JPH08202080A - Electrostatic charge image developing toner and image forming method - Google Patents

Abstract

PURPOSE: To provide an electrostatic charge image developing toner excellent in transferability by giving excellent developability under a high humidity and preventing the deterioration of developability by leaving for a long time. CONSTITUTION: In the electrostatic charge image developing toner containing a binder resin, a coloring agent and an inorganic fine powder, the inorganic fine powder is processed with a polysiloxane having a siloxy unit having an alkyl group and an aryl group as substituents, in which part or all of hydrogen atoms can be replaced by fluorine atoms and a siloxy unit, in which at least one of subtituents is hydrogen.

Description

Detailed Description of the Invention

[0001]

The present invention relates to electrophotography, electrostatic recording,
The present invention relates to a toner and an image forming method for developing an electrostatic charge image in electrostatic printing or the like.

[0002]

2. Description of the Related Art In recent years, demands for high definition and high image quality of electrophotography have been increasing in the market, and attempts have been made in this technical field to achieve high image quality and full color. In the case of full-color electrophotography, toners of three to four colors are superposed to form an image, but if the toners of the respective colors are not developed in the same manner, the color reproduction may be poor or uneven color may occur. . However, these colorings are performed by pigments and dyes, and they have a great influence on development. Further, in a full-color image, fixability, color mixing property, and anti-offset property at the time of fixing are important, and a binder resin suitable for this performance is selected, but this binder resin also has a great influence on the developability. One of the influences is the influence of temperature and humidity on the charge amount, and there is an urgent need to develop a color toner having a stable charge amount even in a wide range of environments.

On the other hand, one of the means for solving these problems is to add various external additives to the toner. In particular, for the purpose of improving various image characteristics such as resolution, density uniformity, and fog, it has been widely practiced to add various fine powders in order to improve chargeability and fluidity of toner. There is.

Inorganic fine powders surface-treated with silicone oil, silicone varnish, and silane compound are preferably used as the inorganic fine powders generally used as additives to improve various properties of the toner. As an example of the inorganic fine powder treated with polysiloxanes, Japanese Patent Laid-Open No. Sho 5
9-200252, JP-A-61-277964, JP-A-1-114857, and JP-A-2-10.
No. 9058, No. 2-197851, No. 3-130779, No. 4-204748, No. 5-34984, No. 5-289.
No. 391, etc. In these proposals, although the electrophotographic characteristics are certainly improved, the uniformity of hydrophobization is insufficient and a sufficient triboelectric charge amount cannot be obtained under high humidity, resulting in a decrease in image density and fogging. There was a chance
In addition, the toner may not be sufficiently released from the drum, the transferability may be insufficient, and the transfer efficiency may be lowered or the void may occur in the transfer, and there is no solution to these problems. It was Further, when applied to full-color toner, it was not particularly strict and satisfactory.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an electrostatic charge image developing toner and an image forming method which solve the above-mentioned problems.

That is, an object of the present invention is to provide a toner for developing an electrostatic charge image, which can obtain a sufficient developability even under high humidity.

A further object of the present invention is to provide a toner for developing an electrostatic charge image, which is hardly affected by humidity and maintains sufficient developability even when left standing for a long period of time.

Further, an object of the present invention is to provide a toner for developing an electrostatic charge image and a method for forming an image, which imparts releasability to the toner, enhances transfer efficiency, and facilitates formation of a beautiful pictorial full-color image. is there.

A further object of the present invention is to provide a toner for developing an electrostatic charge image and an image forming method which do not cause a void in the transfer in the line image portion.

A further object of the present invention is to provide a toner for developing an electrostatic charge image and an image forming method capable of obtaining good developability in a one-component developing method.

[0011]

The present invention provides a toner for developing an electrostatic charge image containing a binder resin, a colorant and an inorganic fine powder, wherein the inorganic fine powder contains a part or all of hydrogen atoms. It is an inorganic fine powder treated with a polysiloxane having a siloxy unit having an alkyl group or an aryl group as a substituent, which may be substituted with a fluorine atom, and a siloxy unit having at least one substituent being hydrogen. With regard to the featured toner, excellent developability and transferability can be obtained.

Further, according to the present invention, in the image forming method in which the latent image formed by the charges on the latent image holding member is visualized by the toner, the member contacting the latent image holding member by the charging step,
The present invention relates to an image forming method characterized by using the above-mentioned toner as a toner in at least one of a transfer step and a cleaning step, and further transferring a toner image formed on a latent image holding member onto the same recording material. The present invention relates to an image forming method, wherein a plurality of toner images are formed on a sheet, and the toner is used as the toner. That is, since the toner of the present invention is excellent in transferability, it is suitable for the above-mentioned image forming method.

Further, according to the present invention, the latent image on the latent image carrier is
An image forming method of developing with a one-component toner on a toner carrier carrying one-component toner, using a developing method having a regulating member for regulating the layer thickness of the one-component toner on the toner carrier to a thin layer, The present invention relates to an image forming method using the above toner as a toner. That is, since the toner of the present invention has excellent developability, it is suitable for the above-mentioned image forming method. The structure of the present invention will be described in detail below.

In the present invention, a siloxy unit having an alkyl group or an aryl group as a substituent and a siloxy unit having at least one substituent being hydrogen, in which a part or all of hydrogen atoms may be substituted with a fluorine atom. By treating the inorganic fine powder with a polysiloxane having, it is possible to impart releasability, lubricity, hydrophobicity and charge stability to the inorganic fine powder. A toner containing this treated inorganic fine powder has excellent transferability. And developability can be obtained. For example, a polysiloxane represented by the following general formula (1) may be mentioned. In the present invention, the polysiloxane may have a cyclic structure or a branched structure.

[0015]

Embedded image

[R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ and R ₉ may be an alkyl group, an aryl group or hydrogen, in which some or all of the hydrogen atoms may be replaced by fluorine atoms. Alternatively, other arbitrary substituents are shown, which may be the same or different.

R ₇ and R ₈ represent an alkyl group or an aryl group in which some or all of hydrogen atoms may be replaced by fluorine atoms, and they may be the same or different.

R ₁₀ and R ₁₁ represent arbitrary substituents in which the unit of z is not the unit of x and the unit of y, and they may be the same or different.

X represents the sum of siloxy units satisfying the unit condition of x and represents an integer of 1 or more.

Y represents the sum of siloxy units satisfying the condition of the unit of y and represents an integer of 1 or more.

Z represents the sum of siloxy units satisfying the unit condition of z and represents 0 or an integer of 1 or more.

Preferably, x, y and z are x: y = 1: 3 to
The relationship of 100: 1, 5z <x + y is satisfied.

The arrangement of x units, y units, and z units may be alternating, random, or block, and is arbitrary. ]

A specific example is polysiloxane represented by the formula 2.

[0025]

Embedded image

[M and n are integers of 1 or more, preferably satisfying the relationship of m: n = 1: 3 to 100: 1, and m unit,
The arrangement of n units may be alternating, random, or block, and is arbitrary. Part of the methyl group may have an arbitrary substituent. ]

In the present invention, an alkyl group in which some or all of hydrogen atoms may be replaced by fluorine atoms,
The siloxy unit having an aryl group as a substituent means a silylene which is an alkyl group or an aryl group in which a substituent on silicon in a siloxane chain may have some or all of hydrogen atoms substituted with fluorine atoms. A siloxane constituent unit as an element (e.g., a unit of x in the general formula 1),
Preferred substituents are methyl and phenyl groups, and particularly preferred siloxy units are dimethylsiloxy units.
A siloxy unit in which at least one substituent is hydrogen means a siloxane constitutional unit containing silylene in which the substituent on the silicon in the siloxane chain is hydrogen and any substituent (for example, y in the general formula 1). Equivalent to the unit),
Preferred optional substituents are methyl and phenyl groups, and particularly preferred siloxy units are methyl hydrogen siloxy units. In the polysiloxane having these units, the siloxy unit of the siloxane chain has the above-mentioned one (a siloxy unit of any other substituent may be partially contained. For example, it corresponds to the unit of z in the general formula 1). A polysiloxane in which the substituent on the terminal silicon is an alkyl group, an aryl group, or hydrogen or any other substituent in which part or all of hydrogen atoms may be replaced by fluorine atoms,
Of these, a methyl group, a phenyl group and hydrogen are preferable, and a methyl group is particularly preferable. Further, these structural units may be present at random, may be present alternately, may be present in blocks, or may be present in a branched structure.

These polysiloxanes are adsorbed on the surface of the inorganic fine powder, and depending on the conditions, a part of the Si--O bond reacts with the OH group and other functional groups on the inorganic fine powder, and the alkyl group and aryl group become inorganic. Hydrophobization is performed by orienting toward the outside of the fine powder, but since two alkyl groups, aryl groups and two siloxane bonds on silicon of siloxy units having alkyl groups or aryl groups as substituents can be oriented, polysiloxane As a result, the lubricating effect and the releasing effect can be exhibited. Further, the Si-H bond is easily baked, and OH groups or other functional groups on the inorganic fine powder or other Si-H bonds are formed.
A siloxy unit reacting with a bond to form a Si-O bond, and at least one substituent is hydrogen, the alkyl group and other substituents are oriented toward the outside of the inorganic fine powder, or have a two-dimensional or three-dimensional structure. And a hydrophobizing effect is obtained. The toner containing the inorganic fine powder treated with such polysiloxane is provided with releasability and lubricity, and can have transferability, cleaning property, non-staining property, and further sufficient hydrophobicity. In addition, good triboelectric chargeability is obtained, the developability becomes excellent, and the good developability can be maintained even under high humidity.

In the present invention, a siloxy unit having an alkyl group or an aryl group as a substituent, in which a part or all of hydrogen atoms may be substituted with a fluorine atom, and a siloxy unit in which at least one substituent is hydrogen. Characterized in that it contains an inorganic fine powder treated with a polysiloxane having, and can obtain the advantages of each of the above-mentioned units and achieve both developability and transferability, Even better results are obtained than the effects obtained in. That is, a siloxy unit in which at least one substituent is hydrogen in one molecule and a siloxy unit having an alkyl group or an aryl group as a substituent, in which a part or all of hydrogen atoms may be substituted with a fluorine atom, By being present at the same time, high hydrophobicity due to baking can be obtained and, in addition, the releasing property and lubricity of polysiloxane can be further exhibited. In addition, since it is possible to exert both actions with one molecule, the inorganic fine powder is treated extremely uniformly,
There is no variation between the inorganic fine powder particles, and it is easy to achieve both developability and transferability.

The viscosity of these polysiloxanes at 25 ° C. is preferably 1 to 2,000 mm ² / s. More preferably, it is 5 to 1,000 mm ² / s. If it is less than 1 mm ² / s, sufficient releasability and lubricity may not be obtained, and if it exceeds 2,000 mm ² / s, it may be difficult to uniformly process the inorganic fine powder or agglomerates may be generated. May occur and sufficient fluidity may not be obtained.

In the present invention, the following polysiloxane may be used in combination. Such polysiloxanes include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, different functional group-modified reactive polysiloxanes; polyether-modified, methylstyryl-modified, alkyl-modified , Non-reactive polysiloxanes such as fatty acid-modified, alkoxy-modified, and fluorine-modified; straight polysiloxanes such as methylphenylpolysiloxane, diphenylpolysiloxane, dimethylpolysiloxane, and methylhydrogenpolysiloxane. Further, other silane compounds, silane coupling agents, organic silicon compounds such as silicone varnish, organic aluminum compounds, organic titanium compounds and the like may be used in combination for treatment.

In the present invention, the treatment amount of the polysiloxane featured in the present invention is preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the inorganic fine powder. If it is less than 2 parts by mass, the treatment effect does not appear, and if it exceeds 40 parts by mass, aggregates are easily generated. When using other treatment agents in combination, the total treatment amount is preferably 60 parts by mass or less,
More preferably 2 to 50 parts by mass, particularly preferably 4 to 4 parts.
It is 0 part by mass. If it exceeds 60 parts by mass, aggregates are likely to be generated and the treatment tends to be non-uniform.

The ratio of the siloxy unit having an alkyl group or an aryl group as a substituent, in which a part or all of the hydrogen atoms may be replaced by a fluorine atom, and the siloxy unit having at least one substituent hydrogen is 1: It is preferably 3 to 100: 1, more preferably 1: 2 to 20: 1, particularly 2: 3 to 10: 1, and further 1: 1 to 5: 1. When treated in this ratio, effective release properties, lubricity, and non-staining properties are easily obtained, and further high hydrophobicity and excellent developability are provided, and both functions can be effectively combined. .

The inorganic fine powder used in the present invention includes:
Oxides, double oxides, metal oxides, metals, silicon compounds, carbon, carbon compounds, fullerenes, boron compounds, carbides,
Nitrides, silicides, ceramics and chalcogen compounds are used, preferably metal oxides. Among the metal oxides, silica, alumina, titania and zirconia are particularly preferable. Alumina and titania, which have an appropriate charge saturation value and have stable environmental chargeability, are particularly preferable.

The silica used in the present invention may be obtained by a dry method by vapor phase oxidation of a silicon halogen compound (for example, thermal decomposition oxidation reaction in oxygen or hydrogen flame), or sodium silicate, alkaline earth metal silicate, silicate and the like. Acid, ammonia, salts,
Silica obtained by a wet method using decomposition with alkali salts is used, and an amorphous one is used as a crystal type. It is also possible to obtain fine powders of oxides of silicon and other metals by using them together with metal halides such as aluminum chloride, titanium chloride, germanium chloride, tin chloride, zirconium chloride, lead chloride and the like, and use them. it can.

The titania used in the present invention is a sulfuric acid method,
Chlorine method, titania obtained by low-temperature oxidation (thermal decomposition, hydrolysis) of volatile titanium compounds such as titanium alkoxide, titanium halide, titanium acetylacetonate is used, and the crystal system is anatase type, rutile type, or mixed crystal of these. Either type or amorphous can be used.

Alumina used in the present invention includes a Bayer method, an improved Bayer method, an ethylene chlorohydrin method, an underwater spark discharge method, an organic aluminum hydrolysis method, an aluminum alum thermal decomposition method, an ammonium aluminum carbonate thermal decomposition method, and a chloride. Alumina obtained by the flame decomposition method of aluminum is used. As a crystal system, α, β,
γ, δ, ξ, η, θ, κ, χ, ρ type, mixed crystal type of these,
Any of amorphous can be used, and α, γ, δ,
θ, mixed crystal type, and amorphous ones are preferably used.

