JPH1048872A - Toner for developing electrostatic images - Google Patents

Abstract

(57) [Problem] To provide an electrostatic image developing toner capable of obtaining a high quality image without causing "retransfer" under a wide range of transfer current conditions. SOLUTION: In a toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, the inorganic fine particles have an average particle diameter of 0.05 to 2 particles. (1) M _x O _y (1) wherein M represents an aluminum element, a titanium element, a zinc element or a zirconium element, O represents an oxygen element, and x and y represent Characterized in that the toner has one or more endothermic peaks in differential thermal analysis at 120 ° C. or lower. For toner.

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 a recording method utilizing an electrophotographic method, an electrostatic recording method, a magnetic recording method, or the like. More specifically, the present invention relates to a toner used in a copying machine, a printer, and a facsimile, which forms an image by forming a toner image on an electrostatic latent image carrier in advance and transferring the toner image onto a transfer material.

[0002]

2. Description of the Related Art Conventionally, many methods have been known as electrophotography. In general, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means.
The latent image is developed with a toner to make it a visible image, and if necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat / pressure to obtain a final image. Things.

In recent years, there has been a great demand for color copying machines, printers and faxes using electrophotography. Generally, it is difficult to use a magnetic toner containing a magnetic material because of the color of the color toner. Therefore, a non-magnetic toner is used. When a magnetic toner is used for the black toner and a non-magnetic toner is used for the color toner, the optimum transfer current value of the non-magnetic toner tends to be higher than the optimum transfer current value of the magnetic toner. When the transfer condition of the device body is adjusted to the non-magnetic toner, a phenomenon called “re-transfer” occurs in which the magnetic toner once transferred onto the transfer material returns to the latent image carrier, resulting in a black image. Causes a decrease in concentration.

[0004] In recent years, further diversification of paper materials has been progressing, and it is required that copiers, printers, and faxes using electrophotography can cope with such versatile paper materials. However, the optimum transfer conditions differ depending on the paper material as the transfer material. For example, in the case of thick paper or an OHT film, the optimum transfer current value is high. On the other hand, for thin paper, the optimum transfer current value is low, and if the transfer conditions of the apparatus main body are optimized for thick paper or OHT film, the "re-transfer" phenomenon also occurs.

[0005] JP-A-2-66559, JP-A-2-
JP-A-87159, JP-A-2-146557, JP-A-2-167566, JP-A-5-61251 and the like have proposed that the transfer rate can be improved by subjecting toner to mechanical shock treatment. I have.

In the methods proposed in these publications, the transfer rate is surely improved when the transfer condition is set to the highest transfer efficiency for the toner. However, the transfer efficiency when the transfer current value is set higher than that. Is hardly improved and has no effect on the improvement of “retransfer”.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner for developing an electrostatic image which solves the above-mentioned problems of the prior art.

That is, an object of the present invention is to provide a toner for developing an electrostatic charge image capable of obtaining a high image density without causing "retransfer" under a wide range of transfer current conditions (particularly under a high transfer current condition).

It is a further object of the present invention to provide a toner for developing an electrostatic image capable of obtaining an image of high image density and good quality.

[0010]

According to the present invention, there is provided a toner for developing an electrostatic image having toner particles containing at least a binder resin and a colorant, and inorganic fine particles externally added to the toner particles. , Average particle size 0.05-2.
Formula of _{0μm (1) M x O y} ··· (1) ( wherein, M is aluminum element, titanium element, shows the zinc element or zirconium element, O represents an oxygen element, x and y are 0 Wherein the toner has one or more endothermic peaks at 120 ° C. or less in differential thermal analysis. Related to toner. Hereinafter, the “present invention 1” particularly means a toner having this configuration.

The present invention also relates to a toner for developing an electrostatic image comprising toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles.
The inorganic fine particles have an average particle diameter of 0.1 to 3.0 μm and are represented by the following formula (2) or (3): M _x Ti _y O _z (2) M _x Si _y O _z (3) ( In the formula, M indicates a metal element, Ti indicates a titanium element, Si indicates a silicon element, O indicates an oxygen element,
x and y are non-zero positive numbers. ), The toner has one or more endothermic peaks in differential thermal analysis at 120 ° C. or lower, and the toner has a shape factor measured by an image analyzer. S
The value of F-1 is in the range of 110 to 180, the value of the shape factor SF-2 is in the range of 110 to 140, and S
A ratio B / A of a value B obtained by subtracting 100 from the value of F-2 and a value A obtained by subtracting 100 from the value of SF-1 is 1.0 or less, and . Hereinafter, the “present invention 2” particularly means a toner having this configuration.

Further, the present invention provides a toner for developing an electrostatic charge image comprising toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles.
The inorganic fine particles include inorganic carbide fine particles having an average particle size of 0.05 to 2.0 μm, and the toner has one or more endothermic peaks at 120 ° C. or lower in differential thermal analysis. The present invention relates to a toner for developing a charge image. Hereinafter, the “present invention 3” particularly means a toner having this configuration.

According to the present invention, there is provided a toner for developing an electrostatic charge image comprising toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles.
The inorganic fine particles have metal carbonate fine particles having an average particle size of 0.05 to 2.0 μm, and the toner has one or more endothermic peaks in differential thermal analysis at 120 ° C. or lower. The present invention relates to a toner for developing a charge image. Hereinafter, the “present invention 4” particularly means a toner having this configuration.

Further, the present invention provides a toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, wherein the inorganic fine particles contain a silicone oil. The fine particles of silicon oxide or silicon composite oxide having an average particle diameter of 0.03 to 50 μm. The toner has one or more endothermic peaks in differential thermal analysis at 120 ° C. or lower. Is that the value of the shape factor SF-1 measured by the image analyzer is in the range of 110 to 180, the value of the shape factor SF-2 is in the range of 110 to 140, and 100 is calculated from the value of SF-2. The present invention relates to a toner for developing an electrostatic image, wherein a ratio B / A of a subtracted value B and a value A obtained by subtracting 100 from the value of SF-1 is 1.0 or less.
Hereinafter, the “present invention 5” particularly means a toner having this configuration.

The present inventors have studied for the purpose of solving "retransfer" and found that "retransfer" can be solved by increasing the charge amount of the toner before transfer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The above-mentioned fine particles are externally added to toner base particles, and a toner having one or more endothermic peaks at 120 ° C. or lower in differential thermal analysis is used, so that the above-described electrostatic latent image carrying before transfer is carried out. The charge amount of the toner on the body or the intermediate transfer body can be made higher than before, and "retransfer" can be prevented.

At the time of development and transfer, the fine particles are separated from the toner matrix, and the fine particles impart a charge to the toner matrix itself, so as to increase the amount of charge of the toner before transfer.
We think that we can prevent.

When the average particle diameter of the fine particles is less than 0.05 μm in the present inventions 1, 3 and 4, and the average particle diameter of the fine particles is less than 0.1 μm in the present invention 2, the adhesion of the fine particles to the toner surface is too large, At the time of development / transfer, the toner is not sufficiently separated from the mother toner, and the amount of charge of the toner before transfer cannot be increased.

When the average particle diameter of the fine particles exceeds 2.0 μm in the present inventions 1, 3 and 4, and the average particle diameter of the fine particles exceeds 3.0 μm in the present invention 2, the surface area of the fine particles is small and the toner tribo before transfer is reduced. The effect of enhancing is small and there is no effect of preventing "retransfer". In addition, aggregation of toner particles may occur with fine particles as nuclei, which may cause an increase in fog.

The toner of the present invention 5 has a particle diameter of 0.1.
Silicon oxide fine particles or silicon composite oxide fine particles having a relatively large particle diameter containing silicone oil having a particle size of 03 to 50 μm (preferably 0.04 to 1 μm) are externally added. When the particle size is less than 0.03 μm, the fine particles containing silicone oil strongly adhere to the toner surface too much, and do not sufficiently separate from the toner matrix during development / transfer, and charge of the toner before transfer. Since the amount cannot be increased, there is no effect in preventing "retransfer".

If the particle diameter of the fine particles containing silicone oil exceeds 50 μm, the effect of preventing “retransfer” cannot be sufficiently obtained.

The fine particles are used in a form externally added to the toner matrix. If the fine particles are in the state of being internally added to the toner matrix and in the state of being firmly fixed to the toner surface, the charge amount of the toner before transfer cannot be increased, and there is no effect in preventing “re-transfer”.

