JPH10142833A - Electrostatic charge image developing toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner which gives high density without fog under various conditions from low temp. low humidity to high temp. high humidity and produces a little amt. of waste toner. SOLUTION: This electrostatic charge image developing toner contains fine particle aggregates and toner particles containing at least a binder resin and a coloring agent. The fine particle aggregates contain 20 to 90wt.% silicone oil or silicone varnish. The fine particles which form the fine particle aggregates are treated with a silane coupling agent having nitrogen atoms at least in side chains and with a hydrophobic agent, or treated with a silicone oil or silicone varnish having nitrogen atoms at least in side chains.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic image developing toner used in electrophotography and the like, and is applied to a printer, a copying machine, a facsimile, and the like.

[0002]

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

[0003] In recent years, devices using electrophotography have become more numerous than conventional copiers, such as printers and facsimile machines, and have been used in general offices and homes.

In office copiers, higher speed,
The direction of stabilization is always desired, and high-speed use, image density from the initial stage to long-term use, and stability of image quality have become important. Especially in high humidity, high temperature, low humidity
There is a need for image quality stability at low temperatures, image quality stability in the morning, image quality stability before and after toner replenishment, and the like.

Conventionally, as a developing method for electrophotography, a one-component developing method and a two-component developing method have been known. Above all, the one-component developing method is being adopted because the structure of the developing device can be simplified while ensuring high reliability.

However, in the one-component magnetic developing system, it is necessary to uniformly coat a thin layer of toner on the surface of a roll-shaped toner carrier such as a developing sleeve. For this reason, a strong rubbing force is applied to the toner, which causes deterioration of the toner and the surface of the toner carrier when used for a long period of time, and deterioration of the durability characteristic remains as a problem. The prior art did not provide a sufficient solution, and a technique for improving the durability was desired.

Further, as a charging means in the electrophotographic method,
Means utilizing corona discharge have been used. However, when corona discharge is used, a large amount of ozone is generated, so that it is necessary to provide a filter, and there has been a problem that the apparatus becomes large or the running cost increases.

As a technique for solving such a problem, a charging member such as a roller or a blade is brought into contact with the surface of a photoreceptor to form a narrow space in the vicinity of the contact portion, and interpreted according to the so-called Paschen's law. A charging method has been developed in which the generation of ozone is suppressed as much as possible by forming a discharge as possible, and among them, a roller charging method using a charging roller as a charging member is particularly preferably used in terms of charging stability. .

For example, JP-A-63-149669 and JP-A-2-123385 have been proposed. These are related to a contact charging method and a contact transfer method. However, a conductive elastic roller is brought into contact with an electrostatic latent image carrier, and the electrostatic latent image carrier is pressed while applying a voltage to the conductive roller. Then, a toner image is obtained by an exposure and development process, and then, while pressing another conductive roller to which a voltage is applied to the electrostatic latent image carrier, a transfer material is passed therebetween while the electrostatic latent image carrier is pressed. After the toner image on the image carrier is transferred to a transfer material, a copy image is obtained through a fixing process.

However, even in such a contact charging device, the essential charging mechanism uses a discharging phenomenon from the charging member to the photosensitive member, so that the voltage required for charging as described above is used. Requires a value equal to or higher than the photoconductor surface potential. When AC charging is performed for uniform charging, vibration and noise (hereinafter referred to as AC charging noise) of the charging member and the photoconductor due to the electric field of the AC voltage are generated, and the surface of the photoconductor is discharged. Deterioration and the like become remarkable, and accordingly, fusion or filming in which toner or a part of the toner component adheres to the surface of the photoreceptor is a new problem.

In such a roller transfer method that does not use corona discharge, the transfer member is brought into contact with the photoreceptor via the transfer member at the time of transfer. When the toner image formed on the photoreceptor is transferred to a transfer material, the toner image is pressed against the transfer material, and a partial transfer defect called so-called “transfer dropout” occurs. It is a big problem.

In order to solve this problem, Japanese Patent Laid-Open Publication No.
No. 62 proposes an image forming apparatus using a developer containing hydrophobic inorganic fine powder treated with silicone oil. However, thick transfer paper or OHP sheet having a weight per unit area of more than 100 g / m ² , such as postcards and Kent paper, has not been sufficiently improved.
Further, high image quality is required.

Further, in Japanese Patent Application Laid-Open No. 6-230601, the amount of silicone oil and silicone varnish is 20
Fine particle aggregates of up to 90% by weight have been proposed. However, the influence on the charging characteristics under high or low humidity is great, and a toner to which these fine particle aggregates are added is required to have more stable and high developing characteristics.

Further, since these charging members are in contact with each other, the untransferred toner and toner that has passed through the cleaner adhere to the transfer member and the charging member. In the toned image,
Streaks appear or unevenness appears.

Further, toner particles remaining on the photoreceptor without being transferred onto the transfer material are removed from the photoreceptor by a cleaning step.
Conventionally, blade cleaning, fur brush cleaning, roller cleaning, and the like have been used. In either method, the toner remaining after transfer is mechanically scraped off or dammed and collected in a waste toner container. Therefore, due to such a member being pressed against the surface of the photoreceptor, for example, the member is strongly pressed to wear the photoreceptor, causing a scratch on the photoreceptor and appearing in an image, and the toner on the surface of the drum. Problems such as sticking (fusing) to the surface of the drum and adhesion of the external additive such as silica to the drum surface (filming).

Further, copiers, printers, facsimile machines and the like using electrophotography have been used in general offices and homes, and miniaturization and energy saving are required. For the toners used for these, there is a demand for toners that can be fixed at lower temperatures because of the need for energy saving.

[0017] Recently, it has been required to reduce the amount of waste from the viewpoint of ecology. Due to such necessity, the recycling of toner is required also in copiers and printers, and the reduction of the amount of waste toner is required as a new technical problem.

[0018]

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

That is, an object of the present invention is to provide a toner whose density is stable from the beginning, a uniform coating of toner on a toner carrier such as a developing sleeve, and a uniform density without fog or unevenness even under low humidity and high humidity. An object of the present invention is to provide a toner for developing an electrostatic image capable of obtaining the above-mentioned image.

It is a further object of the present invention to provide a toner for developing an electrostatic image, which has a high fluidity, a high resolution and a high sharpness, and forms a faithful image of a document. .

It is a further object of the present invention to provide a halftone image,
An object of the present invention is to provide a toner for developing an electrostatic charge image which is uniform and has no roughness even in a solid black image.

It is a further object of the present invention to provide a toner for developing an electrostatic charge image having high transfer efficiency with no omission during transfer and no chipped image even in an image forming method using contact transfer means.

Another object of the present invention is to provide a toner for developing an electrostatic image, which is excellent in fixability and anti-offset properties.

It is a further object of the present invention to provide a toner for developing an electrostatic image, which has high releasability from a photoreceptor, exhibits high transfer efficiency, and reduces the amount of waste toner produced.

Another object of the present invention is to provide a toner for developing an electrostatic charge image, which prevents the toner from adhering, fusing and filming to the photoreceptor even after long-term use, and reduces shavings and scratches on the photoreceptor. It is.

[0026]

According to the present invention, there is provided a toner for developing an electrostatic charge image having toner particles and a fine particle aggregate containing at least a binder resin and a colorant. Alternatively, the fine particles forming a fine particle aggregate containing 20 to 90% by mass of a silicone varnish are treated with a silane coupling agent having at least a nitrogen atom in a side chain and a hydrophobizing agent, or have at least a nitrogen atom in a side chain. The present invention relates to a toner for developing an electrostatic image, which is treated with a silicone oil having an atom or a silicone varnish.

As a result of extensive studies, the present inventors have found that, in a toner containing a fine particle aggregate, the fine particle aggregate contains 20 to 90% by mass of silicone oil or silicone varnish, and the fine particles forming the fine particle aggregate are An electrostatic charge containing fine particle aggregates treated with a silane coupling agent having at least a nitrogen atom in the side chain and a hydrophobizing agent, or treated with a silicone oil or silicone varnish having at least a nitrogen atom in the side chain It has been found that the toner for image development provides an image free from fog, scattering, and unevenness at a sufficient density, and also provides an excellent image without missing an image due to omission during transfer.

Further, it has been found that the fine particle aggregate preferably contains a silicone oil or a silicone varnish containing a nitrogen atom in a side chain, from the viewpoint of developing characteristics.

The inventors of the present invention have studied in detail the lack of an image due to omission during transfer. As a result, when the toner containing the fine particle aggregate is used, the degree of omission during transfer becomes worse as copying with the same toner is continued. Stabilizes at a certain number of sheets.