The average particle size of the treated inorganic fine powder is 0.
The thickness is preferably less than 1 μm, and when the thickness is 0.1 μm or more, sufficient fluidity and uniform chargeability cannot be obtained, resulting in poor developability and durability. Here, the average particle diameter is obtained by actually measuring the particle diameter of 400 arbitrary primary particles from a transmission electron microscope image of 100,000 times, and calculating the number average diameter. For the diameter, the major axis is measured, and when the major axis / minor axis ratio is 2 or more, the average value is measured and calculated.

Furthermore, the inorganic fine powder of the present invention preferably has a degree of methanol hydrophobicity of 50% or more, more preferably 55% or more, and particularly 60% or more. Fifty
If it is less than%, the hydrophobicity tends to become insufficient, and as this value becomes lower, the moisture resistance becomes poorer, and the developability under high humidity and the developability with standing are deteriorated with time.

A beaker with a hydrophobicity of methanol of 200 cm ³ was charged with 50 cm ³ of ion-exchanged water to prepare a sample 0.200.
g is measured and put in it, methanol is dripped with a burette while stirring, and the point at which the sample floating on the liquid surface is completely removed is taken as the end point, and the hydrophobicity is calculated from the following equation.

Hydrophobicity (%) = {titer (cm ³ ) /
[Titration amount (cm ³ ) +50 (cm ³ )]} × 100

Furthermore, the water content of the inorganic fine powder after treatment is 3.
It is preferably 0% by mass or less, and good moisture resistance can be obtained. When the water content is more than 3.0% by mass, the inorganic fine powder has a high hygroscopic property, and the developability after high humidity or after long-term storage becomes poor and fogging occurs. The water content is more preferably 2.5% by mass or less, and particularly preferably 2.0% by mass or less.

In the present invention, the water content is measured using a fully automatic moisture measuring system AQS-624 type (manufactured by Hiranuma Sangyo Co., Ltd.). Sample is 1g of sample at 23 ℃, 60% RH
What is left for 12 hours in the above environment and about 0.2 g of which is accurately weighed (Ag) is measured. 20 samples
Heat at 0 ° C to evaporate the adsorbed moisture,
The adsorbed water content (B μg) and the reference water content (C μg) of the sample are obtained by titration for a minute. The water content is calculated by the following formula.

Moisture content (mass%) = [(BC) / (A ×)
1,000,000)] × 100

Other physical properties are based on the BET one-point method.
Specific surface area of 15m² / G or more,
More preferably 20 m²/ G, particularly preferably 2
5m²/ G or more. Specific surface area is 15m²</ G
Then, it becomes inferior in fluidity and releasability, and developability and transfer
Affect sexuality.

[0046] It is preferable that a bulk density of 0.5 g / cm ³ or less, preferably further is 0.45 g / cm ³ or less, particularly preferably 0.4 g / cm ³
It is the following. When the bulk density exceeds 0.5 g / cm ³ , the fluidity and the charging uniformity become poor, the developing property becomes non-uniform, and the density unevenness occurs.

The content of the inorganic fine powder of the present invention is toner 1
The amount is preferably 0.2 to 5.0 parts by mass, more preferably 0.3 to 4.0 parts by mass, and particularly preferably 0.4 to 3.5 parts by mass with respect to 00 parts by mass. 0.
When the amount is less than 2 parts by mass, the effect of addition becomes small,
If it exceeds 5.0 parts by mass, the charging property tends to be environmentally dependent.

In the present invention, the specific surface area is a flow type automatic specific surface area measuring apparatus Micromeritics Flowsorb I.
I 2300 type (manufactured by Shimadzu Corp.) is used, and 0.2 g of the sample is subjected to degassing treatment at 70 ° C. for 30 minutes using a mixed gas flow of 30% by volume of nitrogen and 70% by volume of helium.

Bulk density is measured according to JIS K-5101.

Examples of the method for treating the inorganic fine powder particles with various treatment agents include a treatment method in an aqueous medium, a treatment method in an organic solvent, and a treatment method in a gas phase.

In the method of treating in an aqueous medium, inorganic fine powder is dispersed so as to form primary particles, and in the case of a polysiloxane type treating agent, the treatment is carried out using an emulsion, and the treating agent of the silane compound type is treated with water. Process while disassembling.
In this treatment method, it is possible to disperse the aqueous paste as it is in the aqueous medium without passing through the drying step after producing the particles to be treated, so that it is easy to disperse in the primary particles, but after the treatment, the treated particles show lipophilicity. Therefore, coalescence of particles tends to start and aggregates tend to be formed. When treating with several kinds of treatment agents, they may be added simultaneously or sequentially.

In the vapor phase method, the treatment agent is dropped or sprayed while mechanically or sufficiently stirring the particles to be treated (this is referred to as "vapor phase method 1"). ). At this time, the reactor is replaced with nitrogen, or
It is also preferable to heat to 350 ° C. Further, when the viscosity of the treating agent is high, it may be diluted with a solvent such as alcohol, ketone or hydrocarbon. Ammonia, amine, alcohol, water, etc. may be added to enhance the reactivity during the treatment. This treatment method is a preferable method because the reaction is carried out firmly, so that it is easy to obtain high hydrophobicity and uniformity, but if untreated particles are strongly stirred for a long time, coalescence of particles may occur, Care must be taken as it is likely to cause non-uniformity of the. Further, they may be added simultaneously when they are treated with several kinds of treatment agents, or may be added sequentially.

As another method of the gas phase method, a treatment agent is directly added (without being taken out) immediately after the particles to be treated are formed in the carrier gas by the gas phase method (chlorine method, low temperature oxidation method, etc.). In some cases, there is a method of diluting with a solvent, vaporizing and atomizing, and treating the particles to be treated in the vapor phase (this is referred to as "vapor phase method 2"). In this method, in addition to the advantages of the vapor phase method 1,
Since the treatment is carried out before the particles to be treated are coalesced, it is a preferable method because aggregates are less likely to form.

The method of treating in an organic solvent is a method in which the particles to be treated are dispersed in an organic solvent, treated with a treating agent, filtered or the solvent is distilled off and then dried. In order to reduce the agglomerates, it is also preferable to subsequently perform a crushing treatment with a pin mill, a jet mill or the like. The drying step may be carried out by standing or flowing, preferably by heating at about 50 to 350 ° C., or by reducing the pressure. As the organic solvent, hydrocarbon-based organic solvents such as toluene, xylene, hexane, and isoper are preferably used. As a method of dispersion treatment, a stirrer, a shaker, a crusher, a mixer, and a disperser are used. Among them, ceramics, agate,
A disperser using a medium such as balls or beads made of alumina or zirconia is preferably used. For example,
Sand mill, Glen mill, Basket mill, Ball mill, Sand grinder, Visco mill, Paint shaker, Attritor, Dyno mill, Pearl mill etc. As a particularly preferred treatment method, a method of dispersing particles to be treated in an organic solvent and then applying a treating agent to a disperser, a method of applying a treated particle paste of an organic solvent containing a treating agent to a disperser, There are a method of adding a treating agent and particles to be treated to an organic solvent to form a paste, and applying the paste to a dispersing machine, and a method of adding the treating agent while applying the paste to the dispersing machine. The method of treating in an organic solvent is a preferable method since the treated particles can be treated in a dispersed state, coalescence hardly occurs even after the treatment, and aggregates are less likely to occur. Further, when treating with several kinds of treating agents, they may be added simultaneously at the time of preparing the slurry, may be added sequentially, or may be additionally added when being applied to the dispersing machine. Repeat the disperser several times,
Each time it is applied to the disperser, it may be added and mixed in the slurry in advance or added sequentially while being applied to the disperser.

As the processing method, the above four methods can be used,
The treatment agents may be treated at the same time or may be treated in several steps in any order. Further, in the case of performing the processing in plural times, any combination of processing methods may be used.

In addition, even if any process is used, after the treatment, a pulverizer such as a pin mill, a hammer mill, a jet mill or the like may be used to perform a crushing treatment to reduce aggregates and sufficiently exert the effect of the inorganic fine powder of the present invention. It is also preferable for

In the present invention, the following binder resins can be used as the binder resin of the toner.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, and substitution products thereof; styrene-p-chlorostyrene copolymers, styrene-vinyltoluene copolymers, styrene-vinylnaphthalene. Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene 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 -Based copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyol resin, polyurethane, polyamide resin, furan resin , Epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binder substances include styrene copolymers, polyester resins and epoxy resins, and particularly polyester resins, epoxy resins and polyol resins.

Examples of the comonomer for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, acrylic acid-
2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide and the like monocarboxylic acids having a double bond or substituted products thereof;
For example, a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like; and substituted compounds thereof; for example, vinyl chloride,
Vinyl esters such as vinyl acetate, vinyl benzoate, etc .; Ethylenic olefins such as ethylene, propylene, butylene, etc .; Vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, etc .; eg vinyl methyl ether, vinyl Vinyl ethers such as ethyl ether, vinyl isobutyl ether, etc .;

The styrenic polymer or styrenic copolymer may be crosslinked or may be a mixed resin.

As the crosslinking agent for the binder resin, a compound mainly having two or more polymerizable double bonds may be used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; Divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone; and 3
A compound having at least one vinyl group; is used alone or as a mixture.

Since the inorganic fine powder of the present invention is excellent in moisture resistance, it is preferably used for a toner containing a polyester resin, an epoxy resin or a polyol resin, which is easily affected by humidity in charging property. That is, the adverse effects of these resins can be compensated for, and good developability under high humidity can be maintained. Polyester resins, polyol resins, and epoxy resins are preferably used because they have excellent fixability, and particularly in full-color toner, they have excellent color mixing properties. That is,
When the inorganic fine powder of the present invention is used with a toner containing a polyester resin, a polyol resin, or an epoxy resin as a binder resin component, fixability, developability under high humidity, and leaving stability over time can be obtained. Further, in the color toner, excellent transferability and color mixing property can be obtained, so that a beautiful pictorial image can be obtained.

For the above reason, the styrene resin,
A mixture of a polyester resin, a polyol resin and an epoxy resin, a graft copolymer of these resins, a block copolymer and a mixture thereof are also preferably used.

The epoxy resin and polyol resin used in the present invention are as follows. For example, skeleton bisphenol A type, halogenated bisphenol A
Type, biphenyl type, saligenin type, sulfone type, long-chain bisphenol type, resorcin type, bisphenol F
Type, tetrahydroxyphenylethane type, novolak type, alcohol type, polyglycol type, polyol type,
Glycerin triether type, polyolefin type, epoxidized soybean oil, alicyclic type and the like are used, and bisphenol type is preferably used. In addition to these, those reacted with a curing agent, those reacted with a compound having an active hydrogen terminal epoxy group, those reacted with phenol / polyphenols, amines / polyamines Reacted, reacted with carboxylic acid, polybasic acid, acid anhydride, ester derivative, lactone,
Those reacted with a polyamide and those reacted with an oligomer having a carboxylic acid group are preferably used. Further, those obtained by reacting a hydroxyl group with a carboxylic acid / anhydride / lactone / lactam are particularly preferably used.

Examples of the active hydrogen-containing compound include the following. Phenols include phenol, cresol, isopropylphenol, aminophenol, nonylphenol, dodecylphenol, xylenol, p-cumylphenol, and the like, and divalent phenols include bisphenol A, bisphenol F, bisphenol AD, bisphenol S, and the like. Can be mentioned. As the carboxylic acid, acetic acid, propionic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, oleic acid, margaric acid,
Examples thereof include araginic acid, linoleic acid and linolenic acid.
Examples of the ester derivative include alkyl esters of the above carboxylic acids, of which lower alkyl esters are preferable, and methyl ester and ethyl ester are particularly preferable. As lactones, β-propiolactone, δ-valerolactone, ε-caprolactone, γ
-Butyrolactone, β-butyrolactone, γ-valerolactone and the like. As amine, methylamine,
Ethylamine, propylamine, isopropylamine,
Examples include butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, laurylamine, stearylamine and the like.

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

Examples of the dihydric alcohol component include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol and 1,5-pentanediol. 1,6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
Hexanediol, hydrogenated bisphenol A, bisphenol represented by the formula (A) and derivatives thereof;

[0068]

Embedded image

(Wherein R is an ethylene or propylene group, x and y are each an integer of 0 or more, and
The average value of x + y is 0-10. )

Further, diols represented by the formula (B);

[0071]

[Chemical 4]

(In the formula, R ′ is —CH ₂ CH ₂ — or

[0073]

Embedded image Where x ′ and y ′ are integers greater than or equal to 0, and x ′
The average value of + y 'is 0 to 10. ) Is mentioned.

Examples of the divalent acid component include phthalic acid,
Benzene dicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride, or their anhydrides, lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid or their anhydrides, lower alkyl esters; n- Alkenyl succinic acids such as dodecenyl succinic acid and n-dodecyl succinic acid, or alkyl succinic acids, or their anhydrides, lower alkyl esters; unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid, itaconic acid, or their anhydrides, lower Examples thereof include dicarboxylic acids such as alkyl ester; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component, which also functions as a crosslinking component, and a trivalent or higher valent acid component, in order to improve durability.

The trihydric or higher polyhydric alcohol component is
For example, sorbitol, 1,2,6-hexanetriol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3.
5-trihydroxybenzene etc. are mentioned.

Examples of the trivalent or higher polycarboxylic acid component in the present invention include trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid, 1,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octane tetracarboxylic acid, empol trimer acid, and their anhydrides, lower alkyl esters;

[0078]

[Chemical 6]

(Wherein, X is an alkylene group or alkenylene group having 30 or less carbon atoms, which may have one or more side chains having 1 or more carbon atoms), etc., and their anhydrides. , Polycarboxylic acids such as lower alkyl esters and derivatives thereof.

The alcohol component used in the present invention is 40 to 60 mol%, preferably 45 to 55 mol.
%, 60-40 mol% as an acid component, preferably 5
It is preferably 5 to 45 mol%.

It is also preferable that the trivalent or higher polyvalent component accounts for 1 to 60 mol% of all components.

From the viewpoint of developability, fixability, durability and cleaning property, a styrene copolymer, a polyester resin, a polyol resin, an epoxy resin, a block copolymer thereof, a graft copolymer thereof or a resin thereof is used. Mixtures are preferred.

The styrene resin and the mixture with the styrene resin preferably have a peak in the region of 10 ⁵ or more in the molecular weight distribution measured by GPC, and also in the region of 3 × 10 ^{3 to} 5 × 10 ^4. It is preferable to have a peak in terms of fixability and durability.

Such a resin component can be obtained, for example, by the following method.