In the present invention, the fine particles preferably have the same charge polarity to the iron powder carrier as that of the toner. When the charging polarity of the fine particles is the same as the charging polarity of the toner, the image density is higher and the fog can be further suppressed.

Further, in the present invention 1, 2, and 4, the above-mentioned fine particles have an absolute value of a charge amount to an iron powder carrier.
20 | μC / g or less, more preferably | 10 | μC / g
The following is preferred. In the case of the inorganic carbide of the present invention 3, the charge amount of the iron powder carrier with respect to the iron powder carrier is | 30 | μC / g or less in absolute value, more preferably | 20 | μC / g.
g or less. When the charge amount of the fine particles is in the above range, the image density is higher and fog can be further suppressed.

In the inventions 1 to 4, the amount of the fine particles added to the toner may be 0.01 to 100 parts by mass of the toner.
It is preferably 3.0 parts by mass (more preferably 0.05 to 1.0 part by mass). In the present invention 5, the toner 100
It is preferably 0.1 to 10 parts by mass (more preferably 0.1 to 2.0 parts by mass) with respect to parts by mass.

If the amount of the fine particles added to the toner falls below the lower limit, the effect of increasing the charge amount of the toner before transfer is insufficient, and the effect of preventing "retransfer" cannot be sufficiently obtained. When the amount of fine particles added to the toner exceeds the upper limit,
Fog tends to occur.

Next, the material of each fine particle according to the present invention 1 to 5 will be described in detail.

In the fine particles of the compound represented by the chemical formula M _x O _y used in the toner of the present invention 1, M is any one of aluminum, titanium, zinc and zirconium.

Of these, titanium oxide is more preferred. When titanium oxide fine particles are used, the image density is further increased and fog can be further suppressed.

In particular, in the case of a titanium oxide having a rutile type crystal form, the effect of preventing "retransfer" is further enhanced.

Further, and forms one of M ¹ _x O _y different M ² _x O _y on the surface of the fine particles are adhered, coated, in the form of two or more of M _x O _y is mixed I don't care. Further, the surface of the fine particles may be subjected to a hydrophobic treatment.

[0032] M _x Ti _y O _z for use in the present invention second toner, M is, for example, strontium, barium, magnesium, elements such as calcium. Also,
The M _x Si _y O _z, M is, for example, strontium, barium, magnesium, elements such as calcium.

Of these, the case where M is strontium is particularly preferred because of its high effect of preventing "retransfer".

In addition, a form in which one kind is adhered / coated on the surface of another kind, or a form in which two or more kinds are mixed crystals may be used. Further, the surface of the fine particles may be subjected to a hydrophobic treatment.

The inorganic carbide used in the present invention 3 includes carbides such as boron, silicon, titanium, vanadium, zirconium, molybdenum and tungsten. Of these, carbides of boron or silicon are more preferred because of the effect of preventing "retransfer". Furthermore, among these, silicon carbide in particular is more re-transferred
The effect of prevention is higher and preferable.

As the metal carbonate fine particles used in the present invention 4, carbonates such as magnesium, calcium, strontium and barium can be mentioned. Among them, strontium carbonate fine particles are more preferable because they have a higher effect of preventing "retransfer". It may be in the form of a bicarbonate. Further, the surface may be subjected to a hydrophobic treatment.

The silicon oxide fine particles used in the present invention 5 are produced, for example, from dry silica called so-called dry method or fumed silica produced by vapor phase oxidation of silicon halide, and water glass. Both of so-called wet silicas can be used, but there are few silanol groups on the surface and inside the silica fine powder, and Na
Dry silica with less production residue such as ₂ O and SO ³⁻ is preferred. Further, as the silicon composite oxide fine particles, in the production process, for example, a composite oxide of silicon oxide and another metal oxide obtained by using another metal halide such as aluminum chloride and titanium chloride together with the silicon halide is used. Substance fine particles, which are also included in the present invention.

When the silicon oxide or composite oxide fine particles do not contain silicone oil, the effect of preventing retransfer is hardly obtained. Interaction between the relatively strong surface of silicon oxide or composite oxide and silicone oil causes the silicone oil to become a kind of highly active state, thereby increasing the charge amount of the toner developed on the photoreceptor. It is thought that it is possible.

As the form of the silicone oil, in addition to the form of coating the surface of the fine particles, a form in which the fine particles take the form of an agglomerate formed by the silicone oil is preferably used.

When the surface of the fine particles is coated with silicone oil, the BET specific surface area of the original fine particles is 10%.
It is preferably 0 m ² / g or less, more preferably 70 m ² / g or less. Also, if particles are in the form of aggregates, which are granulated with a silicone oil, it preferably has a BET specific surface area is 100m ² / g~400m ² / g.

Further, as the silicon oxide or composite oxide particles, those which have been made hydrophobic by a coupling agent or the like before containing silicone oil may be used.

The preferred viscosity of the silicone oil is such that when the silicone oil covers the surface of the fine particles, the viscosity at 25 ° C. is 0.5 to 10,000 centistokes, preferably 1 to 1,000 centistokes, more preferably 10 to 1000 centistokes. ~ 200 centistokes are used. When the fine particles are in the form of an aggregate formed by granulation with silicone oil, those having a viscosity at 25 ° C. of 50 to 200,000 centistokes, preferably 500 to 150,000 centistokes are used.

Preferred examples of the silicone oil include dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil, and amino-modified silicone oil.

As a method of treating silicone oil, for example, silica fine powder treated with a silane coupling agent and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or silica fine powder serving as a base may be mixed. A method of spraying silicone oil on the body may be used.
Alternatively, a method of dissolving or dispersing a silicone oil in an appropriate solvent, adding a silica fine powder, mixing and removing the solvent may be used.

After the treatment, it is more preferable to heat the inorganic fine powder to 200 ° C. or higher (more preferably 250 ° C. or higher) in an inert gas to stabilize the surface coat.

These toners of the present invention have an endothermic peak of 120 ° C. or less in differential thermal analysis (preferably 11 ° C.).
One or more).

The endothermic peak in the differential thermal analysis is 120 ° C.
If not, the effect of preventing "retransfer" by externally adding the fine particles of the present invention cannot be sufficiently obtained.

The endothermic peak in the differential thermal analysis is 120 ° C.
The following toners have a unique state in which the dispersion state of the magnetic substance / charge control agent in the binder resin in the melt-kneading step in the production thereof is different from the toner having an endothermic peak not higher than 120 ° C. It is presumed. It is considered that such a specific state makes the effect of preventing "retransfer" of the specific fine particles of the present invention easy to work.

The endothermic peak in the differential thermal analysis is 120 ° C.
At least one of the following is effective, and the endothermic peak may be at a temperature exceeding 120 ° C.
However, it is preferable that the endothermic peak in the differential thermal analysis does not exist at 60 ° C. or lower (preferably 70 ° C. or lower). When the endothermic peak in the differential thermal analysis exists at 60 ° C. or lower, the image density tends to be low. In addition, storage stability tends to be unstable.

The endothermic peak in the differential thermal analysis was 120 ° C.
As a means for providing the following mode, a method of internally adding a compound having an endothermic peak at 120 ° C. or lower in differential thermal analysis to the toner is preferable.

The endothermic peak in the differential thermal analysis was 120 ° C.
Examples of the substance having one or more of the following include a resin and a wax.

Examples of the resin include a crystalline polyester resin and a silicone resin.

As the wax, paraffin wax,
Microcrystalline wax, petroleum wax such as petrolactam and its derivatives, montan wax and its derivatives, hydrocarbon wax and its derivatives by Fischer-Tropsch method, polyolefin wax and its derivatives represented by polyethylene, carnauba wax,
Natural waxes such as candelilla wax and derivatives thereof and the like, and derivatives include oxides, block copolymers with vinyl monomers, and graft-modified products. Alcohols such as higher aliphatic alcohols; fatty acids such as stearic acid and palmitic acid or compounds thereof; acid amides, esters, ketones, hydrogenated castor oil and derivatives thereof, vegetable waxes, animal waxes, etc .;
Any material having a temperature of not more than ° C can be used.

Among them, when the compound having an endothermic peak at 120 ° C. or lower in the differential thermal analysis is polyolefin, hydrocarbon wax or petroleum wax or higher alcohol by Fischer-Tropsch method, furthermore, polyolefin or Fischer-Tropsch method Is particularly preferable in the toner of the present invention.

When the above specific compound is used,
The effect of preventing "retransfer" is further enhanced.