More specifically, as copying is continued from the beginning, the degree of omission during transfer becomes worse, and the level is constant at about 3000 sheets. In the range where the number of copies exceeds 3,000, a fine particle aggregate containing only silicone oil or silicone varnish is more excellent than a toner containing fine particle aggregate containing only silicone oil or silicone varnish containing a nitrogen atom in a side chain. The contained toner is more excellent in preventing omission during transfer. However, in the case of a fine particle aggregate containing only silicone oil or silicone varnish, fog or a decrease in image density may be caused when added to a positively chargeable toner. Further, in the case of a fine particle aggregate containing only silicone oil or silicone varnish having a nitrogen atom in a side chain, when the number of copies exceeds 3,000, image chipping due to omission during transfer is slightly inferior, and low and high humidity. Under low humidity, a phenomenon called a blotch in which the toner is unevenly coated on the developing sleeve of the toner carrier may occur under low humidity. Therefore, a silicone oil or silicone varnish having a nitrogen atom in a side chain and a silicone oil or silicone varnish are further contained, and the combined content thereof is 20 to 90.
Incorporation of a mass% of fine particle aggregates gives an image without fogging, scattering, and unevenness, and also provides an excellent image without missing images due to omission during transfer.

Further, the fine particles in the fine particle aggregate are
By treating with a silane coupling agent containing a nitrogen atom in at least a side chain and a hydrophobizing agent, or by treating with a silicone oil or silicone varnish having at least a nitrogen atom in a side chain, hydrophobicity is improved and high humidity The chargeability under the high humidity is stable, the development characteristics under high humidity are stable for a long time, and the stable development characteristics can be obtained even after long-term storage. Further, by treating the fine particles by these methods, spot-like white spots in a solid black image are reduced. Also, when used in an elastic blade development system,
A uniform image can be obtained in a halftone image and a solid black image without white streaks missing on the sleeve. This is presumably because the treatment of the fine particles by the method of the present invention reduced the generation of coarse powder in the fine particle aggregates.

When incorporated in a positively chargeable toner, the fine particle aggregate has a charge amount of 0 to iron powder.
It is preferably ~ 100 mC / kg. Within this range, the uniformity of the toner on the sleeve is excellent, and +100
If it exceeds mC / kg, blotching is likely to occur, and 0 mC / kg
If the weight is smaller than kg, fog and a decrease in density are likely to occur.

Further, the effect of the present invention is remarkable when the toner particles contain a wax having an endothermic peak temperature of 120 ° C. or less as measured by a DSC meter. When the wax is contained in the toner, a part of the wax is present as a free component in the toner. In particular, a wax having an endothermic peak temperature of 120 ° C. or lower has poor dispersibility in a binder resin, and tends to generate many free components. This free component may cause non-uniform charging, hindering uniform coating of the toner on the developing sleeve, and coating the toner in an uneven or wavy shape. However, the presence of the fine particle aggregate of the present invention can prevent the uneven coating on the developing sleeve due to the uneven charging. Although the reason for this is not clear, it is considered that these fine particle aggregates adsorb the free wax component.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION Fine particles of an inorganic compound or organic compounds are used as the fine particles used in the fine particle aggregate containing silicone oil or silicone varnish, which is a feature of the present invention.

Examples of the organic compound include resin particles such as styrene resin, acrylic resin, silicone resin, silicone rubber, polyester resin, urethane resin, polyamide resin, polyethylene resin, and fluorine resin, and aliphatic compounds.

The inorganic fine powder used in the present invention includes:
Metal oxides of metals such as silicon, titanium, aluminum, germanium, magnesium, zinc, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony, molybdenum, and tungsten; or oxides such as boron oxide Nitrides such as silicon nitride and germanium nitride; composite metal oxides such as calcium titanate, magnesium titanate, strontium titanate, phosphotungstic acid, and phosphomolybdic acid;
Metal salts such as calcium carbonate, magnesium carbonate and aluminum carbonate; clay minerals such as kaolin; phosphate compounds such as apatite; carbides such as silicon carbide and titanium carbide; silicon compounds; carbon powders such as carbon black and graphite. .

Specific examples thereof include silicon oxide, aluminum oxide, titanium oxide, cerium oxide, germanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, tungsten oxide, strontium oxide, boron oxide, silicon nitride, and titanium nitride. Examples thereof include calcium oxide, magnesium titanate, strontium titanate, phosphotungstic acid, phosphomolybdic acid, calcium carbonate, magnesium carbonate, and aluminum carbonate.

Among these inorganic fine powders, silicon oxide,
Aluminum oxide and titanium oxide are preferred. These have many forms and types. Among them, the main components are SiO ₂ and Al ₂ O.
₃ , fine powdered silica represented by TiO ₂ , fine powdered alumina,
Fine powder titania is preferred. Particularly, fine powder silica is preferred.

As the inorganic fine powder, fine powder of an inorganic compound can be used under production by a dry method or a wet method. The dry method referred to here is a method for producing an inorganic fine powder produced by vapor phase oxidation of a halide. For example, the basic reaction formula in the method utilizing the thermal decomposition oxidation reaction of a halide gas in oxygen-hydrogen is as follows.

MX_Four+2 H_Two+ ／ O_Two → MO_Two+4
HX (M: tetravalent)

In this formula, for example, M is a metal or metalloid element, X is a halogen element, and n is a reaction formula representing an integer. Specifically, AlCl ₃ , TiCl ₄ , GeCl ₄ ,
When SiCl ₄ , POCl ₃ , and BBr ₃ are used, Al ₂ O ₃ , TiO ₂ , GeO ₂ , SiO ₂ , P ₂ O ₅ , and B ₂ O are used, respectively.
₃ is obtained. At this time, if a mixture of halides is used, a composite compound can be obtained.

In addition, a dry fine powder can be obtained by applying a manufacturing method such as thermal CVD or plasma CVD. Among them, SiO ₂ , Al ₂ O ₃ , TiO _{2 and the} like are preferably used.

On the other hand, as a method for producing the inorganic fine powder used in the present invention by a wet method, various conventionally known methods can be applied. For example, the decomposition of sodium silicate with an acid is represented by the following general reaction formula.

Na ₂ O.xSiO ₂ + 2HCl + nH ₂ O
→ xSiO ₂ · nH ₂ O + 2NaCl

Also, a method of decomposing sodium silicate with ammonium salts or alkali salts, forming an alkaline earth metal silicate from sodium silicate and then decomposing it with acid to form silicic acid, and ion-exchanging the sodium silicate solution There are a method of using silicic acid with a resin, a method of using natural silicic acid or silicate, and the like. Other methods include hydrolysis of metal alkoxides. The general reaction formula is shown below.

M (OR) ₄ O + 2H ₂ O → MO ₂ +4
ROH (M: tetravalent)

In this formula, for example, M is a metal or metalloid element, R is an alkyl group, and n is an integer. At this time, if two or more metal alkoxides are used, a composite can be obtained.

Among these, inorganic compounds are particularly preferable because they have an appropriate electric resistance. Particularly, oxides and double oxides of Si, Al and Ti are preferable.

Further, a material whose surface has been previously rendered hydrophobic with a coupling agent or the like may be used.

The average particle size of the fine particles is desirably in the range of 0.001 to 20.0 μm in terms of the number average of the primary particles, and particularly preferably 0.005 to 10.0 μm. BE
The specific surface area by nitrogen adsorption measured by the T method is 10
~500m ² / g, more preferably 50~400m ² /
g, more preferably 100 to 350 m ² / g.
If it is less than 10 m ² / g, it tends to be difficult to hold a large amount of silicone oil or silicone varnish within the range of the present invention as particles having a suitable particle size.

The specific surface area was determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus, Autosorb 1 (manufactured by Yuasa Ionics) according to the BET method, and calculating the specific surface area using the BET multipoint method.

A feature of the present invention is that these fine particles in the fine particle aggregate are treated with a silane coupling agent having at least a nitrogen atom in a side chain and a hydrophobizing agent, or a silicone oil having at least a nitrogen atom in a side chain. Alternatively, it is characterized by being treated with a silicone varnish.

When treated with a silane coupling agent having a nitrogen atom in the side chain and a hydrophobizing agent, the silane coupling agent having a nitrogen atom in the side chain may be an aminosilane coupling agent or a silane having a nitrogen-containing heterocyclic ring. Coupling agents and the like can be mentioned. Among them, aminosilane coupling agents are preferred.

Examples of such an aminosilane coupling agent include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrimethoxysilane. Methoxysilane, monobutylaminopropyltrimethoxysilane, dioctylaminopropyltrimethoxysilane, dibutylaminopropyldimethoxysilane, dibutylaminopropylmonomethoxysilane, dimethylaminophenyltriethoxysilane, trimethoxysilyl-γ-propylphenylamine, trimethoxy Silyl-γ-propylbenzylamine, trimethoxysilyl-γ-propylpiperidine, trimethoxysilyl- -Propylmorpholine, trimethoxysilyl-γ-propylimidazole, γ-aminopropyldimethylmethoxysilane, γ-aminopropylmethyldimethoxysilane, 4-aminobutyldimethylmethoxysilane, 4-aminobutylmethyldiethoxysilane, N- (2 -Aminoethyl) aminopropyldimethylmethoxysilane, 1,3-bis (3-aminopropyl)
-1,1,3,3-tetramethyldisilazane, 1,3-
Bis (4-aminobutyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis {N (2-aminoethyl) aminopropyl} -1,1,3,3-tetramethyldisilazane , 1,3-bis (dimethylaminopropyl)
-1,1,3,3-tetramethyldisilazane, 1,3-
Bis (diethylaminopropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (3-propylaminopropyl) -1,1,3,3-tetramethyldisilazane, 1,3-bis (3-aminopropyl) -1,1,1
3,3-tetramethyldisilazane and the like can be mentioned.

