terms of fluctuations in charging characteristics, it is one important factor to improve the mixing properties of the toner and the carrier and to give the toner a desired fluidity in order to obtain stable charging characteristics. Means of externally adding silica fine particles having excellent heat resistance and impact resistance, inorganic fine particles represented by titanium oxide fine particles, aluminum oxide fine particles, and the like to a toner as a fluidity imparting agent have been performed as a known technique. . However, today, in order to obtain higher-quality copies, the technology for further fine-graining toners and carriers has advanced, so that the charge amount may fluctuate in response to slight changes in temperature and humidity, or the flowability of the fluidity imparting agent from the toner surface may increase. The generation of non-uniform mixing properties due to the detachment tends to cause a reduction in mixing properties, a lump of toner, and the like, which causes a problem that it is difficult to provide a desired charge amount.

Another problem is that the function of imparting charge to the toner from the fluidity-imparting agent itself is impaired by the detachment of the fluidity-imparting agent from the toner surface, causing a change in the charge amount.

With respect to the variation of the charge amount with respect to temperature and humidity, inorganic fine particles whose surface is subjected to a hydrophobic treatment are often used. However, although the effect of narrowing the environmental difference of the charge amount is certainly obtained, the use of silica fine particles causes the aging. This causes a problem that the charge amount of the toner tends to fluctuate, and the toner tends to aggregate when stored for a long time. Also, Japanese Unexamined Patent Publication No.
JP-A-52255, JP-A-60-238849, etc., when using hydrophobic titania,
The use of hydrophobic aluminum oxide / titanium oxide disclosed in Japanese Patent Application Laid-Open No. 0-238849 and the use of aluminum oxide treated with an amino-modified silicone oil described in Japanese Patent Application Laid-Open No. 61-275860 are proposed. Even in this case, since the absolute charge amount is lower than that of the silica fine particles, problems such as toner scattering in a low-humidity environment, and detachment of the toner surface due to the low charge amount held on the toner surface easily occur, and the fluidity is impaired. As a result, there is a concern that the charge amount may fluctuate due to a decrease in the mixing property of the developer, and at present, satisfactory performance has not been derived by each of them.

As means for suppressing the detachment of the inorganic fine particles externally added to the toner surface, inorganic fine particles disclosed in JP-A-2-61649 and JP-A-2-77756 are subjected to a mechanochemical reaction (mechanical impact). In this case, the inorganic fine particles are fixed, but the desired fluidity cannot be obtained, and as a result, the developer is not stable due to a decrease in the mixing property of the developer. It is difficult to obtain charging characteristics.

On the other hand, while improving the charging characteristics on the toner surface as described above, the toner for developing an electric latent image is also required to improve the durability when an external additive is used. Various charge control agents and the like have been used in toners in order to eliminate unstable elements such as adhesion, segregation and desorption, and in particular to stabilize charging characteristics.

At present, color toners having negative charging characteristics are mainly used in full-color copying machines and the like in the market, but generally, when a negative charge is imparted to the toner by using the charge control agent, a metal-containing dye is used. Is often used. When producing a toner using these metal-containing dyes, melt kneading must be performed at a very high temperature in order to obtain uniform dispersion in the toner, and at this time, the dye may be thermally decomposed. The color tone often changes. In addition, when the carrier and the toner are mixed in the developing device, the electric charge applied by mechanical friction and impact becomes non-uniform, causing image density unevenness and fogging, resulting in deterioration of image quality.

As a means for solving these problems, as disclosed in JP-A-57-167033, a metallizable azo compound is treated with a metal-imparting agent by a known method, and then treated with an acidic or mineral acid. By using an azo-based metal complex obtained by diluting and precipitating with water containing the same and filtering the same, it has become possible to obtain a negatively chargeable toner having stable charging characteristics.

However, in the melt-kneading process of toner production, the charge control agent mainly composed of the above-mentioned organometallic complex has a small primary particle diameter of 0.01 to 0.05 μm in many cases.
Furthermore, since the dry powder has very high cohesiveness, there is a limit in enhancing the dispersibility, and it is often difficult to maintain a desired charge amount by itself.

Therefore, a charge control agent as disclosed in JP-A-64-72168 and JP-A-2-308262 is coated on the toner surface,
Japanese Patent Application Laid-Open No. 61649 and Japanese Patent Application Laid-Open No. 2-77756 disclose a method of firmly fixing a charge control agent to the toner surface by mechanochemical. However, although the toner obtained by these means initially has a stable charging characteristic, the charge control agent adhered or fixed to the toner surface in the course of continuous copying over a long period of time in the configuration of the two-component developer. Transfer to the surface of the carrier, and eventually, the ability to apply charge from the carrier is reduced and the charge amount of the toner is significantly reduced, which may cause adverse effects such as toner scattering and member contamination to the copying machine main body. high.

Further, if the charge control agent on the surface is lost due to some impact and remains on the photoreceptor, there may be minute scratches on the photoreceptor or nuclei such as residual toner that cannot be completely transferred. In addition, the charge control agent is easily trapped in the nucleus, which may cause adverse effects such as toner slippage from the cleaning blade and occurrence of toner filming.

As another known means for suppressing the loss of the external additive from the toner surface, JP-A-9-43892 discloses an anatase-type titania having an average primary particle size of 10 to 90 nm by using a hydrophobizing agent and a charge controlling agent. An example in which surface treatment is performed by the method is disclosed. In this publication, it is difficult to separate from the toner surface by using substantially disc-shaped or substantially columnar titania particles that do not grow to needle-like crystals, and the surface of the toner is treated with a charge control agent by treating the titania surface with a charge control agent. Although the effect of stabilizing the charging characteristics is shown, the particles are particles having a substantially average primary particle size of 50 nm or less as shown in the examples, and in an anatase type crystal system, the shape thereof is substantially disk-shaped or substantially circular. Since the shape is close to columnar and spherical particles, the contact area between the toner surface and titania particles is small,
It is presumed that the toner is likely to be detached by a load near the developer regulating member disclosed in the above-mentioned publication because it is difficult to be sufficiently trapped in minute irregularities and gaps on the toner surface.

Further, in recent years, demands for higher definition and higher image quality of copying machines and printers have been increasing in the market, while demands for higher productivity due to higher speed have been increasing. To cope with such demands, when a large number of continuous copies are made by an electronic copying machine using a two-component developer, clear and good images are initially obtained, but after several tens of thousands of copies, fog increases significantly, and The resulting image is poor in tonality and sharpness.

When a large number of continuous copies are made in this manner, a copy having a high image density is usually obtained in the initial stage, but the supply of toner to the two-component developer gradually becomes insufficient, causing a decrease in the density or charging. In an insufficient state, the replenishment toner and the carrier are mixed, causing fogging and causing a partial increase or decrease in the toner density on the developing sleeve, resulting in image blurring and uniform image density. Tend not to be able to.

As a means for imparting stable charging characteristics to the toner as described above, it is common to apply an electric charge from an external additive or a charge controlling agent.
When detachment, migration, etc. occur, various obstacles are given to the charging characteristics, and the final image quality is reduced.

[0019]

SUMMARY OF THE INVENTION An object of the present invention is to provide an external additive which can solve the above-mentioned drawbacks and can maintain good fluidity and stable charging characteristics, and a toner which is excellent in multi-sheet durability. It is in.

That is, one of the objects of the present invention is to reduce the environmental difference of the toner charge amount depending on the temperature and humidity by using an external additive having both an improvement in fluidity and a stable charge imparting property for a long time. An object of the present invention is to provide a toner capable of maintaining good charging characteristics.

One of the objects of the present invention is to reduce the loss or detachment of the external additive from the toner surface, thereby reducing the deterioration of the toner, the surface of the toner carrier, and the surface of the image carrier due to long-term use. An object of the present invention is to provide a toner having excellent durability characteristics by preventing toner and external additives from sticking to the surface of a photoreceptor.

An object of the present invention is to provide a toner which can cope with an increase in the speed of the apparatus and which can withstand a stress factor caused by agitation in a developing device.

[0023]

According to the present invention, in a toner having at least toner particles and inorganic fine particles, the average primary long axis diameter of the inorganic fine particles is 10 to 100 nm.
Wherein the inorganic fine particles are at least surface-treated with a charge control agent.

In many cases, the charging ability of the toner mainly depends on the charging ability on the surface of the toner. Therefore, in order to control the charging of the toner, a charge controlling agent such as the organometallic complex shown in the present invention is added to the toner. Is an effective means, but if the effect is more directly derived, the charge is adjusted on the toner surface like an external additive within a range that does not adversely affect other electrophotographic characteristics. This is used as a more suitable means.

The inventors of the present invention have conducted intensive studies based on such knowledge, and as a result, in order to permanently maintain stable charging characteristics, first, it is necessary to prevent detachment from the surface of toner particles. Thought it was important.

The main feature of the present invention is that the use of inorganic fine particles in the form of needle-like particles or rod-like particles as an external additive makes it possible to reduce the desorption from the toner surface. Thus, stable charging characteristics can be obtained even in long-term continuous copying, and image quality has been improved.

By using the inorganic fine particles having the above-mentioned shape, the anatase type fine particle titanium oxide has a small contact area with the toner surface, but the toner particles have a needle-like or rod-like shape even if the sphericalness of the toner particles increases. The result is an increased contact area and improved adhesion. In addition, not only the adhesion is improved, but also the shape of the anatase type is almost spherical because the shape is sharper than the spherical shape, so it is easy to be trapped in minute irregularities and minute gaps on the toner surface. It is considered that detachment from the toner surface is smaller than that of titanium oxide.