These compounds have relatively low polarities themselves and are considered to stabilize the charge of the toner matrix. It is believed that this further enhances the effect of preventing "retransfer" of the fine particles of the present invention.

Among these compounds, compounds having an endothermic peak at 120 ° C. or lower in differential thermal analysis are polyolefins, hydrocarbon waxes by Fischer-Tropsch method, petroleum waxes and higher alcohols, and their weight average molecular weights measured by GPC. (Mw)
And the number average molecular weight (Mn) ratio (Mw / Mn) is 1.0
When it is 2.0, the effect of preventing "retransfer" is further enhanced. By adding the wax having a sharp molecular weight distribution (Mw / Mn) of 1.0 to 2.0 to the toner, the magnetic material in the binder resin, charge control in the melt-kneading step in the production of the toner. It is considered that the state of dispersion of the agent and the like is more preferable for the present invention.

In the toners of the present inventions 2 and 5, the value of the shape factor SF-1 measured by an image analyzer for toner particles is 110 <SF-1 ≦
180 (more preferably, 120 <SF-1 ≦ 16
0), the value of the shape factor SF-2 is 110 <SF-2 ≦ 14
0 (more preferably, 115 <SF−2 ≦ 140), and a value B obtained by subtracting 100 from the value of SF−2 and SF
The ratio B / A to the value A obtained by subtracting 100 from the value of −1 is 1.0.
Must be: The shape in the above range is a shape in which the toner surface is relatively smooth and has few irregularities. In the case of such a shape, it is considered that the fine particles externally added to the toner work more effectively, and the effect of preventing “retransfer” is enhanced.

When SF-1 is 110 or less, SF-
When 2 is 110 or less, and when B / A is less than 1.0, it is difficult to clean the transfer residual toner remaining on the latent image carrier, and cleaning failure tends to occur. When SF-1 exceeds 180 and when SF-2 exceeds 140, further improvement in the effect of preventing "retransfer" cannot be sufficiently obtained.

The toners 1, 3 and 4 of the present invention are sufficiently effective in preventing "retransfer" of the toner irrespective of the shape of the toner particles.
If (−1, SF-2) satisfies the above range, the “re-transfer” prevention effect can be further enhanced by combination with the “re-transfer” prevention effect by the shape of the toner particles.

The following method can be used to adjust the shape of the toner of the present invention to the above range.

A method of pulverizing using a mechanical impact type pulverizing apparatus or a method of jet pulverizing, in which the pulverizing pressure is reduced from a normal level to increase the number of circulations, and pulverizing is performed. In addition, a hot water bath method in which finely pulverized or further classified toner particles are dispersed in water and heated, a heat treatment method in which the toner particles are passed through a hot air flow, and a mechanical impact method in which mechanical energy is applied to treat the toner particles are exemplified. .

Among these, the method of applying treatment by mechanical impact is preferable. Examples of the treatment for applying a mechanical impact force include, for example, a method of applying a mechanical impact force to a toner by a mechanical impact type pulverizer such as a Kryptron system manufactured by Kawasaki Heavy Industries, Ltd. or a turbo mill manufactured by Turbo Industries, Inc., and Hosokawa Micron. Like high-speed rotating blades, the toner is pressed against the inside of the casing by centrifugal force, and applied to the toner by compressive and frictional forces, as in devices such as Mechanofusion System manufactured by Nara Corporation and hybridization systems manufactured by Nara Machinery. There is a method of applying a mechanical impact force.

When the treatment for applying the mechanical impact force is performed after the fine pulverizing step of the toner or after the classification step, the effect of preventing “retransfer” is further enhanced, which is particularly preferable. It is also considered that the mechanical impact treatment causes the toner surface to have a “certain unique surface state” in which the action of the fine particles of the present invention is more likely to work.

Examples of the binder resin usable in the present invention include the following. In the case of the toner for heat fixing, for example, polystyrene, poly-p-chlorostyrene, a homopolymer of styrene such as polyvinyltoluene and a substituted product thereof; a styrene-vinylnaphthalene copolymer, a styrene-acrylate copolymer, Styrene-methacrylic acid ester copolymer, styrene-maleic acid ester copolymer, styrene-acrylic acid copolymer, styrene-methacrylic acid copolymer, styrene-maleic acid copolymer, styrene-α-chloromethyl methacrylate Copolymer, styrene-acrylonitrile copolymer, styrene-
Styrenes such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymer; polyvinyl chloride,
Phenol resin, natural modified phenolic resin, natural resin modified maleic resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, tempen resin , Coumarone indene resin, petroleum resin and the like can be used.

Among these, the styrene copolymer is
The effect of preventing "retransfer" is further enhanced, which is particularly preferable.

The styrene copolymer has a relatively low polarity of its own main chain, and is considered to stabilize the charge of the toner matrix. It is believed that this further enhances the effect of preventing "retransfer" of the fine particles of the present invention.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. Monocarboxylic acid having a heavy bond or a substituted product thereof; acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and α- or β-alkyl derivatives thereof, fumaric acid, maleic acid, citraconic acid Unsaturated dicarboxylic acids and monoester derivatives thereof, maleic anhydride and the like can be used. Such a monomer can be used alone or as a mixture and copolymerized with another monomer to produce a desired polymer.

Among these, it is particularly preferable to use a monoester derivative of an unsaturated dicarboxylic acid. More specifically, for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, monooctyl maleate, monoallyl maleate, monophenyl maleate,
Α-, β such as monomethyl fumarate, monoethyl fumarate, monobutyl fumarate, monophenyl fumarate, etc.
Monoesters of unsaturated dicarboxylic acids; alkenyl dicarboxylic acids such as monobutyl n-butenylsuccinate, monomethyl n-octenylsuccinate, monoethyl n-butenylmalonate, monomethyl n-dodecenylglutarate, monobutyl n-butenyladipate and the like. Monoesters of aromatic dicarboxylic acids such as monomethyl phthalate, monoethyl phthalate and monobutyl phthalate; vinyls such as vinyl chloride, vinyl acetate and vinyl benzoate Esters, for example, ethylene olefins such as ethylene, propylene, butylene, etc .; for example, vinyl ketones, for example, vinyl methyl ketone, vinyl hexyl ketone, etc .; for example, vinyl methyl ether, vinyl ethyl ether, vinyl iso Vinyl ethers such as Chirueteru; vinyl monomers are used alone or in combination.

Here, as the cross-linking agent, a compound having two or more polymerizable double bonds is mainly used, for example, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene, etc .; Carboxylic acid esters having two double bonds such as acrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and three or more Can be used alone or as a mixture.

The toner of the present invention is particularly effective when the toner contains a magnetic substance.

The magnetic substance contained in the toner of the present invention is preferably an alloy or compound powder containing a ferromagnetic element. Examples of such materials include magnetite, maghemite, ferrite, and the like, and alloys and compounds such as iron, cobalt, nickel, manganese, and zinc, and other ferromagnetic alloys.

[0073] As a BET specific surface area by nitrogen gas adsorption method of the magnetic powder, 1~40m ² / g, more 2～30M ²
/ G is preferred.

The average particle size of the magnetic powder is 0.05 to 1
μm, preferably 0.1 to 0.6 μm.

Further, the magnetic material contains the binder resin 100 in the toner.
It is preferable to contain 60 parts by mass to 200 parts by mass, more preferably 80 parts by mass to 150 parts by mass, based on parts by mass.

The toner of the present invention is particularly preferable when it contains a magnetic substance having a substantially spherical shape. In the melt-kneading step in the production, the state of dispersion of the magnetic material in the binder resin is different from the case where the shape of the magnetic material is substantially other than spherical, and a specific surface state is more preferable. It is believed that the effect of preventing "retransfer" of the fine particles further works. When the shape of the magnetic material is “substantially spherical”, the average of the ratio of the major axis to the minor axis (major axis / minor axis) of each particle (100 or more particles measured) is 1. 0
~ 1.2.

In the toner of the present invention, a charge control agent can be used by mixing (internal addition) with the toner particles or by mixing (externally adding) the toner particles with the toner particles. The charge control agent makes it possible to control the amount of charge optimally according to the development system. In particular, in the present invention, the balance between the particle size distribution and the amount of charge can be further stabilized. Examples of substances that control the toner to be negatively charged include the following substances.

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

The toner of the present invention preferably has a form in which a second inorganic fine powder is externally added to the developer for the purpose of adding fluidity to the toner. In the fifth aspect, the average particle size of the second inorganic fine powder is set to 0.03 μm or less.