These treating agents may be used alone or in combination of two or more, or in combination or in multiple treatments.

As the hydrophobizing agent, any organic compound which imparts hydrophobicity can be used, but an organosilicon compound, a titanium coupling agent and the like are preferable. Of these, organosilicon compounds are preferred, and silane coupling agents and silicone oils are particularly preferred.

Examples of such organosilicon compounds include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyl Ethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetra Methyldisiloxane, 1,
Examples include 3-diphenyltetramethyldisiloxane and dimethylpolysiloxane having from 2 to 12 siloxane units per molecule and having hydroxyl groups bonded to Si each of which is located at one terminal unit. These are used alone or as a mixture of two or more.

Silicone oil can be used as a hydrophobizing agent for the fine particles of the present invention. Above all, the silicone oil is generally preferably represented by the following formula.

[0059]

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[Wherein, R ₁ represents a methyl group, another alkyl group, an aryl group, or hydrogen;
₂ represents a methyl group, another alkyl group, an aryl group, a vinyl group, an alkyl group or an aryl group which may have a hydroxyl group, a fluorine-substituted alkyl group, or hydrogen. m and n indicate integers. Among them, as the silicone oil used in the present invention,
Dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil are preferred.

The viscosity of the silicone oil is 25 ° C.
Is preferably 2 to 1000 cSt, and 10 to 3
00cSt is more preferred.

The treatment amount of the silane coupling agent having a nitrogen atom in the side chain for the fine powder cannot be unconditionally limited because the specific surface area of the fine powder is also affected. The silane coupling agent having a nitrogen atom in the chain is used in an amount of 20 parts by mass or less. 20
If the amount exceeds the mass part, the specific surface area becomes small and the fluidity becomes poor. Preferably it is 0.1 to 15 parts by mass.

The amount of the hydrophobizing agent to be treated with respect to the fine powder cannot be unconditionally limited because the specific surface area of the fine powder is also affected. Used. If it exceeds 20 parts by mass, the specific surface area becomes small and the fluidity becomes poor. Preferably it is 0.1 to 10 parts by mass.

The processing amount of the silane coupling agent having a nitrogen atom in the side chain and the hydrophobizing agent is preferably 0.5 to 30 parts by mass in total.

The treatment ratio between the silane coupling agent having a nitrogen atom in the side chain and the hydrophobizing agent is preferably from 1:20 to 10: 1 from the viewpoint of chargeability.

It is also preferable to treat these fine particles in the fine powder aggregate of the present invention with a silicone oil or silicone varnish having at least a nitrogen atom in a side chain. Among them, silicone oil having a nitrogen atom in a side chain is preferable, and among them, amino-modified silicone oil is preferable.

The silicone oil or silicone varnish having a nitrogen atom in the side chain for treating the fine particles may be the same as or different from the silicone oil or silicone varnish having a nitrogen atom in the side chain contained in the fine particle aggregate. You may.

As the amino-modified silicone oil used in the present invention, those having at least a partial structure represented by the following formula can be preferably used. These partial structures may be present at the end of the silicone oil.

[0069]

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(Wherein, R ₁ represents hydrogen, an alkyl group, an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, R ₃ and R ₄ represent a hydrogen, an alkyl group, or an aryl group; R ₅ represents a nitrogen-containing heterocyclic group) The above-mentioned alkyl group, aryl group, alkylene group, and phenylene group may have an organo group having a nitrogen atom, and may be halogen or the like as long as the chargeability is not impaired. May have the following substituents.

The amine equivalent (g / mol) in the amino-modified silicone oil is preferably 300 or more and 10,000 or less. If the amine equivalent is less than 300, it is difficult to uniformly coat the fine particles and the hydrophobicity is low. If the amine equivalent is more than 10,000, the chargeability will be low, and the fine particle aggregates will also be negatively chargeable, causing a decrease in image density. More preferably, the amine equivalent is 300 or more and 8000 or less.

The viscosity of the amino-modified silicone oil is preferably from 2 to 1000 cSt. More preferably,
10 to 300 cSt.

If necessary, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil may be simultaneously treated.

The treatment amount of the silicone oil or silicone varnish having a nitrogen atom in the side chain with respect to the fine powder cannot be unequivocally limited because the specific surface area of the fine powder is also affected. A silicone oil or silicone varnish having a nitrogen atom in a side chain is used in an amount of 25 parts by mass or less. If it exceeds 25 parts by mass, the specific surface area becomes small and the fluidity becomes poor. Preferably it is 3 to 20 parts by mass.

The fine particles in the present invention may be obtained by treating an untreated fine powder with a silane coupling agent containing at least a nitrogen atom in a side chain and a hydrophobizing agent, or a silicone oil or a silicone oil containing at least a nitrogen atom in a side chain. It is characterized by being treated with a silicone varnish.

As a treatment method, a silane coupling agent containing at least a nitrogen atom in a side chain, a hydrophobizing agent,
Alternatively, either a method in which a silicone oil or silicone varnish containing at least a nitrogen atom in a side chain and a silicone oil and a varnish are mixed and sprayed, or a method in which each is sprayed sequentially may be used.

If necessary, a silane coupling agent containing at least a nitrogen atom in the side chain and a hydrophobizing agent, or a silicone oil containing at least a nitrogen atom or a silicone varnish, a silicone oil and a varnish are dissolved in a suitable solvent. Alternatively, they may be dispersed and used. They can be obtained by a method of mixing and spraying each, or spraying each of them sequentially, and then removing the solvent.

The silicone oil used in the fine powder aggregate of the present invention is represented by the general formula

[0079]

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(Where R represents an alkyl group having 1 to 3 carbon atoms, R ′ represents a silicone oil-modified group such as alkyl, halogen-modified alkyl, phenyl, and modified phenyl, and R ″ represents 1 to 3 carbon atoms. And m and n each represent an integer.) For example, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, vinyl group-containing silicone oil, and alkyl-modified silicone are preferable. Oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil and the like.

As the silicone varnish used in the present invention, known substances can be used, and examples thereof include KR-251 and KP-112 manufactured by Shin-Etsu Silicone Co., Ltd.

In the present invention, an amino-modified silicone oil having a structure represented by the formula (I) can be used as the silicone oil.

[0083]

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(Where R ₁ and R ₆ are hydrogen, an alkyl group,
R ₂ represents an alkylene group or a phenylene group; R ₃ represents a compound having a nitrogen-containing heterocyclic ring in its structure; R ₄ and R ₅ represent a hydrogen, an alkyl group, or an aryl group . R ₂ may not be present. However, the above-mentioned alkyl group, aryl group, alkylene group and phenylene group may contain an amine or may have a substituent such as halogen as long as the chargeability is not impaired. M is a number of 1 or more, and n and k are positive numbers including 0. Here, n + k is a positive number of 1 or more. )

The most preferred structure among the above structures is one in which the number of nitrogen atoms in the side chain containing a nitrogen atom is one or two.

Examples of the nitrogen-containing unsaturated heterocycle are shown below.

[0087]

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Examples of the nitrogen-containing saturated heterocycle are shown below.

[0089]

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The present invention is not limited to the above compound examples, but preferably has a 5-membered or 6-membered heterocyclic ring.

As the derivatives, a hydrocarbon group, a halogen group, an amino group, a vinyl group, a mercapto group,
Derivatives into which a methacryl group, a glycidoxy group, a ureido group, etc. are introduced are exemplified.

These may be used alone or in a mixture of two or more.

The silicone varnish used in the present invention includes, for example, methyl silicone varnish, phenylmethyl silicone varnish and the like, and methyl silicone varnish is particularly preferred.

Methyl silicone varnish is a polymer composed of T ³¹ units, D ³¹ units and M ³¹ units represented by the following structural formula, and a three-dimensional polymer containing a large amount of T ³¹ units.

[0095]

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The methyl silicone varnish or the phenylmethyl silicone varnish is, for example, a substance having a chemical structure represented by the following structural formula (II).

[0097]

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(R ³¹ represents a methyl group or a phenyl group.)

In the above silicone varnish, in particular, T ³¹
The unit is an effective unit for imparting good thermosetting properties and forming a three-dimensional network structure. The T ³¹ unit is 10 to 90 mol% in a silicone varnish, in particular 30 to 80 mol%
Is preferably contained at a ratio of

Such a silicone varnish has a hydroxyl group at a terminal or a side chain of a molecular chain, and is cured by dehydration condensation of the hydroxyl group. Examples of the curing accelerator that can be used to accelerate this curing reaction include fatty acid salts such as zinc, lead, cobalt, and tin; amines such as triethanolamine and butylamine; and the like. Of these, amines can be particularly preferably used.