By applying solution polymerization, bulk polymerization, suspension polymerization, emulsion polymerization, block copolymerization, grafting, etc., a polymer (L) having a main peak in the molecular weight range of 3 × 10 ^{3 to} 5 × 10 ⁴ is obtained. A polymer having a main peak in the region of 10 ⁵ or more or a polymer (H) containing a gel component is formed. It can be obtained by blending these components during melt-kneading. The gel component can be partially or wholly cleaved during melt-kneading, and becomes a THF-soluble component to be measured by GPC as a component in a region of 10 ⁵ or more.

As a particularly preferred method, the polymer (L) is used.
Alternatively, the polymer (H) is formed by solution polymerization, and at the end of the polymerization, the other is blended in a solvent, the other polymer is polymerized in the presence of one polymer, and the polymer (H) is suspended. A method of forming by polymerization and polymerizing the polymer (L) by solution polymerization in the presence of this polymer, a method of blending the polymer (H) in a solvent at the end of the solution polymerization, and the presence of the polymer (L) Then, there is a method in which the polymer (H) can be polymerized by suspension polymerization. By using these methods, a polymer in which a low molecular weight component and a high molecular weight component are uniformly mixed can be obtained.

As the binder resin for the toner to be subjected to the pressure fixing method, low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-
Examples thereof include acrylic acid ester copolymers, higher fatty acids, polyamide resins, and polyester resins. These can be used alone or as a mixture.

When a styrene type copolymer is used as the binder resin, the following toners are preferable in order to obtain good fixing property, blocking resistance and developing property.

In the molecular weight distribution of the toner by GPC (gel permeation chromatography), 3 × 10
Area of ^{3 to} 5 × 10 ⁴ , preferably 3 × 10 ^{3 to} 3 × 10 ^4.
The presence of at least one peak (P ₁ ) in the region ( ₁ ), particularly preferably in the region of 5 × 10 ³ to 2 × 10 ⁴ ,
Good fixability, developability, and blocking resistance can be obtained. If it is less than 3 × 10 ³ , good blocking resistance cannot be obtained, and if it exceeds 5 × 10 ⁴ , good fixing property cannot be obtained. Also, an area of 10 ⁵ or more, preferably 3 ×
10 ⁵ to 5 × 10 least one peak (P ₂₎ is present in ⁶ area of 10 ⁵ to 3 × 10 ⁵ to 2 × 10 ⁶ regions of
It is particularly preferable that there is a maximum peak in the above region,
Good high temperature offset resistance, blocking resistance, and developability are obtained. The higher this peak molecular weight is, the stronger the high temperature offset becomes. However, when there is a peak in the region of 5 × 10 ⁶ or more, there is no problem with a heat roll that can apply pressure, but when pressure is not applied, , The elasticity becomes large and the fixability is affected. Therefore,
In heat fixing with a relatively low pressure used in a medium to low speed machine, there is a peak in the region of 3 × 10 ⁵ to 2 × 10 ⁶ , and it is preferable that this is the maximum peak in the region of 10 ⁵ or more.

The component in the region of 10 ⁵ or less is 50% or more, preferably 60 to 90%, particularly preferably 65 to 8%.
5%. Within this range, good fixability and offset resistance can be obtained. When it is less than 50%, not only is sufficient fixing property not obtained, but also the pulverizability becomes poor.
If it exceeds 90%, the offset resistance,
It tends to be weak against blocking resistance.

When a polyester resin, an epoxy resin, or a polyol resin is used, the molecular weight distribution by GPC of the toner is in the range of 3 × 10 ^{3 to} 2.0 × 10 ⁴ , preferably 4 × 10 ^{3 to} 1.7. × 10 ⁴ region, particularly preferably it is preferred that the main peak is present in the region of ^{5 × 10 3 ~1.5 × 10 4} . When used for a magnetic toner, at least one peak or shoulder is present in a region of 1.5 × 10 ⁴ or more, or 5 × 10 ⁴ or more.
The area of 10 ⁴ or more is preferably 5% or more, and M
It is also preferable that w / Mn is 10 or more.

When the molecular weight distribution is as described above, good developability, blocking resistance, fixability and offset resistance can be obtained.

When the main peak is less than 3 × 10 ³ , blocking resistance and developability are likely to be lowered.
When the main peak exceeds 2.0 × 10 ⁴ , good fixability cannot be obtained. Good offset resistance is obtained when peaks and shoulders are present in the area of 1.5 × 10 ⁴ or more, when the area of 5 × 10 ⁴ or more is 5% or more, and when Mw / Mn is 10 or more. It becomes possible to obtain.

The binder resin used in the toner of the present invention preferably has a glass transition point (Tg) of 50 to 70 ° C. When Tg is less than 50 ° C, the blocking resistance is deteriorated. Further, when Tg exceeds 70 ° C., the fixability deteriorates.

In the present invention, the molecular weight distribution of the chromatogram of the toner by GPC is measured under the following conditions.

That is, the column was stabilized in a heat chamber at 40 ° C., and THF (tetrahydrofuran) as a solvent was caused to flow through the column at this temperature at a flow rate of 1 ml / min, and about 100 μl of a THF sample solution was injected. taking measurement. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithmic value and the count number of the calibration curve prepared from several kinds of monodisperse polystyrene standard samples. As the standard polystyrene sample for preparing the calibration curve, for example, a product having a molecular weight of about 10 ² to 10 ⁷ manufactured by Tosoh Corporation or Showa Denko KK is used, and at least 10
It is appropriate to use a standard polystyrene sample of about the point. 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, Shodex GPC KF-801, 802, 80 manufactured by Showa Denko KK
3,804,805,806,807,800P combination and TOSgel G1000H (H manufactured by Tosoh Corporation
_XL ), G2000H (H _XL ), G3000H (H _XL ),
G4000H (H _XL ), G5000H (H _XL ), G60
00H (H _XL ), G7000H (H _XL ), TSKgua
A combination of rdcolumns can be mentioned.

A sample is prepared as follows.

The sample is placed in THF, left for several hours, shaken well and mixed well with THF (until the coalescence of the sample disappears), and left still for 12 hours or more. At this time T
The time of leaving in HF should be 24 hours or more.
Then sample processing filter (pore size 0.45
.About.0.5 .mu.m, for example, Mysholydisc H-25
-5 manufactured by Tosoh Co., Ltd., available from Ekikurodisc 25CR Gelman Science Japan Co., Ltd.) are used as GPC samples. The sample concentration is adjusted so that the resin component is 0.5 to 5 mg / ml.

The glass transition point is measured by ASTM D
3418-82. DS used in the present invention
The C curve is the DS measured when the temperature is raised at a temperature rate of 10 ° C./min after the temperature is raised and lowered once to take a previous history.
C curve is used. The definition is defined as follows.

Glass transition point (Tg) The temperature at the intersection of the DSC curve and the line connecting the midpoints of the baselines before and after the specific heat change appears in the DSC curve during temperature rise.

Further, the following waxes may be contained in the toner in order to improve the releasability from the fixing member during fixing and the fixing property.

Paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, etc. Includes block copolymers and graft modified products with vinyl monomers. In addition, alcohols, fatty acids, acid amides, esters, ketones, hydrogenated castor oil and its derivatives, vegetable waxes, animal waxes, mineral waxes, petrolactam and the like can be used.

Among them, the wax which is preferably used is a low molecular weight polyolefin obtained by radically polymerizing an olefin under high pressure or using a Ziegler catalyst, and a by-product at this time, and a low molecular weight obtained by thermally decomposing a high molecular weight polyolefin. The waxes obtained from the distillation residue of hydrocarbons obtained by using a catalyst from a synthesis gas consisting of polyolefin, carbon monoxide, and hydrogen, or the synthetic hydrocarbons obtained by hydrogenating these are used as antioxidants. May be added. Or alcohol,
It is a fatty acid, an acid amide, an ester, or a montan derivative. Further, it is also preferable that impurities such as fatty acids have been removed in advance.

The colorant that can be used in the toner of the present invention includes any appropriate pigment or dye. For example, pigments such as carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow,
Rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, and indanthrene blue. These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and preferably 0.1 to 100 parts by mass of the resin.
The amount added is preferably 20 parts by mass, more preferably 0.2 to 10 parts by mass.

Examples of the dye include azo dyes, anthraquinone dyes, xanthene dyes, and methine dyes, and basic dyes and oil-soluble dyes are suitable. 0.1 parts by mass to 20 parts by mass, preferably 0.1 part by mass relative to 100 parts by mass of the binder resin.
The addition amount of 3 to 10 parts by mass is good.

Specific dyes include C.I. I. Direct Red 1, 4; C.I. I. Acid Red 1; C.I. I.
Basic Red 1, 3b, 12; C.I. I. Mordant Red 3; C.I. I. Solvent Red 4, 52, 10
9; C.I. I. Direct Blue 1 and 2; Acid Blue 9 and 15; Basic Blue 3 and 5; Modant Blue 7 and the like.

As specific pigments, among the chromatic pigments, organic pigments having high lipophilicity are preferable, and examples thereof include Naphthol Yellow S, Hansa Yellow G, Permanent Yellow NCG, Permanent Orange GTR, Pyrazolone Orange G, Benzidine Orange G, Permanent red 4
R, Watching Red Calcium Salt, Brilliant Carmine 38, First Violet B, Methyl Violet Lake, Phthalocyanine Blue, First Sky Blue, Induslen Blue BC and the like.

Highly weather-resistant pigments such as polycondensed azo pigments, insoluble azo pigments, quinacridone pigments, isoindolinone pigments, perylene pigments, anthraquinone pigments, and copper phthalocyanine pigments are preferable.

Examples of magenta color pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9,
10, 11, 12, 13, 14, 15, 16, 17, 1
8, 19, 20, 21, 22, 23, 30, 31, 3
2,37,38,39,40,41,48,49,5
0,51,52,53,54,55,57,58,6
0,63,64,68,81,83,87,88,8
9, 90, 112, 114, 122, 123, 163
202, 206, 207, 209; C.I. I. Pigment Violet 19; C.I. I. Bad red 1,2,1
0, 13, 15, 23, 29, 35 and the like.

Examples of the yellow coloring pigment include C.I. I. Pigment Yellow 1,2,3,4,5,6,7,10,1
1, 12, 13, 14, 15, 16, 17, 23, 6
5,73,83,97,173,180; C.I. I. Bad yellow 1, 3, 20 and the like can be mentioned.

As the color pigment for cyan, C.I. I. Pigment Blue 2, 3, 14, 15, 16, 17; C.I.
I. Bad Blue 6; C.I. I. Acid Blue 45 or a copper phthalocyanine pigment in which 1 to 5 phthalimidomethyl groups are substituted in the phthalocyanine skeleton having a structure represented by the following general formula (C), and the like can be given.

[0112]

[Chemical 7]

When used as a colorant for a full-color toner, its content is preferably 15 parts by mass or less, and more preferably 0.5 to 10 parts by mass for 100 parts by mass of the binder resin because of the transparency of the OHP sheet. Parts by mass. 15
If the amount exceeds the mass part, the reproducibility of the mixed colors red, green, and blue deteriorates, and the reproducibility of human skin color also decreases. If the amount is less than 0.5 parts by mass, it is difficult to obtain the desired coloring power and it is difficult to obtain a high-quality image with high image density.

As the black colorant, carbon black, a metal oxide exhibiting black color, a mixture of dyes and pigments, and the like are preferably used. These colorants are used in an amount of 0.1 to 15 parts by mass, preferably 1 to 10 parts by mass, based on 100 parts by mass of the binder resin.

When a coloring agent having magnetism is used, it can also serve as a magnetic material and can be used as a magnetic toner. Magnetic powders as such colorants include magnetite, hematite, iron oxides of ferrite; metals such as iron, cobalt and nickel, or aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony of these metals, Alloys of metals such as beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium and mixtures thereof are used, and oxides of metal ions such as Si, Al and Mg are used on the surface or inside of magnetic iron oxide. Those containing compounds such as, hydroxides, and hydroxides are preferably used. Particularly, magnetic iron oxide containing silicon element is preferable,
The content is preferably 0.1 to 3 mass% based on the magnetic powder. More preferably 0.15 to 3 mass%
And particularly preferably 0.2 to 2.0% by mass.

The shape of the magnetic powder is hexahedron, octahedron,
A polyhedron such as a decahedron, a dodecahedron, a tetrahedron, a needle, a scale, a sphere, or an irregular shape is used.

[0117] As a BET specific surface area by nitrogen gas adsorption method of the magnetic ^{powder, 1m 2 / g~40m 2 / g} , more 2m
² / g to 30 m ² / g is preferable, and further 3 m
It is preferably ² / g to ²⁰ m ² / g.

The saturation magnetization of the magnetic powder is 796 kA /
5 to 200 Am ² / kg, and further 10 to 10 in a magnetic field of m
The range of 150 Am ² / kg is preferable.

The residual magnetization of the magnetic powder is 796 kA /
1 to 100 Am ² / kg, further 1 to 7 in a magnetic field of m
0 Am ² / kg is preferred.

The average particle diameter of the magnetic powder is 2.0 μm.
Below, preferably 0.03 to 1.0 μm, more preferably 0.05 to 0.6 μm, and further preferably 0.1 to
0.4 μm is preferable.

The amount of the magnetic powder contained in the toner is 10 to 200 parts by mass with respect to 100 parts by mass of the binder resin.
Preferably 20 to 170 parts by mass, particularly preferably 30 to
It is 150 parts by mass.

The toner of the present invention using the above colorants is used as a one-component developer or a two-component developer.

In order to provide the toner of the present invention with an appropriate charge amount, it is also preferable to add the following charge control agent. The degree of the charge control agent is controlled depending on the type of the compound to be added and the amount of the compound to be added depending on other constituent materials. can do.

The following substances control the toner to be positively charged.

Modified products of nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts such as phosphonium salts and the like, lake pigments thereof, triphenylmethane dyes and lake pigments thereof (as the laker, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannin Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; dibutyltin oxide, dioctyltin oxide, diorganotin oxide such as dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin. Diorganotin borates such as borates; guanidine compounds, imidazole compounds. These can be used alone or in combination of two or more. Among these, a triphenylmethane compound and a quaternary ammonium salt whose counter ion is not halogen are preferably used. In addition, the general formula (D)

[0126]

Embedded image A monomer homopolymer represented by: styrene described above,
A copolymer with a polymerizable monomer such as acrylic acid ester and methacrylic acid ester can be used as a positive charge control agent. In this case, these charge control agents also function as (all or part of) the binder resin.

The following substances control the toner to be negatively charged.

Organic metal complexes and chelate compounds are effective, for example, monoazo metal complexes, acetylacetone metal complexes, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid type 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.

Further, the azo metal complex represented by the general formula (E) shown below is preferable.