Since the rutile-type titanium oxide or γ-type alumina of the present invention has a needle-like or rod-like shape, when it is externally added to the toner surface, it may impair the fluidity of the toner. is there. Therefore, as a further feature of the inorganic fine particles of the present invention, the average primary long axis diameter is 10 to 100.
It has been found that the use of a material having a thickness of 12 nm, preferably 12 to 60 nm is suitable for suppressing a decrease in fluidity.

[0029]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

In the toner of the present invention, as an external additive,
At least inorganic fine particles having an average primary long axis diameter of 10 to 100 nm surface-treated with a charge control agent are used.

By fixing the above-mentioned inorganic fine particles to the toner surface as an external additive, the triboelectric charging characteristics generated on the toner surface are stabilized, and the detachment of the external additive from the toner surface is suppressed for a long time. This makes it possible to withstand continuous continuous copying and achieve a longer life of the developer.

As the external additive for full-color toner, titanium oxide or alumina is often used as a known technique. Its properties are that it has excellent dispersibility when externally added to the toner surface, has the effect of increasing the fluidity of the developer under the role of a spacer between toner particles, and has a higher charging speed than other inorganic fine particles. When a hydrophobic treatment with a surface treatment agent or the like is performed quickly, it is used as a more general material in order to obtain stable toner charging characteristics because the environmental difference in charge amount from low to high humidity is small. I have.

However, since titanium oxide and alumina have lower charging characteristics than silica particles and the like, they have little electrostatic adhesion even after externally added to the toner. In general, when the added toner is filled, the charge between the powder and the vinyl becomes strong, and a phenomenon such that titanium oxide or alumina adhering to the toner surface is detached generally occurs.

There are three types of industrial titanium oxides: anatase type (sharpstone), rutile type (golden stone), and brookite type (sheet titanium stone) having different crystal forms. Is used, and has little industrial use, and practically, anatase type and rutile type are used. As described above, anatase-type titanium oxide having a spherical shape or a disc-like shape for the purpose of enhancing the dispersibility on the toner surface is widely used as a general-purpose toner. The reason for this is that the average primary particle size of the anatase type is about 20% smaller than that of the rutile type, and when externally added to the toner surface, it is more easily dispersed evenly, thereby improving the fluidity of the toner. By obtaining stable charging characteristics, durability characteristics are increased,
Since the Mohs' hardness is about 7.0 to 7.5 for the rutile type and about 5.5 to 6.0 for the anatase type, it is difficult to damage the drum surface layer. Many.

Anatase-type titanium oxide is very suitable as an external additive for full-color toners in terms of enhancing the fluidity of the toner and obtaining a stable charge amount. With the change in toner morphology, such as miniaturization of toner particles and the spheroidization of toner particles to enhance transfer characteristics, the use of fine-particle spherical titanium oxide found in the above-described anatase-type titanium oxide causes contact between the toner and titanium oxide. This reduces the number of dots and creates a state in which titanium oxide is hardly retained on the toner surface.

Furthermore, titanium oxide has a charge characteristic almost neutral as compared with silica particles and the like whose charge characteristics are generally known. Therefore, titanium oxide is externally added to the toner as described above to reduce the number of contact points. In this state, it is difficult to increase the amount of charge to such an extent that the charge can be stably held even if the charge is concentrated at the contact point.

Even if titanium oxide is in the form of fine particles in a spherical form, the titanium oxide is trapped in irregularities, fine gaps, pores, etc., which were conventionally present on the surface of the toner. , And fully played a role in improving the charging characteristics in low-humidity and high-humidity environments.However, if the toner surface becomes more spherical due to its spherical shape, Thus, the number of titanium oxide holding portions is reduced, and it becomes more difficult for titanium oxide to be held on the toner surface.

From the above, the main point of the present invention is that the titanium oxide adhered to the toner surface by the external addition step does not desorb, and is in a state where it is permanently and uniformly dispersed on the toner surface. This is to achieve charging stability.

The rutile-type titanium oxide or γ-type alumina used in the present invention has a rod-like or needle-like particle shape, and has a relatively large contact area when externally added to toner than spherical anatase-type titanium oxide. Even when there are minute recesses and gaps on the toner surface, even if the toner surface is in a smooth state, it is more easily trapped,
There is little desorption.

On the other hand, there is a concern that the use of the inorganic fine particles having such a shape may impair the fluidity of the toner. However, the inorganic fine particles used in the present invention have an average primary long axis diameter of 10 to 100 nm. Therefore, the fluidity of the toner is not impaired.

When the average primary diameter is less than 10 nm, the toner is peeled off from the toner surface by a developing bias potential or the like applied to a developing site in a copying process, and these are adhered to a latent image area on a photoreceptor. It also causes image defects such as white spots in the visible image area of the obtained copy. On the other hand, when the thickness is more than 100 nm, the fluidity of the toner is remarkably reduced, and extremely fine scratches on the surface of the photoreceptor and the residual toner are trapped to easily cause filming.

The inorganic fine particles are used as an external additive in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the toner particles. The inorganic fine particles may be used alone or in combination with other inorganic fine particles. However, it is more preferable that each of the inorganic fine particles is subjected to a hydrophobic treatment described below.

Other inorganic fine particles according to the present invention include, for example, metal oxides (such as strontium titanate, cerium oxide, magnesium oxide, chromium oxide, tin oxide, and zinc oxide), nitrides (such as silicon nitride), and carbides (such as silicon nitride). Such as silicon carbide), metal salts (calcium sulfate, barium sulfate, calcium carbonate, etc.), fatty acid metal salts (zinc stearate, calcium stearate, etc.), carbon black, silica and the like. It is not limited to these unless the effect of (1) is hindered.

The surface treatment with the hydrophobizing agent is carried out in order to suppress the environmental stability of the toner, in particular, the change in the amount of charge of the toner due to the influence of humidity. This is carried out in order to improve the chargeability and maintain the stability, thereby suppressing adverse effects such as fog which affect the image quality.

The hydrophobizing agent is not particularly limited as long as it is a generally known treating agent. For example, silane coupling agents, titanate coupling agents, silicone oils, silicone varnishes and the like can be used. However, in the present invention, a silane-based organic compound is preferable. The silane-based organic compound may be appropriately selected depending on the purpose of surface modification (for example, control of charging characteristics and further stabilization of charging under high humidity) and the reactivity of the silane-based organic compound. For example, a silane-based organic compound such as an alkoxysilane, an alkylalkoxysilane, a siloxane, a silane, or a silicone oil, which does not itself thermally decompose at the reaction treatment temperature is preferable.

It is particularly preferable to use an alkoxysilane having both a volatile group and a highly reactive bonding group, such as a coupling agent.

Specifically, for example, the silane coupling agent is represented by the general formula RmSiYn R: alkoxy group m: an integer of 1 to 3 Y: alkyl group, vinyl group, phenyl group, methacryl group, amino group, epoxy group, mercapto group Or a derivative of n: an integer of 1 to 3, preferably vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, isobutyl Trimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane and the like It can be.

The treatment amount is preferably 1 to 60 parts by mass, more preferably 3 parts by mass, per 100 parts by mass of titanium oxide.
５０50 parts by mass.

[0049] Particularly preferred in the present invention is a general formula _{C n H 2n + 1 -Si- (} OC m H 2m + 1) coupling agent represented by ₃ n = _4~12 m = _1~3. Here, when n in the general formula is smaller than 4, the treatment becomes easy, but the degree of hydrophobicity cannot be sufficiently achieved. When n is larger than 12, hydrophobicity is sufficient, but coalescence between titanium oxides is increased, and the ability to impart fluidity is reduced.

On the other hand, if m is larger than 3, the reactivity will be reduced and the hydrophobicity will not be sufficiently achieved. Therefore,
In the present invention, n is 4 to 12, preferably 4 to 8, m
Is 1 to 3, preferably 1 to 2.

The treatment amount is preferably 1 to 50 parts by mass, more preferably 3 parts by mass, per 100 parts by mass of the inorganic fine particles.
-40 mass parts is good.

Further, the hydrophobizing treatment may be performed with a hydrophobizing agent alone, or two or more hydrophobizing agents may be used. For example, one type of coupling agent may be used alone for the hydrophobic treatment, or two types of the coupling agent may be used simultaneously or after performing the hydrophobic treatment using the coupling agent, and then further hydrophobicized using another coupling agent. May be performed. There is no particular limitation on the method of using the hydrophobizing agent or the method of adding the hydrophobizing agent.

In the present invention, one of the features is that the above-mentioned inorganic fine particles are subjected to a surface treatment with a charge control agent simultaneously with the hydrophobic treatment and used as an external additive.

As described above, the inorganic fine particles enhance the fluidity of the toner and have a small environmental difference in the charging characteristics. On the other hand, since the absolute charging amount of the inorganic fine particles is neutral and low, the charging of the inorganic fine particles from the inorganic fine particles themselves is performed. There is not much ability. Generally, as a means for supplementing them, a combination with a fluidity-imparting agent having a high charge-imparting ability, such as silica particles, is used, or as a means for improving the charge characteristics of the toner itself (not added externally). Means for adding a charge-imparting agent, which is a charge control agent, at the toner production stage are widely known technologies.

Although the means for enhancing the charge imparting property on the toner surface by the external addition means is directly and effective, the means for containing the charge control agent in the toner is based on the method of producing the toner, the content and the charge. Due to factors such as the particle size of the control agent, the state of dispersion in the toner is not uniform, and there is a great possibility that adverse effects such as uneven charging may partially occur even in frictional charging on the toner surface.

