JP3459734B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing toner used in electrophotography and the like, and is applied to printers, copying machines, facsimiles and the like.

[0002]

2. Description of the Related Art Conventionally, a number of electrophotographic methods are known, but generally, a photoconductive material is used to form an electric latent image on a photoconductor by various means, and then the electrophotographic image is formed. The latent image is developed with toner to make it a visible image. 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 or pressure to obtain a copy. It is a thing.

In recent years, a large number of devices using electrophotography have been used in addition to conventional copying machines such as printers and facsimiles, and have come to be used in general offices and homes.

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

Conventionally, as a developing system for electrophotography, a one-component developing system and a two-component developing system are known. Among them, the one-component developing method is being adopted from the viewpoint that 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 the surface of a roll-shaped toner carrier such as a developing sleeve with toner in a thin layer. For this reason, a strong rubbing force is applied to the toner, which causes deterioration of the toner, deterioration of the surface of the toner carrier, and the like after long-term use, and deterioration of durability characteristics remains a problem. The conventional technology has not sufficiently solved the problem, and a technology for improving durability characteristics has been desired.

Further, as the charging means in the electrophotographic method,
Means utilizing corona discharge have been used. However, since the use of corona discharge generates a large amount of ozone, it is necessary to provide a filter, and there are problems such as an increase in the size of the device and an increase in running cost.

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 the photosensitive member to form a narrow space in the vicinity of the contact portion, which is interpreted by the so-called Paschen's law. A charging method that suppresses ozone generation as much as possible by forming such a discharge has been developed. Among them, the roller charging method using a charging roller as a charging member is preferably used from the viewpoint of charging stability. .

For example, JP-A-63-149669 and JP-A-2-123385 have been proposed. These are related to the contact charging method and the contact transfer method, but a conductive elastic roller is brought into contact with the electrostatic latent image carrier and the electrostatic latent image carrier is removed while applying a voltage to the conductive roller. As described above, and then a toner image is obtained by the exposure and development processes, and then a transfer material is passed through while pressing another conductive roller to which a voltage has been applied to the electrostatic latent image carrier to pass the electrostatic latent image carrier. After the toner image on the image carrier is transferred to a transfer material, a copied image is obtained through a fixing process.

However, even in such a contact charging device, since the essential charging mechanism uses the discharging phenomenon from the charging member to the photosensitive member, the voltage required for charging as described above. Is required to have a value equal to or higher than the surface potential of the photoconductor. When AC charging is performed for uniform charging, vibration and noise of the charging member and the photoconductor due to the electric field of the AC voltage (hereinafter referred to as AC charging sound) are generated, and the surface of the photoconductor is discharged. Deterioration and the like have become remarkable, and along with that, there have been new problems such as fusion and filming in which a part of the toner or toner components adheres to the surface of the photoconductor.

Further, in such a roller transfer system which does not use corona discharge, since the transfer member is brought into contact with the photoconductor through the transfer member during transfer, the toner is rubbed against the photosensitive member during idle rotation before and after passing the paper. The transfer of the toner image formed on the photoconductor to the transfer material causes the toner image to come into pressure contact with the toner image. It's a big problem.

To solve this, Japanese Patent Laid-Open No. 3-1214
In Japanese Patent Laid-Open No. 62-62, there is proposed an image forming apparatus using a developer containing a hydrophobic inorganic fine powder treated with silicone oil. However, with thick transfer paper or OHP sheet whose weight per unit area exceeds 100 g / m ² such as postcards and Kent paper, it has not been sufficiently improved,
Higher image quality is required.

Further, in JP-A-6-230601, the amount of silicone oil or silicone varnish is 20.
~ 90 wt% fine particle agglomerates have been proposed. However, there is a great influence on these charging characteristics under high humidity and low humidity, and toners to which these fine particle aggregates are added are required to have more stable and high developing characteristics.

Further, since these charging members are in contact with each other, the transfer residual toner and the toner that has slipped through the cleaner adhere to the transfer member and the charging member, and if a large amount is accumulated, uniform charging and uniform transfer are hindered, and half charging is performed. In the toned image,
Streaks may appear or unevenness may appear.

Toner particles remaining on the photoconductor without being transferred onto the transfer material are removed from the photoconductor by a cleaning process. Regarding this cleaning process,
Conventionally, blade cleaning, fur brush cleaning, roller cleaning, etc. have been used. In any of the methods, the transfer residual toner is mechanically scraped off or dammed to be collected in a waste toner container. Therefore, due to the fact that such a member is pressed against the surface of the photoconductor, for example, by pressing the member strongly, the photoconductor is worn and scratches appear on the photoconductor, and toner appears on the surface of the drum. However, there are problems such as easy sticking (fusion) to the surface of the drum, and external additives such as liberated silica adhering to the drum surface (filming).

Further, since copying machines, printers, facsimiles and the like using electrophotography have come to be used in general offices and homes, miniaturization and energy saving are required. Even for the toner used for these, there is a demand for a toner that can be fixed at a lower temperature because of the need for energy saving.

Recently, it has been required to reduce the amount of waste from the viewpoint of ecology. Due to such a need, even in copying machines and printers, it is required to recycle toner and to reduce the amount of waste toner as a new technical subject.

[0018]

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

That is, the object of the present invention is that the density is stable from the beginning, the toner is uniformly coated on the toner carrier such as the developing sleeve, and the density is uniform without fog or unevenness even under low and high humidity. To provide an electrostatic charge image developing toner capable of obtaining the above image.

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

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

A further object of the present invention is to provide an electrostatic charge image developing toner having a high transfer efficiency, which is free from voids in the transfer and image defects even in the image forming method using the contact transfer means.