[0130]

[Chemical 9]

Particularly, Fe and Cr are preferable as the central metal, halogen, an alkyl group and an anilide group are preferable as the substituent, and hydrogen, alkali metal, ammonium and aliphatic ammonium are preferable as the counter ion.
Also, a mixture of complex salts having different counter ions is preferably used.

Alternatively, the basic organic acid metal complex represented by the following general formula (F) also imparts a negative charging property and can be used in the present invention.

[0133]

[Chemical 10]

Particularly, as the central metal, Fe, Cr, Si,
Zn and Al are preferable, the alkyl group, anilide group, aryl group and halogen are preferable as the substituent, and hydrogen, ammonium and aliphatic ammonium are preferable as the counter ion.

As a method of incorporating the charge control agent into the toner, there are a method of adding it inside the toner and a method of adding it externally. The amount of these charge control agents used is determined according to the type of binder resin, the presence or absence of other additives, and the toner manufacturing method including the dispersion method, and is not uniquely limited. It is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the binder resin. In addition, when adding externally, resin 1
It is preferably 0.01 to 10 parts by mass relative to 00 parts by mass, and particularly preferably mechanochemically fixed to the surface of the toner particles.

In producing the toner according to the present invention, the toner constituent materials as described above are thoroughly mixed by a ball mill, a Henschel mixer, or other mixing machine,
A method in which the toner is well kneaded using a heat kneader such as a hot roll kneader or an extruder, the kneaded product is cooled and solidified, and mechanically pulverized and the pulverized product is classified to obtain a toner is preferable. Another method is to obtain a toner by dispersing constituent materials in a solution of a binder resin and then spray-drying; a predetermined material is mixed with a monomer that constitutes the binder resin, and an emulsion suspension is obtained. Then, there is a method for producing a toner by a polymerization method in which the toner is polymerized to obtain a toner. The toner according to the present invention may be a microcapsule toner including a core material and a shell material.

The toner of the present invention can be obtained by sufficiently mixing the above-mentioned toner with the inorganic fine powder characterizing the present invention with a mixer such as a Henschel mixer.

If necessary, the following additives may be added.

The following inorganic powders can be added to improve the developability and durability. Magnesium, zinc,
Metal oxides such as aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin and antimony; complex metal oxides such as calcium titanate, magnesium titanate and strontium titanate; calcium carbonate, magnesium carbonate, carbonic acid Examples thereof include metal salts such as aluminum; clay minerals such as kaolin; phosphoric acid compounds such as apatite; silicon compounds such as silica, silicon carbide and silicon nitride; carbon powders such as carbon black and graphite. Of these, zinc oxide, aluminum oxide, cobalt oxide, manganese dioxide, strontium titanate, magnesium titanate and the like are preferable.

For the same purpose, the following organic particles and composite particles can be added. Resin particles such as polyamide resin particles, silicone resin particles, silicone rubber particles, urethane particles, melamine-formaldehyde particles, and acrylic resin particles; rubbers, waxes, fatty acid compounds, resins, etc. and metals, metal oxides, salts, carbon black, etc. Examples of the composite particles include the above-mentioned inorganic particles.

Further, the following lubricant powder can be added. Fluorine resins such as Teflon and polyvinylidene fluoride; fluorine compounds such as carbon fluoride; fatty acid metal salts such as zinc stearate; fatty acid derivatives such as fatty acids and fatty acid esters; molybdenum sulfide, amino acids and amino acid derivatives.

When the toner of the present invention is used as a two-component developer, it is used by mixing it with a carrier, and the mixing ratio of the toner and the carrier is 0.1 to 50% by mass as the toner concentration, and it is preferable. Is 0.5 to 20% by mass, and more preferably 3 to 10% by mass.

As the carrier core material, for example, surface-oxidized or unoxidized iron, cobalt, nickel, copper, zinc, manganese, chromium rare earth metals, their alloys, compounds, oxides, magnetic ferrites and the like are used. Above all, those containing 98% by mass or more of the ferrite carrier are preferably used. There are no particular restrictions on the method of manufacturing the carrier. A coated carrier in which the surface of the core material is coated with resin or the like is particularly preferable. As a coating method, a coating material such as a resin is dissolved or suspended in a solvent to prepare a coating solution, and the coating solution is applied to the surface of carrier particles and adhered to the surface of carrier particles, or simply carrier particles and coating. A conventionally known method such as a method of dry mixing powders can be applied.

Examples of the binder resin used for coating the coated carrier include styrenes such as styrene and chlorostyrene; monoolefins such as ethylene, propylene, butylene and isobutylene; vinyl acetate and vinyl propionate.
Vinyl esters such as vinyl benzoate and vinyl butyrate; methyl acrylate, ethyl acrylate, butyl acrylate,
Dodecyl acrylate, octyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate,
Α-methylene aliphatic monocarboxylic acid esters such as butyl methacrylate and dodecyl methacrylate, vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl butyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and vinyl isopropenyl ketone. Examples include homopolymers and copolymers,
Particularly typical binder resins are polystyrene, styrene-alkyl acrylate copolymer, styrene-acrylonitrile, from the viewpoints of dispersibility of conductive fine particles, film-forming property as a coat layer, toner spent prevention, and productivity. Examples thereof include copolymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyethylenes and polypropylenes. Further, polycarbonate, phenol resin, polyester, polyurethane, epoxy resin, polyolefin, fluororesin, silicone resin, polyamide and the like can be mentioned. In particular, from the viewpoint of preventing spent, it is more preferable to contain a resin having a small critical surface tension, such as polyolefin, fluororesin, and silicone resin.

As for the blending amount, the proportion of the fluororesin, the polyolefin resin or the silicone resin with respect to the total amount of the binder is appropriately 1.0 to 60% by mass, and particularly preferably 2.0 to 40% by mass. Content is 1.
If it is less than 0% by mass, the effect of surface modification is insufficient and the toner spent is not effective. On the other hand, if it exceeds 60% by mass, it is difficult to uniformly disperse the both, so that partial unevenness occurs in the volume resistance value, and the charging characteristics deteriorate.

Examples of the fluororesin used as the binder resin for coating the carrier include vinyl fluoride, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, dichlorodifluoroethylene, tetrafluoroethylene, hexafluoropropylene and the like. And a solvent-soluble copolymer with another monomer.

As the silicone resin used as the binder resin for coating the carrier, for example, KR271, KR282, KR311, KR25 manufactured by Shin-Etsu Silicone Co., Ltd.
5, KR155 (straight silicone varnish), KR
211, KR212, KR216, KR213, KR2
17, KR9218 (modified silicone varnish), SA
-4, KR206, KR5206 (Silicone alkyd varnish), ES1001, ES1001N, ES10
02T, ES1004 (silicone epoxy varnish),
KR9706 (Silicone acrylic varnish), KR52
03, KR5221 (Silicone polyester varnish)
And Toray Silicone SR2100, SR2101,
SR2107, SR2110, SR2108, SR21
09, SR2400, SR2410, SR2411, S
H805, SH806A, SH840 and the like are used.

The amount of the above-mentioned materials used may be appropriately determined, but generally, the total amount is preferably 0.1 to 30% by mass (preferably 0.5 to 20% by mass) based on the carrier.

The average particle size of the carrier is 20 to 100 μm,
Preferably 25-70 μm, more preferably 25-65
It is preferable to have μm.

A particularly preferred carrier is Cu-Z.
n-Fe [composition weight ratio (5 to 20): (5 to 20):
(30-80)] ternary ferrite particles, the surface of which is coated with a fluorine resin, a styrene resin, a silicone resin, or a mixed resin thereof. For example, polyvinylidene fluoride and styrene-methyl methacrylate resin as mixed resins; polytetrafluoroethylene and styrene-methyl methacrylate resin;
Fluorine-based copolymer and styrene-based copolymer; 90: 1
Mixtures in a weight ratio of 0 to 20:80, preferably 70:30 to 30:70 are mentioned. Apply the coating agent to 0.
As a preferred carrier, a coated magnetic ferrite carrier having a mean particle size of 01 to 5% by mass, preferably 0.1 to 1% by mass, and having 70% by mass or more of carrier particles passing through 250 mesh and turned on to 350 mesh is 70% by mass or more. Can be mentioned. As the fluorine-based copolymer, vinylidene fluoride-tetrafluoroethylene copolymer (1
0:90 to 90:10), and the styrene-based copolymer is a styrene-2-ethylhexyl acrylate copolymer (20:80 to 80:20), styrene-2-ethylhexyne acrylate-methyl methacrylate. The copolymer (20-60: 5-30: 30-10) is illustrated.

The above coated magnetic ferrite carrier having a sharp particle size distribution has an effect of imparting preferable triboelectrification to the toner of the present invention and further improving electrophotographic characteristics.

When a two-component developer is prepared by mixing the toner of the present invention and a carrier, the mixing ratio is 1% by mass to 15% by mass, preferably 2% by mass to 13% by mass as the toner concentration in the developer. Good results are usually obtained when the content is% by mass. If the toner concentration is less than 1% by mass, the image density will be low, and if it exceeds 15% by mass, fog and in-machine scattering will increase, and the useful life of the developer tends to be shortened.

In the charging / transferring process using the toner of the present invention, there are a non-contact type system using a corona charger and a contact type system using a roller, a blade or the like. To be The contact type is preferably used for efficient uniform charging, simplification and low ozone generation. Among these, the toner of the present invention is of a contact type, and the effect is particularly remarkable.

Further, an example of an image forming method having the contact charging / transferring method will be described with reference to the schematic configuration diagram of FIG.

Reference numeral 101 denotes a rotary drum type electrostatic latent image holding member (hereinafter referred to as a photoconductor), and the photoconductor 101 includes a conductive base layer 101b such as aluminum and a photoconductive layer 102a formed on the outer surface thereof. Is the basic constituent layer,
It is rotated clockwise at a predetermined peripheral speed (process speed) in the drawing.

Cleaning members 112 and 113 clean the charging roller and the transfer roller.

Reference numeral 102 denotes a charging roller, which has a basic structure of a cored bar 102b at the center and a conductive elastic layer forming the outer periphery thereof. The charging roller 102 is the photoreceptor 1.
The surface 01 is pressed against the surface 01 with a pressing force and is rotated by the rotation of the photoconductor 101. 103 is a charging bias current V ₂ for applying a voltage to the charging roller 102, and when the bias is applied to the charging roller 102, the photosensitive member 1
The surface of 01 is charged to a predetermined polarity and potential. Then, an electrostatic charge image is formed by image exposure 104, and the developing unit 1
The toner images are sequentially visualized by 05.

A bias V ₁ is applied to the developing sleeve constituting the developing means 105 by the bias applying means 113. The toner image formed on the latent image carrier by development is electrostatically transferred to the transfer material 108 by the contact transfer means 106, and the toner image on the transfer material is heated and pressed and fixed by the heating and pressing means 111.

A transfer bias V ₃ is applied to the contact transfer means 106.
Is applied.

In the image forming apparatus having such a contact charging / transferring system, as compared with corona charging and corona transfer, it is possible to uniformly charge and sufficiently transfer the photosensitive member with a bias of a relatively low voltage. It is excellent in miniaturizing the discharger itself and suppressing corona discharge products such as ozone.

As other means, there are a method using the charging blade shown in FIG. 2 and a method using a conductive brush. These contact charging means have the effects of not requiring high voltage and reducing the generation of ozone, but
Since the member directly contacts the photoconductor, the problem of toner fusion is likely to occur. Therefore, the toner of the present invention is optimal when used as a specific contact charging means. The present invention does not limit what kind of method the contact charging means to be applied has and what kind of effect it has, and any method of directly contacting a member with a photoconductor to charge it can be applied to the present invention. It is possible.

A preferable process condition when using a charging roller is that the contact pressure of the roller is 0.5 to 50 kg.
/ M, when an AC voltage superimposed on a DC voltage is used, AC voltage = 0.5 to 5 kVpp, AC frequency = 5
0 to 5 kHz, DC voltage = ± 0.2 to ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2 to ±
It is 5 kV.

As the material of the charging roller and the charging blade, conductive rubber is preferable, and a releasing film may be provided on the surface thereof. As the releasable coating, nylon resin,
PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), etc. are applicable.

In FIG. 1, reference numeral 106 denotes a transfer roller, which basically has a core metal bar 106b at the center and a conductive elastic layer 106a forming the outer periphery thereof. The transfer roller 106 is pressed against the surface of the photoconductor 101 with a pressing force, and is rotated at a constant speed or a peripheral speed different from that of the photoconductor 101. The transfer material 108 is conveyed between the photoconductor 101 and the transfer roller 106, and at the same time, a bias having a polarity opposite to that of the toner is applied from the transfer bias current 107 to the transfer roller 106 so that the toner image on the photoconductor 101 is transferred. It is transferred to the front surface side of the material 108.

As the material of the transfer rotary member applicable to the present invention, the same material as the charging roller can be used, and the preferable transfer process condition is that the contact pressure of the roller is 0.5 to 50 kg / DC voltage is ± 0.2 at m
~ ± 10 kV.

Next, the transfer material 108 is conveyed to a fixing device 111 having a heating roller 111a having a halogen heater built therein and an elastic pressure roller 111b pressed against the heating roller 111a as a basic structure, and 111a and 111b.
The toner image is fixed by passing through the space. Alternatively, a method of fixing with a heater through a film may be used. Further, pressure fixing may be performed using a developer used for pressure fixing. After the transfer of the toner image, the surface of the photoconductor 101 is cleaned of adhered contaminants such as residual toner by a cleaning device equipped with an elastic cleaning blade that is pressed against the photoconductor 101 in the counter direction. It is made and is repeatedly imaged.

Examples of the contact type transfer device include a transfer roller as shown in FIG. 3 or a transfer belt or transfer drum as shown in FIG.

FIG. 3 is a schematic side view of the essential part of a typical image forming apparatus of this type. The apparatus shown in the drawing is a cylindrical latent image extending in the direction perpendicular to the plane of the drawing and rotating in the direction of arrow A. A holder (hereinafter referred to as a photoconductor) 301 and a conductive transfer roller 302 that contacts the holder are provided.

The transfer roller 302 is composed of a cored bar 302a and a conductive elastic layer 302b, and the conductive elastic layer 302b is made of urethane or ethylene in which a conductive material such as carbon is dispersed.
It is made of an elastic material such as propylene-diene terpolymer (EPDM) having a volume resistance of about 10 ⁶ to 10 ¹⁰ Ωcm. A bias is applied to the cored bar 302a by a constant voltage power supply 308. Bias condition is ± 0.2
~ ± 10 kV is preferred.