For this purpose, there is also a means for enhancing the triboelectric charging property on the toner surface by directly externally adding a charge control agent to the toner surface. In the two-component developing method used in high-quality full-color copiers and the like, the toner and the carrier are subjected to frictional charging. The control agent component is transferred to the carrier surface due to a mechanical impact force or a thermal factor, resulting in the contamination of the carrier surface and a reduction in the charge amount.

The present inventors have focused on the fact that the use of the above-mentioned rutile-type titanium oxide or γ-type alumina reduces the desorption from the toner surface, and aims at further improving the chargeability on the toner surface. Furthermore, it has been found that by simultaneously performing the hydrophobizing treatment and the charge control agent simultaneously, it is possible to have a permanently high triboelectric charging ability.

As the charge control agent, known ones can be used. In the case of a color toner, the charge control agent is particularly colorless, the charge speed of the toner is fast, and a constant charge amount can be stably maintained. Agents are preferred. Further, when the toner is internally added to a toner obtained by a polymerization method, a charge control agent having no polymerization inhibition and having no water-soluble substance is particularly preferable.

In general, a toner using a metal compound of an organic acid as a charge control agent sometimes shows a relatively high triboelectric charge, but a decrease in triboelectric charge is observed under high humidity. On the other hand, under low humidity, a decrease in the charging speed of the toner is observed.

The reason for this is considered to be the adsorption and desorption of water near metal atoms. Under high humidity, the amount of water adsorbed on the metal compound increases, so that the triboelectric charge decreases. It is considered that the resistance increases and the charging speed decreases due to the decrease in the charge.

In the study of the present inventors, a specific amount of the aromatic oxycarboxylic acid (A) was added to the toner in addition to the metal compound to reduce the triboelectric charge amount under high humidity and reduce the amount of triboelectric charge under low humidity. It has been found that a decrease in the charging speed can be suppressed.

Although the reason is not clear, it is considered that the coexisting predetermined amount of the aromatic oxycarboxylic acid (A) controls the adsorption of water to the metal compound.

However, the effect of the coexisting aromatic oxycarboxylic acid is small unless it is the same as the aromatic oxycarboxylic acid constituting the metal compound. This is considered to be related to the stability of the metal compound based on the acid strength or symmetry of the aromatic oxycarboxylic acid.

In the case of a monoalkyl or dialkyl aromatic oxycarboxylic acid, it has been found that a high charge amount can be obtained even under high humidity. In this regard, in the case of a monoalkyl or dialkyl aromatic oxycarboxylic acid, since the negative structure of the oxygen of the carboxyl group is small due to the resonance structure, the electron density on the metal atom does not increase so much even when bonded to the metal, It is conceivable that the compound has a high negative chargeability and that the monoalkyl or dialkyl-substituted aromatic oxycarboxylic acid that coexists has a sterically large structure, so that it is likely to block water molecules.

The valence and ionic radius of the metal in the metal compound are correlated with the strength of the bond to the aromatic oxycarboxylic acid. The higher the valence of the metal and the smaller the ionic radius, the more the aromatic oxycarboxylic acid and the ionic radius. Bond is strong, the bond in the metal compound is hardly broken even during the production of the toner or during long-term use of the toner, and the metal compound is stably fixed in the toner particles.

According to the study of the present inventors, the valence of the metal constituting the metal compound is preferably 2 or more.
For the ion radius, see "Chemical Handbook Basic Edition II" (Revision 3)
With reference to the numerical values in Tables 15 and 23 on page 718 of the Chemical Society of Japan, the metal is preferably 0.8% or less.

Preferred metals are Al, Cr, Zn
And Al (III) is particularly preferred.

As the aromatic oxycarboxylic acid (A),
Preferably, salicylic acid, alkyl salicylic acid, dialkyl salicylic acid, and hydroxynaphthoic acid are used.
More preferably, examples thereof include alkyl salicylic acid and dialkyl salicylic acid. As alkyl salicylic acid, t
-Butylsalicylic acid and 5-tert-octylsalicylic acid, and dialkylsalicylic acid includes di-t-
Butylsalicylic acid. In particular, di-t-butylsalicylic acid is most preferred as the aromatic oxycarboxylic acid (A).

The mixing ratio of the metal compound of the aromatic oxycarboxylic acid (A) and the aromatic oxycarboxylic acid is 90: 1.
The ratio is preferably from 0 to 99: 1, and more preferably from 91: 9 to 98: 2. When coexisting in this range, the adsorption of water to the metal compound can be suppressed, and the triboelectric charge of the toner under high humidity decreases. Can be suppressed, and toner scattering in the machine can be prevented. On the other hand, the frictional charging speed of the toner under low humidity can be increased, and a good toner image can be obtained from the beginning of image formation. Further, when used in the above mixing ratio, the distribution width of the triboelectric charge amount of the toner becomes sharp, and the fluidity of the toner also improves. When the polymerizable monomer in the polymerizable monomer composition particles granulated in an aqueous medium is directly polymerized to form toner particles, a predetermined amount of aromatic oxycarboxylic acid is used. (A) acts as a surfactant, improves the granulation of the polymerizable monomer composition in an aqueous medium, and provides toner particles having a sharp particle size distribution.

When the compounding mass ratio of the aromatic oxycarboxylic acid (A) is less than 1/99, the effect of addition is small. The compounding mass ratio of the aromatic oxycarboxylic acid (A) is 10/90.
If more, the charging speed of the toner under low humidity is slow,
Further, at the time of fixing with a heating and pressing roller, an aromatic layer such as a silicone rubber layer on the surface of the heating roller is easily contaminated with aromatic oxycarboxylic acid, and the contaminated elastic layer is easily deteriorated and easily damaged. Further, when the compounding mass ratio of the aromatic oxycarboxylic acid (A) is more than 10/90, a transesterification reaction occurs between the polyester resin and the aromatic oxycarboxylic acid (A) at the time of melt-kneading with the polyester resin. In some cases, the polyester resin may have a low molecular weight and the offset resistance and the moisture resistance may be reduced.

In order to further stabilize the triboelectric charging characteristics at low and high humidity of the toner, the metal compound of the aromatic oxycarboxylic acid (A) is a mixture of metal compounds having different numbers of bonds of the aromatic oxycarboxylic acid. It is preferred that
A metal compound (I) having a smaller number of bonds of the aromatic oxycarboxylic acid (A), a metal compound (II) having a larger number of bonds of the aromatic oxycarboxylic acid (A), and an aromatic oxycarboxylic acid ( The relative mass ratio to (A) is (20 to 8)
0): (80-20): (1-10), preferably (3
0 to 70): (70 to 30): (2 to 9).

As specific metal compounds, di-ter
Zinc compound of t-butylsalicylic acid, chromium compound of di-tert-butylsalicylic acid, aluminum compound of di-tert-butylsalicylic acid, zinc compound of 5-tert-octylsalicylic acid, chromium compound of 5-tert-octylsalicylic acid and 5- Aluminum compounds of tert-octylsalicylic acid may be mentioned.

As specific metal compounds, the following compounds are exemplified.

In the case of an aluminum compound, two molecules of an aromatic oxycarboxylic acid are bonded to one aluminum atom, and three molecules of an aromatic oxycarboxylic acid are bonded to two aluminum atoms. In some cases, it is preferable to use a mixture of them in terms of environmental stability of the toner.

In order to achieve the above effects favorably, when the toner is used by being dispersed in a binder resin during the production of the toner, the metal compound of the aromatic oxycarboxylic acid (A) is
Preferably, the toner particles are contained in the toner particles in an amount of 0.45 to 13.5 parts by mass per 0 parts by mass. Further, the aromatic oxycarboxylic acid (A) itself is preferably contained in the toner particles in an amount of 0.05 to 1.5 parts by mass per 100 parts by mass of the binder resin.

The charge control agent is desirably surface-treated in the same amount as the hydrophobizing agent to be treated in the same manner or in a ratio of 30% of the hydrophobizing agent, and more preferably in the same amount as the hydrophobizing agent. It is effective that the surface is treated with 50% of the hydrophobizing agent.

Further, at the same time as the surface treatment of the rutile type titanium oxide, a charge control agent may be internally added to the toner as in the related art. In that case, the amount is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the binder resin. However, in the present invention, the addition of a charge control agent to the toner is not essential, and when a two-component developing method is used, a non-magnetic one-component blade coating developing method using frictional charging with a carrier is used. Also, the toner does not necessarily need to contain a charge control agent by positively utilizing the triboelectric charging with the blade member and the sleeve member.

The toner of the present invention is obtained by externally adding an inorganic fine particle surface-treated with the above-mentioned charge controlling agent (metal compound) and hydrophobizing agent. Either of these surface treatments may be performed first, but these treatment agents may be mixed and the surface treatment may be performed collectively. To perform a surface treatment with a hydrophobizing agent, for example, diluting the hydrophobizing agent with a solvent, adding and mixing the diluent with untreated inorganic fine particles, and heating the mixture,
After drying, a dry method of crushing, or a wet method of dispersing the inorganic fine particles in an aqueous system to form a slurry, adding and mixing a hydrophobizing agent, heating and drying, and then crushing. And so on. To perform a surface treatment with an organometallic complex, for example, an organometallic complex is dissolved in a solvent, the solution is added to and mixed with inorganic fine particles, and after the mixture is dried,
It can be performed by a crushing method or the like. In particular, the inorganic fine particles are subjected to hydrophobic treatment in an aqueous system from the viewpoint of uniformity of the surface treatment of the inorganic fine particles with the hydrophobizing agent, anti-aggregation properties of the inorganic fine particles, and the like. It is preferable to perform a surface treatment with a metal complex.