Another object of the present invention is to provide an electrostatic image developing toner which is excellent in fixing property and offset preventing property.

A further object of the present invention is to provide a toner for developing an electrostatic image which has a high releasability from a photoconductor, exhibits high transfer efficiency, and produces a small amount of waste toner.

Another object of the present invention is to provide a toner for developing an electrostatic charge image, which prevents toner adhesion, fusion, and filming on a photoconductor even during long-term use and reduces abrasion and scratches on the photoconductor. Is.

[0026]

The present invention relates to an electrostatic charge 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 is a silicone oil. Alternatively, the fine particles that contain 20 to 90% by mass of silicone varnish and form the fine particle aggregate include i) a silane coupling agent having a nitrogen atom in at least a side chain, and hexamethyldisilazane or
Treated with dimethyl silicone oil , or
ii) it relates to a toner for electrostatic image development according to claim being more processed silicone O <br/> Lee le having at least a side chain to the nitrogen atom.

As a result of intensive studies by the present inventors, in the toner containing the 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 a nitrogen atom in at least a side chain and a hydrophobizing agent, or treated with silicone oil or silicone varnish having a nitrogen atom in at least a side chain It has been found that the image-developing toner gives an image without fog, scattering, and unevenness at a sufficient density, and also gives an excellent image in which the image is not missing due to voids in the 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 in view of developing characteristics.

The present inventors have made a detailed study of image defects due to voids in the transfer. When a toner containing the agglomerates of fine particles is used, the extent of voids in the transfer becomes worse as copying with the same toner continues. Stable with a certain number of sheets.

Specifically, as copying is continued from the initial stage, the degree of voids in transfer becomes worse, and the level becomes constant at about 3000 sheets. When the number of copies exceeds 3,000, a fine particle aggregate containing only silicone oil or silicone varnish is more preferable than a toner containing fine particle aggregate containing only silicone oil or silicone varnish containing a nitrogen atom in its side chain. The toner contained is more excellent in preventing the dropout during transfer. However, in the case of an agglomerate of fine particles containing only silicone oil or silicone varnish, when added to a positively chargeable toner, fog or a decrease in image density may be caused. Further, in the case of fine particle aggregates containing only silicone oil or silicone varnish having a nitrogen atom in the side chain, when the number of copies exceeds 3000, image defects due to voids in transfer are slightly inferior, and under low humidity / high humidity conditions. In some cases, the charging property is not stable below, and under low humidity, a phenomenon called blotch may occur in which the toner is unevenly coated on the developing sleeve of the toner carrier. Therefore, a silicone oil or silicone varnish having a nitrogen atom in its side chain and a silicone oil or silicone varnish are further included, and the total content thereof is 20 to 90.
When a mass% of fine particle aggregates are contained, an image having no fog, scattering, and unevenness is provided, and an excellent image is obtained in which the image is not missing due to voids in the transfer.

Further, the fine particles in the fine particle aggregate are
By treating with a silane coupling agent containing at least a nitrogen atom in the side chain and a hydrophobizing agent, or by treating with a silicone oil or silicone varnish having at least a nitrogen atom in the side chain, the hydrophobicity is improved and high humidity is obtained. The chargeability under the condition is stable, the developing property under high humidity is stable for a long time, and the stable developing property is obtained even after long-term storage. Furthermore, by treating the fine particles by these methods, dot-like white spots are reduced in a solid black image. 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 causing white stripes on the sleeve. This is considered to be because the treatment of the fine particles by the method of the present invention reduced the production of coarse powder in the fine particle aggregates.

When the fine particle agglomerates are contained in the positively chargeable toner, the charge amount thereof is 0 relative to the iron powder.
It is preferably ˜ + 100 mC / kg. Within this range, the toner evenly coats on the sleeve with excellent +100
If it exceeds mC / kg, blotch is likely to occur and 0 mC / kg
If it is less than kg, it is likely to cause fog and decrease in density.

Further, the present invention is remarkably effective when the toner particles contain a wax having an endothermic peak temperature of 120 ° C. or less measured by a DSC measuring instrument. When the wax is included in the toner, a part of the wax is present in the toner as a free component. In particular, a wax having an endothermic peak temperature of 120 ° C. or less has poor dispersibility in a binder resin and a large amount of its free component is likely to occur. This free component may cause non-uniform charging, hinder the uniform coating of the toner on the developing sleeve, and may coat the toner in an uneven or wavy form. However, the presence of the fine particle aggregate of the present invention makes it possible to prevent the uneven coating on the developing sleeve due to the uneven charging. The reason for this is not clear, but 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 fine particles of an organic compound are used as the fine particles used in the fine particle aggregate containing the above 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 fluororesin, 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, or oxides such as boron oxide. Nitrides such as silicon nitride and germanium nitride; complex metal oxides such as calcium titanate, magnesium titanate, strontium titanate, phosphotungstic acid and phosphomolybdic acid;
Metal salts such as calcium carbonate, magnesium carbonate, aluminum carbonate; clay minerals such as kaolin; phosphoric acid 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. Calcium acid, magnesium titanate, strontium titanate, phosphotungstic acid, phosphomolybdic acid, calcium carbonate, magnesium carbonate, aluminum carbonate and the like can be mentioned.

Among these inorganic fine powders, silicon oxide,
Aluminum oxide and titanium oxide are preferred. There are many morphologies and types, but the main components are SiO ₂ and Al ₂ O.
₃ , fine powder silica represented by TiO ₂ , fine powder alumina,
Finely divided titania is preferred. Finely divided silica is particularly preferable.

As the inorganic fine powder, an inorganic compound fine powder produced by a dry method or a wet method can be used. 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 for a method utilizing a thermal decomposition oxidation reaction of a halide gas in oxygen hydrogen is as follows.