In order to make the above-mentioned silicone varnish into an amino-modified silicone varnish, the above-mentioned T ³¹ unit, D ³¹
Units, some of the methyl group or a phenyl group present in the M ³¹ unit may be replaced with a group having an amino group. Examples of the group having an amino group include, but are not limited to, those represented by the following structural formula.

[0102]

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The above silicone oil or silicone varnish, when used alone or mixed, has a viscosity at 25 ° C.
50-200,000 centistokes, preferably 5
00-150,000 centistokes, more preferably 1,500-100,000 centistokes.

If the viscosity is less than 50 centistokes, it is difficult to form a large amount of silicone oil or silicone varnish with good particles, and the fine particle aggregate has no stability.
Thermal and mechanical stresses tend to degrade image quality. If over 200,000 centistokes,
Particles of silicone oil or silicone varnish tend to be difficult.

The viscosity of the silicone oil or silicone varnish is measured using a Visco Tester VT500 (manufactured by Haake). One of several viscosity sensors for VT500 is selected (arbitrary), and a measurement sample is put in a measurement cell for the sensor to measure. The viscosity (pas) displayed on the device is converted to cSt (centistokes).

In the present invention, any silicone oil or silicone varnish having a nitrogen atom in the side chain can be used as long as it is described in the present invention, and among them, amino-modified silicone oil is preferable.

The amine equivalent (g / mol) in the amino-modified silicone oil is preferably 300 or more and 10,000 or less. If the amine equivalent is less than 300, the viscosity of the silicone oil becomes too low, making it difficult to form fine particle aggregates. When the amine equivalent is more than 10,000, the chargeability is low, and the fine powder aggregate also has a strong negative chargeability, which may cause a decrease in image density. More preferably, the amine equivalent is 300 or more and 8000 or less.

As the silicone oil or silicone varnish in the present invention, any of those described in the present invention can be used. Among them, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil, It is preferable to contain at least one or more silicone oils selected from fluorine-modified silicone oils from the viewpoint of omission during transfer. Among them, dimethyl silicone oil, methyl hydrogen silicone oil, and fluorine-modified silicone oil are preferred, and dimethyl silicone oil and fluorine-modified silicone oil are more preferred.

In the fine particle aggregate of the present invention, the silicone oil or silicone varnish having a nitrogen atom in the side chain is an amino-modified silicone oil, and the silicone oil or silicone varnish is dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen It is preferable to contain at least one or more silicone oils selected from silicone oils, alkyl-modified silicone oils, and fluorine-modified silicone oils.

In the present invention, the mass ratio of the silicone oil or silicone varnish having a nitrogen atom in the side chain thereof to the silicone oil or silicone varnish is preferably 1:30 to 10: 1. If the ratio of the silicone oil or varnish having a nitrogen atom in the side chain to the silicone oil or varnish having no nitrogen atom in the side chain is less than 1:30, the toner becomes strongly negatively charged and is contained in the positively chargeable toner. In this case, the density may be reduced or fogging may occur. Preferably it is 1:20 or more. If the ratio is greater than 10: 1, the effect on hollowing out is not sufficiently different from the case of using only silicone oil or silicone varnish having a nitrogen atom in the side chain. 1:20
~ 3: 1 is preferred.

The fine particle aggregate in the present invention contains a silicone oil or silicone varnish having a nitrogen atom in a side chain, and a silicone oil or silicone varnish,
The combined content is preferably 20 to 90% by mass of the fine particle aggregate. More preferably, 30 to 85
%, More preferably 40 to 80% by mass.

When the total amount of the silicone oil or silicone varnish is less than 20% by mass, the effect of improving omission during transfer is small. On the other hand, when the amount exceeds 90% by mass, the silicone oil or silicone varnish aggregates the toner particles, Image quality is likely to deteriorate.

The fine particle aggregate in the present invention has a ratio of silicone oil or silicone varnish having a nitrogen atom in a side chain to silicone oil or silicone varnish,
Any of the mass ratios described above can be used. Further, the charge amount of the fine particle aggregate when the fine particle aggregate is mixed with iron powder is preferably 0 to +100 mC / kg.

In the case of the negative charging property with respect to the iron powder, even when mixed in the toner, it tends to become the oppositely charged component, and fogging occurs in the non-image area. On the other hand, if it exceeds +100 mC / kg, the coat on the developing sleeve becomes non-uniform, resulting in unevenness or wavy fog in a halftone image or solid image.

For measuring the charge amount, an iron powder carrier is used. The carrier used in the present invention is a flat iron powder carrier having an average particle size of 70 μm according to a measuring method according to JIS-H2601. For example, EFV200 manufactured by Powder Tech
-300 can be used.

0.2 g of the fine particle aggregate and 9.8 g of the iron powder carrier are placed in a 50 ml poly bottle, covered, and stirred sufficiently by a stirrer to sufficiently charge the toner. As the stirrer, for example, YSLD manufactured by Yayoi Co., Ltd.
Can be used. 125 rpm /
After shaking for 1 minute under the conditions of minutes, the triboelectric charge is measured.

The fine particle aggregate in the present invention is a fine particle treated with a silane coupling agent and a hydrophobizing agent containing at least a nitrogen atom in a side chain, or a silicone oil or silicone varnish containing at least a nitrogen atom in a side chain. It can be obtained by mixing and treating with silicone oil and varnish.

As a method of mixing and processing, for example,
It can be obtained by mixing silicone oil or varnish as needed, and directly mixing and stirring with the treated fine particles using a mixer such as a Henschel mixer or a turbuler mixer.

The silicone oil or varnish can also be obtained by dissolving or dispersing in a solvent as necessary, followed by mixing and stirring to remove the solvent.

The conditions of the mixing and stirring cannot be generally limited depending on the mixing method of the mixer used, the size of the model, and the like. However, depending on the stirring conditions, fine particle aggregates are not formed. It is preferred to use a Henschel mixer at a suitable speed.

Further, after the silicone oil treatment, the fine particle aggregate may be heated at a temperature of 350 ° C. or lower, if necessary.

The fine particle aggregate thus treated can be used even if its hydrophobicity is low, but is preferably 30% or more. If it is less than 30%, the image density may be slightly lower under high humidity conditions. More preferably 5
0% or more.

For the measurement of the hydrophobicity, 1.0 g of the sample and 100 g of ion-exchanged water are put into a 200 ml bottle and stirred vigorously for 1 minute. Then, after leaving still for 5 minutes, it is dispersed in a UV cell having a thickness of 10 mm. The light transmittance at 500 nm is measured using ion-exchanged water as a reference. This is defined as the hydrophobicity.

The fine particle aggregate of the present invention is suitable for a positively chargeable toner.

The fine particle aggregate comprising the silicone oil or silicone varnish and the fine particles has a specific surface area of 0.01 to 50 m ² / g (preferably 0.05 to 50 m ² / g).
30 m ² / g, more preferably 0.1 to 10 m ² / g)
In the case of the above, good results are obtained.

When the viscosity exceeds 50 m ² / g, the silicone oil or silicone varnish is not easily retained as particles, causing aggregation of the toner, and image quality is likely to deteriorate. In addition, the effect of improving the omission during transfer tends to decrease. If it is less than 0.01 m ² / g, the image quality tends to deteriorate.

The specific surface area is a value calculated by the following method. According to the BET method, nitrogen gas is adsorbed on the sample surface using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics), and the specific surface area is calculated using the BET multipoint method.

The application amount of the fine particle aggregate containing the silicone oil or silicone varnish was 100 toner particles.
The amount is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, and still more preferably 0.05 to 2 parts by mass with respect to the parts by mass. If it is less than 0.01 parts by mass,
The coating effect on the photoreceptor and the contact charging member is small.
If it exceeds 0 parts by mass, the fixability of the toner tends to be impaired.

The fine particle aggregate according to the present invention contains a relatively large amount of the above-mentioned silicone oil or silicone varnish having a good releasability of 20% to 90% by mass, which is used as the toner fine powder and the photosensitive powder. It works to improve the releasability from the body surface and the contact charging member surface.

Here, the method of measuring the triboelectric charge amount of the toner with respect to the carrier in the present invention will be described in detail with reference to FIG.