In the toner of the present invention, a polymerized toner obtained by polymerizing a polymerizable monomer composition can obtain a desired charge amount in the present invention, maintain stable image quality for a long period of time, and It is suitable for realizing it.

The polymerized toner has no problems such as breaking of the molecular chains of the high molecular weight components and pulverizability which occur in steps such as melt kneading and pulverization in the production of the pulverized toner. This is because it can be easily obtained in achieving good light transmittance.

The particle size distribution and the particle size of the toner can be controlled by changing the type and amount of the hardly water-soluble inorganic salt or the dispersing agent that acts as a protective colloid, or by changing the mechanical device conditions, such as the peripheral speed and the path of the rotor. By controlling the stirring conditions such as the number of times and the shape of the stirring blade, the shape of the container, and the solid content concentration in the aqueous solution, the predetermined toner of the present invention can be obtained.

The polymerizable monomer used in the present invention includes styrene, o (m-, p-)-methylstyrene, m
Styrene-based monomers such as (p-)-ethylene styrene;
Methyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, behenyl (meth) acrylate, ( (Meth) acrylate monomers such as 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, and diethylaminoethyl (meth) acrylate; butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylic acid Ene monomers such as amides are preferably used.

These can be used alone or generally in the published Polymer Handbook, 2nd edition, pp. 139-192 (Jo).
hnWiyey & Sons) and the monomers are appropriately mixed and used so that the theoretical glass transition temperature (Tg) thereof is 40 to 80 ° C. If the theoretical glass transition temperature is lower than 40 ° C., problems arise in terms of the storage stability of the toner and the durability stability of the developer. On the other hand, if the theoretical glass transition temperature exceeds 80 ° C., the fixing point is increased. In the case of (1), the color mixture of the toners of the respective colors is insufficient, and the color reproducibility is poor. Further, the transparency of the OHP image is remarkably reduced, which is not preferable from the viewpoint of high image quality.

As the polymerization initiator used in the present invention, for example, 2,2′-azobis- (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,4-
Dimethylvaleronitrile, azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis-4-methoxy-2,
Azo-based polymerization initiators such as 4-dimethylvaleronitrile and azobisisobutylnitrile; benzoyl peroxide;
Methyl ethyl ketone peroxide, diisopropyl peroxy carbonate, cumene hydroxy peroxide,
A peroxide-based polymerization initiator such as 2,4-dichlorobenzoyl peroxide and lauroyl peroxide is used.

The amount of the polymerizable initiator varies depending on the target component ratio of the present invention, but it is generally used in an amount of 0.5 to 20% by mass based on the monomer. In the toner of the present invention, for example, a polymer having a molecular weight of 2,000 to 5,000 is reduced because the initiator acting as a chain transfer agent is reduced by reducing the amount of the initiator, and the polymer growth reaction is continued for a long time. It can be obtained by adding an appropriate amount of a polymer having a top peak between 2,000 and 5,000 to a monomer composition before granulation, to a reaction system that has been confirmed to be hardly formed. .

In order to control the molecular weight distribution as in the present invention, it is preferable to further use a known crosslinking agent, chain transfer agent, polymerization inhibitor and the like.

When the suspension polymerization is used as the toner production method of the present invention, for example, tricalcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate may be used as the dispersant used as the inorganic oxide. , Magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate,
Examples thereof include calcium sulfate, barium sulfate, bentonite, silica, alumina, a magnetic substance, and ferrite.

As the organic compound, for example, polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, sodium salt of carboxymethylcellulose, starch and the like are used by being dispersed in an aqueous phase.

These dispersants are used in the polymerizable monomer composition 1
It is preferable to use 0.2 to 10.0 parts by mass with respect to 00 parts by mass.

As these dispersants, commercially available ones may be used as they are, but in order to obtain finely dispersed particles having a uniform particle size, the inorganic compound is formed under high-speed stirring in a dispersion medium. Can also be obtained. For example, in the case of calcium phosphate, a dispersant suitable for a suspension polymerization method can be obtained by mixing an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under high-speed stirring.

In addition, these dispersants may be used in an amount of 0.001 to
0.1 parts by mass of a surfactant may be used in combination. Specifically, commercially available nonionic, anionic, and cationic surfactants can be used, such as sodium dodecyl sulfate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate, and olein. Calcium acid and the like are preferably used.

As a method for producing the toner according to the present invention, a resin, a release agent composed of a material having a low softening point, a colorant, a charge control agent, and the like are uniformly mixed using a pressure kneader, an extruder, or a media disperser. After being dispersed, the target is collided mechanically or under a jet stream, finely pulverized to a desired toner particle diameter, and further subjected to a classification step to sharpen the particle size distribution to produce a toner by a pulverization method of forming a toner. There are ways.

A method for producing a polymerized toner is as follows: a mold release agent, a colorant, a charge control agent, a polymerization initiator, and other additives are added to a polymerizable monomer, and the mixture is treated with a homogenizer / ultrasonic disperser or the like. The monomer composition dissolved or dispersed uniformly is dispersed in an aqueous phase containing a dispersion stabilizer by a homomixer or the like. The granulation is stopped when the droplets of the monomer composition have the desired toner particle size. Thereafter, by the action of the dispersion stabilizer, stirring may be performed to such an extent that the particle state is maintained and the particles are prevented from settling. The polymerization temperature is 40 ° C. or higher, generally 50 to 90 ° C.
The polymerization is carried out at a temperature set to.

In order to obtain the molecular weight distribution of the present invention,
The temperature may be raised in the latter half of the polymerization reaction, and a part of the aqueous medium may be distilled off in the latter half of the reaction or after completion of the reaction in order to remove unreacted polymerizable monomers and by-products. After completion of the reaction, the generated toner particles are collected by washing and filtration, and dried. In the suspension polymerization method, the monomer composition 1 is usually used.
It is preferable to use 300 to 3,000 parts by weight of water as a dispersion medium with respect to 00 parts by weight.

In the present invention, as a colorant used for each color of the yellow toner, cyan toner and magenta toner, a dye colorant and a pigment colorant may be used alone or in combination with a dye and a pigment. I do not care. In particular, when a dye-based colorant is used, the color reproducibility of the primary color is dramatically improved, the color reproducibility of the secondary colors represented by red, green, and blue is improved, and the color reproduction range is expanded. ,
Good optical transparency is also achieved in OHP images.

However, when the dye-based colorant is used alone, the weather resistance is poor and the color may be lost due to long-term storage. Therefore, when the dye-based colorant is used to enhance the color reproducibility,
It is desirable to use a pigment colorant having a relatively high hiding power in combination.

The above-mentioned colorants are appropriately selected from the following groups, and are used alone or in combination, but are not necessarily limited thereto.

As the yellow colorant, a compound represented by a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, an allylamide compound, or the like is used as a pigment colorant. Specifically, C.I. I. Pigment Yellow 1
2, 13, 14, 15, 17, 62, 74, 83, 9
3, 94, 95, 109, 110, 111, 128, 1,
29, 147, 168, 180 and the like are preferably used.

Solvent yellows such as Solvent Yellow 9, 17, 24, 31, 35, 58, 93, 10
0, 102, 103, 105, 112, 162, 16
3, Disperse Yellow 3, 42, 64, 82, 16
0, 201, etc. are preferably used.

Those used as magenta colorants include, as pigment colorants, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazole compounds, thioindigo compounds, and perylene compounds. Are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48: 2, 48: 3, 4
8: 4, 57: 1, 81: 1, 122, 144, 14
6, 166, 169, 177, 184, 185, 20
2, 206, 220, 221, 254 and Pigment Violet 19 are particularly preferred.

As the dye-based coloring agent, a condensed azo compound, an anthraquinone compound or the like is used. Specifically, C.I. I. Disperse Violet 26, 31, C.I.
I. Disperse Red 4, 5, 60, 91, C.I. I.
Solvent Red 8, 49, 52, BASF Ne
open Magenta 525, Ma manufactured by Bayer
crolex RED H is particularly preferred.

As the cyan colorant used in the present invention, copper phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds and the like can be used. Examples of pigment-based colorants include C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15:
3, 15: 4, 60, 62, 66, etc. can be used particularly preferably.

The dye colorants include Solvent Blue 36, 63, 64, 67, 68, 70, 97, B
Aopen's Neopen Cyan742, Baye
Macrolex Blue 3R manufactured by R Company is particularly preferred.

In the case of a color toner, the colorant is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in the toner. Is preferably used by adding 1 to 20 parts by mass to 100 parts by mass of the binder resin. When the addition amount is below the lower limit, the transparency is improved but the coloring power is extremely reduced, so that it is not possible to obtain an image density that maintains good visible image quality. In addition, when the value exceeds the upper limit, the light transmissivity is remarkably reduced, so that the color reproducibility of the projected image by the OHP is hindered or the fixing is peeled off.

When an image is formed by using the color toner of the present invention, it is possible to use a black toner mainly for the purpose of reproducibility of fine lines.

In this case, the same polymerizable monomer as that used for the color toner described above can be used. However, when a black-and-white image is formed alone, the image quality is output from a black-and-white copying machine. Since it is conceivable that the glossiness is low as seen in the image, the composition of the polymerizable monomers is not necessarily the same, and it is not necessary to obtain the composition at an arbitrary composition ratio.