It is preferable that the second inorganic fine powder is contained by stirring and mixing with a developer and a mixer such as a Henschel mixer.

As the second inorganic fine powder used in the present invention, inorganic fine powders such as silica fine powder, titanium oxide and aluminum oxide are preferable, and fine silica powder is particularly preferable.
For example, as the silica fine powder, both a so-called dry method produced by the vapor phase oxidation of a silicon halide or a so-called fumed silica and a so-called wet silica produced from water glass or the like can be used. However, dry silica having less silanol groups on the surface and in the interior of the silica fine powder and having less production residues such as Na ₂ O and SO ₃ ²⁻ is preferred. In the case of fumed silica, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride and titanium chloride together with a silicon halide in the production process. They are also included.

Further, a material whose surface has been previously rendered hydrophobic with an organic compound may be used. Examples of such an organic treatment method include a method of treating with an organic metal compound such as a silane coupling agent or a titanium coupling agent that reacts or physically adsorbs with the inorganic fine powder; or a treatment with a silane coupling agent, or a treatment with silane. A method of treating with a coupling agent and treating with an organosilicon compound such as silicone oil at the same time.

The second inorganic fine powder used in the present invention is B
The specific surface area by nitrogen adsorption measured by the ET method is 30 m ² /
g or more, particularly preferably in the range of 50 to 400 m ² / g.

The weight average particle diameter of the toner is preferably 10.0 μm (preferably 8.0 μm) or less. When the weight average particle diameter of the toner is 10.0 μm or less, the effect of preventing “retransfer” is further enhanced. It is considered that when the weight average particle diameter of the toner is 10.0 μm or less, the charge amount of the toner on the latent electrostatic image bearing member or the intermediate transfer member before transfer is further increased.

Further, as a method for producing the toner of the present invention, the following method can be mentioned. In producing the toner according to the present invention, the above-described constituent materials were mixed using a Henschel mixer, a ball mill, a V-type mixer or other mixer, and a hot kneader such as a hot roll kneader or an extruder. Kneading step, after cooling and solidifying the kneaded material, a pulverizing step using a pulverizer such as a jet mill,
It is preferable to be manufactured through a manufacturing step having at least the above steps. Further, if necessary, it is preferable to go through a classifying step of the pulverized material.

Among these, a production method having at least a step of melt-kneading the binder resin and the other composition and a pulverization step of finely pulverizing the same is particularly preferable.

In the melt-kneading step, when the endothermic peak in the differential thermal analysis is 120 ° C. or less, the dispersion state of the magnetic substance and the charge control agent in the binder resin becomes a preferable state for the present invention, and it is pulverized. Thus, the specific state is exposed to the toner surface as it is, and the effect of preventing "retransfer" of the toner of the present invention is exhibited.

In the present invention, SF-
1. SF-2 is, for example, FE-SEM manufactured by Hitachi, Ltd.
Using (S-800), 100 toner images of 2 μm or more that were enlarged 1000 times were randomly sampled, and the image information was introduced into an image analyzer (Luzex III) manufactured by Nicolet, for example, via an interface and analyzed. And the values calculated from the following equation are used as shape factors SF-1, S
Defined as F-2.

[0089]

(Equation 1)

(Where MXLNG is the absolute maximum length of the particle,
PERIME indicates the perimeter of the particle, and AREA indicates the projected area of the particle. )

The shape coefficient SF-1 indicates the degree of roundness of the toner particles, and the shape coefficient SF-2 indicates the degree of unevenness of the toner particles.

The endothermic peak in the differential thermal analysis according to the present invention is measured with a high-precision internal heating type input compensation type differential scanning calorimeter. For example, DSC- manufactured by PerkinElmer, Inc.
7 can be used. The measuring method is ASTM D3418-
Perform according to 82. The DSC curve used in the present invention is:
After raising the temperature once and taking the pre-history, the temperature rate is 10 ° C / mi
n, a DSC curve measured when the temperature is lowered and raised in the temperature range of 0 to 200 ° C. The endothermic peak temperature is
In the DSC curve, a peak temperature in a positive direction, that is, a point at which the differential value of the peak curve becomes 0 when the differential value changes from positive to negative.

The weight average particle diameter of the toner of the present invention is measured using a Coulter Counter TA-II or Coulter Multisizer (manufactured by Coulter). The electrolyte is 1
A 1% NaCl aqueous solution is prepared using graded sodium chloride. For example, ISOTONR-II (manufactured by Coulter Scientific Japan) can be used. As a measurement method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and the measurement sample is further added to 2 to 50 ml.
Add 20 mg. The electrolytic solution in which the sample was suspended was subjected to dispersion treatment for about 1 to 3 minutes using an ultrasonic
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, the weight-based weight average particle diameter D4 (the median value of each channel is set as a representative value for each channel) obtained from the volume distribution according to the present invention was obtained.

As a method for measuring the charge amount of the fine particles of the present invention, EFV200 / 300 (manufactured by Powder Deck Co., Ltd.) is used as a carrier under the environment of temperature: 23 ° C. and humidity: 60%
Then, 10.0 g of the carrier and 0.2 g of the fine particles are placed in a polyethylene container having a capacity of 50 ml, and shaken by hand 90 times. Next, about 1 g of the mixture is placed in a metal measuring container 2 having a 500-mesh screen 3 at the bottom as shown in FIG. At this time, the weight of the entire measurement container 2 is measured and is defined as W1 (g). Next, it is placed on a suction machine (the part in contact with the measurement container 2 is an insulator), and suction is performed from the suction port 7 at a pressure of 2450 Pa (250 mmAq).
In this state, suction is performed for 2 minutes to remove fine particles. The potential of the electrometer 9 at this time is set to V (volt). Here, 8 is a capacitor whose capacity is C (mF).
The weight of the whole measuring container 2 after suction is measured,
(G). The charge amount T (mC / kg) of the fine particles is obtained by the above formula of charge amount T (mC / kg) = C × V / (W1−W2).

[0095]

EXAMPLES The present invention will be described below in more detail with reference to Examples, which should not be construed as limiting the present invention.

Example 1 Styrene-butyl acrylate-butyl maleate-half ester copolymer 100 parts by mass Magnetite (shape: spherical, average particle size: 0.2 μm) 100 parts by mass Iron complex of monoazo dye (negative) Charge controlling agent) 2 parts by mass Low molecular weight polyethylene (endothermic peak of differential thermal analysis: 102 ° C., Mw / Mn: 1.3) 4 parts by mass After pre-mixing the above materials, a biaxial kneading extruder set at 130 ° C. To perform melt-kneading. After cooling the kneaded material, it was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier. Further, surface treatment was performed by mechanical impact force to obtain black powder (toner particles) A.

With respect to 100 parts by mass of the toner particles A, titanium oxide fine particles (crystal form: rutile type, average particle diameter: 0.3 μm, charge amount: −2.8 mC / kg): 0.5 parts by mass, and 1.2 parts by mass of dry silica treated with hexamethyldisilazane / dimethylsilicone oil: 1.2 parts by mass with a Henschel mixer 10B.
The mixture was stirred and mixed at 200 rpm for 2 minutes to obtain a toner.

The weight average particle size of the obtained toner is 6.9 μm.
m, SF-1 was 144, and SF-2 was 126. The endothermic peak in the differential thermal analysis was at 102 ° C.

When the surface of the toner was observed with an electron microscope, it was found that the fine particles 1 were attached to the surface of the toner particles as they were and were not embedded in the surface.

(Examples 2 to 8 and Comparative Examples 1 and 2) The fine particles added in Example 1 were replaced with fine particles 2 to 7 shown in Table 1.
A toner shown in Table 6 was obtained in the same manner as in Example 1 except that the particles were changed to fine particles 9 to 11.

(Examples 9 and 10) Toners shown in Table 6 were obtained in the same manner as in Example 1 except that the amount of the fine particles 1 added in Example 1 was changed to the amount shown in Table 6.

(Examples 11 to 17) Toner particles B were prepared in the same manner as in Example 1 except that the substances shown in Table 5 were added instead of the low molecular weight polyethylene added in Example 1.
To H, and the other conditions were the same as in Example 1 to obtain toners shown in Table 6.

(Examples 18 to 20) The same procedure as in Example 1 was carried out except that the mechanical impact treatment performed in Example 1 was not performed, and the shape shown in Table 5 was adjusted by adjusting the conditions of the mechanical impact treatment. In the same manner, toner particles I to K were obtained, and in the same manner as in Example 1, the toners shown in Table 6 were obtained.