MX_Four+2 H₂+ 1 / 4O₂  → MO₂+4
HX (M: In case of 4 values)

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 ,
If 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, respectively.
You get ₃ . At this time, if a halide is mixed and used, a composite compound is obtained.

Alternatively, a dry type 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 the method for producing the inorganic fine powder used in the present invention by the wet method, various conventionally known methods can be applied. For example, decomposition of sodium silicate by an acid, and the general reaction formula is shown below.

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

Further, a method of decomposing sodium silicate with ammonia salts or alkali salts, generating an alkaline earth metal silicate from sodium silicate, and then decomposing with acid to obtain silicic acid, and ion-exchange of sodium silicate solution There are a method of making silicic acid by a resin, a method of using natural silicic acid or a silicate, and the like. Other methods include hydrolysis of metal alkoxides. This general reaction formula is shown below.

M (OR) ₄ O + 2H ₂ O → MO ₂ +4
ROH (in the case of 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, a composite is obtained by using two or more kinds of metal alkoxides.

Among these, inorganic compounds are preferable, and metal oxides are particularly preferable because they have an appropriate electric resistance value. In particular, oxides of Si, Al and Ti, and complex oxides are preferable.

It is also possible to use one whose surface has been previously made hydrophobic by a coupling agent or the like.

The average particle size of the fine particles is preferably in the range of 0.001 to 20.0 μm in terms of the number average of primary particles, and particularly preferably 0.005 to 10.0 μm. BE
The specific surface area by nitrogen adsorption measured by T method is 10
~500m ² / g, more preferably 50~400m ² /
g, and more preferably 100 to 350 m ² / g.
If it is less than 10 m ² / g, it tends to be difficult to retain 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 according to the BET method by using a specific surface area measuring device Autosorb 1 (manufactured by Yuasa Ionics) to adsorb nitrogen gas on the surface of the sample, and calculating the specific surface area using the BET multipoint method.

The feature of the present invention is that these fine particles in the fine particle aggregate are treated with a silane coupling agent having a nitrogen atom in at least a side chain and a hydrophobizing agent, or a silicone oil having a nitrogen atom in at least 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, examples of the silane coupling agent having a nitrogen atom in the side chain include an aminosilane coupling agent and a silane having a nitrogen-containing heterocycle. Examples thereof include coupling agents. Of these, aminosilane coupling agents are preferred.

Examples of such aminosilane coupling agents include aminopropyltrimethoxysilane, aminopropyltriethoxysilane, dimethylaminopropyltrimethoxysilane, diethylaminopropyltrimethoxysilane, dipropylaminopropyltrimethoxysilane, dibutylaminopropyltrisilane. 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,
3,3-tetramethyldisilazane and the like can be mentioned.

These treatment agents may be used alone or as a mixture of two or more kinds, or may be used in combination or in multiple treatments.

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

Examples of such organosilicon compounds are hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, Benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethyl Ethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetra Methyldisiloxane, 1,
Examples include 3-diphenyltetramethyldisiloxane and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and each terminally located unit containing a hydroxyl group bonded to Si. 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. Among them, as the silicone oil, those represented by the following formula are generally preferable.

[0059]

[Chemical 1]

[In the formula, R ₁ represents a methyl group, another alkyl group, an aryl group, or hydrogen, and R ₁ independently represents R 1.
₂ represents a methyl group, other alkyl group, aryl group, vinyl group, alkyl group or aryl group which may have a hydroxyl group, fluorine-substituted alkyl group or hydrogen. m and n show integers. Above all, 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.
The viscosity at 2 to 1000 cSt is preferably 10 to 3
00cSt is more preferable.

The treatment amount of the silane coupling agent 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 also affects, but it cannot be limited to 100 parts by mass of the fine powder. 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 it exceeds the mass part, the specific surface area becomes small and the fluidity becomes poor. It is preferably 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 also affects, but if the hydrophobizing agent is 20 parts by mass or less with respect to 100 parts by mass of the fine powder. Used. If it exceeds 20 parts by mass, the specific surface area becomes small and the fluidity becomes poor. It is preferably 0.1 to 10 parts by mass.

The total 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.

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

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 a nitrogen atom in at least a side chain. Among them, silicone oil having a nitrogen atom in the side chain is preferable, and amino-modified silicone oil is preferable among them.

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. May be.

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 have a silicone oil terminal.

[0069]

[Chemical 2]

(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 hydrogen, an alkyl group or an aryl group, R ₅ represents a nitrogen-containing heterocyclic group) The above 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 within a range not impairing the charging property. It may have a substituent.

The amine equivalent (g / mol) in the amino-modified silicone oil is preferably 300 or more and 10,000 or less. When the amine equivalent is less than 300, it is difficult to uniformly coat the fine particles and the hydrophobicity is low. When the amine equivalent is more than 10,000, the chargeability is lowered, and the fine particle aggregates are also negatively charged, which may cause 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 2 to 1000 cSt. More preferably,
It is 10 to 300 cSt.

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

The amount of the silicone oil or silicone varnish having a nitrogen atom in the side chain to the fine powder cannot be unconditionally limited because the specific surface area of the fine powder also influences the amount of the fine powder to be treated. Silicone oil or silicone varnish having a nitrogen atom in the 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. It is preferably 3 to 20 parts by mass.

The fine particles in the present invention are obtained by treating untreated fine powder with 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 in the side chain or It is characterized by being treated with a silicone varnish.