FIG. 1 is an explanatory view of a device for measuring the amount of triboelectric charge. A magnetic brush (toner and toner) on a developer carrier whose frictional charge is to be measured is measured in a metal measuring container 12 having a conductive screen 13 of 400 mesh (which can be appropriately changed to a size not allowing the passage of carrier particles) at the bottom. (Mixture of magnetic particles) and a metal lid 14 is formed. At this time, the weight of the entire measurement container 12 is weighed and defined as W ₁ (g). Next, in the suction device 11 (at least the portion in contact with the measuring container 12 is at least an insulator), the pressure of the vacuum gauge 15 is adjusted to 0.2 × 10 ⁵ Pa (the differential pressure ). In this state, suction is sufficiently performed (about 1 minute) to remove the toner by suction. The potential of the electrometer 19 at this time is V
(Volts). Here, reference numeral 18 denotes a capacitor having a capacity of C (μF). Further, the weight of the whole measurement container after suction is weighed to be W ₂ (g). This triboelectric charge amount Q (μC
/ G; mC / kg) is calculated as follows.

[0132]

(Equation 1)

However, the measurement conditions are 23 ° C. and 60% RH.

The average particle size of the fine particle aggregate in the present invention is in the range of 1.0 to 20.0 μm in terms of the 50% number average particle size. If the thickness is less than 1.0 μm, a sufficient effect for hollowing out cannot be obtained, and if it exceeds 20.0 μm, uniform dispersibility in the toner is poor and separation is easy. More preferably, 3.0 to 17.
0 μm, more preferably in the range of 3.0 to 15.0 μm.

The average particle size of the fine particle aggregate is SYMPAT
EC HELOS Particle size an
The measurement was carried out by analysis.

In the present invention, the bulk density of the fine particle aggregate is as follows:
0.10 to 0.80 g / cm ³ is preferable. 0.10g
If it is less than / cm ³ , a sufficient effect on hollowing out cannot be obtained,
If it exceeds 0.80 g / cm ³ , the particles are excessively aggregated, have poor uniform dispersibility in the toner, and are difficult to disperse. More preferably, it is in the range of 0.40 to 0.80 g / cm ³ .

As the binder resin used in the toner of the present invention, the following binder resins can be used.

For example, homopolymers of styrene such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene and their substituted polymers; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene Copolymer, styrene-acrylate copolymer, styrene-methacrylate 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, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester 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 binders include styrene copolymers or polyester resins.

As comonomers for the styrene monomer of the styrene copolymer, for example, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, acrylic acid-
Monocarboxylic acid having a double bond such as 2-ethylhexyl, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, and the like;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like;
Vinyl esters such as vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene, butylene; vinyl ketones such as vinyl methyl ketone and vinyl hexyl ketone; vinyl methyl ether and vinyl Vinyl monomers such as ethyl ether, vinyl isobutyl ether and the like; and vinyl monomers such as one or two or more are used.

The styrene-based polymer or styrene-based copolymer may be cross-linked, or may be a mixed resin.

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

The method for synthesizing the binder resin may be any of bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

In the bulk polymerization method, a polymer having a low molecular weight can be obtained by increasing the termination reaction rate by polymerizing at a high temperature, but there is a problem that the reaction is difficult to control.
In the solution polymerization method, a low molecular weight polymer can be easily obtained under mild conditions by utilizing the difference in chain transfer of radicals depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferable when a low molecular weight compound is obtained in the composition.

As a solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like are used. In the case of a styrene monomer mixture, xylene, toluene or cumene is preferred. It is appropriately selected depending on the polymer to be polymerized.

The reaction temperature varies depending on the solvent used, the initiator and the polymer to be polymerized.
It is better to carry out at 0 ° C. In solution polymerization, solvent 100
It is preferable to carry out with 30% by weight to 400% by weight of monomer based on% by weight.

It is also preferable to mix another polymer in the solution at the end of the polymerization, and several types of polymers can be mixed well.

As a polymerization method for obtaining a high molecular weight component or a gel component, an emulsion polymerization method or a suspension polymerization method is preferable.

Among them, the emulsion polymerization method is a method in which a monomer (monomer) almost insoluble in water is dispersed as small particles in an aqueous phase with an emulsifier, and polymerization is carried out using a water-soluble polymerization initiator. . In this method, it is easy to control the heat of reaction, and since the phase in which the polymerization is carried out (the oil phase composed of the polymer and the monomer) and the aqueous phase are different, the termination reaction rate is small, and as a result, the polymerization rate is large. , With a high degree of polymerization.
Further, the reason is that the polymerization process is relatively simple, and that the polymerization product is fine particles, so that it is easy to mix with a colorant, a charge control agent, and other additives in the production of a toner. This is advantageous as compared with other methods as a method for producing a binder resin for a toner.

However, the resulting polymer tends to be impure due to the added emulsifier, and an operation such as salting out is required to remove the polymer. Therefore, suspension polymerization is a simple method.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is
(0 to 90 parts by mass). Examples of usable dispersants include polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, and the like. There is an appropriate amount in terms of the amount of the monomer relative to the aqueous solvent, and generally 0.05 to 1 based on 100 parts by mass of the aqueous solvent. Used in parts by weight. The polymerization temperature is suitably from 50 to 95 ° C, but should be appropriately selected depending on the initiator used and the intended polymer. As the type of initiator, any initiator that is insoluble or hardly soluble in water can be used.

Examples of the initiator used include t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, -T-butyl peroxide, t
-Butylcumyl peroxide, dicumyl peroxide, 2,2′-azobisisobutyronitrile, 2,2 ′
-Azobis (2-methylbutyronitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1-bis (t-butylperoxy)
3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,4-bis (t-butylperoxycarbonyl) cyclohexane, 2,2-bis (t-butylperoxy) Octane,
n-butyl 4,4-bis (t-butylperoxy) valerate, 2,2-bis (t-butylperoxy) butane, 1,3-bis (t-butylperoxy-isopropyl) benzene, 2,5 -Dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5
-Di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane,
Di-t-butyldiperoxyisophthalate, 2,2-
Bis (4,4-di-t-butylperoxycyclohexyl) propane, di-t-butylperoxy α-methylsuccinate, di-t-butylperoxydimethylglutarate, di-t-butylperoxyhexahydro Terephthalate, di-t-butylperoxyazelate, 2,
5-dimethyl-2,5-di (t-butylperoxy) hexane, diethylene glycol-bis (t-butylperoxycarbonate), di-t-butylperoxytrimethyladipate, tris (t-butylperoxy) triazine, Vinyl tris (t-butylperoxy) silane and the like can be mentioned, and these can be used alone or in combination.

The amount is used at a concentration of 0.05 parts by mass or more (preferably 0.1 to 15 parts by mass) with respect to 100 parts by mass of the monomer.

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, and bisphenol represented by formula (A) and derivatives thereof;

[0155]

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. )

Diols represented by the formula (B):

[0158]

Embedded image

(Wherein R ′ is —CH ₂ CH ₂ — or

[0160]

Embedded image X 'and y' are integers of 0 or more, and x '
The average value of + y 'is 0 to 10. ).

As the divalent acid component, for example, phthalic acid,
Benzenedicarboxylic acids such as terephthalic acid, isophthalic acid and phthalic anhydride or their anhydrides and lower alkyl esters; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or their anhydrides and lower alkyl esters; n- Alkenyl succinic acids or alkyl succinic acids such as dodecenyl succinic acid, n-dodecyl succinic acid, or anhydrides and lower alkyl esters thereof; fumaric acid, maleic acid, citraconic acid, unsaturated dicarboxylic acids such as itaconic acid or anhydrides, lower acids And dicarboxylic acids such as alkyl esters; and derivatives thereof.

Further, it is preferable to use a trivalent or higher valent alcohol component and a trivalent or higher valent acid component which also function as a crosslinking component.

The trihydric or higher polyhydric alcohol component includes
For example, sorbitol, 1,2,3,6-hexanetetrol, 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 and the like.

The polyvalent carboxylic acid component having 3 or more valences in the present invention includes, for example, trimellitic acid, pyromellitic acid, 1,2,4-benzenetricarboxylic acid,
2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,2
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-
Octanetetracarboxylic acid, empol trimer acid, and anhydrides and lower alkyl esters thereof;

[0165]

Embedded image

(Wherein X is an alkylene or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), such as tetracarboxylic acids, and anhydrides and lower alkyl esters thereof. And polyvalent carboxylic acids and derivatives thereof.

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

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

From the viewpoints of developability, fixability, durability and cleaning properties, a styrene-unsaturated carboxylic acid derivative copolymer,
Polyester resins, block copolymers thereof, grafted products thereof, and furthermore, mixtures of styrene copolymers and polyester resins are preferred.

The binder resin used in the toner of the present invention has a molecular weight distribution of 10 ⁵ as measured by GPC.
It is preferable to have a peak in the above region, and 3 ×
It is preferable to have a peak in the region of 10 ^{3 to} 5 × 10 ^{4 from} the viewpoint 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 region of 3 × 10 ^{3 to} 5 × 10 ⁴ can be used. A polymer having a peak in a region of 10 ⁵ or more or a polymer (H) containing a gel component is formed. These components can be obtained by blending during melt kneading. The gel component can be partially or completely cut at the time of melt-kneading, becomes a THF-soluble component, and is measured by GPC as a component in a region of 10 ⁵ or more.