(Examples 21 to 25) Styrene-butyl acrylate copolymer 100 parts by mass Magnetite (shape: spherical, average particle size: 0.2 μm) 80 parts by mass Triphenylmethane dye (positive charge control agent) 2 parts by mass Low molecular weight polyethylene (endothermic peak of differential thermal analysis: 102 ° C., Mw / Mn: 1.3) 4 parts by mass After pre-mixing the above materials, melt kneading was performed by a biaxial kneading extruder set at 130 ° C. Was. After cooling the kneaded material, the mixture was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier.

Further, the surface was treated by a mechanical impact force to obtain a black powder (toner particles) L.

To 100 parts by mass of the toner particles L, 0.5 parts by mass of each of the fine powders 1, 3, 4, 6, and 8 were added.
8 parts by mass with a Henschel mixer 10B for 3200r
The mixture was stirred and mixed at pm for 2 minutes to obtain a toner.

The weight average particle diameter of the obtained toner is 7.6 μm.
m, SF-1 was 146, SF-2 was 124, and the ratio B / A was 0.52. The endothermic peak in the differential thermal analysis was at 102 ° C.

(Examples 26 to 30) Example 1 was repeated except that the fine particles added in Example 1 were changed to fine particles of metal titanate or fine particles of metal silicate 12 to 16 shown in Table 2.
A toner was obtained in the same manner as described above.

(Examples 31 and 32) A toner was obtained in the same manner as in Example 29 except that the addition amount of the fine particles 15 added in Example 29 was changed to the amount shown in Table 7.

Examples 33 to 39 Toners shown in Table 7 were obtained in the same manner as in Example 1 except that the fine particles 15 were added to the toner particles B to H shown in Table 5.

Examples 40 and 41 Toners shown in Table 7 were obtained in the same manner as in Example 1 except that the fine particles 15 were added to the toner particles J and K shown in Table 5.

Example 42 A toner was obtained in the same manner as in Example 21 except that the fine particles 15 were used instead of the fine particles used in Example 21.

(Examples 43 to 45) The fine particles added in Example 1 were replaced with metal carbide fine particles 17 to 1 shown in Table 3.
A toner was obtained in the same manner as in Example 1, except for changing the toner to 9.

(Examples 46 and 47) A toner was obtained in the same manner as in Example 43 except that the addition amount of the fine particles 17 added in Example 43 was changed to the amount shown in Table 8.

Examples 48 to 54 Toners shown in Table 8 were obtained in the same manner as in Example 1 except that the fine particles 17 were added to the toner particles B to H shown in Table 5.

(Examples 55 to 57) Toners shown in Table 8 were obtained in the same manner as in Example 1 except that the fine particles 17 were added to the toner particles I to K shown in Table 5.

Example 58 A toner was obtained in the same manner as in Example 21 except that the fine particles 17 were used instead of the fine particles used in Example 21.

(Examples 59 to 61) The fine particles added in Example 1 were replaced with metal carbonate fine particles 20 to 2 shown in Table 4.
A toner was obtained in the same manner as in Example 1, except for changing the toner to 2.

(Examples 62 and 63) A toner was obtained in the same manner as in Example 59, except that the addition amount of the fine particles 20 to be added was changed to the amount shown in Table 9.

Examples 64 to 70 Toners shown in Table 9 were obtained in the same manner as in Example 1 except that the fine particles 20 were added to the toner particles B to H shown in Table 5.

(Examples 71 to 73) Toners shown in Table 9 were obtained in the same manner as in Example 1 except that the fine particles 20 were added to the toner particles I to K shown in Table 5.

Example 74 A toner was obtained in the same manner as in Example 21 except that the fine particles 20 were used instead of the fine particles used in Example 21.

Comparative Example 3 Polyester resin (condensed polymer of propoxylated bisphenol and fumaric acid) 100 parts by mass Magnetite (shape: octahedron, average particle size: 0.2 μm) 60 parts by mass Iron complex of monoazo dye (negative) Charge controlling agent) 2 parts by mass Low molecular weight polypropylene (endothermic peak of differential thermal analysis: 145 ° C., Mw / Mn: 8.8) 4 parts by mass After pre-mixing the above materials, a biaxial kneading extruder set to 130 ° C. To perform melt-kneading. After cooling the kneaded material, the mixture was roughly pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier to obtain black powder (toner particles) M.

To 100 parts by mass of the toner particles M, 0.4 parts by mass of dry silica treated with hexamethyldisilazane / dimethylsilicone oil was stirred and mixed at 3200 rpm for 2 minutes using a Henschel mixer 10B to obtain a toner.

The weight average particle diameter of the obtained toner is 11.3.
μm, SF-1 was 160, and SF-2 was 154.
The endothermic peak in differential thermal analysis was at 145 ° C.

<Evaluation> The toners of the above Examples and Comparative Examples were each evaluated by the following methods. Table 6-
The results are shown in FIG.

1) Evaluation of transferability Laser beam printer LBP-1260 manufactured by Canon
Using a device equipped with a variable transfer bias power supply and developing a solid black image in an environment of 23 ° C./60% RH,
The image was transferred onto a transfer paper of 75 g / m ² , and the transfer residual image remaining on the photoreceptor was peeled off with a transparent polyester adhesive tape and pasted on white paper. The reflection density was measured with a Macbeth reflection densitometer, and was used as a standard. The density of the portion where only the tape was stuck on the white paper was evaluated by subtracting the density therefrom. The transfer voltage was evaluated in increments of 0.5 kV from 1.0 to 3.0 kV.

2) Evaluation of image density / fog Laser beam printer LBP-1260 manufactured by Canon
32 ° C./80 using a Canon copier PC330
After leaving 1,000 images in an environment of 100% for 2 days, a solid black image was printed, and the image density was measured and evaluated with a Macbeth reflection densitometer.

At the same time, a solid white image was printed, and the difference between the whiteness on unused transfer paper measured by a reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and the whiteness of the transfer paper after printing solid white was measured. Was evaluated for fog.

[0130]

[Table 1]

[0131]

[Table 2]

[0132]

[Table 3]

[0133]

[Table 4]

[0134]

[Table 5]

[0135]

[Table 6]

[0136]

[Table 7]

[0137]

[Table 8]

[0138]

[Table 9]

[0139]

[Table 10]

(Production Example 1 of Silicon Oxide Fine Particles Containing Silicone Oil) Silica fine powder (specific surface area: 52 m ² / g) synthesized by a dry method was placed in a closed Henschel mixer heated to 80 ° C. Put the silica fine powder 10
The dimethyl silicone oil (viscosity at 25 ° C .: 50 cSt) diluted with xylene so as to be 10 parts by mass with respect to 0 parts by mass was stirred at a high speed while spraying, and then the solvent was volatilized to contain the silicone oil. Silica (silicon oxide) fine particles a were obtained.

(Production Example 2 of Silicon Oxide Fine Particles Containing Silicone Oil) Fine silica powder (specific surface area: 15 m ² / g) synthesized by a dry method was placed in a closed Henschel mixer heated to 80 ° C. Put the silica fine powder 10
Dimethyl silicone oil (viscosity at 25 ° C .: 50 cSt) diluted with xylene so as to be 8.5 parts by mass and amino-modified silicone oil diluted with xylene so as to be 1.5 parts by mass with respect to 0 parts by mass (Viscosity at 25 ° C .: 50 cSt), and the mixture was stirred at high speed, and then the solvent was volatilized to obtain silica (silicon oxide) fine particles b containing silicone oil.

(Production Example 3 of Silicon Oxide Fine Particles Containing Silicone Oil) Except for using, as the original silica fine powder, a powder surface-treated with hexamethyldisilazane (specific surface area: 47 m ² / g) In the same manner as in Production Example 1, silica (silicon oxide) fine particles c containing silicone oil were obtained.

(Production Example 4 of Silicon Oxide Fine Particles Containing Silicone Oil) Silicone oil was prepared in the same manner as in Production Example 1, except that the original silica fine powder had a specific surface area of 100 m ² / g. Oil-containing silica (silicon oxide) fine particles d were obtained.

(Production Example 5 of Silicon Oxide Fine Particles Containing Silicone Oil) Silica fine powder (specific surface area: 200 m ² / g) synthesized by a dry method was placed in a closed Henschel mixer heated to 80 ° C. Put the silica fine powder 1
The dimethylsilicone oil (viscosity at 25 ° C .: 10,000 cSt) diluted with xylene to 100 parts by mass with respect to 00 parts by mass was stirred at a high speed while spraying, and then the solvent was volatilized to contain the silicone oil. Silica (silicon oxide) fine particles e were obtained.