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

The silicone oil used in the fine powder aggregate of the present invention has a general formula

[0079]

[Chemical 3]

(Here, R represents an alkyl group having 1 to 3 carbon atoms, R'represents a silicone oil modifying group such as alkyl, halogen modified alkyl, phenyl, modified phenyl, etc., and R "represents 1 to 3 carbon atoms. Which represents an alkyl group or an alkoxy group, and m and n are integers), such as dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, vinyl group-containing silicone oil, and alkyl-modified silicone. Oil, α-methylstyrene modified silicone oil, chlorophenyl silicone oil, fluorine modified silicone oil and the like can be mentioned.

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

[0083]

[Chemical 4]

(Here, R ₁ and R ₆ are hydrogen, an alkyl group,
Represents an aryl group or an alkoxy group, R ₂ represents an alkylene group or a phenylene group, R ₃ represents a compound having a nitrogen-containing heterocycle in its structure, and R ₄ and R ₅ represent hydrogen, an alkyl group or an aryl group. . R ₂ may be omitted. However, the above-mentioned alkyl group, aryl group, alkylene group and phenylene group may contain an amine, and may have a substituent such as halogen within a range not impairing the charging property. Further, m is a number of 1 or more, and n and k are positive numbers including 0. However, n + k is a positive number of 1 or more. )

The most preferable structure among the above structures is one in which the number of nitrogen atoms in the side chain containing a nitrogen atom is 1 or 2.

One example of the unsaturated heterocycle containing nitrogen is given below.

[0087]

[Chemical 5]

An example of the saturated heterocycle containing nitrogen will be given below.

[0089]

[Chemical 6]

However, the present invention is not limited to the above-mentioned compound examples, but those having a 5-membered or 6-membered heterocycle are preferable.

Examples of the derivative include hydrocarbon groups, halogen groups, amino groups, vinyl groups, mercapto groups,
Examples of the derivative include a methacryl group, a glycidoxy group, and a ureido group.

These may be used alone or in combination of two or more.

Examples of the silicone varnish used in the present invention include methylsilicone varnish and phenylmethylsilicone varnish, with methylsilicone varnish being particularly preferred.

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

[0095]

[Chemical 7]

Methylsilicone varnish or phenylmethylsilicone varnish is specifically a substance having a chemical structure represented by the following structural formula (II).

[0097]

[Chemical 8]

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

In the above silicone varnish, especially T ³¹
The unit is a unit effective for imparting good thermosetting property and forming a three-dimensional network structure. The T ³¹ unit is contained in the silicone varnish in an amount of 10 to 90 mol%, particularly 30 to 80 mol%.
It is preferable to be contained in the ratio

Such a silicone varnish has a hydroxyl group at the terminal or side chain of the molecular chain, and is cured by dehydration condensation of this hydroxyl group. Examples of the curing accelerator that can be used to accelerate the 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 preferably used.

In order to use the above-mentioned silicone varnish as an amino-modified silicone varnish, the above-mentioned T ³¹ unit and D ^{31 are used.}
A part of the methyl group or phenyl group present in the unit or 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 formulas.

[0102]

[Chemical 9]

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

If it is less than 50 centistokes, it is difficult to form a large amount of silicone oil or silicone varnish into fine particles, and the fine particle agglomerates are not stable.
Thermal and mechanical stresses tend to degrade image quality. If it exceeds 200,000 centistokes,
It tends to be difficult to granulate the silicone oil or silicone varnish.

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

The silicone oil or silicone varnish having a nitrogen atom in the side chain in the present invention may be any of those described in the present invention. 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, which makes it difficult to form fine particle aggregates. Further, when the amine equivalent exceeds 10,000, the chargeability becomes low, and the fine powder agglomerates also have 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, methylhydrogen silicone oil, alkyl-modified silicone oil, It is preferable to contain at least one silicone oil selected from fluorine-modified silicone oils in terms of voids in transfer. Of these, dimethyl silicone oil, methyl hydrogen silicone oil, and fluorine-modified silicone oil are preferable, and dimethyl silicone oil and fluorine-modified silicone oil are more preferable.

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 or methyl hydrogen. It is preferable to contain at least one silicone oil selected from silicone oil, alkyl-modified silicone oil, and fluorine-modified silicone oil.

In the present invention, the mass ratio of the silicone oil or silicone varnish having a nitrogen atom in the side chain of the fine particle aggregate 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 not having a nitrogen atom in the side chain is less than 1:30, the toner has a strong negative charging property and is included in the positive charging toner. In some cases, it causes density decrease and fog. It is preferably 1:20 or more. When the ratio is larger than 10: 1, the effect on hollow voids is not sufficiently different from the case of using only silicone oil or silicone varnish having a nitrogen atom in the side chain. Furthermore 1:20
~ 3: 1 is preferred.

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

When the total amount of silicone oil or silicone varnish is less than 20% by mass, it is less effective in improving voids during transfer, while when it exceeds 90% by mass, the silicone oil or silicone varnish aggregates toner particles, The image quality is likely to deteriorate.

In the fine particle aggregate of the present invention, the ratio of the silicone oil or silicone varnish having a nitrogen atom in the side chain to the silicone oil or silicone varnish is
Any mass ratio as 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.

When the iron powder is negatively charged, it tends to become an oppositely charged component even when mixed in the toner, causing fog in the non-image area. On the other hand, when it exceeds +100 mC / kg, the coat on the developing sleeve becomes non-uniform, resulting in unevenness in a halftone image or a solid image, or wavy fogging.

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

0.2 g of the fine particle aggregate and 9.8 g of the iron powder carrier were put in a 50 ml polybin, covered with a lid, stirred by a stirrer and sufficiently charged, and then triboelectrification was measured. As a stirrer, for example, YSLD manufactured by Yayoi Co., Ltd.
Can be used. 125 rotations / with this shaker
After shaking for 1 minute under the condition of minute, the triboelectric charge amount is measured.