As a particularly preferred method, the polymer (L)
Alternatively, the polymer (H) is formed by solution polymerization, and when the polymerization is completed, 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 in which a polymer (L) is formed by polymerization in the presence of the polymer, and a method in which the polymer (H) is blended in a solvent at the end of the solution polymerization; And 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.

In the case of a positively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acryl copolymer, a styrene-methacryl copolymer, a styrene-butadiene copolymer, and an acid value of 10 or less are used. Polyester resins and their block copolymers, grafted products,
Blend resins are preferable, and in the case of a negatively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acryl copolymer, a styrene-methacryl copolymer and a copolymer of these with a maleic acid monoester, Polyester resins, and their block copolymers, grafts, and blend resins are preferred in terms of developability.

In particular, examples of the binder resin for the toner subjected to the pressure fixing method include low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylate copolymer, higher fatty acid, and polyamide resin. And polyester resins. They are,
It is preferable to use them alone or as a mixture.

From the viewpoint of improving the releasability from the fixing member at the time of fixing and improving the fixing property, it is preferable to include the following waxes in the toner.

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 derivatives thereof, vegetable waxes, animal waxes, mineral waxes, petrolactam and the like can also be used.

The wax preferably used is a low-molecular-weight polyolefin obtained by radical polymerization of an olefin under a high pressure or a low-pressure polymerization using a Ziegler catalyst or another catalyst, and a by-product of the polymerization and a high-molecular-weight polyolefin by thermal decomposition. Specific components from low molecular weight polyolefins, carbon monoxide, and the synthesis residue consisting of hydrogen, from the distillation residue of hydrocarbons obtained by the Age method, or from synthetic hydrocarbons obtained by hydrogenating them. May be used, and an antioxidant may be added. Alternatively, it is a linear alcohol, fatty acid, acid amide, ester or montan derivative. It is also preferable that impurities such as fatty acids have been removed in advance.

Among them, preferred are those obtained by polymerizing olefins such as ethylene using a Ziegler catalyst or other catalysts, and by-products at this time, such as Fischer-Tropsch wax having a carbon number of several thousand, especially about 1,000. Those having a hydrocarbon as a base are preferred.

From these waxes, the waxes are subjected to press sweating, a solvent method, vacuum distillation, supercritical gas extraction, fractional crystallization (for example, melt liquid crystal precipitation and crystal filtration), and the like to obtain waxes having different molecular weights. The fractionated wax is used in the present invention. After fractionation, oxidation, block copolymerization, or graft modification may be performed. For example, those obtained by removing low-molecular-weight components, those obtained by extracting low-molecular-weight components,
Further, those having an arbitrary molecular weight distribution such as those obtained by removing low molecular weight components from these.

The wax fractionated by molecular weight is particularly preferable because it hardly affects triboelectric charging and does not adversely affect developability.

Among them, the wax used in the toner of the present invention is particularly preferably a wax having an endothermic peak temperature of 120 ° C. or less as measured by a DSC meter from the viewpoint of improving fixability. When the wax is contained in the toner, a part of the wax is present as a free component in the toner.
In particular, a wax having an endothermic peak temperature of 120 ° C. or lower has poor mixing properties with a binder resin, and tends to generate many free components. The separated components may cause non-uniform charging, hinder uniform coating of the toner on the developing sleeve, and may coat the toner in an uneven or wavy manner. However, the presence of the fine particle aggregates of the present invention prevents the non-uniform coating on the developing sleeve due to the non-uniform charging because the fine particle aggregates adsorb the free wax component.

In the present invention, it is preferable to add 0.1 to 15 parts by mass of wax to 100 parts by mass of the binder resin, and more preferably 0.5 to 10 parts by mass.

In the DSC measurement of the present invention, since the exchange of heat of the wax is measured and the behavior thereof is observed, it is preferable from the principle of measurement that the measurement be performed with a high-precision internal heat input compensation type differential scanning calorimeter. For example, DSC-7 manufactured by PerkinElmer can be used.

The measuring method is as described in ASTM D3418-82.
Perform according to. The DSC curve used in the present invention is obtained by raising and lowering the temperature once, taking a pre-history, and then setting the temperature rate to 10 ° C./m.
In, a DSC curve measured when the temperature is raised is used.

In order to provide the toner of the present invention with an appropriate charge amount, it is preferable to add the following charge control agent. The degree of the charge control is controlled by the type and 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 such as nigrosine and fatty acid metal salts; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate and tetrabutylammonium tetrafluoroborate;
And onium salts thereof such as phosphonium salts, which are analogs thereof, and lake pigments thereof, triphenylmethane dyes and these lake pigments (as the lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannin Acid, lauric acid, gallic acid, ferricyanide, ferrocyanide), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; dibutyltin borate, dioctyltin borate, dicyclohexyltin Diorganotin borates such as borate; 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. The general formula (D)

[0190]

Embedded image Monomer of a monomer represented by: styrene described above,
Copolymers with polymerizable monomers such as acrylates and methacrylates can be used as positive charge control agents. In this case, these charge control agents also act as (all or part of) the binder resin.

The following substances control the toner to be negatively charged.

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

An azo metal complex represented by the following general formula (E) is preferred.

[0194]

Embedded image

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

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

[0197]

Embedded image

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

As a method for 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 use amount of these charge control agents is determined by the type of the binder resin, the presence or absence of other additives, the toner manufacturing method including the dispersion method, and is not limited to a specific one. Preferably, it is used in the range of 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the binder resin. When adding externally, use resin 1
It is preferably 0.01 to 10 parts by mass with respect to 00 parts by mass, and particularly preferably mechanochemically fixed to the surface of the toner particles.

In the toner of the present invention, a coloring agent may be used if necessary.

As the coloring agent, conventionally known inorganic and organic dyes and pigments can be used. For example, carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, low dam lake, alizarin lake , Bengara, phthalocyanine blue, indanthrene blue and the like, and these can be used alone or in combination. These are usually binder resins 10
0.5 to 20 parts by mass is used per 0 parts by mass.

Further, colored magnetic powder can be used as the coloring agent. The content of the magnetic powder is 100
5 to 200 parts by mass, more preferably 10 to 15 parts by mass,
The amount is preferably 0 parts by mass.

As the magnetic powder used in the case of the magnetic toner, a powder of an alloy or a compound containing a ferromagnetic element is preferably used. For example, magnetite, maghemite,
Alloys and compounds such as ferrite, such as iron, cobalt, nickel, manganese, and zinc, and other ferromagnetic alloys, which are conventionally known as magnetic materials, can be used.

[0204] Further, S
oxides of metal ions such as i, Al, Mg, etc., hydrated oxides,
A material containing a compound such as a hydroxide can be used.

Further, a magnetic powder particle may be used in which an organic compound such as a coupling agent, a fatty acid compound, or a resin reacts, adsorbs, or adheres to the surface.

The shape of the magnetic material may be octahedron, hexahedron,
Spherical, pot-like, scale-like, etc.

[0207] As a BET specific surface area by nitrogen gas adsorption method of the magnetic ^{body, 1m 2 / g~40m 2 / g} , more 2m
It is preferred in ² / ^{g~30m 2} / g.

The saturation magnetization of the magnetic material is preferably in the range of 5 emu / g to 200 emu / g, more preferably 10 emu / g to 150 emu / g at a magnetic field of 10 K Oersted.

The residual magnetization of the magnetic material is preferably 1 emu / g to 100 emu / g, more preferably 1 emu / g to 70 emu / g at a magnetic field of 10 K Oersted.

The average particle size of the magnetic material is 0.05 to
The thickness is preferably 1.0 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.1 to 0.4 μm.

The content of the magnetic powder in the toner is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the binder resin. If the amount is less than 5 parts by mass, the magnetic force of the toner is small, and fogging and scattering are likely to occur. If the amount exceeds 200 parts by mass, the fixability tends to be impaired.

In producing the toner according to the present invention, the above-mentioned toner constituent materials are sufficiently mixed by a ball mill, a Henschel mixer, or other mixers.
It is preferable to knead well using a hot kneader such as a hot roll kneader or an extruder, cool and solidify the kneaded material, and then mechanically pulverize and classify the pulverized material to obtain a toner. Another method is to obtain a toner by dispersing the constituent materials in a binder resin solution and then spray-drying; emulsifying suspension by mixing a predetermined material with a monomer to form the binder resin. After that, there is a method for producing a toner by a polymerization method of polymerizing to obtain a toner. The toner according to the present invention may be a microcapsule toner composed of a core material and a shell material.

Further, if necessary, desired additives are sufficiently mixed with a mixer such as a Henschel mixer to obtain the toner according to the present invention.

Further, the chargeability, durability, and
It is also preferable to externally mix the following materials in order to provide cleaning properties and fluidity.