(Production Example 6 of Silicon Oxide Fine Particles Containing Silicone Oil) Silica fine powder (specific surface area: 200 m ² / g) synthesized by a dry method was placed in a closed Henschel mixer heated to 80 ° C. Put the silica fine powder 1
While spraying dimethyl silicone oil (viscosity at 25 ° C .: 10,000 cSt) diluted with xylene to 85 parts by mass and amino-modified silicone oil diluted with xylene to 15 parts by mass with respect to 00 parts by mass. The mixture was stirred at a high speed, and then the solvent was volatilized to obtain silica (silicon oxide) fine particles f containing silicone oil.

(Production Example 7 of Silicon Oxide Fine Particles Containing Silicone Oil) Silicon-aluminum composite oxide containing 1% of an aluminum element (specific surface area: 45 m ²⁾
/ G) into a closed Henschel mixer heated to 80 ° C., and 10 parts by mass with respect to 100 parts by mass of the silica fine powder.
The mixture was stirred at a high speed while spraying dimethyl silicone oil (viscosity at 25 ° C .: 50 cSt) diluted with xylene so as to be in parts by mass, then the solvent was volatilized, and the silicon-aluminum composite oxide containing silicon oil (silicon) was added. (Compound oxide) fine particles g were obtained.

Table 11 shows various physical property values of the fine particles a to g of the obtained silicon oxide or silicon composite oxide.

[0148]

[Table 11]

Example 75 Styrene-butyl acrylate-butyl maleate-half ester copolymer 100 parts by mass Magnetite (shape: spherical, average particle size: 0.2 μm) 100 parts by mass Iron complex of monoazo dye (negative) Charge controlling agent) 2 parts by mass Low molecular weight polyethylene (endothermic peak of differential thermal analysis: 102 ° C., Mw / Mn: 1.3) 4 parts by mass After pre-mixing the above materials, a biaxial kneading extruder set at 130 ° C. To perform melt-kneading. After cooling the kneaded material, it was coarsely pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier. Further, surface treatment was performed by mechanical impact to obtain black powder (toner particles) N.

[0150] Based on 100 parts by mass of the toner particles N, 0.5 parts by mass of fine particles a surface-treated with dimethylsilicone oil, dry silica treated with hexamethyldisilazane / dimethylsilicone oil (average particle size: 0.1 part by mass). 01
μm): 1.2 parts by mass was stirred and mixed with a Henschel mixer 10B at 3200 rpm for 2 minutes to obtain a toner.

The weight average particle diameter of the obtained toner is 6.9 μm.
m, SF-1 was 144, and SF-2 was 126. The endothermic peak in the differential thermal analysis was at 102 ° C.

When the surface of the toner was observed with an electron microscope, the average particle size of the fine particles a surface-treated with dimethyl silicone oil was 0.04 μm. There was no.

(Examples 76 to 80 and Comparative Example 4) The fine particles added in Example 75 were replaced with the fine particles b shown in Table 11.
Except for using ｇg, a toner was obtained in the same manner as in Example 75.

(Examples 81 to 83) A toner was obtained in the same manner as in Example 75 except that the addition amount of the fine particles a added in Example 75 was changed to the amount shown in Table 13.

(Examples 84 to 90) Toner particles O to U were obtained in the same manner as in Example 75 except that the substances shown in Table 12 were added instead of the low molecular weight polyethylene added in Example 75. Was obtained in the same manner as in Example 75.

(Examples 91 and 92) By adjusting the conditions of the opportunity impact treatment performed in Example 75, Table 1 was obtained.
The toner particles V and W were obtained in the same manner as in Example 75 except that the shape was adjusted to the shape shown in FIG.

(Comparative Example 5) Polyester resin (condensed polymer of propoxylated bisphenol and fumaric acid) 100 parts by mass Magnetite (shape: octahedral, average particle size: 0.2 μm) 60 parts by mass Iron complex of monoazo dye (negative) Charge controlling agent) 2 parts by mass Low molecular weight polypropylene (Differential thermal analysis endothermic peak: 145 ° C., Mw / Mn: 8.8) 4 parts by mass After pre-mixing the above materials, a biaxial kneading extruder set at 130 ° C. To perform melt-kneading. After cooling the kneaded material, it was roughly pulverized, finely pulverized by a pulverizer using a jet stream, and further classified using an air classifier.
A black fine powder (toner particle) X shown in FIG. 2 was obtained. The endothermic peak in the differential thermal analysis was at 145 ° C.

Hexamethyldisilazane / dimethylsilicone oil-treated dry silica (average particle diameter: 0.01 μm): 0.4 part by mass with respect to 100 parts by mass of the toner particles X: 3200 rpm for 2 minutes using a Henschel mixer 10B. The mixture was stirred and mixed to obtain a toner.

The weight average particle size of the obtained toner is 11.3.
μm, SF-1 was 160, and SF-2 was 154.

<Evaluation> The toners of Examples 75 to 92 and Comparative Examples 4 and 5 were evaluated by the following methods.
The results are shown in Tables 13 and 14.

1) Evaluation of transferability The evaluation was performed in the same manner as in Examples 1 to 74.

2) Evaluation of Image Density / Fog Examples 1 to 74 except that the number of images to be output was 2,000
The same was done.

[0163]

[Table 12]

[0164]

[Table 13]

[0165]

[Table 14]

[0166]

According to the present invention, "retransfer" does not occur even under a high transfer current condition, and an image of high quality and high image quality can be obtained.

[Brief description of the drawings]

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

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication G03G 9/08 381 9/10 311 (72) Inventor Hiroshi Yusa 3-30 Shimomaruko, Ota-ku, Tokyo 2 Canon Inc. (72) Kazuo Maruyama, Inventor 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Masao Takano 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inside the corporation

Claims (109)