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

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

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

The mixing and stirring conditions cannot be unconditionally limited depending on the mixing method of the mixer to be used, the size of the model, etc., but depending on the stirring conditions, fine particle agglomerates are not formed, and for example, a Turbula mixer is used. 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 it is preferably 30% or more. When it is less than 30%, the image density may be slightly low under high humidity conditions. More preferably 5
It is 0% or more.

To measure the hydrophobicity, 1.0 g of the sample and 100 g of ion-exchanged water are put in a 200 ml bottle and vigorously stirred 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 the hydrophobicity.

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

The fine particle aggregate composed of the above 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 0.1-10 m ² / g)
In the case of, good results are obtained.

If it exceeds 50 m ² / g, the silicone oil or silicone varnish is difficult to hold as particles, causing aggregation of the toner, and deterioration of image quality is likely to occur. In addition, the effect of improving voids in transfer tends to be small. 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. In accordance with 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 amount of the fine particle aggregate containing the above silicone oil or silicone varnish applied is 100
It 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 parts by mass. If it is less than 0.01 parts by mass,
Has little effect on the photoreceptor and contact charging member, and
If it exceeds 0 parts by mass, the fixing property of the toner tends to be impaired.

The fine particle agglomerate according to the present invention contains a relatively large amount of the above silicone oil or silicone varnish having a good releasing property in an amount of 20% by mass to 90% by mass. 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 in the present invention with respect to the carrier will be described in detail with reference to FIG.

FIG. 1 is an explanatory view of a triboelectric charge amount measuring device. A magnetic brush (deposited with toner) on the developer carrier for measuring the triboelectric charge amount in a metal measuring container 12 having a conductive screen 13 of 400 mesh at the bottom (the size can be appropriately changed so that carrier particles do not pass). A mixture 14 of magnetic particles is put and the lid 14 made of metal is placed. At this time, the weight of the entire measuring container 12 is weighed and set as W ₁ (g). Next, in the suction device 11 (at least the portion in contact with the measurement container 12 is an insulator), suction is performed from the suction port 17 to adjust the air volume control valve 16 to adjust the pressure of the vacuum gauge 15 to 0.2 × 10 ⁵ Pa (differential pressure). ). In this state, suction is sufficiently performed (for about 1 minute) to remove the toner by suction. The potential of the electrometer 19 at this time is V
(Bolt). Here, 18 is a capacitor, and the capacitance is C (μF). The weight of the entire measuring container after suction is weighed and is W ₂ (g). This triboelectric charge amount Q (μC
/ G; mC / kg) is calculated by the following formula.

[0132]

[Equation 1]

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

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

The average particle size of the fine particle aggregate is SYMPAT.
EC HELOS Particle size an
It was measured by alysis.

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

The following binder resins can be used as the binder resin used in the toner of the present invention.

For example, polystyrene, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and the like, or a substitution product thereof; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene. Copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer -Based copolymer; polyvinyl chloride, phenol resin, natural modified phenol resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Preferred binder materials include styrene copolymers and polyester resins.

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

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

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

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, it is possible to obtain a low molecular weight polymer by polymerizing at a high temperature to accelerate the termination reaction rate, 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 radical chain transfer depending on the solvent, and by adjusting the amount of the initiator and the reaction temperature. It is preferred when low molecular weight products are obtained in the composition.

As the solvent used in the solution polymerization, xylene, toluene, cumene, cellosolve acetate, isopropyl alcohol, benzene and the like can be used. In the case of a styrene monomer mixture, xylene, toluene or cumene are 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, but is 70 ° C to 23 ° C.
It is better to do it at 0 ° C. Solvent 100 in solution polymerization
Preference is given to using 30% to 400% by weight of monomers, based on% by weight.

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

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

Of these, 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, the heat of reaction can be easily adjusted, and the termination reaction rate is low because the phase in which the polymerization is performed (oil phase consisting of polymer and monomer) and the aqueous phase are different, resulting in a high polymerization rate. A high degree of polymerization can be obtained.
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 toner. Therefore, it is advantageous as a method for producing a binder resin for toner as compared with other methods.

However, the resulting polymer is apt to become impure due to the added emulsifier, and suspension polymerization is a simple method because an operation such as salting out is required to take out the polymer.

In the suspension polymerization, 100 parts by mass or less of the monomer (preferably 1 part by mass) is used with respect to 100 parts by mass of the aqueous solvent.
0 to 90 parts by mass) is preferable. As the dispersant that can be used, polyvinyl alcohol, partially saponified polyvinyl alcohol, calcium phosphate, etc. are used, and there is an appropriate amount such as the amount of monomers in the aqueous solvent, but generally 0.05 to 1 per 100 parts by weight of the aqueous solvent. Used in parts by weight. The polymerization temperature is suitably 50 to 95 ° C., but it should be appropriately selected depending on the initiator used and the target polymer. As the initiator, any initiator that is insoluble or hardly soluble in water can be used.

Examples of the initiator to be used are t-butylperoxy-2-ethylhexanoate, cumin perpivalate, t-butylperoxylaurate, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, diester. -T-butyl peroxide, t
-Butyl cumyl 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-butylperoxytrimethyl adipate, tris (t-butylperoxy) triazine, Examples thereof include vinyltris (t-butylperoxy) silane, and these can be used alone or in combination.

The amount used is 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, bisphenol represented by the formula (A) and derivatives thereof;

[0155]

[Chemical 10]

(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]

[Chemical 11]

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

[0160]

[Chemical 12] Where x ′ and y ′ are integers greater than or equal to 0, and x ′
The average value of + y 'is 0 to 10. ) Is mentioned.

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

Further, it is preferable to use an alcohol component having a valence of 3 or more and an acid component having a valence of 3 or more, which also serve as a crosslinking component.