FIG. 4 shows the transfer belt to which the present invention is applied. The transfer belt 409 is supported and driven by the conductive roller 410. The pressure of the transfer device is usually the core metal 402a.
Alternatively, it is performed by pressing the end bearing of the core bar 410.

The contact pressure of the charger with respect to the photoconductor is 0.1 kg / m or more (preferably 0.1) as a linear pressure.
~ 30 kg / m, particularly preferably 0.3-10 kg / m
It is preferable to set to m).

The linear pressure is calculated by the following formula. (Linear pressure) [kg / m] = (Total pressure applied to transfer member)
[Kg] ÷ (contact length) [m]

If the contact pressure is less than 0.1 kg / m, transfer failure of the transfer member and transfer failure due to insufficient transfer current occur, which is not preferable. The toner of the present invention is particularly effective in transferability and voids in transfer when the transfer roller rotates at the same speed as the photosensitive member.

When using the charging roller and the charging blade,
The toner of the present invention has excellent releasability and lubricity, does not contaminate these members, and does not cause abnormal images due to uneven charging. Even if it adheres, it is easily detached so that the photoreceptor is not scratched or scraped more than necessary.

Further, since the releasing property from the photosensitive member is excellent, the transferring property is excellent, the transfer efficiency can be improved, and the phenomenon of void in transfer can be prevented. The effect is particularly remarkable in contact transfer systems such as transfer rollers, transfer belts, and transfer drums.

Further, since the transferability is excellent, good transferability can be obtained even if the transfer current and transfer voltage are reduced, and therefore the damage to the photoconductor is small and the life can be extended.

Further, in the present invention, it is difficult for the toner particles to directly adhere to the surface of the contact charging member, the surface of the contact transfer member and the surface of the photoconductor, and the releasability of the toner particles to those surfaces is improved to fix the toner. Even if the toner particles adhere to the surface of the contact charging member, the surface of the contact transfer member, and the surface of the photoconductor, the toner adhesion position is determined by the lubricity and releasability of the toner particles. If the toner particles do not move to the same position as the member and the photosensitive member and stay at the same position and the toner particles are not fixed, and the cleaning member is brought into contact with the contact charging member and the contact transfer member, The releasability sufficiently improves the cleaning property of the toner particles adhered to the surface of the contact charging member and the surface of the contact transfer member.

As the cleaning method, blade cleaning is preferable. For blade cleaning, urethane rubber, silicone rubber, or a resin having elasticity is used as a blade, or a chip-shaped resin is held at the tip of a blade such as metal in the forward or reverse direction with respect to the moving direction of the photoconductor. It is known as abutted or pressed. Preferably, the blade is brought into pressure contact in the direction opposite to the moving direction of the photoconductor. At this time, the contact pressure of the blade with respect to the photosensitive member is preferably 0.5 kg / m or more, more preferably 1 to 5 kg / m in terms of linear pressure. Further, the blade cleaning method may be combined with a mag brush cleaning method, a fur brush cleaning method, a roller cleaning method, or the like.

Since the toner of the present invention can obtain appropriate friction and is excellent in releasability and lubricity, not only does it show good cleaning performance by blade cleaning, but also when the blade is brought into contact with the photosensitive member. Hard to scratch and sharpen. On the other hand, fusion and filming are less likely to occur.

In the developing step, the toner of the present invention is
A one-component developing method such as a magnetic one-component developing method or a non-magnetic one-component developing method or a two-component developing method including a toner and a carrier is used.

The toner of the present invention is charged rapidly, has stable chargeability, and is uniformly charged, so that the toner is easily transported in the developing device, and the toner is charged even if the surface area of the frictional charge imparting member is small. The charge rises quickly, and the charge amount is quickly made uniform. Therefore, in the image forming method of developing the latent image on the electrostatic latent image carrier with the one-component toner on the toner carrier that carries the one-component toner, the layer thickness of the one-component toner on the toner carrier is reduced. It is a toner that is preferably used in an image forming method using a developing method that has a regulating member that regulates the toner amount to 1. Particularly, the magnetic force cannot be expected, it is difficult to supply the toner onto the toner carrier, and the effect is great in the non-magnetic one-component developing method having a small triboelectric charge imparting ability.

That is, the toner of the present invention provides excellent developability, durability and environmental stability even in the one-component developing method, and produces a vivid image with high density without fog.
Even when left in high humidity or during durability, there is no fogging or a decrease in concentration. In addition, a uniform solid halftone image can be obtained, the gradation can be smoothly reproduced, and a beautiful graphic image with gradation can be obtained.

Further, the toner of the present invention is difficult to fuse,
Since the supply to the regulated portion is smooth, the toner sufficient for toner consumption can be supplied, the friction can be reduced, and the torque can be reduced, it is also preferably used in the image forming method in which the regulating member is made thin by pressing the elastic member. .

The magnetic one-component developing method of the above developing method will be described with reference to FIG.

In FIG. 5, the substantially right half peripheral surface of the developing sleeve 90 is constantly in contact with the toner pool in the toner container 91, and the toner near the developing sleeve surface is on the developing sleeve surface of the magnetism generating means 92 in the sleeve. Attached and held by magnetic force and / or electrostatic force. When the developing sleeve 90 is rotationally driven, the magnetic toner layer on the sleeve surface passes through the position of the doctor blade 93 and is layered as a thin magnetic toner T ₁ having a substantially uniform thickness at each portion. The charging of the magnetic toner is mainly performed by frictional contact between the sleeve surface and the magnetic toner in the toner pool in the vicinity of the rotation of the developing sleeve 90, and the magnetic toner thin layer surface on the developing sleeve 90 is rotated by the rotation of the developing sleeve. It rotates to the side of the latent image holding member 94 which does not exist, and passes through the developing area portion A which is the closest portion of the latent image holding member 94 and the developing sleeve 90. In the course of this passage, the magnetic toner in the thin layer of magnetic toner on the surface of the developing sleeve 90 flies by the direct current and the alternating electric field due to the direct current and the alternating voltage applied between the latent image holding member 94 and the developing sleeve 90, and the latent image in the developing area A. It reciprocates between the surface of the image carrier 94 and the surface of the developing sleeve 90 (gap α). Finally, the magnetic toner on the developing sleeve 90 side is selectively transferred and adhered to the surface of the latent image holding member 94 surface according to the potential pattern of the latent image, and the toner images T ₂ are sequentially formed.

The developing sleeve surface on which the magnetic toner is selectively consumed after passing through the developing area A is re-rotated to the toner reservoir of the hopper 91 to be re-supplied with the magnetic toner, and the developing area A is developed. The surface of the magnetic toner thin layer T _{1 of the} sleeve 90 is transferred and the developing process is repeated.

The doctor blade used in the present invention is
A metal blade or a magnetic blade (for example, 93 shown in FIG. 5) arranged with a certain gap from the sleeve is used.

Instead of the doctor blade as the toner layer thinning regulating member, a rigid roller or sleeve made of metal, resin, ceramic or the like may be used, and a magnetism generating means may be provided inside.

In the magnetic one-component developing method and the non-magnetic one-component developing method, an elastic blade that comes into elastic contact with the sleeve surface is used as the doctor blade. An elastic roller may be used as the toner layer thinning regulating member instead of the doctor blade. The toner of the present invention is particularly preferably used in a developing method in which a toner is coated in a thin layer by a regulating member having elastic force contacting a toner carrier.

As the elastic blade and elastic roller, a rubber elastic body such as silicone rubber, urethane rubber or NBR; a synthetic resin elastic body such as polyethylene terephthalate; a metal elastic body such as stainless steel or steel can be used. Moreover, even those composites can be used. A rubber elastic body is preferable.

The materials of the elastic blade and the elastic roller have a great influence on the charging of the toner on the toner carrier.
Therefore, an organic substance or an inorganic substance may be added, melt-mixed, or dispersed in the elastic body. For example, metal oxide, metal powder, ceramics, carbon allotrope,
Examples include whiskers, inorganic fibers, dyes, pigments and surfactants. Further, rubber, synthetic resin, or metal elastic body may be used in which a substance such as resin, rubber, metal oxide, or metal is attached to the sleeve abutting portion so as to control the charging property of the toner. When durability is required for the elastic body and the toner carrier, it is preferable to bond the resin and rubber to the metal elastic body so as to contact the sleeve contact portion.

When the toner is negatively charged, urethane rubber, urethane resin, polyamide, nylon, or a positively chargeable toner is preferable. When the toner is positively charged, urethane rubber, urethane resin, silicone rubber, silicone resin, polyester resin, fluorine resin (for example, Teflon resin), polyimide resin, or a material that is easily negatively charged is preferable. The sleeve contact part is resin,
In the case of a molded product such as rubber, in order to adjust the charging property of the toner, a metal oxide such as silica, alumina, titania, tin oxide, zirconia, zinc oxide, carbon black, a charge generally used for toner It is also preferable to include a control agent or the like.

The base of the elastic blade, which is the upper side, is fixedly held on the developer container side, and the lower side is flexed in the forward or reverse direction of the developing sleeve against the elasticity of the blade to make the inner side of the blade flexible. The outer surface side (in the case of the opposite direction) is brought into contact with the sleeve surface with an appropriate elastic pressure. An example of the image forming apparatus is shown in FIG. According to such a device, a thin and dense toner layer can be obtained more stably against environmental changes. The reason for this is not clear, but the toner environment is forcibly rubbed against the sleeve surface by the elastic blade as compared to a commonly used device in which a metallic blade is mounted at a certain distance from the sleeve. It is presumed that the charging is always performed in the same state regardless of the change in behavior due to the change.

On the other hand, the toner is easily charged excessively and the toner on the sleeve and the blade is easily fused, but the toner of the present invention is preferably used because it has stable triboelectric charging property.

In the case of the magnetic one-component developing method, the contact pressure between the blade and the sleeve is 0.1 kg / m or more, preferably 0.3 to 25 kg, as the linear pressure in the sleeve generatrix direction.
/ M, more preferably 0.5 to 12 kg / m is effective. If the contact pressure is less than 0.1 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fog and scattering. The contact pressure is 2
If it exceeds 5 kg / m, a large pressure is applied to the developer,
Since the developer is deteriorated, aggregation of the developer occurs, which is not preferable. In addition, a large torque is required to drive the developer carrier, which is not preferable.

The gap α between the latent image carrier and the toner carrier is
For example, it is set to 50 to 500 μm, and when a magnetic blade is used as the doctor blade, the gap between the magnetic blade and the toner carrier is preferably set to 50 to 400 μm.

The layer thickness of the magnetic toner layer on the toner carrier is
It is most preferable that the gap is smaller than the gap α between the latent image carrier and the toner carrier, but in some cases, a part of many ears of the magnetic toner forming the magnetic toner layer is magnetic enough to contact the latent image carrier. You may regulate the layer thickness of a toner layer.

Further, the sleeve is 10 times larger than the latent image carrier.
It is rotated at a peripheral speed of 0 to 200%. The alternating bias voltage is 0.1 kV or more in peak-to-peak, preferably 0.2 to 3.0 kV, more preferably 0.3 to 2.0 kV.
Good to use with V. The alternating bias frequency is 1.0 to
It is used at 5.0 kHz, preferably 1.0 to 3.0 kHz, and more preferably 1.5 to 3.0 kHz. A rectangular wave, a sine wave, a sawtooth wave, a triangular wave, or the like can be applied to the alternating bias waveform. Further, positive and reverse voltages and asymmetrical AC biases with different times can also be used. It is also preferable to superimpose a DC bias.

In the present invention, the sleeve is made of a material such as metal or ceramics, but aluminum, SUS or the like is preferable in terms of chargeability to the toner. The sleeve can be used as it is pulled out or cut, but in order to control the toner transporting property and the triboelectrification imparting property, it may be polished, roughened in the circumferential or longitudinal direction, or blasted. , Coating, etc. are performed. In the present invention, a blast treatment may be performed, and the regular particles and the irregular particles are used as the blasting agent, and they may be used alone or in combination, and may be overlaid.

Any abrasive grains can be used as the irregular particles.

As the regular particles, for example, various hard spheres made of metal such as stainless steel, aluminum, steel, nickel and brass having a specific particle diameter or various hard spheres such as ceramics, plastics and glass beads can be used. it can. As the regular particles, spherical or spheroidal particles having a substantially curved surface and a major axis / minor axis ratio of 1 to 2 (preferably 1 to 1.5, more preferably 1 to 1.2). Is preferred. Therefore, the fixed particles used for the blast treatment on the surface of the developing sleeve preferably have a diameter (or major axis) of 20 to 250 μm. In the case of repeated hitting, the size of the regular blast particles is preferably larger than that of the irregular blast particles, particularly preferably 1 to 20 times, more preferably 1.5 to 9 times.

When performing the over-strike treatment with the regular particles, it is preferable that at least one of the treatment time and the collision force of the treated particles be smaller than that of the irregular particle blast.

As the developing sleeve, it is also preferable that the sleeve surface has a coating layer containing conductive fine particles formed thereon. The conductive fine particles are preferably carbon fine particles, or carbon fine particles and crystalline graphite, or crystalline graphite.

The crystalline graphite used in the present invention is roughly classified into natural graphite and artificial graphite. Artificial graphite is made by solidifying pitch coke with tar pitch or the like, firing it once at about 1,200 ° C, and then putting it in a graphitization furnace.
By treating at a high temperature of about 2,300 ° C., carbon crystals grow and change into graphite. Natural graphite is completely graphitized from the ground by natural geothermal heat and underground high pressure for a long time. These graphites have a wide range of industrial uses because they have various excellent properties. Graphite is a very soft, slippery crystalline mineral with a dark gray to black luster. It is used in pencils, etc. and has heat resistance and chemical stability, so it is powdered in lubricants, refractory materials, electrical materials, etc. It is used in the form of solids and paint. The crystal structure includes hexagonal crystal and others belonging to the rhombohedral system, and has a completely layered structure. Regarding the electrical characteristics, free electrons are present between carbon-carbon bonds, making it a good conductor of electricity. The graphite used in the present invention may be natural or artificial.

The graphite used in the present invention preferably has a particle size of 0.5 μm to 20 μm.

The polymeric material forming the coating layer is, for example, styrene resin, vinyl resin, polyether sulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, fibrin resin, acrylic resin. It is possible to use thermoplastic resins such as resins, epoxy resins, polyester resins, alkyd resins, phenol resins, melamine resins, polyurethane resins, urea resins, silicone resins, polyimide resins and other thermosetting resins or photocurable resins. it can. Among them, those having releasability such as silicone resin and fluororesin, or those having excellent mechanical properties such as polyether sulfone, polycarbonate, polyphenylene oxide, polyamide, phenol resin, polyester, polyurethane and styrene resin are more preferable. preferable.