[Claims] 1. A toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, wherein the inorganic fine particles have an average particle diameter of 0.05 to The following formula (1) of 2.0 μm: M _x O _y (1) (wherein, M represents an aluminum element, a titanium element, a zinc element or a zirconium element, O represents an oxygen element, x and y Represents a positive number other than 0). The toner has an endothermic peak of 120 ° C. in differential thermal analysis.
A toner for developing an electrostatic image, comprising at least one of the following. 2. The metal oxide fine particles have an average particle size of 0.1.
The electrostatic image developing toner according to claim 1, wherein the toner particle diameter is in a range of 1 to 1.0 m. 3. The electrostatic charge image according to claim 1, wherein the charge polarity of the metal oxide fine particles to the iron powder carrier is the same as the charge polarity of the toner particles to the iron powder carrier. Development toner. 4. The electrostatic image developing toner according to claim 1, wherein the charge polarity of the metal oxide fine particles with respect to the iron powder carrier is | 20 | μC / g or less. . 5. The electrostatic image developing toner according to claim 1, wherein the charged polarity of the metal oxide fine particles with respect to the iron powder carrier is | 10 | μC / g or less. . 6. The electrostatic image developing toner according to claim 1, wherein M in the formula of the metal oxide fine particles is a titanium element. 7. The electrostatic image developing toner according to claim 1, wherein the metal oxide fine particles are rutile-type titanium oxide. 8. The electrostatic image developing toner according to claim 1, wherein the toner has one or more endothermic peaks in differential thermal analysis in a range of 60 ° C. to 120 ° C. 9. The electrostatic image developing toner according to claim 8, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 70 ° C. or higher. 10. The toner for developing an electrostatic image according to claim 8, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 110 ° C. or lower. 11. The toner particles according to claim 1, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax by Fischer-Tropsch method, petroleum wax and higher alcohol. 11. The electrostatic image developing toner according to any one of 1 to 10. 12. The toner according to claim 1, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, and petroleum wax.
11. The toner for developing an electrostatic image according to any one of items 1 to 10. 13. The wax component according to claim 11, wherein Mw / Mn is in a range of 1.0 to 2.0 in a molecular weight distribution measured by gel permeation chromatography (GPC). 3. The toner for developing an electrostatic image according to item 1. 14. The toner according to claim 1, wherein the shape factor SF-1 measured by an image analyzer is in the range of 110 to 180, the shape factor SF-2 is in the range of 110 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
14. The electrostatic image developing toner according to claim 1, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 15. The toner according to claim 1, wherein the value of the shape factor SF-1 measured by the image analyzer is in the range of 120 to 160, the value of the shape factor SF-2 is in the range of 115 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
14. The electrostatic image developing toner according to claim 1, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 16. The toner for developing an electrostatic image according to claim 1, wherein a styrene copolymer is used as the binder resin. 17. The toner according to claim 1, wherein a magnetic material is contained as the colorant in the toner particles.
The toner for developing electrostatic images according to any one of the above. 18. The toner according to claim 17, wherein the magnetic material is a magnetic iron oxide having a substantially spherical shape. 19. The toner has a weight average particle diameter of 10.0.
The toner for developing an electrostatic image according to any one of claims 1 to 18, wherein the particle diameter is not more than μm. 20. The toner has a weight average particle size of 8.0 μm.
19. The electrostatic image developing toner according to claim 1, wherein m is equal to or less than m. 21. The toner particles according to claim 1, wherein the toner particles are obtained through a manufacturing process including at least a step of melt-kneading a binder resin and a colorant and a step of pulverizing the binder resin and the colorant. 20. The toner for developing an electrostatic image according to any one of 20. 22. The electrostatic image developing toner according to claim 1, wherein the toner particles have been subjected to a spheroidizing treatment for applying at least a mechanical impact force. 23. The electrostatic image developing toner according to claim 21, wherein the toner particles are subjected to a spheroidizing treatment for applying a mechanical impact force after the pulverizing step. 24. In a toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a coloring agent and inorganic fine particles externally added to the toner particles, the inorganic fine particles have an average particle diameter of 0.1 to 0.1. 3.0 μm of the following formula (2) or (3): M _x Ti _y O _z (2) M _x Si _y O _z (3) (wherein, M represents a metal element, and Ti represents Indicates a titanium element, Si indicates a silicon element, O indicates an oxygen element,
x and y are non-zero positive numbers. ), And the toner has an endothermic peak in differential thermal analysis of 120 ° C.
The toner has a shape factor SF-1 measured by an image analyzer.
Is in the range of 110 to 180, and the shape factor SF
-2 is in the range of 110 to 140, and SF-2
A value obtained by subtracting 100 from the value of B and 100 from the value of SF-1
Wherein the ratio B / A to the value A obtained by subtracting is less than or equal to 1.0. 25. The electrostatic image developing toner according to claim 24, wherein the composite metal oxide fine particles have an average particle diameter in a range of 0.2 to 2.0 μm. 26. The electrostatic charge according to claim 24, wherein the charge polarity of the composite metal oxide fine particles with respect to the iron powder carrier has the same polarity as the charge polarity of the toner particles with respect to the iron powder carrier. Image developing toner. 27. The electrostatic image developing method according to claim 24, wherein the charge polarity of the composite metal oxide fine particles with respect to the iron powder carrier is | 20 | μC / g or less. toner. 28. The electrostatic image developing method according to claim 24, wherein the composite metal oxide fine particles have an electrifying polarity to an iron powder carrier of | 10 | μC / g or less. toner. 29. The electrostatic image developing toner according to claim 24, wherein the composite metal oxide fine particles are strontium titanate or strontium silicate. 30. The electrostatic image developing toner according to claim 24, wherein the composite metal oxide fine particles are a mixed crystal of strontium titanate and strontium silicate. 31. The toner for developing an electrostatic image according to claim 24, wherein the toner has one or more endothermic peaks in a differential thermal analysis in a region of 60 ° C. to 120 ° C. 32. The toner for developing an electrostatic image according to claim 31, wherein the toner has one or more endothermic peaks in the region of 70 ° C. or higher in differential thermal analysis. 33. The toner for developing an electrostatic charge image according to claim 31, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 110 ° C. or lower. 34. The toner according to claim 34, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, petroleum wax and higher alcohol. 34. The electrostatic image developing toner according to any one of 24 to 33. 35. The toner according to claim 2, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, and petroleum wax.
34. The toner for developing an electrostatic image according to any one of items 4 to 33. 36. The wax component according to claim 34, wherein Mw / Mn is in a range of 1.0 to 2.0 in a molecular weight distribution measured by gel permeation chromatography (GPC). 3. The toner for developing an electrostatic image according to item 1. 37. The toner according to claim 37, wherein the value of the shape factor SF-1 measured by the image analyzer is in the range of 120 to 160, the value of the shape factor SF-2 is in the range of 115 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
The electrostatic image developing toner according to any one of claims 24 to 36, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 38. The toner for developing an electrostatic image according to claim 24, wherein a styrene copolymer is used as the binder resin. 39. The toner according to claim 24, wherein a magnetic material is contained in the toner particles as the colorant.
8. The toner for developing an electrostatic image according to any one of 8. 40. The toner according to claim 39, wherein the magnetic material is a magnetic iron oxide having a substantially spherical shape. 41. The toner has a weight average particle diameter of 10.0.
41. The electrostatic image developing toner according to any one of claims 24 to 40, wherein the particle diameter is not more than μm. 42. The toner has a weight average particle diameter of 8.0 μm.
41. The electrostatic image developing toner according to claim 24, wherein m is equal to or less than m. 43. The toner particles according to claim 24, wherein the toner particles are obtained through a manufacturing process including a step of melt-kneading at least a binder resin and a colorant and a step of pulverizing the binder resin and the colorant. 42. The electrostatic image developing toner according to any one of the above items 42. 44. The electrostatic image developing toner according to claim 24, wherein the toner particles have been subjected to a spheroidizing treatment for applying at least a mechanical impact force. 45. The electrostatic image developing toner according to claim 43, wherein the toner particles are subjected to a spheroidizing treatment for applying a mechanical impact force after the pulverizing step. 46. A toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, wherein the inorganic fine particles have an average particle diameter of 0.05. The toner has an endothermic peak of 120 ° C. in differential thermal analysis.
A toner for developing an electrostatic image, comprising at least one of the following. 47. The electrostatic image developing toner according to claim 46, wherein the inorganic carbide fine particles have an average particle size in a range of 0.1 to 1.0 μm. 48. The toner according to claim 4, wherein the charging polarity of the inorganic carbide fine particles to the iron powder carrier is the same as the charging polarity of the toner particles to the iron powder carrier.
48. The toner for developing an electrostatic image according to 6 or 47. 49. The electrostatic image developing toner according to claim 46, wherein the charged polarity of the inorganic carbide fine particles to the iron powder carrier is | 30 | μC / g or less. 50. The electrostatic image developing toner according to claim 46, wherein the charged polarity of the inorganic carbide fine particles to the iron powder carrier is | 20 | μC / g or less. 51. The electrostatic image developing toner according to claim 46, wherein the inorganic carbide fine particles are silicon carbide. 52. The toner for developing an electrostatic charge image according to claim 46, wherein the toner has one or more endothermic peaks in differential thermal analysis in a range of 60 ° C. to 120 ° C. 53. The toner according to claim 52, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 70 ° C. or higher. 54. The toner for developing an electrostatic charge image according to claim 52, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 110 ° C. or lower. 55. The toner according to claim 55, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, petroleum wax and higher alcohol. 56. The electrostatic image developing toner according to any one of 46 to 54. 56. The toner according to claim 4, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, and petroleum wax.