As the polyhydric alcohol component having 3 or more valences,
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 etc. are mentioned.

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

[0165]

[Chemical 13]

(Wherein, X is an alkylene group or alkenylene group having 5 to 30 carbon atoms having at least one side chain having 3 or more carbon atoms), etc., and their anhydrides and lower alkyl esters. 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.
%, 60-40 mol% as an acid component, preferably 5
It is preferably 5 to 45 mol%.

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

From the viewpoints of developing property, fixing property, durability and cleaning property, a styrene-unsaturated carboxylic acid derivative copolymer,
Preferred are polyester resins, block copolymers and graft products thereof, and further mixtures of styrene copolymers and polyester resins.

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

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

Further, in the case of a positively chargeable toner, a styrene-acryl copolymer, a styrene-methacryl-acrylic copolymer, a styrene-methacryl copolymer, a styrene-butadiene copolymer, and an acid value of 10 or less. Polyester resin and block copolymers, graft products thereof,
A blend resin is preferable, and in the case of a negatively chargeable toner, a styrene-acrylic copolymer, a styrene-methacrylic-acrylic copolymer, a styrene-methacrylic copolymer and a copolymer of these with a maleic acid monoester, Polyester resins, and block copolymers, graft products, and blend resins thereof are preferable in terms of developability.

As the binder resin for the toner which is particularly subjected to the pressure fixing method, low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid ester copolymer, higher fatty acid, polyamide resin are used. , And polyester resin. They are,
It is preferably used alone or as a mixture.

It is also preferable to include the following waxes in the toner from the viewpoint of improving the releasability from the fixing member during fixing and the fixing property.

Paraffin wax and its derivatives, montan wax and its derivatives, microcrystalline wax and its derivatives, Fischer-Tropsch wax and its derivatives, polyolefin wax and its derivatives, carnauba wax and its derivatives, etc. Includes block copolymers and graft modified products with vinyl monomers.

In addition, alcohols, fatty acids, acid amides,
Esters, ketones, hydrogenated castor oil and its derivatives, vegetable wax, animal wax, mineral wax, 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 high pressure or a Ziegler catalyst or other catalyst under low pressure, and a by-product at this time, or a high molecular weight polyolefin by thermal decomposition. Specific components from the distillation residue of hydrocarbons obtained by the Arge process from the synthesis gas consisting of low molecular weight polyolefin obtained by the above, carbon monoxide, and hydrogen, or from synthetic hydrocarbons obtained by hydrogenating these A wax obtained by extracting and fractionating the above is used, and an antioxidant may be added. Alternatively, it is a linear alcohol, fatty acid, acid amide, ester, or montan derivative. Further, it is also preferable that impurities such as fatty acids have been removed in advance.

Among these, preferred are those obtained by polymerizing olefins such as ethylene using a Ziegler catalyst or other catalysts, by-products at this time, and Fischer-Tropsch wax having a carbon number of several thousand, particularly up to about 1,000. It is preferable to use hydrocarbon as a base material.

Then, from these waxes, the wax was separated according to its molecular weight by using a press perspiration method, a solvent method, a vacuum distillation, a supercritical gas extraction method, a fractional crystallization (for example, melted liquid crystal precipitation and a crystal filtration). Fractionated wax is used in the present invention. In addition, oxidation, block copolymerization, or graft modification may be performed after the fractionation. For example, in these methods, those with low molecular weight removed, those with low molecular weight extracted,
Furthermore, it has an arbitrary molecular weight distribution such as those obtained by removing low molecular weight components from these.

The wax fractionated by the molecular weight is particularly preferable because it has little influence on the triboelectric charge and does not adversely affect the 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 measuring device, from the viewpoint of improving fixability. When the wax is included in the toner, a part of the wax is present in the toner as a free component.
In particular, a wax having an endothermic peak temperature of 120 ° C. or lower has poor mixability with the binder resin and is likely to generate a large amount of its free components. This loosened portion may cause non-uniform charging, which may hinder the 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 agglomerates of the present invention allows the free wax components to be adsorbed by these fine particle agglomerates, so that the uneven coating on the developing sleeve due to the uneven charging can be prevented.

In the present invention, it is preferred 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, the heat exchange of the wax is measured and the behavior thereof is observed. Therefore, it is preferable to measure with a highly accurate internal heat input compensation type differential scanning calorimeter from the principle of measurement. For example, DSC-7 manufactured by Perkin Elmer can be used.

The measuring method is ASTM D3418-82.
Carry out according to. The DSC curve used in the present invention has a temperature rate of 10 ° C./m after the temperature has been raised and lowered once and the previous history is taken.
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 also preferable to add the following charge control agent. The degree of the charge control agent is controlled by the type of the compound to be added and the amount of the compound added depending on the other constituent materials. can do.

The following substances control the toner to have a positive charge property.

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

[0190]

[Chemical 14] A monomer homopolymer represented by: styrene described above,
A copolymer with a polymerizable monomer such as acrylic acid ester and methacrylic acid ester can be used as a positive charge control agent. In this case, these charge control agents also function as (all or part of) the binder resin.

The following substances control the toner to be negatively charged.

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

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

[0194]

[Chemical 15]

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

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

[0197]

[Chemical 16]

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

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

A colorant may be used in the toner of the present invention if necessary.

As the colorant, conventionally known inorganic / organic dyes / pigments can be used. Examples thereof include carbon black, aniline black, acetylene black, naphthol yellow, Hansa yellow, Rhodamune lake, and alizarin lake. , Red iron oxide, phthalocyanine blue, indanthrene blue, etc., and these may be used alone or in combination. These are usually binder resin 10
0.5 to 20 parts by mass is used with respect to 0 parts by mass.