Also, the colorant used does not need to improve the characteristics such as light transmittance of the black toner, and various materials can be applied, and the triboelectric charging characteristics which greatly contribute to the electrophotographic characteristics are greatly adversely affected. If not, its use is not restricted. For example, it is possible to use a single carbon black to form a black toner, or to mix a yellow toner, a magenta toner, and a cyan toner at an arbitrary ratio to obtain a black toner.

When a black toner is used, unlike other colorants, 40 to 150 parts by mass per 100 parts by mass of the binder resin is used.
It is used by adding parts by mass. The addition amount in this case does not relate to the color reproduction characteristics required for the color toner described above, and if the amount deviates from the range, the triboelectric charging characteristics important for image formation by electrophotography become unstable, and the invisible image This is because adverse effects such as fogging to the portion and scattering of the toner may occur.

The toner of the present invention preferably has a substantially spherical shape having an average circularity of 0.950 to 0.995, preferably 0.960 to 0.990, in order to secure transferability and developability. When the average circularity of the toner is less than 0.950, the toner particles become amorphous, and the contact area on the toner surface increases. It becomes difficult to fly, which results in adverse effects such as a decrease in transferability and a decrease in image density. If the average circularity of the toner is more than 0.995, there are problems such as difficulty in obtaining uniform charging characteristics and impairing fluidity.

It is desirable that the toner of the present invention contains a toner having a circularity of less than 0.950 by 2 to 40% by number, preferably 3 to 30% by number.

When the content of the toner having a circularity of less than 0.950 is 2
When the amount is less than the number%, the toner is apt to be finely filled, and as a result, the triboelectric charging becomes non-uniform, and fog or the like in the non-image area is liable to occur. When the content of the toner having a circularity of less than 0.950 exceeds 40% by number, the fluidity of the toner is reduced, and image deterioration such as the reproducibility of fine lines is easily caused.

Here, the “average circularity of the toner” means
This is a value obtained by statistically performing image analysis of particle imaging using a flow-type particle image measurement device, and the average circularity is calculated by the arithmetic mean of the circularity obtained by the following equation using the device.

Circularity = perimeter of equivalent circle / perimeter of particle projected image

In the above equation, the “perimeter of the particle projected image” is the length of the contour obtained by connecting the edge points of the binarized particle image, and the “perimeter of the equivalent circle” is , The length of the circumference of a circle having the same area as the binarized particle image.

In the toner of the present invention, since a full-color image is formed by superimposing the toner, high-speed copying and continuous copying can be performed without causing toner filming on the photoreceptor or the like and without contaminating the surface of the toner carrier. In addition, low-temperature fixability, which can sufficiently fix even under a situation where heat is easily taken away, is required.

As a result of intensive studies, the present inventors have been able to satisfy the above-mentioned required characteristics by including a low softening point substance called a release agent component for enhancing the release effect as a so-called toner component. I found something.

The low softening point substance is preferably a component having a molecular weight of 300 to 3,000, and more preferably the component having a molecular weight of 300 to 3,000 has Mw / Mn of 3.0 or less.

As the low softening point substance, ASTM D3418
−8, the main peak value measured in accordance with −8 is 40 to 1
Compounds exhibiting 20 ° C. are preferred. If the maximum peak is less than 40 ° C., the self-cohesive force of the low softening point substance becomes weak, and as a result, the hot offset resistance becomes weak, which is not preferable. On the other hand, if the maximum peak exceeds 120 ° C., the fixing temperature increases, which is not preferable. Further, if the temperature of the maximum peak value is high, a substance having a low softening point is deposited mainly during granulation, which disturbs the suspension system, which is not preferable.

More specifically, paraffin wax, polyolefin wax, Fischer-Tropsch wax,
Amide waxes, higher fatty acids, ester waxes and their derivatives, or their graft / block compounds can be used.

In the measurement of the temperature of the maximum peak value of the present invention,
For example, DSC-7 manufactured by PerkinElmer is used. For the temperature correction of the device detecting unit, an empty pan was set as a control using the melting points of indium and zinc, and the measurement was performed at a heating rate of 10 ° C./min.

It is preferable that the low softening point substance is included in the toner from the viewpoint of durability. As a specific method of enclosing the low softening point substance, the polarity of the material in the aqueous medium is mainly determined. By setting the low softening point substance smaller than the monomer and adding a small amount of a large polar resin or monomer, a toner having a desired core / shell structure in which the low softening point substance is coated with an outer shell resin is obtained. Can be obtained.

As a specific method for confirming the core / shell structure, a cured product obtained by sufficiently dispersing a toner in a room-temperature curable epoxy resin and curing it in an atmosphere at a temperature of 40 ° C. for two days is used. After staining with ruthenium trioxide and, if necessary, osmium tetroxide, a flaky sample is cut out using a microtome equipped with diamond teeth, and the tomographic morphology of the toner is observed using a transmission electron microscope (TEM). In the present invention, it is preferable to use a ruthenium tetroxide dyeing method in order to give a contrast between materials by utilizing a slight difference in crystallinity between the low softening point substance used and the resin constituting the outer shell.

The low softening point substance is the binder resin 100 of the toner.
5 to 40 parts by mass, preferably 10 to 30 parts by mass with respect to parts by mass
It is good to mix by mass parts.

If the amount of the low softening point substance is less than the lower limit, the effect of preventing offset tends to decrease.
The blocking resistance is reduced and the offset resistance is likely to be adversely affected, and filming and sleeve fusion are liable to occur. Particularly, in the case of a polymerization toner production method, a toner having a wide particle size distribution tends to be generated.

The toner according to the present invention is mixed and prepared with magnetic particles for development called carrier (hereinafter referred to as carrier particles) and used as a two-component developer. As carrier particles used in this case, for example, surface oxidized or unoxidized iron,
Nickel, copper, zinc, cobalt, manganese, chromium, rare earth and other metals and their alloys or oxides and ferrites, and magnetic oxides and metal magnetic oxides are dispersed in a binder resin. Can also be used. In addition, there is no particular limitation on the method of manufacturing them.

Further, the surface of the carrier particles may be coated with a resin or the like for the purpose of charge adjustment or the like. As a method, a coating material such as a resin is dissolved or suspended in a solvent and coated. Conventionally known methods such as a method of attaching to a carrier particle and a method of simply mixing with a powder can be applied, but it is preferable that the coating material be dissolved in a solvent for the purpose of stabilizing the coating layer.

The material for coating the surface of the carrier particles varies depending on the toner material. For example, an aminoacrylate resin, an acrylic resin, or a copolymer of such a resin with a styrene resin is preferable. As the resin to be negatively charged, silicone resin, polyester resin, fluororesin, polytetrafluoroethylene, monochlorotrifluoroethylene polymer, poly (vinylidene fluoride), etc. are located on the negative side in the charging series, and it is preferable. Not restricted. The coating amount of these compounds may be appropriately determined so as to satisfy the charge imparting characteristics of the carrier particles.
0% by mass (preferably 0.3 to 20% by mass).

The carrier particles used in the present invention are made of a phenol resin on the surface of spherical composite core particles obtained by combining ferromagnetic iron compound particles and non-magnetic iron compound particles with a phenol resin as a binder. A typical example is a resin carrier composed of spherical composite particles having an average particle diameter of 1 to 1000 μm formed by forming a coating layer. However, there is no restriction unless the performance is impaired. % Or more of a carrier such as ferrite particles having a composition of Cu—Zn—Fe (composition ratio [5 to 20]: [5 to 20]: [30 to 80]).

The volume average particle diameter of these carrier particles is 35.
It preferably has a thickness of from 65 to 65 μm, preferably from 40 to 60 μm. Further, when the volume distribution is 26 μm or less is 2 to 6%, and when the volume distribution is 35 to 43 μm is 5% or more and 25% or less, and when 74 μm or more is 2% or less, a good image can be maintained.

The volume average particle size of the carrier particles was randomly extracted by an optical microscope or a scanning electron microscope, and 100 or more particles were extracted, the volume particle size distribution was calculated with the maximum chord length in the horizontal direction, and the 50% average particle size was calculated. Average particle size may be used, or laser diffraction type particle size distribution measuring device HER
Using an OS (manufactured by JEOL Ltd.), the range of 0.05 to 200 μm may be measured by 32 logarithmic division, and a 50% average particle size may be used as the average particle size.

When the mixing ratio of the above-mentioned carrier particles and toner particles is 2 to 9% by mass, preferably 3 to 8% by mass as the toner concentration in the developer, usually good results can be obtained. If the toner density is less than 2%, the image density is low, making it impractical. If the toner density is more than 9%, fog and scattering inside the machine are increased, and the useful life of the developer is shortened.

Next, methods for measuring various characteristic values of the toner of the present invention will be listed.

(Measurement Method of Toner Particle Size) The average particle size and the particle size distribution of the toner were measured with a Coulter Counter TA-II.
It can be measured by various methods such as a mold or a Coulter Multisizer (manufactured by Coulter Inc.). In the present invention, an interface (manufactured by Nikkaki Co., Ltd.) that outputs a number distribution and a volume distribution using a Coulter Multisizer (manufactured by Coulter Inc.) ) And PC9801 personal computer (manufactured by NEC) are connected, and a 1% aqueous NaCl solution is prepared using primary sodium chloride as an electrolytic solution. For example, I
SOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, a surfactant, preferably an alkylbenzene sulfonate, is used as a dispersant in 100 to 150 ml of the electrolytic aqueous solution.
Add 1 to 5 ml, and further add 2 to 20 mg of the measurement sample.
The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and a 100 μm aperture was used as an aperture by the Coulter Multisizer.
A volume distribution and a number distribution were calculated by measuring the volume and the number of toner particles having a size of μm or more. Then, a volume-based volume average diameter (D4: the median value of each channel is a representative value of the channel) determined from the volume distribution of the present invention was determined.