56. The electrostatic image developing toner according to any one of 6 to 54. 57. The wax component according to claim 55 or 56, wherein Mw / Mn is in a range of 1.0 to 2.0 in a molecular weight distribution measured by gel permeation chromatography (GPC). 3. The toner for developing an electrostatic image according to item 1. 58. The toner, wherein the value of the shape factor SF-1 measured by the image analyzer is in the range of 110 to 180, the value of the shape factor SF-2 is in the range of 110 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
The electrostatic image developing toner according to any one of claims 46 to 57, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 59. The toner according to claim 59, wherein the value of the shape factor SF-1 measured by the image analyzer is in the range of 120 to 160, the value of the shape factor SF-2 is in the range of 115 to 140. The value B obtained by subtracting 100 from the value of −2 and SF−
The electrostatic image developing toner according to any one of claims 46 to 57, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 60. The toner for developing an electrostatic image according to claim 46, wherein a styrene copolymer is used as the binder resin. 61. The toner according to claim 46, wherein a magnetic material is contained in the toner particles as the colorant.
0. The toner for developing an electrostatic image according to any one of 0 to 0. 62. The electrostatic image developing toner according to claim 61, wherein the magnetic material is a magnetic iron oxide having a substantially spherical shape. 63. The toner has a weight average particle size of 10.0.
63. The electrostatic image developing toner according to any one of claims 46 to 62, wherein the particle diameter is not more than μm. 64. The toner has a weight average particle diameter of 8.0 μm.
63. The toner according to claim 46, wherein m is equal to or less than m. 65. The toner according to claim 46, wherein the toner particles are obtained through a manufacturing process including a step of melt-kneading at least a binder resin and a colorant and a step of pulverizing the binder resin and the colorant. 65. The toner for developing an electrostatic image according to any one of items 64. 66. The electrostatic image developing toner according to claim 46, wherein the toner particles are subjected to a spheroidizing treatment for applying at least a mechanical impact force. 67. The electrostatic image developing toner according to claim 65, wherein the toner particles are subjected to a spheroidizing treatment for applying a mechanical impact force after the pulverizing step. 68. A toner for developing an electrostatic image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, wherein the inorganic fine particles have an average particle diameter of 0.05 to 0.05. The toner has a metal carbonate fine particle of 2.0 μm.
A toner for developing an electrostatic image, comprising at least one of the following. 69. The electrostatic image developing toner according to claim 68, wherein the metal carbonate fine particles have an average particle diameter in a range of 0.1 to 1.0 μm. 70. The charge polarity of the metal carbonate fine particles to the iron powder carrier is the same as the charge polarity of the toner particles to the iron powder carrier.
70. The toner for developing an electrostatic image according to 8 or 69. 71. The electrostatic image developing toner according to claim 68, wherein the charged polarity of the metal carbonate fine particles to the iron powder carrier is | 20 | μC / g or less. . 72. The electrostatic charge image developing toner according to claim 68, wherein the charged polarity of the metal carbonate fine particles with respect to the iron powder carrier is | 10 | μC / g or less. . 73. The toner for developing an electrostatic image according to claim 68, wherein said metal carbonate fine particles are strontium carbonate. 74. The electrostatic image developing toner according to claim 68, wherein the toner has one or more endothermic peaks in a differential thermal analysis in a range of 60 ° C. to 120 ° C. 75. The electrostatic image developing toner according to claim 74, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 70 ° C. or higher. 76. The toner according to claim 74, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 110 ° C. or lower. 77. The toner according to claim 77, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, petroleum wax and higher alcohol. 77. The electrostatic image developing toner according to any one of items 68 to 76. 78. The toner particles according to claim 6, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, and petroleum wax.
81. The toner for developing an electrostatic image according to any one of items 8 to 76. 79. The wax component according to claim 77 or 78, wherein Mw / Mn is in a range of 1.0 to 2.0 in a molecular weight distribution measured by gel permeation chromatography (GPC). 3. The toner for developing an electrostatic image according to item 1. 80. The toner, wherein the value of the shape factor SF-1 measured by an image analyzer is in the range of 110 to 180, the value of the shape factor SF-2 is in the range of 110 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
80. The electrostatic image developing toner according to any one of claims 68 to 79, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 81. The toner according to claim 81, wherein the value of the shape factor SF-1 measured by the image analyzer is in the range of 120 to 160, the value of the shape factor SF-2 is in the range of 115 to 140, The value B obtained by subtracting 100 from the value of −2 and SF−
80. The electrostatic image developing toner according to any one of claims 68 to 79, wherein a ratio B / A to a value A obtained by subtracting 100 from the value of 1 is 1.0 or less. 82. The toner according to claim 68, wherein a styrene copolymer is used as the binder resin. 83. The toner according to claim 68, wherein the toner particles contain a magnetic material as the colorant.
3. The toner for developing an electrostatic image according to any one of 2. 84. The toner according to claim 83, wherein the magnetic material is a magnetic iron oxide having a substantially spherical shape. 85. The toner has a weight average particle diameter of 10.0.
The electrostatic image developing toner according to any one of claims 68 to 84, wherein the particle diameter is not more than μm. 86. The toner has a weight average particle size of 8.0 μm.
The electrostatic image developing toner according to any one of claims 68 to 84, wherein m is equal to or less than m. 87. The toner according to claim 68, wherein the toner particles are obtained through a manufacturing process including a step of melt-kneading at least a binder resin and a colorant and a step of pulverizing the same. 86. The toner for developing an electrostatic image according to any of 86. 88. The electrostatic image developing toner according to claim 68, wherein the toner particles have been subjected to a spheroidizing treatment for applying at least a mechanical impact force. 89. The toner according to claim 87, wherein the toner particles are subjected to a spheroidizing treatment for applying a mechanical impact force after the pulverizing step. 90. A toner for developing an electrostatic charge image having toner particles containing at least a binder resin and a colorant and inorganic fine particles externally added to the toner particles, wherein the inorganic fine particles are average particles containing silicone oil. It has silicon oxide fine particles or silicon composite oxide fine particles having a diameter of 0.03 to 50 μm, and the toner has an endothermic peak in differential thermal analysis of 120 ° C.
The toner has a shape factor SF-1 measured by an image analyzer.
Is in the range of 110 to 180, and the shape factor SF
-2 is in the range of 110 to 140, and SF-2
A value obtained by subtracting 100 from the value of B and 100 from the value of SF-1
Wherein the ratio B / A to the value A obtained by subtracting is less than or equal to 1.0. 91. The electrostatic image development according to claim 90, wherein the silicon oxide fine particles or the silicon composite oxide fine particles have an average particle diameter in a range of 0.04 to 1.0 μm. For toner. 92. The toner has an average particle size of 0.03 μm.
92. The toner for developing an electrostatic image according to claim 90, further comprising fine particles having a particle size of less than an external additive. 93. The electrostatic image developing toner according to claim 92, wherein the fine particles having an average particle diameter of less than 0.03 μm include silicon oxide fine particles or silicon composite oxide fine particles. 94. The electrostatic image developing toner according to claim 92, wherein the fine particles having an average particle size of less than 0.03 μm contain silicone oil. 95. The toner for developing an electrostatic charge image according to claim 90, wherein the toner has one or more endothermic peaks in differential thermal analysis in a range of 60 ° C. to 120 ° C. 96. The toner for developing an electrostatic image according to claim 95, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 70 ° C. or higher. 97. The toner according to claim 95, wherein the toner has one or more endothermic peaks in differential thermal analysis in a region of 110 ° C. or lower. 98. The toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax by Fischer-Tropsch method, petroleum wax and higher alcohol. 90. The electrostatic image developing toner according to any one of 90 to 97. 99. The toner particles according to claim 9, wherein the toner particles contain at least one wax component selected from the group consisting of polyolefin wax, hydrocarbon wax obtained by Fischer-Tropsch method, and petroleum wax.
98. The toner for developing an electrostatic image according to any one of 0 to 97. 100. The wax component according to claim 98 or 99, wherein Mw / Mn is in the range of 1.0 to 2.0 in the molecular weight distribution measured by gel permeation chromatography (GPC). 3. The toner for developing an electrostatic image according to item 1. 101. The toner has a shape factor SF-1 value measured by an image analyzer within a range of 120 to 160, a shape factor SF-2 value of 115 to 140, and B and SF obtained by subtracting 100 from the value of −2
The ratio B / A to the value A obtained by subtracting 100 from the value of −1 is 1.0.
The toner for developing an electrostatic image according to any one of claims 90 to 100, wherein: 102. The toner for developing an electrostatic image according to claim 90, wherein a styrene copolymer is used as the binder resin. 103. The toner for developing an electrostatic image according to claim 90, wherein a magnetic material is contained as the colorant in the toner particles. 104. The toner according to claim 103, wherein the magnetic material is a magnetic iron oxide having a substantially spherical shape. 105. The toner has a weight average particle size of 10.
11. The structure according to claim 9, wherein the thickness is 0 μm or less.
5. The toner for developing an electrostatic image according to any one of 4. 106. The toner has a weight average particle size of 8.0.
108. The structure according to claim 90, wherein the thickness is not more than μm.
The toner for developing electrostatic images according to any one of the above. 107. The toner according to claim 90, wherein the toner particles are obtained through a manufacturing process having at least a step of melt-kneading the binder resin and the colorant and a step of pulverizing the same. 106. The toner for developing an electrostatic image according to any of 106. 108. The toner for developing an electrostatic image according to claim 90, wherein the toner particles have been subjected to a spheroidizing treatment for applying at least a mechanical impact force. 109. The toner for developing an electrostatic charge image according to claim 107, wherein the toner particles are subjected to a sphering treatment for applying a mechanical impact force after the pulverizing step.