Conductive amorphous carbon is generally defined as "an aggregate of crystallites formed by burning or pyrolyzing a hydrocarbon or a compound containing carbon in a state where the supply of air is insufficient". . In particular, it is widely used because it has excellent electric conductivity, and it can be filled with a polymer material to give conductivity, or it can obtain an arbitrary conductivity to some extent by controlling the amount added. The particle size of the conductive amorphous carbon used in the present invention is preferably 10 mμ to 80 mμ, and more preferably 15 mμ to 40 mμ.

Next, an example of a developing method in the case of performing non-magnetic one-component development using the toner of the present invention will be described, but the developing method is not necessarily limited to this. FIG. 7 shows an apparatus for developing an electrostatic image formed on a latent image carrier. 70
Reference numeral 8 denotes a latent image holder, which is formed by an electrophotographic process means or an electrostatic recording means (not shown). 709
Is a developing sleeve, which is a non-magnetic sleeve made of aluminum or stainless steel.

As the developing sleeve, a rough tube made of aluminum or stainless steel may be used as it is, but preferably the surface thereof is uniformly roughened by blowing glass beads or the like, a mirror-finished one, or coated with a resin or the like. Good ones, which are similar to those used in the magnetic one-component developing method.

The toner 700 is stored in the hopper 701, and is supplied onto the developer carrier by the supply roller 702. The supply roller is made of a foam material such as polyurethane foam and rotates in a forward or reverse direction at a relative speed that is not 0 with respect to the toner carrier, and at the same time as the toner supply, the toner (developed toner on the toner carrier is not developed). Toner) is also stripped off. The toner applied onto the toner carrier is uniformly and thinly applied by the toner applying blade 703.

The contact pressure between the toner applying blade and the toner carrier is 0.3 to 2 as a linear pressure in the sleeve generatrix direction.
5 kg / m, preferably 0.5 to 12 kg / m is effective. When the contact pressure is less than 0.3 kg / m, it becomes difficult to apply the toner uniformly, and the charge amount distribution of the toner becomes broad, causing fog and scattering. On the other hand, if the contact pressure exceeds 25 kg / m, a large pressure is applied to the toner and the toner deteriorates, which is not preferable because the toner agglomerates. In addition, a large torque is required to drive the toner carrier, which is not preferable. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, it becomes possible to effectively loosen the aggregation of the toner of the present invention, and it is possible to instantly raise the charge amount of the toner. Become.

The toner layer-thinning regulating member conforms to that used in the magnetic one-component developing method. As the elastic blade and elastic roller, it is preferable to use materials of triboelectric charging series suitable for charging the toner to a desired polarity, which is similar to that used in the magnetic one-component developing method. In the present invention, silicone rubber, urethane rubber, styrene-butadiene rubber and the like are suitable. In addition, polyamide,
Polyimide, nylon, melamine, melamine cross-linked nylon, phenol resin, fluorine resin, silicone resin,
An organic resin layer of polyester resin, urethane resin, styrene resin or the like may be provided. In addition, conductive rubber, conductive resin, etc. are used, and fillers such as metal oxides, carbon black, inorganic whiskers, and inorganic fibers and charge control agents are used in the rubber of the blade in accordance with those used in the magnetic one-component developing method. It is preferable that the toner can be appropriately charged by imparting appropriate conductivity and charge imparting property such as being dispersed in a resin.

In the system proposed by the present invention for coating a thin layer of toner on the developing sleeve with a blade, in order to obtain a sufficient image density, the thickness of the toner layer on the developing sleeve is set to be the same as that of the developing sleeve. It is preferable that the length is smaller than the length of the air gap opposed to the image carrier, and an alternating electric field is applied to the air gap. That is, a bias power source 704 shown in FIG. 7 applies an alternating electric field or a developing bias in which a direct current electric field is superimposed on the alternating electric field between the developing sleeve 709 and the latent image holding member 708 to apply a latent image holding member from the developing sleeve. It is possible to facilitate the movement of the toner to the upper side and obtain a higher quality image. These conditions also conform to the magnetic one-component developing method.

Since the toner of the present invention has good releasability and excellent transferability, it is used in the image forming method for transferring the toner image formed on the latent image holding member to the recording material or the intermediate transfer material. It is preferably used for an image forming method in which toner images on a plurality of latent image holding members are transferred in multiple layers onto the intermediate transfer member or the intermediate transfer member.

Further, in the image forming method of transferring the toner image formed on the latent image holding member or the intermediate transfer member to the recording material, a plurality of toners are formed on the latent image holding member or the intermediate transfer member. It is also preferably used in an image forming method for collectively transferring multiple toner images onto a recording material.

Further, since the toner of the present invention is excellent in non-aggregating property and uniform charging property, a minute latent image can be faithfully reproduced and a digital latent image can be beautifully developed. Especially in full-color images, it is excellent in highlight part reproduction and minute color difference reproduction, and is full of texture, smooth,
Since a fresh and pictorial full-color image can be obtained, a graphic image and a line character image can be beautifully obtained, and the image can be suitably used for a digital full-color copying machine, a printer, or the like.

The above-mentioned multiple transfer method will be described with reference to FIG. 8 by taking the full-color electrophotographic method as an example.

The electrostatic latent image formed on the photosensitive drum 1 by an appropriate means is a rotary developing unit 2 which rotates in the direction of the arrow.
It is visualized by the developer having the first color toner and carrier in the developing device 2-1 attached to. The color toner image on the photosensitive drum is transferred by the transfer charger 8 onto the transfer material S held on the transfer drum 6 by the gripper 7.

A corona charger or a contact charger is used as the transfer charger, and when the transfer charger 8 is a corona charger, a voltage of -10 kV to +10 kV is applied.
The transfer current is −500 μA to +500 μA. A holding member is stretched around the outer peripheral surface of the transfer drum 6, and the holding member is made of a film-like dielectric sheet such as a polyvinylidene fluoride resin film or polyethylene terephthalate. For example, a sheet having a thickness of 100 μm to 200 μm and a volume resistance of 10 ¹² to 10 ¹⁴ Ω · cm is used.

Next, the rotary developing unit for the second color rotates, and the developing device 2-2 faces the photosensitive drum 1. Then, it is developed with the developer having the second color toner and carrier in the developing device 2-2, and this color toner image is also transferred onto the same transfer material as described above.

Further, the third and fourth colors are similarly processed.
In this way, the transfer drum 6 is rotated a predetermined number of times while holding the transfer material, and the toner images of a predetermined number of colors are transferred in multiple. The transfer current for electrostatic transfer is preferably increased in the order of the first color <second color <third color <fourth color in order to reduce transfer residual toner remaining on the photosensitive drum.

On the other hand, if the transfer current is increased, the transferred image is disturbed, which is not preferable. However, since the toner of the present invention is excellent in transferability, it is possible to firmly transfer the second color, the third color, and the fourth color when performing multiple transfer. Therefore, an image of any color can be properly formed, and a multicolor image with a sharp touch can be obtained. Further, in a full-color image, a beautiful image excellent in color reproduction can be obtained. Moreover, since it is not necessary to increase the transfer current so much, the disturbance of the image in the transfer process can be reduced. Further, when the transfer material is separated from the transfer drum 6, the charge is removed by the separation charger 9. However, if the transfer current is large, the electrostatic attraction of the transfer material to the transfer drum becomes large, and the current at the time of separation is not increased. Can no longer be separated. Then, since the polarity is opposite to that of the transfer current, the toner image is disturbed and the toner is scattered from the transfer material, which pollutes the inside of the image forming apparatus. Since the toner of the present invention is easily transferred, it is not necessary to increase the separation current, and the separation can be facilitated.
As a result, it is possible to prevent the image from being disturbed at the time of separation and the toner from scattering. Therefore, the toner of the present invention is preferably used in an image forming method for forming a multicolor image or a full color image having a multiple transfer step.

The multiple-transferred transfer material is separated from the transfer drum 6 by a separation charger 9 and has a heating and pressure roller fixing device 1 having a web impregnated with silicone oil.
The image is fixed at 0, and the color is mixed at the time of fixing to form a full-color copy image.

The replenishment toner supplied to the developing devices 2-1 to 2-4 is supplied from the replenishment hopper provided for each color to the center of the rotary developing unit 2 via the toner conveying cable in a predetermined amount based on the replenishment signal. It is conveyed to the toner replenishing cylinder in and is sent to each developing device.

The above-mentioned multiple development batch transfer method will be described with reference to FIG. 9 using a full-color electrophotographic printer as an example.

The electrostatic latent image formed on the photosensitive drum 21 by the charger 22 and the exposure section 23 using laser light is the developing unit 2
4, 25, 26 and 27 sequentially develop the toner to make it visible. In the developing process, a non-contact developing method is preferably used. According to the non-contact developing method, the developer layer in the developing device does not rub the surface of the image forming body, so
In the second and subsequent development steps, development can be performed without disturbing the image formed in the preceding development step. In the order of development, in the case of multi-color, it is preferable to develop a color other than black, and to develop a color with high lightness and saturation. In the case of full color, it is preferable to develop in order of yellow, then magenta or cyan, then the remaining magenta or cyan, and finally black.

Multicolor multiplex image formed on the photosensitive drum,
The full-color image is transferred onto the transfer material S by the transfer roller 29. In the transfer step, the electrostatic transfer method is preferably used, and the corona discharge or contact transfer method is used. In this method, a transfer charger that causes corona discharge through a transfer material is arranged so as to face the image, and corona discharge is applied from the back surface of the transfer material to electrostatically transfer the image. The other is a method in which a transfer roller and a transfer belt are brought into contact with an image forming body via a transfer material to apply a bias to the roller or electrostatically transfer from the back surface of the belt. By this electrostatic transfer method, the multicolor toner images carried on the surface of the image forming body are collectively transferred to the transfer material. In such a batch transfer method, since the amount of toner to be transferred is large, the transfer residual amount is large, transfer unevenness is likely to occur, and color unevenness is likely to occur in a full-color image.

However, the toner of the present invention is excellent in transferability, and any color is properly formed in a multicolor image. In a full-color image, a beautiful image with excellent color reproducibility can be obtained. Further, since the transfer efficiency is good even at a low current, it is possible to reduce the disturbance of the image at the time of transfer. Further, since the separation is facilitated, the disturbance of the image at the time of separation and the toner scattering can be reduced. Further, since it is also excellent in releasability, it shows good transferability even in the contact transfer means. Therefore, the toner of the present invention is also preferably used in an image forming method having a multiple development batch transfer step.

The transfer material on which the multicolor toner images are transferred at once is
A multicolor image is formed by being separated from the photosensitive drum 21 and fixed by the heat roller fixing device 32.

Further, an image forming method using the intermediate transfer member will be described with reference to FIG. The exposure roller 43 forms a latent image on the photosensitive drum 41 by providing a surface potential on the photosensitive drum 41 by the charging roller 42 that rotates in contact with the photosensitive drum 41. The latent image is developed by the developing devices 44, 45, 46 and 47 to form a toner image. The toner images are multi-transferred on the intermediate transfer member 48 for each color to form a multi-toner image. A drum-shaped intermediate transfer member 48 is used, and a holding member is stretched on the outer peripheral surface, and a conductivity-imparting member such as carbon black, zinc oxide, tin oxide, silicon carbide or titanium oxide is sufficiently provided on the base material. A material having a dispersed elastic layer (for example, nitrile butadiene rubber) is used. Alternatively, a belt-shaped intermediate transfer member may be used. The hardness of the intermediate transfer member is 10
It is preferable that the elastic member is formed of an elastic layer of ˜50 degrees (JIS K-6301), or in the case of a transfer belt, it is formed of a supporting member having an elastic layer having this hardness at a transfer portion onto a transfer material. From the photosensitive drum 41 to the intermediate transfer body 48
In the transfer to, the bias current is applied from the power source 49 to the cored bar 55 of the intermediate transfer member 48 to obtain a transfer current, and the toner image is transferred. Corona discharge from the back surface of the holding member or the belt or roller charging may be used. The toner images on the intermediate transfer body 48 are collectively transferred onto the transfer material S by the transfer means 51. As the transfer means, a contact electrostatic transfer means using a corona charger, a transfer roller, or a transfer belt is used. Also in such an image forming method, the effects of the above-described two methods can be obtained, and therefore it is preferably used.

An image forming method in which images of a plurality of colors are formed in the image forming section and the images are sequentially superposed and transferred on the same transfer material will be described with reference to FIG.

A color electrophotographic apparatus using a multicolor electrophotographic system for obtaining a color image is provided with a plurality of image forming units, and each image forming unit forms a visible image (toner image) of a different color, There is an image forming method in which the toner images are sequentially transferred and superposed on the same transfer material.

This image forming method is shown in FIG.
There is a configuration shown in. Here, first, second,
Third and fourth image forming portions _{P a, P b, P c} , and P _d are arranged, an image bearing member dedicated each said imaging unit,
It is provided with a so-called photosensitive drum 61 _a, 61 _b, 61 _c and 61 _d.

[0234] photosensitive drum 61 _a to 61 _d is a latent image forming unit 62 _a on the outer peripheral side, 62 _b, 62 _c and 62 _d, the developing unit 63 _a, 63 _b, 63 _c and 63 _d, transferring discharge section 6
4 _a, 64 _b, 64 _c and 64 _d, and the cleaning unit 65 _a, 65 _b, 65 _c and 65 _d are disposed.

With such a structure, first, the latent image forming section 62 _a forms _a latent image of, for example, a yellow component color in the original image on the photosensitive drum 61 _{a of} the first image forming section P _a . Latent image is a visible image with a developer having a yellow toner of the developing unit 63 _a, at the transfer portion 64 _a, is transferred to the transfer material S.

On the other hand, while the yellow image is being transferred onto the transfer material S as described above, a latent image of a magenta component color is formed on the photosensitive drum 61 _b in the second image forming portion P _b , and subsequently, development is performed. It is visible image with a developer having a magenta toner in parts 63 _b. This visible image (magenta toner image)
, When the transfer material S that transfer of the first image forming portion P _a of the is finished it is carried to the transfer section 64 _b, are transferred to overlap the position of the transfer material S.

Thereafter, the third and fourth steps are performed in the same manner as described above.
Cyan and black images are formed by the image forming units P _c and P _d , respectively, and cyan and black are formed on the same transfer material.
The black color is superimposed and transferred. When such an image forming process is completed, the transfer material S is transferred to the fixing unit 67.
Then, the image on the transfer material is fixed. As a result, a multicolor image can be obtained on the transfer material S. On the other hand, the photosensitive drums 61 _a , 61 _b , 61 _c and 61 _d , which have completed the transfer, are cleaned by the cleaning units 65 _a , 65 _b , 65 _c and 65.
_The residual toner is removed by _d , and the toner is provided for subsequent latent image formation.