(Measurement Method of Circularity Distribution) In the present invention, the circularity distribution of the toner equivalent circle diameter is measured using a flow type particle image distribution apparatus FPIA-1000 (manufactured by Toa Medical Electronics Co., Ltd.) as follows. You.

In the measurement, fine dust is removed through a filter, and as a result, the measurement range (for example, a circle equivalent diameter of 0.60 μm or more, 159.21) is placed in 10 ⁻³ cm ² of water.
surfactant (preferably Contaminone manufactured by Wako Pure Chemical Industries, Ltd.) in ion-exchanged water having a particle number of 20 or less (less than μm).
０．５0.5% by mass and uniformly dispersed. As a means for dispersing, an ultrasonic dispersing machine UH-50 manufactured by SMT Co., Ltd. (vibrator is a titanium alloy chip having a diameter of 5 mm) was used. The dispersion time was set to 5 minutes or more. At that time, the dispersion medium was appropriately cooled so that the temperature of the dispersion medium did not reach 40 ° C. or more. Using the above-mentioned flow type particle image measuring apparatus, 0.60
The particle size distribution and the circularity distribution of particles having a circle equivalent diameter of not less than μm and less than 159.21 μm are measured.

The outline of the measurement is described in the catalog of FPIA-1000 (June 1995 version) issued by Toa Medical Electronics Co., Ltd., the operation manual of the measuring apparatus, and Japanese Patent Application Laid-Open No. 8-136.
No. 439, which is as follows.

The sample dispersion liquid is passed through a flow path (spread along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). The strobe light and C
The CD cameras are mounted so as to be located on opposite sides of the flow cell. While the sample dispersion is flowing, strobe light is applied at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a range parallel to the flow cell. Photographed as a two-dimensional image. The diameter of a circle having the same area is calculated as the equivalent circle diameter from the area of the two-dimensional image of each particle. Furthermore, the circularity of each particle is calculated by dividing the perimeter of a circle (equivalent circle) having the same area as the two-dimensional image of each particle by the perimeter of the two-dimensional image of each particle.

As shown in Table 1, the results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in a range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

[0139]

[Table 1]

(Measurement method of average primary long axis diameter of inorganic fine particles)
In the present invention, a method of taking a photograph of the inorganic fine particles with a transmission electron microscope and measuring the major axis diameter of the primary particles directly from the photograph is used.

Although the shape of the primary particles is relatively easy to analyze, if the overlap of a plurality of particles forms one shadow, the shadow is divided into unit particles for measurement. Further, in order to statistically process the particle size distribution of the particles, about 300
It is necessary to measure the number of primary particles or more.

(Measurement method of molecular weight distribution) In the present invention, the resin soluble in tetrahydrofuran (THF) soluble
The molecular weight distribution of a chromatogram by GPC (gel permeation chromatography) using F as a solvent is measured as follows.

The measurement sample is measured as follows.

About 0.5 to 5 mg / ml of the sample and THF
(E.g., 5 mg / ml), left at room temperature for several hours (e.g., 5-6 hours), shake well,
The THF and the sample are mixed well (until the sample is no longer united) and allowed to stand at room temperature for at least 12 hours (for example, 24 hours). At this time, the time from the start of the mixing of the sample and THF to the end of the standing is set to be 24 hours or more. After that, the sample processing filter (pore size 0.4
.About.0.5 .mu.m, e.g.
Liquid chromatography disk 25CR manufactured by Tosoh Corporation and German Man Science Japan, etc. can be preferably used. ) Is used as a GPC sample. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

In the GPC measuring apparatus, the column is stabilized in a heat chamber column at 40 ° C., and THF is flowed as a solvent at a flow rate of 1 ml per minute into the column at this temperature, and about 100 μl of a THF sample solution is injected for measurement. . In measuring the molecular weight of a sample, the molecular weight distribution of the sample is calculated from the relationship between the logarithmic value of a calibration curve created from several types of monodisperse polystyrene standard samples and the count number. As a standard polystyrene sample for preparing a calibration curve, for example, a molecular weight of 10 ² manufactured by Tosoh Corporation or Showa Denko
Used of about 10 ^7, it is appropriate to use at least about 10 standard polystyrene samples. An RI (refractive index) detector is used as the detector. As the column, it is preferable to combine a plurality of commercially available polystyrene gel columns. For example, a Shodex GPC manufactured by Showa Denko KK
KF-801,802,803,804,805,80
6,807,800P combination and Tosoh T
SKgel G1000H (Hxl), G2000H
(Hxl), G3000H (Hxl), G4000H
(Hxl), G5000H (Hxl), G6000H
(Hxl), G7000H (Hxl), TSKguard
dcolumn can be mentioned.

(Method of measuring acid value) 1) 0.1 to 0.2 g of a sample was precisely weighed, and the weight was
(G). 2) The sample is placed in a 20 cc Erlenmeyer flask, and 10 cc of a mixed solution of toluene / ethanol (2: 1) is added and dissolved. 3) Add a few drops of phenolphthalein alcohol solution as indicator. 4) Using an alcohol solution of 0.1N KOH, titrate the solution in the flask with a burette. The amount of the KOH solution at this time is defined as S (ml). At the same time, a blank test is performed, and the amount of the KOH solution at this time is defined as B (ml). 5) Calculate the acid value by the following equation.

Acid value (mgKOH / g) = (S−B) × f
× 5.16 / W (f: KOH solution factor)

(Measurement method of triboelectric charge amount) The triboelectric charge amount is measured by the following method after the toner and the carrier are allowed to stand for 24 hours under measurement environment conditions.

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

FIG. 1 is an explanatory view of an apparatus for measuring a triboelectric charge amount of a toner. First, a mixture of a toner and a carrier having a mass ratio of 1:19 to be measured for a triboelectric charge amount is placed in a polyethylene bottle having a volume of 50 to 100 ml in a metal measuring container 22 having a 500-mesh screen 23 at the bottom. The mixture is shaken by hand for 5 to 10 minutes, and about 0.5 to 15 g of the mixture (developer) is put in and the metal lid 24 is closed. At this time, the mass of the entire measurement container 22 is weighed and set as W1 (g).
Next, in the suction device 21 (at least the portion in contact with the measurement container 22 is at least an insulator), the suction is performed through the suction port 27 and the landscape control valve 26 is adjusted to adjust the pressure of the vacuum gauge 25 to 250 mmAq. In this state, suction is sufficiently performed, preferably for 2 minutes, to remove the toner by suction. The potential of the electrometer 29 at this time is V
(Volts). Here, 28 is a capacitor whose capacity is C (μF). The weight of the entire measurement container after suction is weighed and is referred to as W2 (g). The triboelectric charge of this toner (mC
/ Kg) is calculated as follows.

Amount of triboelectric charge of toner (mC / kg) = C ×
V / (W1-W2)

[0152]

Hereinafter, the present invention will be described with reference to specific examples, but the present invention is not limited thereto.
“Parts” means “parts by mass”.

(Toner Production Example 1) 0.1 mol / L
Na of Le_ThreePO_FourAqueous solution and 1 mol / L CaCl
_TwoPrepare an aqueous solution. High-speed stirrer TK-homomixer
Deionized water in a 2 liter four-necked flask equipped with
710 parts and 0.1 mol / l-Na_ThreePO_FourAqueous solution
Add 550 parts and adjust the number of rotations to 10,000.
Warmed to 5 ° C. Here 1.0mol / liter-
CaCl_Two68 parts of aqueous solution is gradually added to make it slightly water-soluble
Dispersant Ca_Three(PO_Four)_TwoWas prepared.

On the other hand, the dispersoid system includes: styrene monomer 160 parts n-butyl acrylate monomer 40 parts Coloring agent (phthalocyanine pigment) 6 parts Saturated polyester 10 parts (terephthalic acid-propylene oxide-modified bisphenol A) Acid value 8, peak molecular weight 7000) 3 parts of aluminum compound of di-tert-butylsalicylic acid 20 parts of ester wax (Mw = 450, Mn = 400, Mw / Mn: 1.1)
3, melting point 68 ° C., viscosity: 6.1 mPa · s Vickers hardness: 1.2, SP value: 8.3) After dispersing the above mixture for 3 hours using an attritor,
A dispersion to which 2 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added was prepared.
This was charged into the dispersion medium and granulated for 8 minutes while maintaining the rotation speed. Thereafter, the stirring was changed from a high-speed stirring machine to a propeller stirring blade, and while stirring at 50 rotations, the internal temperature was raised to 60 ° C. for 4 hours, and then the temperature was raised to 80 ° C. for 4 hours to continue polymerization for a total of 8 hours. After the polymerization was completed, the slurry was cooled, and diluted hydrochloric acid was added to remove the dispersant.

By further washing and drying, the weight average diameter of the cyan toner particles measured by a Coulter counter was 6.8 μm, and the average circularity was 0.975.

(Toner Production Example 2) 100 parts of polyester resin (acid value 7) obtained by condensation polymerization of propoxylated bisphenol and fumaric acid 4 parts of phthalocyanine pigment (CI Pigment Blue 15: 3) Charge control agent no. 1 (Production Example 1 of charge control agent described later) 5 parts The above materials were sufficiently preliminarily mixed with a Henschel mixer, melt-kneaded at a temperature of about 140 ° C. with a twin-screw extruder, cooled, and cooled to about 1 with a hammer mill. It was coarsely pulverized to about 2 mm, and then finely pulverized by a fine pulverizer using an air jet method. The obtained finely pulverized product was classified to obtain cyan toner particles having a weight average particle size of 6.3 μm and an average circularity of 0.912.