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

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

Further, S is formed on the surface or inside of the magnetic powder particles.
oxides of metal ions such as i, Al and Mg, hydrous oxides,
A substance containing a compound such as hydroxide can be used.

Further, it is possible to use those in which an organic compound such as a coupling agent, a fatty acid compound or a resin has reacted, adsorbed or adhered to the surface of the magnetic powder particles.

The shape of the magnetic material is octahedron, hexahedron,
There are spherical, pot-like, and scale-like shapes.

[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 5 emu / g to 200 emu / g, more preferably 10 emu / g to 150 emu / g in a magnetic field of 10 K Oersted.

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

The average particle diameter of the magnetic substance is 0.05 to
The thickness is preferably 1.0 μm, more preferably 0.1 to 0.6 μm, further 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. When 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 it exceeds 200 parts by mass, the fixing property tends to be impaired.

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

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

[0214] Further, the chargeability and durability which are preferable for the toner,
It is also preferable to externally add and mix the following substances in order to impart cleaning properties and fluidity.

For example, finely powdered silica such as wet-process silica and dry-process silica; treated silica obtained by surface-treating these silica with a silane coupling agent, titanium coupling agent, silicone oil, etc .; alumina, titanium oxide (titania) , Inorganic oxides such as metal oxides such as germanium oxide and zirconium oxide; carbides such as silicon carbide and titanium carbide; and nitrides such as silicon nitride and germanium nitride.

These inorganic fine powders used in the present invention are 0.01 to 8 parts by mass with respect to 100 parts by mass of the toner,
It is preferable to use 0.1 to 4 parts by mass.

Preferably, the specific surface area by nitrogen adsorption measured by the BET method is 30 m ² / g or more (particularly 50 to 400).
Silica fine particles or titanium oxide fine particles in the range of m ² / g) give good results in combination with fine particle agglomerates. 0.01 to 8 parts by mass of silica fine powder or titanium oxide fine powder, preferably 0.
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 modified silicone varnishes, silicone oils, various modified silicone oils, and silanes for the purpose of hydrophobizing, controlling chargeability, etc. Coupling agent, silane coupling agent having a functional group, other treating agents such as organic silicon compounds,
Alternatively, it is also preferable that they are treated in combination with various treatment agents.

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

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

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

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

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

As the carrier to be used in the two-component developing method, conventionally known carriers can be used. Specifically, surface-oxidized or unoxidized iron, cobalt, nickel, manganese, chromium, rare earths and the like can be used. Particles having an average particle size of 20 to 300 μm, such as the above metals and alloys or oxides thereof, are used.

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

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

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

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

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

[0230]

EXAMPLES The present invention will be specifically described below with reference to production examples and examples, but the present invention is not limited thereto. In the following formulation, all parts are parts by mass.

(Production Example 1 of fine particles) 100 parts of fine silica powder (specific surface area of about 200 m ² / g) produced by the dry method was put in a stirrer, and amino-modified silicone oil (amine equivalent 830, 25 ° C.) was stirred. Viscosity at 70 cS
t) A solution of 15 parts and 10 parts of hexane was sprayed and stirred. The resulting 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 fine silica powder (specific surface area of about 200 m ² / g) produced by the dry method was put in a stirrer, and 10 parts of γ-aminopropyltriethoxysilane and hexa were added with stirring. A solution of 10 parts of methyldisilazane and 10 parts of hexane was sprayed and stirred. The resulting fine powder was heated to 100 ° C. and stirred, and the solvent was dried to obtain fine particles (2).

(Fine Particle Production Example 3) Fine particles (3) were obtained in the same manner as in the fine particle production example 1 except that the fine powder and the treating agent shown in Table 1 were used.

(Fine Particle Production Example 4) Fine particles (4) were obtained in the same manner as in the fine particle production example 2 except that the fine powder and the treating agent shown in Table 1 were used.

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

[0236]

[Table 1]

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

40 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 while stirring to carry out stirring treatment. 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 charge amount of this fine particle aggregate (1).

[Production Example 2 of fine particle aggregate] 10% of amino-modified silicone oil (amine equivalent 1900, viscosity 250 cSt at 25 ° C.) and dimethyl silicone oil (viscosity 10000 cSt at 25 ° C.) 90% were mixed to obtain 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 container and agitated by a Turbula mixer to obtain fine particle aggregates (2). Table 2 shows the BET specific surface area and charge amount of this fine particle aggregate (2).
It was shown to.

[Production Example 3 of fine particle aggregate] Amino-modified silicone oil (amine equivalent 1700, viscosity 1300 cSt at 25 ° C.) 20% and fluorine-modified silicone oil (viscosity 10000 cSt at 25 ° C.) 80% were mixed to obtain silicone oil ( 3) was prepared.

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

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

[Production Examples 16 to 18 of fine particle agglomerate] Untreated silica fine powder (specific surface area of about 200 m ² / g) produced by a dry method was used as fine particles and silicone oil
Fine particle aggregates (16) to (18) in the same manner as the fine particle aggregate (1) except that the varnish shown in Table 2 is used.
Got

[Production Example 19 of fine particle agglomerate] 5 parts of the treated fine particles (8) were placed in a Henschel mixer, and a solution of 95 parts of dimethyl silicone oil (viscosity 100 cSt at 25 ° C.) and 10 parts of hexane was sprayed while stirring. Then, when the mixture was stirred to produce fine particle aggregates, the product became a paste and the fine particle aggregates could not be produced. It is considered that this is because the mixing ratio of the fine particles and the silicone oil / varnish was not preferable.

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

The formulations of the above-mentioned 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 After premixing the above materials well with a Henschel mixer, 1
Melt kneading was carried out by a twin-screw kneading extruder set at 40 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverized powder was classified by an air classifier. A classified fine powder (1) having a weight average particle diameter of 7.6 μm was obtained.