For example, finely divided silica such as wet-process silica and dry-process silica; treated silica obtained by subjecting the silica to a surface treatment with a silane coupling agent, a titanium coupling agent, silicone oil, etc .; alumina, titanium oxide (titania) Metal oxides such as germanium oxide and zirconium oxide; carbides such as silicon carbide and titanium carbide; and inorganic fine powders such as nitrides such as silicon nitride and germanium nitride.

The inorganic fine powder used in the present invention may be used in an amount of 0.01 to 8 parts by mass per 100 parts by mass of the toner.
Preferably, 0.1 to 4 parts by mass is used.

Preferably, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400 m ² / g).
m ² / g) gives good results in combination with fine particle agglomerates. 0.01 to 8 parts by mass, preferably 0.1 to 8 parts by mass, of silica fine powder or titanium oxide fine powder with respect to 100 parts by mass of the toner.
It is preferable to use 1 to 5 parts by mass.

These inorganic fine powders used in the present invention may contain a small amount of silicone varnish, various kinds of modified silicone varnish, silicone oil, various kinds of modified silicone oil, silane, etc. Coupling agent, a silane coupling agent having a functional group, a treatment agent such as other organosilicon compounds,
Alternatively, it is also preferable that the treatment is carried out in combination with various treatment agents.

Even when the surface treatment is performed, the silica fine powder or titanium oxide fine powder has a BET specific surface area of 30 m ² /
g or more (more preferably, 50 to 400 m ² / g).

Further, the following inorganic powders can be added to improve developability and durability. magnesium,
Metal oxides such as zinc, aluminum, cerium, cobalt, iron, zirconium, chromium, manganese, strontium, tin, antimony; composite metal oxides such as calcium titanate, magnesium titanate, strontium titanate; calcium carbonate, magnesium carbonate Metal salts such as aluminum carbonate; clay minerals such as kaolin; phosphate compounds such as apatite; silicon compounds such as silica, silicon carbide and silicon nitride; and carbon powders such as carbon black and graphite. Among them, 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 or composite particles can be added. Resin particles such as polyamide resin particles, silicone resin particles, silicone rubber particles, urethane particles, melamine-formaldehyde particles, acrylic resin particles; rubbers, waxes, fatty acid compounds, resins and the like and metals, metal oxides, salts, carbon black, etc. And composite particles composed of the above inorganic particles.

Further, the following lubricant powders 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.

The toner of the present invention can be used as a two-component developer in combination with a carrier.

As the carrier for use in the two-component developing method, conventionally known carriers can be used. Specifically, iron, cobalt, nickel, manganese, chromium, rare earth, etc., whose surface has been oxidized or not oxidized, can be used. And particles having an average particle size of 20 to 300 μm, such as metals and alloys or oxides thereof.

Furthermore, a coated carrier in which the surface of these particles is coated or adhered with a resin or the like can be used.

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, vinyl propionate, and the like.
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 Homopolymers or copolymers, and the like,
Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, and styrene-acrylonitrile from the viewpoints of dispersibility of conductive fine particles, film forming property as a coating layer, prevention of toner spent, and productivity. Copolymers, styrene-butadiene copolymers, styrene-maleic anhydride copolymers, polyethylene and polypropylene are exemplified. Further, polycarbonate, phenol resin, polyester, polyurethane, epoxy resin, polyolefin, fluorine resin, silicone resin, polyamide and the like can be mentioned. In particular, from the viewpoint of prevention of spent, it is more desirable to include a resin having a small critical surface tension, for example, a polyolefin, a fluororesin, a silicone resin or the like.

The blending amount of the fluorine-based resin, polyolefin-based resin or silicone-based resin relative to the total binder amount is suitably from 1.0 to 60% by mass, and particularly preferably from 2.0 to 40% by mass. Content is 1.
If the amount is less than 0% by mass, the surface modification effect is not sufficient, and the toner spent is not effective. On the other hand, if it exceeds 60% by mass, it is difficult to uniformly disperse the two, so that a 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 other monomers and a solvent-soluble copolymer.

Examples of the silicone resin used as the binder resin for coating the carrier include KR271, KR282, KR311, and KR25 manufactured by Shin-Etsu Silicone Co., Ltd.
5, KR155 (straight silicone varnish), KR
211, KR212, KR216, KR213, KR2
17, KR9218 (silicone varnish for modification), 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 SR2100, SR2101, manufactured by Toray Silicone Co., Ltd.
SR2107, SR2110, SR2108, SR21
09, SR2400, SR2410, SR2411, S
H805, SH806A, SH840 and the like are used.

[0230]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Production Examples and Examples, but this does not limit the present invention in any way. All parts in the following formulations are parts by mass.

(Preparation Example 1 of Fine Particles) 100 parts of silica fine powder (specific surface area: about 200 m ² / g) manufactured by a dry method is put into a stirrer, and while stirring, an amino-modified silicone oil (amine equivalent: 830, 25 ° C.) Viscosity at 70 cS
t) A solution of 15 parts and 10 parts of hexane was sprayed and stirred. The obtained fine powder was heated to 300 ° C. and stirred, and the solvent was dried to obtain fine particles (1).

(Production Example 2 of Fine Particles) 100 parts of silica fine powder (specific surface area: about 200 m ² / g) produced by a dry method was put into a stirrer, and 10 parts of γ-aminopropyltriethoxysilane and A solution of 10 parts of methyldisilazane and 10 parts of hexane was sprayed and stirred. The obtained fine powder was heated to 100 ° C. and stirred, and the solvent was dried to obtain fine particles (2).

(Preparation Example 3 of Fine Particles) Fine particles (3) were obtained in the same manner as in Preparation Example 1 of fine particles except that the fine powder and the treating agent shown in Table 1 were used.

(Preparation Example 4 of Fine Particles) Fine particles (4) were obtained in the same manner as in Preparation Example 2 of fine particles except that the fine powder and the treating agent shown in Table 1 were used.

(Production Examples 5 to 9 of Fine Particles) Fine particles (5) to (9) were obtained in the same manner as in Production Example 1 of fine particles, except that the fine powder and the treating agent shown in Table 1 were used. Table 1 shows the treatment of these fine particles.

[0236]

[Table 1]

[Production Example 1 of Fine Particle Aggregate] 10% of amino-modified silicone oil (amine equivalent: 1900, viscosity at 25 ° C. 250 cSt) and 90% of dimethyl silicone oil (viscosity at 25 ° C. 3000 cSt) were mixed to form silicone oil (1). ) Was prepared.

Forty parts of the treated fine particles (1) were placed in a Henschel mixer, and a solution of 60 parts of silicone oil (1) and 10 parts of hexane was sprayed with stirring, followed by stirring. The obtained aggregate is heated to 100 ° C. and stirred,
The solvent was dried to obtain a fine particle aggregate (1). Table 2 shows the BET specific surface area and the charge amount of the fine particle aggregate (1).

[Production Example 2 of Fine Particle Aggregate] 10% of an amino-modified silicone oil (amine equivalent: 1900, viscosity at 25 ° C .: 250 cSt) and 90% of dimethyl silicone oil (viscosity at 25 ° C .: 10,000 cSt) were mixed to form a silicone oil (2). ) Was prepared.

30 parts of the treated fine particles (2) and 70 parts of the silicone oil (2) were mixed in a vessel and stirred with a turbuler mixer to obtain fine particle aggregates (2). Table 2 shows the BET specific surface area and charge amount of the fine particle aggregate (2).
It was shown to.

[Production Example 3 of Fine Particle Aggregate] A mixture of 20% of an amino-modified silicone oil (amine equivalent: 1700, viscosity at 1300 cSt at 25 ° C.) and 80% of a fluorine-modified silicone oil (viscosity of 10,000 cSt at 25 ° C.) was mixed with silicone oil ( 3) was prepared.

50 parts of the treated fine particles (3) and 50 parts of the silicone oil (3) were mixed in a vessel and stirred with a turbuler mixer to obtain a fine particle aggregate (3). Table 2 shows the BET specific surface area and charge amount of the fine particle aggregate (3).
It was shown to.

[Production Examples 4 to 15 of Fine Particle Aggregates] Fine particle aggregates (4) to (15) were prepared in the same manner as fine particle aggregate (1) except that those shown in Table 2 were used as fine particles and silicone oil / varnish. I got

[Production Examples 16-18 of Fine Particle Aggregates] Untreated silica fine powder (specific surface area: about 200 m ² / g) produced by a dry method was used as fine particles.
Fine particle aggregates (16) to (18) in the same manner as fine particle aggregates (1) except that the varnish shown in Table 2 is used.
I got

[Production Example 19 of Fine Particle Aggregate] Five parts of the treated fine particles (8) were put into a Henschel mixer, and a solution of 95 parts of dimethyl silicone oil (viscosity at 25 ° C. 100 cSt) and 10 parts of hexane was sprayed while stirring. Then, when an attempt was made to produce a fine particle aggregate by stirring, the product became a paste, and the fine particle aggregate could not be produced. This is probably because the mixing ratio of the fine particles and the silicone oil / varnish was not favorable.