(Toner Production Example 3) Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) obtained by condensation polymerization of propane with fumaric acid and 1,2,5-hexanetricarboxylic acid. 100 parts of polyester resin (acid value 8) obtained 4 parts of phthalocyanine pigment (CI Pigment Blue 15: 3) 5 parts of aluminum compound of di-tert-butylsalicylic acid 5 parts of the above materials were sufficiently premixed with a Henschel mixer. The mixture was melt-kneaded at a temperature of about 140 ° C. by a twin-screw extruder, cooled, roughly pulverized to about 1 to 2 mm using a hammer mill, and then pulverized by an air jet pulverizer. Further, the obtained finely pulverized product is classified, and then, the toner particles are given an impact force by thermal and mechanical energy in a surface reformer, and the toner has an average circularity of 0.971 and a weight average particle size of 0.971. Thus, cyan toner particles having a size of 5.8 μm were obtained.

In a similar production method, a yellow pigment (CI Pigment Yellow) was used instead of the phthalocyanine pigment.
low 17), a yellow toner having an average circularity of 0.974 was obtained, and a red pigment (Pigment Red 1) was obtained.
52) Magenta toner having an average circularity of 0.978 was obtained using 3 parts.

(Toner Production Example 4) In the toner production example 1, Pigment is used as a colorant used for the yellow toner, the magenta toner, and the black toner.
Yellow93 5 copies, Pigment Red1
532 and 6 parts of carbon black, except that the average circularity was 0.979, and the average circularity was 0.979.
0.974 and 0.981 yellow toner, magenta toner and black toner toner were obtained.

[Production Example 1 of Aluminum Compound] NaO
H, a 0.5 mol aqueous solution and 0.4 mol of di-tert-butylsalicylic acid were mixed and dissolved by heating. This solution and A
l ₂ (SO ₄ ) ₃ and a 0.1 molar aqueous solution were mixed, heated and stirred, and then separated by filtration under a condition of a neutral to a weak alkali. The collected white precipitate is washed until the washing water becomes neutral.
After washing with water and drying, per aluminum atom,
Aluminum compound fine powder No. 2 having two di-tert-butylsalicylic acids bonded thereto. 1 was obtained.

[Production Example 2 of Aluminum Compound] NaO
H, 0.3 mol of an aqueous solution and 0.3 mol of di-tert-butylsalicylic acid were mixed and dissolved by heating. This solution and A
l ₂ (SO ₄ ) ₃ and a 0.1 molar aqueous solution were mixed, heated and stirred, and the solution was adjusted from neutral to weakly alkaline, and collected by filtration. The collected white precipitate was washed with hot washing water and dried, and di-te per two aluminum atoms.
Aluminum compound fine powder No. 3 having three rt-butylsalicylic acids bonded thereto 2 was obtained.

[Production Example 3 of Aluminum Compound]
Fine powder of aluminum compound N in the same manner as in Production Example 1 of aluminum compound except that 3-hydroxynaphthalene-2-carboxylic acid was used instead of rt-butylsalicylic acid
o. 3 was obtained.

[Production Example 4 of Aluminum Compound]
Except that 5-tert-octylsalicylic acid was used instead of rt-butylsalicylic acid, aluminum compound fine powder No. 1 was prepared in the same manner as in Production Example 1 of aluminum compound. 4 was obtained.

[Production Example of Chromium Compound] NaOH, 0.4
Molar aqueous solution and di-tert-butylsalicylic acid, 0.4
The moles were mixed and dissolved by heating. This solution and Cr ₂ (S
O _{4) 3,} was mixed with 0.1 molar aqueous solution, it was heated with stirring and filtered off collected to prepare the solution to neutral. The collected white precipitate was washed with heated washing water, and then dried to obtain a fine chromium compound powder in which two di-tert-butylsalicylic acids were bonded to one chromium atom.

[Production Example of Zinc Compound] A 0.2 mol aqueous solution of NaOH and 0.2 mol of di-tert-butylsalicylic acid were mixed and dissolved by heating. This solution and ZnCl ₂ ,
After mixing with a 0.1 molar aqueous solution and stirring with heating, the solution was adjusted from neutral to weakly alkaline, and collected by filtration. The collected white precipitate was washed with hot washing water and then dried to obtain a zinc compound fine powder in which two di-tert-butylsalicylic acids were bound per zinc atom.

[Production Example 1 of Charge Control Agent] The aluminum compound fine powder No. 1 was added to 50 parts of a methyl alcohol solution in which 5 parts of di-tert-butylsalicylic acid was dissolved. 1,
45 parts of the aluminum compound fine powder No. 2,
After dispersing 50 parts and thoroughly mixing, the mixture was spray-dried to obtain a charge control agent No. 1 was obtained.

[Production Example 2 of Charge Control Agent] The aluminum compound fine powder No. 1 was added to 50 parts of a methyl alcohol solution in which 5 parts of di-tert-butylsalicylic acid was dissolved. 1,
95 parts were dispersed and thoroughly mixed, and then spray-dried to obtain a charge control agent No. 2 was obtained.

[Production Example 3 of Charge Control Agent] The aluminum compound fine powder No. 1 was added to 50 parts of a methyl alcohol solution in which 5 parts of di-tert-butylsalicylic acid was dissolved. 2,
95 parts were dispersed and thoroughly mixed, and then spray-dried to obtain a charge control agent No. 3 was obtained.

[Production Example 4 of Charge Control Agent] The above-mentioned chromium compound fine powder (95 parts) was dispersed in 50 parts of a methyl alcohol solution in which 5 parts of di-tert-butylsalicylic acid was dissolved. Spray drying to charge control agent N
o. 4 was obtained.

[Production Example 5 of Charge Control Agent] The above zinc compound fine powder (95 parts) was dispersed in 50 parts of a methyl alcohol solution in which 5 parts of di-tert-butylsalicylic acid was dissolved.
After sufficient mixing, spray drying was carried out to obtain the charge control agent No.
5 was obtained.

[Production Example 6 of Charge Control Agent] The aluminum compound fine powder No. 5 was added to 50 parts of a methyl alcohol solution in which 5 parts of 5-tert-octylsalicylic acid was dissolved.
4,95 parts were dispersed and thoroughly mixed, and then spray-dried to obtain a charge control agent No. 6 was obtained.

[Production Example 7 of Charge Control Agent] The aluminum compound fine powder No. 1 was added to 50 parts of a methyl alcohol solution in which 5 parts of 3-hydroxynaphthalene-2-carboxylic acid was dissolved. 3,95 parts were dispersed and thoroughly mixed, and then spray-dried to obtain a charge control agent No. 7 was obtained.

[0173] The rutile titanium oxide having an average primary major axis diameter 35nm surface treatment [Production of surface-treated titanium oxide A] has not been applied, were dispersed in a toluene solution, i-C ₄ as hydrophobicizing agents H ₉ -Si- (OCH ₃ ) ₃ was added so that the solid content was 20 parts with respect to 100 parts of the above titanium oxide, and the di-tert shown in Production Example 1 of the charge control agent was used as the charge control agent. The liquid temperature of the aluminum compound of -butylsalicylic acid was maintained at 50 ° C., and the mixture was added dropwise with sufficient stirring so as to be 5 parts in solids with respect to 100 parts of the titanium oxide, followed by hydrolysis. Then, after filtration and drying, 1
Bake at 20 ° C. for 2 hours and crushed. The pulverization was performed by a speed mill until the aggregates disappeared, and finally a surface-treated titanium oxide A was obtained.

[Production Example of Surface-treated Titanium Oxide B] An aluminum compound of di-tert-butylsalicylic acid, which is a surface-treated rutile-type titanium oxide having an average primary major axis diameter of 35 nm, was added to 100 parts of the above-mentioned titanium oxide. Except that the liquid temperature is kept at 50 ° C., the mixture is added dropwise with sufficient stirring, and the mixture is hydrolyzed so that the solid content becomes 5 parts, the same treatment as in the production example of the surface-treated titanium oxide A is carried out. Titanium oxide B was obtained.

[Production Example of Surface Treated Titanium Oxide C] An anatase type titanium oxide having an average primary major axis diameter of 35 nm, which has not been subjected to a surface treatment, and has the di-type shown in Production Example 2 of the charge control agent.
An aluminum compound of tert-butylsalicylic acid is treated in the same manner as in the production example of the surface-treated titanium oxide B except that the aluminum compound of tert-butylsalicylic acid is dropped and mixed with 100 parts of the above-mentioned titanium oxide so that the solid content becomes 5 parts. C was obtained.

[Production example of surface-treated γ-alumina] γ-alumina having an average primary long axis diameter of 50 nm, which has not been subjected to surface treatment, is dispersed in a toluene solution, and then iC ₄ H is used as a hydrophobizing agent. _9- Si- (OCH ₃ ) ₃ was added in such a manner that the solid content was 20 parts with respect to 100 parts of the above titanium oxide, and the di-t shown in Production Example 1 of the charge control agent was used as the charge control agent.
The liquid temperature of the tert-butylsalicylic acid aluminum compound was kept at 50 ° C., and the mixture was added dropwise with sufficient stirring so that the solid content was 5 parts with respect to 100 parts of the γ-alumina, and the mixture was hydrolyzed. Then, after filtration and drying, 12
Bake at 0 ° C for 2 hours and crushed. The pulverization was performed by a speed mill until the aggregates disappeared, and finally a surface-treated acid γ-alumina was obtained.