To 100 parts of the obtained classified fine powder (1), silica fine powder (BET specific surface area 200
m ² / g) 100 parts with amino-modified silicone oil (amine equivalent 830, viscosity at 25 ° C. 70 cSt) 20
0.9 parts of hydrophobic silica (1) treated with 1 part and 0.2 parts of fine particle aggregate (1) were added, mixed with a Henschel mixer, and sieved with a mesh having an opening 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 at normal temperature and normal humidity
2000 sheets under low temperature / low humidity, high temperature / high humidity environment
An image evaluation test was performed after copying one sheet. The image density and fog in each environment are evaluated, and the level of image dropout (reproducibility of character image) at room temperature and normal humidity, uniformity in solid black image / halftone image, waste toner generation rate ( Evaluate waste toner amount / consumed toner amount) to determine if blotch development (uneven coat of toner on sleeve) occurs at low temperature and low humidity.
The stability of image density under high temperature and high humidity was evaluated. Also,
The setting temperature of the fixing device was set to 150 ° C., an image was formed and then fixed, and the fixing property of the toner was evaluated from the image reduction rate of the obtained image by a rubbing test.

The evaluation results are shown in Table 4.

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

Image evaluation was carried out in the same manner as in Example 1. The results are shown in Table 4.

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

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

Image evaluation of this was carried out in the same manner as in Example 1. The results are shown in Table 4.

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

Image evaluation was carried out 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 (Fractionated crystallized wax; endothermic peak by DSC is 112 ° C.) Quaternary ammonium salt 2 parts After thoroughly premixing the above materials with a Henschel mixer, 1
Melt kneading was carried out by a twin-screw kneading extruder set at 40 ° C. The obtained kneaded product was cooled, coarsely pulverized by a cutter mill, finely pulverized by a fine pulverizer using a jet stream, and the obtained fine pulverized powder was classified by an air classifier. A classified fine powder (3) having a weight average particle diameter of 8.5 μm was obtained.

To 100 parts of the obtained classified fine powder (3), 0.8 parts of hydrophobic silica (2) treated with aminopropyltrimethoxysilane and hexamethyldisilazane, 0.2 parts of fine particle aggregates (2) Parts were added, mixed with a Henschel mixer, and sieved with a mesh having an opening of 150 μm to obtain a toner.

This toner was applied to a commercially available copying machine FC330 (manufactured by Canon Inc.) to evaluate images.

Image evaluation tests were carried out by copying 1000 sheets under each environment of normal temperature / normal humidity, low temperature / low humidity, high temperature / high humidity. The image density and fog in each environment were evaluated, and the level of image dropout (reproducibility of character image) under normal temperature and normal humidity was evaluated. The voids are at a good level, and the image density is a level that can be used under any environment, at 1.10 or more, in the initial stage and after the endurance. The results are shown in Table 4.

<Comparative Examples 1 to 3> As fine particle aggregates, untreated silica fine powder produced by a dry method (specific surface area: about 2
Fine particle aggregate (16) produced by using 100 m ² / g)
Toners were obtained in the same manner as in Example 1 except that (18) to (18) were used.

Image evaluation was carried out 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.

Image evaluation was carried out 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 the fine particle aggregate was not added.

Image evaluation of this was carried out 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 initial stage, 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 voids in transfer, and free from scattering, offset, and filming.

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

The toner of the present invention produces less waste toner and can reduce waste. In addition, the space for collecting the waste toner can be reduced to save space.

[Brief description of drawings]

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

Continuation of the front page (56) Reference JP-A-8-15891 (JP, A) JP-A-7-301944 (JP, A) JP-A-7-168391 (JP, A) JP-A-7-160039 (JP , A) JP 6-230601 (JP, A) JP 3-101741 (JP, A) JP 3-100662 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB) Name) G03G 9/08

Claims (9)

(57) [Claims] 1. A toner for electrostatic image development comprising 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. and, fine particles forming the fine particle aggregates, i) a silane coupling agent having a nitrogen atom in at least a side chain, hexa
Mechirujishirazan or either by <br/> Ri processed dimethyl silicone oil, or ii) a toner for developing electrostatic images which is characterized in that it is more processed silicone for oil having at least a side chain to the nitrogen atom . 2. The fine particle aggregate comprises silicone oil or silicone varnish having no nitrogen atom in a side chain,
The toner for developing an electrostatic charge image according to claim 1, which contains a total of 20 to 90% by mass of a silicone oil or a silicone varnish having a nitrogen atom in a side chain. 3. A fine particle aggregates toner according to claim 1 or 2, characterized in that the BET specific surface area of 0.01 to 50 m ² / g. 4. 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 toner for developing an electrostatic charge image according to any one of claims 1 to 3 , further comprising: 5. The silicone oil a nitrogen atom fine particle aggregates are contained contained in the side chain, electrostatic charge according to any one of claims 2 to 4, characterized in that it comprises an amino-modified silicone oil Toner for image development. 6. A fine particles forming the fine particle aggregates, toner according to any one of claims 1 to 5, characterized in that an inorganic fine powder. 7. A fine particles forming the fine particle aggregates, silica fine powder, the toner for developing electrostatic images according to any one of claims 1 to 6, characterized in that a fine alumina powder or titania fine powder . 8. fine particles forming the fine particle aggregates, toner according to any one of claims 1 to 7, characterized in that a silica fine powder. 9. The mass ratio of the silicone oil or silicone varnish having a nitrogen atom in the side chain and the silicone oil or silicone varnish not having a nitrogen atom in the side chain contained in the fine particle aggregate is 1:30 to. The electrostatic charge image developing toner according to any one of claims 2 to 8 , which is 10: 1.