In the above image forming apparatus, the conveyor belt 68 is used to convey the transfer material S, as shown in FIG.
1, the transfer material 6 is conveyed from the right side to the left side, and in the course of the conveyance, the transfer sections 64 _a , 64 _b , 64 _c and 64 _{d in the} image forming sections P _a , P _b , P _c and P _d . And is transferred.

In this image forming method, from the viewpoint of easiness of processing and durability as a conveying means for conveying the transfer material, a conveyor belt using a mesh of tetron fiber and a polyethylene terephthalate resin, a polyimide resin, a urethane resin A conveyor belt using a thin dielectric sheet such as is used.

When the transfer material S passes through the fourth image forming portion P _d , an AC voltage is applied to the static eliminator 69, the transfer material S is neutralized and separated from the belt 68, and thereafter, enters the fixing device 67 and the image is formed. It is fixed and discharged from the discharge port 70.

In this image forming method, each image forming section is provided with an independent image bearing member, and the transfer material is sequentially fed to the transfer portion of each image bearing member by the belt type conveying means. It may be configured as follows.

Further, in this image forming method, an image carrier common to the image forming section is provided, and the transfer material is repeatedly sent to the transfer section of the image carrier by the drum type conveying means. You may comprise so that each color may be transferred.

However, since this transport belt has a high volume resistance, as in the color image forming apparatus,
In the process of repeating transfer several times, the conveyance belt increases the charge amount. Therefore, uniform transfer cannot be maintained unless the transfer current is sequentially increased for each transfer.

Since the toner of the present invention is excellent in transferability,
Even if the charge of the conveying means is increased each time the transfer is repeated, the transferability of the toner in each transfer can be made uniform by the same transfer current, and a high quality image of high quality can be obtained.

[0245]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited thereto. The toner constituting materials used in the present invention will be described below.
First, the inorganic fine powder will be described.

Production Example of Treated Inorganic Fine Powder Table 1 shows the fine powder particles to be treated used in the examples.

[0247]

[Table 1]

The treatment method was as follows.

Organic solvent method (solvent method) 1 kg of toluene and 200 g of fine powder particles to be treated were put in a container, stirred by a mixer to make a slurry, and a prescribed amount of the treating agent was added thereto, and further a mixer was sufficient. It was stirred. The slurry was placed on a sand mill using zirconia balls as a medium for 30 minutes.

Remove the slurry from the sand mill and
After removing toluene under reduced pressure at 0 ° C, the mixture was dried at 200 to 300 ° C for 2 hours with stirring in a stainless steel container. The powder obtained here was crushed by a hammer mill to obtain a treated inorganic fine powder.

Gas phase method 1 (gas 1 method) 20 g of fine powder particles to be treated were placed in a closed type high speed stirring mixer, and the atmosphere was replaced with nitrogen. The treatment agent is diluted with an appropriate amount of n-hexane and sprayed while gently stirring, and 180 g of particles to be treated are further added, and at the same time, the remaining formulation amount of the treatment agent is sprayed, and the addition is completed. After stirring at room temperature for 10 minutes, heat at high speed for 200-300.
The temperature was raised to ° C and the mixture was stirred for 1 hour. The temperature was returned to room temperature with stirring, the powder was taken out from the mixer, and crushed with a hammer mill to obtain a treated inorganic fine powder.

Vapor Phase Method 2 (Gas 2 Method) A volatile titanium compound (eg titanium tetraisopropoxide) was vaporized in an evaporator at 200 ° C. under a nitrogen atmosphere. Water is vaporized under nitrogen atmosphere in an evaporator, 500
It was introduced into a heater heated to ℃. The vaporized titanium compound and heated steam were introduced into a reactor heated to 250 ° C. and hydrolyzed to obtain titanium oxide particles. Here, the prescribed amount of the treating agent was vaporized in a nitrogen atmosphere in an evaporator heated to 200 ° C. or atomized in a nitrogen atmosphere at 200 ° C. and introduced into a reaction vessel. The introduction into the reactor was such that it was mixed with the treating agent after the titanium oxide was produced. The above operation was performed under a nitrogen stream, and the treated particles were collected by a filter.

Table 2 shows the manufacturing method and formulation of the treated inorganic fine powder used in the examples, and Table 3 shows the physical properties. The treating agent is a polysiloxane represented by the formula 2, and the main substituents on silicon are methyl group and hydrogen, and the treating amount is the fine powder particles 10 to be treated.
It is a mass part with respect to 0 mass part.

[0254]

[Table 2]

[0255]

[Table 3]

Production Example of Binder Resin Polyester Resin 1 Terephthalic Acid 6.0 mol n-Dodecenyl Succinic Anhydride 3.0 mol Bisphenol A Propylene Oxide 2.2 Mole Adduct 10.0 mol Trimellitic Anhydride 0.7 mol Dibutyltin Oxide 0 .1 g

The above compound was placed in a reactor, equipped with a thermometer, a stir bar, a condenser, and a nitrogen introducing tube. After purging with nitrogen, the temperature was gradually raised with stirring, and the reaction was carried out at 180 ° C. for 5 hours. Then, the temperature was raised to 200 ° C. and the pressure was reduced (15 h
Pa), and the mixture was reacted for 4 hours for dehydration condensation, and the reaction was terminated to obtain polyester resin 1. This polyester resin has a peak molecular weight of 10,700 and a glass transition point of 63 ° C.
Met.

Polyester resin 2 Terephthalic acid 9.5 mol Bisphenol A ethylene oxide 2.2 mol Addition product 5.0 mol Cyclohexanedimethanol 5.0 mol Dibutyltin oxide 1.0 g

The above compound was placed in a reactor, equipped with a thermometer, a stirring bar, a condenser and a nitrogen introducing tube, and after substituting with nitrogen, the temperature was gradually raised with stirring, and the reaction was allowed to proceed at 240 ° C. for 6 hours. It was Next, the pressure was reduced (15 hPa), the reaction was carried out for 2 hours to cause dehydration condensation, and the reaction was terminated to obtain a polyester resin 2.

This polyester resin had a peak molecular weight of 9,100 and a glass transition point of 62 ° C.

Epoxy resin 3 Bisphenol A type liquid epoxy resin 2000 g (condensation product of bisphenol A and epichlorohydrin, epoxy equivalent 188, viscosity 13,000 mPa · s / 25 ° C.) Bisphenol A 937 g p-cumylphenol 559 g xylene 400 g

The above compound was placed in a reactor, equipped with a thermometer, a stir bar, a condenser, and a nitrogen introducing tube. After purging with nitrogen, the temperature was gradually raised to 70 ° C. with stirring, and the lithium chloride content was adjusted to 0. Add 0.64 g of 5N aqueous solution, 170 ° C
The temperature was raised to 0, xylene and water were distilled off under reduced pressure to release the reduced pressure, and the reaction was carried out for 6 hours. 184 g of ε-caprolactone was added thereto and reacted for 6 hours to obtain a modified epoxy polyol resin (epoxy resin 3).

This polyol resin has a peak molecular weight of 7,
The glass transition point was 600 and the glass transition point was 60 ° C.

Styrenic resin 4 Styrene 1600 g Butyl acrylate 400 g 2,2-Bis (4,4-di-t-butylperoxycyclohexyl) propane 4 g

Polymer A was obtained from the above compound by the suspension polymerization method.

Styrene 2550 g Butyl acrylate 450 g Di-t-butyl peroxide 60 g

Polymer B was obtained from the above compound by a solution polymerization method using xylene as a solvent.
The solutions were mixed in a mass ratio of 5:75 to obtain styrene resin 4. This styrene resin has peak molecular weights of 9,400 and 720,000 and a glass transition point of 6
It was 0 ° C.

Production Example of Classified Product Classified Product 1 Polyester Resin 1 100 parts by mass Copper phthalocyanine phthalimide derivative pigment 5 parts by mass Di-t-butylchromic salicylate chromium complex 4 parts by mass

The above raw materials were premixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at 130 ° C. After cooling the kneaded product, it is finely pulverized by a pulverizer using a jet stream and classified by an air classifier,
A cyan classified product 1 having a weight average diameter of 8 μm was obtained.

Further, the pigment may be C.I. I. Pigment Re
d 122 5 parts by mass, C.I. I. Pigment Ye
Magenta classified product 1, yellow classified product 1, and black classified product 1 were obtained in the same manner except that 3.5 parts by mass of low 17 and 5 parts by mass of carbon black were used.

Classification product 2 Polyester resin 2 100 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by mass Di-t-butylsalicylic acid chromium complex 4 parts by mass

The above raw materials were premixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at 130 ° C. After cooling the kneaded product, it is finely pulverized by a pulverizer using a jet stream and classified by an air classifier,
Cyan classified product 2 having a weight average diameter of 8 μm was obtained.

The pigment may be C.I. I. Pigment Re
d 57: 1 5 parts by mass, C.I. I. Pigment Y
ellow 17 3.5 parts by mass, carbon black 5
Magenta classified product 2, except for changing to mass parts
Yellow classified product 2 and black classified product 2 were obtained.

Classification product 3 Epoxy resin 3 100 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by mass Di-t-butylsalicylic acid chromium complex 4 parts by mass

The above raw materials were premixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at 130 ° C. After cooling the kneaded product, it is finely pulverized by a pulverizer using a jet stream and classified by an air classifier,
Cyan classified product 3 having a weight average diameter of 8 μm was obtained.

The pigment may be C.I. I. Pigment Re
d 122 5 parts by mass, C.I. I. Pigment Ye
Magenta classified product 3, yellow classified product 3, and black classified product 3 were obtained in the same manner except that 5 parts by mass of low 83 and 5 parts by mass of carbon black were used.

Classification product 4 Styrenic resin 4 100 parts by mass Copper phthalocyanine phthalimide derivative pigment 5 parts by mass Quaternary ammonium salt 1 part by mass Low molecular weight ethylene propylene copolymer 3 parts by mass

The above raw materials were premixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at 130 ° C. After cooling the kneaded product, it is finely pulverized by a pulverizer using a jet stream and classified by an air classifier,
Cyan classified product 4 having a weight average diameter of 8 μm was obtained.

Further, the pigment may be C.I. I. Pigment Re
d 57: 1 5 parts by mass, C.I. I. Pigment Y
Magenta classified product 4, yellow classified product 4, and black classified product 4 were obtained in the same manner except that the amount of ellow 97 was changed to 5 parts by mass and the amount of carbon black was changed to 5 parts by mass.

Classified product 5 Styrenic resin 4 100 parts by weight Magnetite (magnetic iron oxide) 80 parts by weight Di-t-butylsalicylic acid chromium complex 2 parts by weight Low molecular weight ethylene propylene copolymer 3 parts by weight

The above raw materials were premixed by a Henschel mixer, and then melt-kneaded by a twin-screw extruder set at 130 ° C. After cooling the kneaded product, it is finely pulverized by a pulverizer using a jet stream and classified by an air classifier,
A black classified product 5 having a weight average diameter of 8 μm was obtained.

Production Example of Toner and Developer To 100 parts by mass of a classified product, the formulation shown in Table 4 was sufficiently stirred with a Henschel mixer, and the inorganic fine powder of the present invention was externally added and mixed to obtain a toner.

When it is used as a one-component toner, it is used as it is, and when it is used as a two-component toner, the following developer is used.

Cyan toner 1, magenta toner 1, yellow toner 1, and black toner 1 were mixed with a Cu—Zn—Fe ferrite carrier coated with a silicone resin in an amount of 0.45% by mass so that the toner concentration would be 5% by mass. Used as a developer.

The cyan toner 15, the magenta toner 2, the yellow toner 2 and the black toner 2 are 0.3 parts by weight of a styrene-butyl methacrylate copolymer (mass ratio 80:20).
5 mass% and a Cu—Zn—Fe ferrite carrier coated with 0.15 mass% of a silicone resin were mixed to a toner concentration of 7 mass% to obtain a developer.

Cyan toner 16, magenta toner 3, yellow toner 3, and black toner 3 were styrene-methyl methacrylate copolymer (mass ratio 65:35) 2.5.
A Cu-Fe-based ferrite carrier coated by mass% was mixed with a toner concentration of 7 mass% to prepare a developer.

[0287]

[Table 4]

Example 1 Cyan Toner 1 was used as a commercially available digital full-color electrophotographic copying machine (color laser copier 550) having the structure shown in FIG.
(Canon Co., Ltd.), a printing durability test of 5,000 sheets was performed at 23 ° C. and 60% RH. At this time, the developing device was modified so as to be capable of single-component development. Specifically, a doctor blade is spread over a 150 μm thick phosphor bronze elastic plate with 1 mm thick urethane rubber, and the surface is 20 μm thick.
Was replaced with an elastic blade having a nylon resin layer, and the sleeve was placed so as to contact the sleeve at a linear pressure of 4 kg / m. Also, using urethane foam rubber roller as the supply roller,
The developing sleeve was changed to one in which the magnet was removed from the inside and the surface of the sleeve was blasted with # 600 glass beads. A charging roller is used as a contact charging member for primary charging, and a core metal at the center and a conductive elastic layer having an outer periphery formed of epichlorohydrin rubber containing carbon black are used as a basic structure. The charging roller is pressed against the surface of the photosensitive drum with a pressing force of 4 kg / m and is driven to rotate as the photosensitive drum rotates. Further, a felt pad is in contact with the charging roller as a cleaning member.

Regarding the density, a Macbeth densitometer RD918 (manufactured by Macbeth) was used to measure the reflection density using an SPI filter, and a 5 mm circle image was measured and used as the image density.

The fogging on the image was performed by using a reflection densitometer (Reflectometer model TC-6DS (manufactured by Tokyo Denshoku Co., Ltd.), and the worst value of the white background reflection density after image formation was set to Ds,
Let Dr be the reflection average density of the transfer material before image formation, and Ds-
The fogging was evaluated using Dr as the fogging amount. If this value is 1% or less, fogging is at a very good level, if it is 1.5% or less, the image is substantially good in fogging, and if it is 2% or less, there is no practical problem.

The transfer efficiency is obtained from the change in the Macbeth density of the toner image before and after the transfer on the photosensitive drum when the transfer current is 275 μA. The Macbeth density of the image after fixing on the transfer paper is 1.
When the image becomes 5, the image is transferred with the adhesive tape of the polyester film before and after the transfer on the photosensitive drum, and each and only the tape are attached to the transfer paper, and the Macbeth density is measured. When the density before transfer is D _a , the density after transfer is D _b , and the density of only the tape is D _c , the transfer efficiency is defined by the following formula.