[Production Example of Surface Treated Titanium Oxide D] Di-t shown in Production Example 4 of a charge control agent made of rutile type titanium oxide having an average primary long axis diameter of 110 nm and not subjected to surface treatment.
A chromium compound of tert-butylsalicylic acid is treated in the same manner as in the production example of surface-treated titanium oxide A except that it is dropped and mixed so as to be 5 parts in solid content with respect to 100 parts of the titanium oxide. D was obtained.

[Production Example of Surface-treated Titanium Oxide E] Using a rutile-type titanium oxide having an average primary particle diameter of 9 nm which has not been subjected to a surface treatment, the di-formation shown in Production Example 5 of a charge control agent was carried out.
A zinc compound of tert-butylsalicylic acid is treated in the same manner as in the production example of the surface-treated titanium oxide A except that the zinc compound is dropped and mixed with 100 parts of the titanium oxide so that the solid content becomes 5 parts. E was obtained.

[Production Example of Surface Treated Titanium Oxide F] This is shown in Production Example 7 of a charge control agent using rutile-type titanium oxide (manufactured by Teica Co., Ltd.) having an average primary long axis diameter of 35 nm without surface treatment. The aluminum compound of 3-hydroxynaphthalene-2-carboxylic acid was replaced with the above titanium oxide 10
The same treatment as in the production example of the surface-treated titanium oxide A was carried out except that the mixture was dropped and mixed so that the solid content became 20 parts with respect to 0 part, whereby a surface-treated titanium oxide F was obtained.

[Production Example of Surface-treated Titanium Oxide G] Rutile-type titanium oxide (manufactured by Teica Co., Ltd.) having an average primary long axis diameter of 35 nm without surface treatment was used, and trimethylmethoxysilane was used as a hydrophobizing agent. Titanium oxide 100
The solid compound was added dropwise and mixed so that the solid content became 20 parts, and the aluminum compound of 5-tert-octylsalicylic acid shown in Production Example 6 of the charge control agent was mixed with the above titanium oxide 100
Parts were treated in the same manner as in the production example of the surface-treated titanium oxide A except that the mixture was dropped and mixed so that the solid content was 5 parts, whereby surface-treated titanium oxide G was obtained.

[Production example of surface-treated titanium oxide H] Rutile-type titanium oxide (manufactured by Teica Co., Ltd.) having an average primary long axis diameter of 35 nm without surface treatment was used, and trimethylmethoxysilane and dimethylpolysiloxane were used as hydrophobizing agents. Siloxane was added at a solid content of 10 /
10 parts by weight, and the aluminum compound of di-tert-butylsalicylic acid shown in Production Example 3 of the charge control agent was added to 100 parts of the above titanium oxide in a solid content of 5 parts.
Parts, and treated in the same manner as in the production example of the surface-treated titanium oxide A except that the mixture was dropped and mixed to obtain a surface-treated titanium oxide H.

<Example 1> 98.8 parts of cyan toner particles obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example A were mixed with a Henschel mixer. An external toner having inorganic fine particles on the surface of cyan toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, and the cleaning unit of the full color machine CLC1000 made by Canon shown in FIG. 2 was removed. , The corona charger is a contact roller charging system (in the figure,
2a to 2d) for evaluation (evaluation method and criteria will be described later)
Was done. The results are shown in Tables 2 and 3.

<Example 2> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example B were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Example 3> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example C were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Example 4> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example D were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Comparative Example 1> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example D were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the above-mentioned externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated by a modified full-color machine CLC1000 manufactured by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Comparative Example 2> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example E were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 model manufactured by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Comparative Example 3> 98.8 parts of the cyan toner obtained in Toner Production Example 1 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example F were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the above externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated by a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Comparative Example 4> 98.8 parts of the cyan toner obtained in Toner Production Example 2 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example B were mixed with a Henschel mixer, An externally added toner having inorganic fine particles on the particle surface was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 model manufactured by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

Example 5 98.8 parts of the cyan toner obtained in Toner Production Example 2 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example B were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the above externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated by a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

Example 6 98.8 parts of the cyan toner obtained in Toner Production Example 2 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example C were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Example 7> 98.8 parts of the cyan toner obtained in Toner Production Example 3 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example B were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the above externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

<Example 8> 98.8 parts of the cyan toner obtained in Toner Production Example 3 and 1.2 parts of titanium oxide obtained in Titanium Oxide Production Example C were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated using a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

Example 9 98.8 parts of the cyan toner obtained in Production Example 4 of toner and 1.2 parts of titanium oxide obtained in Production Example C of titanium oxide were mixed with a Henschel mixer. An externally added toner having inorganic fine particles on the surface of the toner particles was obtained.

7 parts of the above externally added toner and 93 parts of a resin carrier obtained by dispersing magnetite particles in a phenol resin were mixed to form a two-component developer, which was evaluated by a modified full-color CLC1000 made by Canon shown in FIG. Was done. The results are shown in Tables 2 and 3.

Evaluation was carried out using yellow toner, magenta toner and black toner in the same manner. As in the case of cyan toner, good results were obtained.

[Evaluation Method / Criterion] Method of Measuring Image Density and Fog Value The image density was determined by using X-Rit (5 mm square, 5 mm round, solid).
e404A color reflection densitometer (X-Rite Inco
rporated). At the time of the measurement, three to five sheets of white copy paper are placed on a desk, and the measurement is performed so that the influence of the background is not picked up.

In the present invention, the amount of fog in the non-image area is measured by a reflection densitometer (TOKYO DENSHOKU CO,
LTD's REFLECOMETER MODEL
TC-6DS) (Ds is the worst value of the reflection density on a white background after printing, and Ds-Dr is the fog amount when the average reflection density of the paper before printing is Dr).
When the fog amount is 2% or less, a good image having substantially no fog is obtained, and when the fog amount exceeds 5%, the image is fuzzy and unclear. As in the case of the image density measurement, the measurement is performed by placing 3 to 5 white copy sheets on a desk so as not to pick up the influence of the background.

Evaluation of Image Quality in Highlight Area The evaluation was visually made in four steps by comparison with the standard sample in the highlight area. ◎… Excellent ○… Good △… Normal ×… Poor

Evaluation Criteria for Toner Scattering The degree of toner scattering from the developing device was visually evaluated in three stages. …: There is substantially no toner scattering. Δ: toner scattering slightly, but little effect. X: toner scattering.

Evaluation criteria for filming The number of adhered substances adhering to the photoreceptor was visually evaluated. …: Substantially not present on the photoreceptor Δ: 5 or less in number, no effect on image quality ×: 10 or more, within the range that can be confirmed on the copy.

[0214]

[Table 2]

[0215]

[Table 3]

[0216]

As described above, according to the present invention, the use of rod-shaped titanium oxide in toner particles having a high spherical shape can reduce the detachment of external additive particles from the toner surface. As a result, the useful life of the developer itself can be increased. As a further effect, by treating the surface of the titanium oxide with a charge control agent, a high charge imparting property can be continuously maintained, and the environment of the toner charge amount can be maintained. Reduction of the difference,
It is possible to provide a constant high image quality.

[Brief description of the drawings]

FIG. 1 is a schematic diagram of an apparatus for measuring a charge amount of a toner used in the present invention.

FIG. 2 is an image evaluation machine (CLC10) used in the present invention.
FIG. 1 is a schematic diagram of a modified 00 (manufactured by Canon).

[Explanation of symbols]

 1 (1a to 1d) Photoconductor 2 (2a to 2d) Charger 3 (3a to 3d) Developing device 4 (3a to 3d) Transfer blade 5 Paper cassette 6 Transfer paper 7 (7a, 7b) Fixing roller 8 Transfer belt 9 Waste toner box 10 (10a, 10b) Heater 11 Tension roller 12 Adsorption charger 13 Registration roller 14 Static eliminator 15 Polygon mirror 16 Fur brush 17 (17a, 17b) Cleaning web 18 (18a-18d) Static eliminator 21 Suction machine 22 Measurement container 23 Conductive screen (500 mesh) 24 Lid 25 Vacuum gauge 26 Air flow control valve 27 Suction port 28 Capacitor 29 Electrometer

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yoji Katsuta 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Naotaka Ikeda 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon F term (reference) 2H005 AA08 AA15 AB02 AB06 CA12 CA25 CA26 CB07 DA02 DA05 EA05 EA10

Claims (7)

[Claims] 1. A toner having at least toner particles and inorganic fine particles, wherein the inorganic fine particles have an average primary long axis diameter of 10 to 100 nm, and the inorganic fine particles are surface-treated with at least a charge control agent. Toner. 2. The toner according to claim 1, wherein the toner particles are polymerized toner particles obtained by polymerizing a polymerizable monomer composition containing a polymerizable monomer and a colorant. toner. 3. The toner according to claim 1, wherein the surface of the inorganic fine particles is subjected to a hydrophobic treatment. 4. The toner according to claim 1, wherein at least the inorganic fine particles are titanium oxide having a rutile-type crystal form or γ-type alumina. 5. The toner according to claim 1, wherein the polymerizable monomer composition containing a colorant contains a metal salicylate compound. 6. The toner according to claim 5, wherein the metal salicylate compound is an aluminum compound. 7. The polymer toner particles have an average circularity of 0.95.
7. The method according to claim 2, wherein the number is from 0 to 0.995.
The toner according to any one of the above.