[Production Example 20 of Fine Particle Aggregate] A fine particle aggregate (20) was obtained in the same manner as for the fine particle aggregate (1) except that the fine particles and silicone oil varnish shown in Table 2 were used.

The formulations of the fine particle aggregates (1) to (20) are shown in Table 2, and the physical properties are shown in Table 3.

[0248]

[Table 2]

[0249]

[Table 3]

<Example 1> Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 83/17, P1 = 9800, P2 = 396000 Mn = 7100, Mw = 204000) Magnetic material 90 parts Polyethylene wax 4 parts (Fractionated crystallized wax; endothermic peak by DSC is 108 ° C.) Triphenylmethane dye 2 parts
The mixture was melt-kneaded by a twin-screw kneading extruder set at 40 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by an air classifier. A classified fine powder (1) having a weight average particle size of 7.6 μm was obtained.

100 parts of the obtained classified fine powder (1) was mixed with a silica fine powder (BET specific surface area 200
m ² / g) 100 parts of an amino-modified silicone oil (viscosity 70cSt at amine equivalent 830,25 ℃) 20
Parts of the treated hydrophobic silica (1) and 0.2 parts of the fine particle aggregate (1) were added, mixed with a Henschel mixer, and sieved with a mesh having an aperture of 150 μm to obtain a toner.

This toner was used in a commercially available copying machine NP6016.
(Manufactured by Canon Inc.) and image evaluation was performed.

[Image Evaluation Test] 6000 under normal temperature and normal humidity
2,000 copies in low-temperature, low-humidity, high-temperature, high-humidity environments
An image evaluation test was performed by copying one sheet. The image density and fog in each environment were evaluated, and the level of image dropout under normal temperature and normal humidity (reproducibility of character image), uniformity in solid black image and halftone image, and waste toner generation rate ( The amount of waste toner / consumed toner) is evaluated to determine whether blotch development (non-uniform toner coating on the sleeve) has occurred at low temperature and low humidity.
The stability of image density under high temperature and high humidity was evaluated. Also,
The set temperature of the fixing device was set at 150 ° C., and after forming the image, the image was fixed. The fixing property of the toner was evaluated from the image reduction rate by a rubbing test of the obtained image.

The evaluation results are shown in Table 4.

<Examples 2 to 11> A toner was obtained in the same manner as in Example 1 except that the fine particle aggregates (2) to (11) were used as the fine particle aggregates.

The image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 12 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 84/16, P1 = 10100, P2 = 396000 Mn = 7000, Mw = 184000) Magnetic material 90 parts Polyethylene wax (separation) Crystallized wax; endothermic peak by DSC at 115 ° C.) 4 parts Triphenylmethane-based dye 2 parts From the above materials, in the same manner as in Example 1, the weight average particle size is 8.
A 1 μm classified fine powder (2) was obtained.

100 parts of the obtained classified fine powder (2) was mixed with a silica fine powder (BET specific surface area 200
m ² / g) 100 parts of an amino-modified silicone oil (viscosity 70cSt at amine equivalent 830,25 ℃) 20
Then, 0.9 parts of the hydrophobic silica (1) and 0.2 parts of the fine particle aggregates (12) were added, mixed with a Henschel mixer, and sieved with a mesh having an aperture of 150 μm to obtain a toner.

The image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

<Examples 13 to 15> A toner was obtained in the same manner as in Example 12, except that the fine particle aggregates (13) to (15) were used as the fine particle aggregates.

The image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

Example 16 Styrene-n-butyl acrylate copolymer 100 parts (St / BA = 84/16, P1 = 10100, P2 = 396000 Mn = 7000, Mw = 184000) Red pigment 4 parts Polyethylene wax 3 parts (Fractional crystallization wax; endothermic peak by DSC at 112 ° C.) Quaternary ammonium salt 2 parts
The mixture was melt-kneaded by a twin-screw kneading extruder set at 40 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, finely pulverized using a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified by an air classifier. A classified fine powder (3) having a weight average particle size of 8.5 μm was obtained.

In 100 parts of the obtained classified fine powder (3), 0.8 parts of hydrophobic silica (2) treated with aminopropyltrimethoxysilane and hexamethyldisilazane, 0.2 part of fine particle aggregate (2) The resulting mixture was mixed with a Henschel mixer and sieved with a mesh having an aperture of 150 μm to obtain a toner.

The toner was applied to a commercially available copying machine FC330 (manufactured by Canon Inc.), and image evaluation was performed.

An image evaluation test was carried out by copying 1000 sheets in each environment of normal temperature and normal humidity, low temperature and low humidity, and high temperature and high humidity. The image density and fog in each environment were evaluated, and the level of image voids (reproducibility of character images) under normal temperature and normal humidity was evaluated. The hollow is a good level, and the image density is a usable level of 1.10 or more in any environment, even at the initial stage and after the endurance. The results are shown in Table 4.

<Comparative Examples 1 to 3> Untreated silica fine powder produced by a dry method (specific surface area of about 2
00m ² / g) particulate aggregate was prepared using (16)
A toner was obtained in the same manner as in Example 1 except that (18) to (18) were used.

The image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

Comparative Example 4 A toner was obtained in the same manner as in Example 1, except that the fine particle aggregate (20) was used as the fine particle aggregate.

The image was evaluated in the same manner as in Example 1. The results are shown in Table 4.

<Comparative Example 5> A toner was obtained in the same manner as in Example 1 except that no fine particle aggregate was added.

This was evaluated for images in the same manner as in Example 1. The results are shown in Table 4.

[0272]

[Table 4]

[0273]

As described above, the toner of the present invention containing the above-mentioned components has a stable image density from the beginning, and has a high density and good image quality without fog from low temperature and low humidity to high temperature and high humidity. Can be provided.

Further, the toner of the present invention can provide a clear and excellent image free from image defects such as omission during transfer and free from scattering, offset and filming.

The toner of the present invention can provide a uniform density image without white spots or streaks, even in a halftone image or a solid black image.

In the toner of the present invention, the production amount of waste toner is small, and the amount of waste can be reduced. Further, the space for collecting the waste toner can be reduced, and the space can be saved.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of an apparatus for measuring a triboelectric charge amount of a toner.

Claims (12)

[Claims] 1. An electrostatic image developing toner having toner particles and a fine particle aggregate containing at least a binder resin and a colorant, wherein the fine particle aggregate contains 20 to 90% by mass of silicone oil or silicone varnish. The fine particles forming the fine particle aggregate are treated with a silane coupling agent having at least a nitrogen atom in a side chain and a hydrophobizing agent, or are treated with a silicone oil or a silicone varnish having at least a nitrogen atom in a side chain. A toner for developing electrostatic images, characterized in that: 2. The fine particle aggregate comprises a silicone oil or a silicone varnish having no nitrogen atom in a side chain,
2. The electrostatic image developing toner according to claim 1, wherein a total amount of the silicone oil or silicone varnish having a nitrogen atom in a side chain is 20 to 90% by mass. 3. The electrostatic image developing toner according to claim 1, wherein the fine particle aggregate has a charge amount of 0 to +100 mC / kg when mixed with iron powder. 4. The toner according to claim 1, wherein the fine particle aggregate has a BET specific surface area of 0.01 to 50 m ² / g. 5. The electrostatic image developing toner according to claim 1, wherein the toner particles contain a wax having an endothermic peak temperature of 120 ° C. or less as measured by a DSC meter. 6. The fine particle aggregate comprises a total of 30 to 85% by mass of a silicone oil or silicone varnish having a nitrogen atom in a side chain and a silicone oil or silicone varnish not having a nitrogen atom in a side chain. The electrostatic image developing toner according to any one of claims 1 to 5, wherein the toner is contained. 7. The silicone oil contained in the fine particle aggregate is one selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, alkyl-modified silicone oil and fluorine-modified silicone oil. 2. The method according to claim 1, wherein said silicone oil is contained.
7. The toner for developing an electrostatic image according to any one of items 1 to 6. 8. The electrostatic charge according to claim 2, wherein the silicone oil containing a nitrogen atom in the side chain contained in the fine particle aggregate contains an amino-modified silicone oil. Image developing toner. 9. The electrostatic charge image developing toner according to claim 1, wherein the fine particles forming the fine particle aggregate are inorganic fine powder. 10. The fine particles forming the fine particle aggregate,
The electrostatic image developing toner according to any one of claims 1 to 9, wherein the toner is a silica fine powder, an alumina fine powder, or a titania fine powder. 11. The fine particles forming the fine particle aggregate are:
11. A silica fine powder, characterized in that it is a silica fine powder.
The toner for developing electrostatic images according to any one of the above. 12. The mass ratio of the silicone oil or silicone varnish having a nitrogen atom in a side chain thereof to the silicone oil or silicone varnish having no nitrogen atom in a side chain contained in the fine particle aggregate is from 1:30. The electrostatic image developing toner according to claim 2, wherein the ratio is 10: 1.