Transfer efficiency = {[(D _a −D _c ) − (D _b −
D _c )] / (D _a −D _c )} × 100

That is, the higher this value, the higher the transfer efficiency and the better the transferability.

With regard to the transfer latitude, a 16-gradation image is formed, and the transfer image obtained by changing the transfer current is fixed by visual inspection. The range of the transfer current is obtained in which an image with all gradations is obtained with transfer unevenness, roughness, and good skipping. That is, if the transferability is excellent, the image can be transferred properly even at a low transfer current, and an image having a stable image density and a gradation can be obtained without transfer unevenness. Further, since the toner having excellent transferability does not cause the transfer current to be higher than necessary, it is possible to obtain an image with good roughness and sharpness. That is, a toner having a good transfer property and a wide range from the low transfer current value to the transfer upper limit is a toner having excellent transfer properties and a wide transfer latitude. That is, if the transfer latitude is wide, the applicable range of the transfer material and the image forming environment is widened, and the transfer control of the image forming apparatus can be facilitated.

The transfer dropout was visually evaluated for the printout. A: There are almost no voids. B: There is a slight hollow. C: There is a hollow, but there is no problem in practical use. D: Hollow-out is conspicuous and practically impossible.

The gradation was judged by visually observing an image of 16 gradations. A: 16 gradations can be confirmed, there is no roughness in the halftone part, and the highlight part is reproduced properly. B:
16 gradations can be confirmed, but some roughness is seen in the halftone part. C: The reproduction of the highlight part is getting worse, but there is no practical problem. D: 14 gradations or more could not be confirmed and practically impossible.

Table 5 shows the fog at the beginning of the test, the fogging of the 5,000th sheet, the image density, the blank portion in the transfer of the line portion, the gradation, the transfer efficiency at the 1,000th sheet, and the transfer latitude.

Table 6 shows image defects due to contamination and scratches on the photoconductor at 5,000 sheets, image defects due to contamination of the charging roller, and defective cleaning.

Image defects due to contamination were judged as follows. A: There are no image defects. B: A spotted or streak pattern due to dirt is slightly generated. C: Spot-like or streak-like patterns appear due to dirt, and uneven density occurs, but there is no problem in practical use. D: The influence of dirt and scratches is large, fusion, filming, etc. occur, many images other than latent images appear on the image, and density unevenness, charge unevenness etc. occur, and the image is disturbed. There is.

Further, a printing durability test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the toner for replenishment were allowed to adapt to the test environment for one week, and then started, and 5,000 sheets were printed. Initial, fogging of the 5,000th sheet, image density,
Table 7 shows the dropouts in the line portion during transfer, gradation, image defects due to contamination and scratches on the photoconductor, image defects due to contamination of the charging roller, and cleaning failure.

As shown in Tables 5 to 7, the cyan toner 1 of the present invention has a high image density, no fog, no omission in the line portion, excellent gradation, and no image defects due to contamination or scratches. A clear cyan image was obtained. Further, the transfer efficiency was good, and the toner had a wide transfer latitude.

Examples 2 to 11 Cyan toner 2,3,4,5,6,7,10,11,1
2 and 13 were evaluated in the same manner as in Example 1 and the results are shown in Table 5.
It is described in ~ 7.

Comparative Example 1 The cyan toner 7 was evaluated in the same manner as in Example 1 and the results are shown in Tables 5 to 7. There was no problem with omission in the character area and transfer latitude, but the initial fog was particularly poor under high humidity.

Comparative Example 2 The cyan toner 8 was evaluated in the same manner as in Example 1 and the results are shown in Tables 5-7. There was no problem with the developability, but the character part was missing and the transfer latitude was inferior.

Example 12 Modified digital full-color electrophotographic copying machine (color laser copier 55) using cyan toner 1, magenta toner 1, yellow toner 1 and black toner 1 in Example 1
(Canon Co., Ltd.) underwent a full-color copying test of 2,000 sheets at 23 ° C. and 60% RH. As a result, a beautiful pictorial image having excellent color reproduction and gradation and no color unevenness was obtained, and almost no color difference was observed in the image during transfer. The fogging was 4% and the worst value was 0.9% or less, and there was no problem during durability.

Further, a copy test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the replenishing toner were soaked in the test environment for one week, and then 2,000 copies were made. As a result, a beautiful full-color image was obtained, and the fog was 1.0% or less in the worst value when four colors were overlaid, and there was no problem in the initial stage.

Example 13 Cyan Toner 1, Magenta Toner 1, Yellow Toner 1
The developer and the black toner 5 prepared from the above are manufactured with a commercially available digital full-color electrophotographic copying machine (color laser copier 550 manufactured by Canon Inc.) at 23 ° C., 60%.
A full color copy test of 2,000 sheets was performed under RH. At this time, the doctor blade of the black developing device was modified (to a magnetic cut type) so that it could be developed and transferred from black, and the two-component developing device was used as it was for cyan, magenta, and yellow. As a result, a beautiful pictorial image having excellent color reproduction and gradation and no color unevenness was obtained, and almost no color difference was observed in the image being copied. The fogging was 1.2% or less in the worst case when four colors were overlaid, and there was no problem during durability.

Further, a copy test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the replenishing toner were soaked in the test environment for one week, and then 2,000 copies were made. As a result, a beautiful full-color image was obtained, and the fog was 4% or less in the worst value of 1.6% or less, and there was no problem in the initial stage.

Example 14 A commercially available digital full-color electrophotographic copying machine (Pretail 550 Co., Ltd.) was used in which a developer prepared from cyan toner 15, magenta toner 2, yellow toner 2 and black toner 2 was used as an intermediate transfer member using a transfer belt. A full-color copying test of 2,000 sheets was conducted at 23 ° C. and 60% RH. As a result, a beautiful full-color image having excellent color reproduction and no color unevenness was obtained, and almost no color difference was observed in the image during copying. The fogging was 4% and the worst value was 1.2% or less, which was not a problem.

Further, a copy test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the replenishing toner were soaked in the test environment for one week, and then 2,000 copies were made. As a result, a beautiful full-color image was obtained, and the fog was 1.4% or less in the worst value when four colors were overlaid, and there was no problem in the initial stage.

Example 15 A developer prepared from cyan toner 16, magenta toner 3, yellow toner 3 and black toner 3 was applied to a commercially available digital full color electrophotographic copying machine (U-Bix 9028 Konica Corporation) of the multiple development batch transfer system. Made)
A full-color copying test of 2,000 sheets was conducted at 23 ° C. and 60% RH. As a result, a beautiful full-color image having excellent color reproduction and no color unevenness was obtained, and almost no color difference was observed in the image during copying. The fogging was also 0.8% or less, which was the worst value when four sheets were stacked, and there was no problem.

Further, a copy test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the replenishing toner were soaked in the test environment for one week, and then 2,000 copies were made. As a result, a beautiful full-color image was obtained, and the fog was 1.1% or less in the worst value when four colors were overlaid, and there was no problem in the initial stage.

Example 16 Cyan toner 14, magenta toner 4, yellow toner 4, and black toner 4 were used in the digital full-color electrophotographic copying machine used in Example 1 to print 2,000 sheets at 23 ° C. and 60% RH. A full color copy test was conducted. However, if the photosensitive drum is a positively charged α-Si photosensitive drum,
The elastic blade was changed to an elastic plate of phosphor bronze plate to which silicone rubber was attached, and the power sources for primary charging, developing bias, transfer charging, and separation charging were modified so that positively charged toner images could be formed.

As a result, a full-color image having excellent gradation and no color unevenness was obtained, and almost no color difference was observed in the image during copying. The fogging was 4% and the worst value was 1.2% or less, which was not a problem.

Further, a copy test was conducted in an environment of 30 ° C. and 80% RH. The developing device and the replenishing toner were soaked in the test environment for one week, and then 2,000 copies were made. As a result, a good full-color image was obtained, and the fogging was 4% or less in the worst case, which was 1.6% or less, and there was no problem in the initial stage.

Examples 17 to 21 Commercially available electrophotographic copying machine NP-6016 (manufactured by Canon Inc.,
The evaluation equipment was a modification of the bias power supply so that the contact charging means, contact transfer means, elastic tip doctor blade, and urethane rubber blade cleaner were installed) so that reversal development was possible. Using this copier, black toner 5-9
Endurance copy test of 20,000 sheets at 23 ℃, 60% RH
And at 30 ° C. and 80% RH. The results are shown in Tables 8 and 9. Image density, fog, filming, cleaning, transfer unevenness, charge unevenness, photoconductor scratches, and charging roller and transfer roller stains were evaluated. The void of transfer was evaluated by using 200 g / m ² thick paper as a transfer material. The evaluation criteria are as follows.

(Scratch on Photoreceptor) A: No scratch appears on the image. B: There are scratches appearing in the halftone part. C: There is a scratch that appears in a normal image.

(Surface condition of each member) A: No toner adhesion or contamination. B: Almost no toner sticking or contamination. C: There is some toner adhesion and contamination. D: Toner adhered / contaminated.

[0319]

[Table 5]

[0320]

[Table 6]

[0321]

[Table 7]

[0322]

[Table 8]

[0323]

[Table 9]

[0324]

Since the toner of the present invention contains the inorganic fine powder treated with polysiloxane having a specific substituent, it is excellent in moisture resistance, releasability and chargeability, and developability,
It is possible to obtain a toner having excellent transferability, durability, leaving stability, and temporal stability.

That is, it is a toner and an image forming method capable of obtaining sufficient developability even under high humidity, aging and durability. Further, it is a toner and an image forming method which have good transfer efficiency and can easily obtain a beautiful pictorial full-color image having a wide transfer latitude.

Further, the present invention is a toner and an image forming method which suppresses voids in transfer even in a line image portion and a character portion.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing an image forming process used in an image forming method of the present invention.

FIG. 2 is a schematic diagram showing a primary charging step used in the image forming method of the present invention.

FIG. 3 is a schematic diagram showing a transfer step used in the image forming method of the present invention.

FIG. 4 is a schematic view showing a transfer step used in the image forming method of the present invention.

FIG. 5 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 6 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 7 is a schematic view showing a developing step used in the image forming method of the present invention.

FIG. 8 is a schematic view showing an image forming step used in the image forming method of the present invention.

FIG. 9 is a schematic view showing an image forming process used in the image forming method of the present invention.

FIG. 10 is a schematic view showing an image forming process used in the image forming method of the present invention.

FIG. 11 is a schematic view showing an image forming process used in the image forming method of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Photosensitive drum 2 Development unit 2-1,2,3,4 Developing device 3 Exposure means 4 Charging device 5 Holding member 6 Transfer drum 7 Gripper 8 Transfer charging device 9 Separation charging device 10 Paper feed roller 11 Separation claw 21 Photosensitive drum 22 Charging device 23 Exposure unit 24, 25, 26, 27 Developing device 28 Cleaner 29 Transfer roller 31 Static eliminator 32 Fixing device 41 Photosensitive drum 42 Charging roller 43 Exposure means 44, 45, 46, 47 Developing device 48 Intermediate transfer body 49 Power source 50 Holding member 51 Transfer roller 53 Photosensitive drum cleaner 54 Intermediate transfer material cleaner 55 Core bar Pa, b, c, d Image forming unit 61-a, b, c, d Photosensitive drum 62-a, b, c, d Latent image formation Section 63-a, b, c, d developing section 64-a, b, c, d transfer discharge section 65-a, b, c, d cleaning section 66- , B, c, d Charger 67 Fixer 68 Conveyor belt 69 Separating static eliminator 70 Ejection port 71, 72 Adsorption charger 73-a, b, c, d Separating static eliminator 90, 96 Development sleeve 91 Hopper 92 Magnetic generation Means 93,97 Doctor blade 94,95 Latent image carrier 101 Latent image carrier (photoreceptor, photosensitive drum) 101a Photoconductive layer 101b Conductive base layer 102 Charging roller 102a Conductive elastic layer 102b Core metal 103 Charging bias power source 104 Image Exposure 105 developing means 106 transfer means 107 transfer bias power supply 108 transfer material 109 cleaning device 110 static eliminator exposure device 111 fixing device 112,113 cleaning member 114 development bias power supply 201 latent image carrier 202 charging blade 203 metal support member 204 conductive rubber 205 Mold release table Layer 206 Charging bias power source 301 Latent image carrier (photoconductor, photosensitive drum) 302 Transfer roller 302a Conductive elastic layer 302b Core metal 308 Transfer bias power source 401 Latent image carrier (photoconductor, photosensitive drum) 408 Transfer bias power source 409 Transport Belt 410 Transfer roller 700 Toner 701 Hopper 702 Supply roller 703 Doctor blade 704 Power supply 708 Latent image holder 709 Development sleeve S Transfer material

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display area G03G 15/08 507 L

Claims (6)

[Claims] 1. An electrostatic charge image developing toner containing a binder resin, a colorant and an inorganic fine powder, wherein the inorganic fine powder is
Treated with a polysiloxane having a siloxy unit having an alkyl group or an aryl group as a substituent, and a siloxy unit having at least one substituent being hydrogen, in which a part or all of hydrogen atoms may be substituted with a fluorine atom. A toner for developing an electrostatic charge image, which is an inorganic fine powder. 2. A ratio of a siloxy unit having an alkyl group or an aryl group as a substituent, in which a part or all of hydrogen atoms may be substituted with a fluorine atom, to a siloxy unit having at least one substituent hydrogen. The electrostatic charge image developing toner according to claim 1, wherein the toner has a ratio of 1: 3 to 100: 1. 3. The electrostatic charge image developing toner according to claim 1, wherein the polysiloxane is a polysiloxane having dimethylsiloxy units and methylhydrogensiloxy units as main siloxy units. 4. An image forming method in which a latent image formed by electric charges on a latent image carrier is visualized by toner.
An image forming method, wherein the member that is brought into pressure contact with the latent image holding member is at least one of a charging step, a transfer step, and a cleaning step, and the toner is the toner according to any one of claims 1 to 3. 5. An image forming method for developing a latent image on a latent image carrier with a one-component toner on a toner carrier carrying one-component toner, wherein the layer thickness of the one-component toner on the toner carrier is thin. Using a developing method having a regulating member for regulating the layer,
An image forming method, wherein the one-component toner is the toner according to any one of claims 1 to 3. 6. An image forming method for transferring a toner image formed on a latent image holding member onto a recording material, wherein the toner image formed on the latent image holding member is transferred and a plurality of toner images are formed on the same recording material. 4. The image forming method, wherein the toner image according to claim 1 is formed, and the toner is the toner according to claim 1.