JP2000214627A - Image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method which is nearly independent of environment such as temperature and humidity, stabilizes the electrostatic charge and conveyance of a toner over a long period of time and gives stable image density. SOLUTION: The image forming method has a latent image forming step in which an electrostatic latent image is formed on a latent image bearing member and a developing step in which the electrostatic latent image is developed with a developer formed as a thin layer with a layer regulating member brought into contact with the surface of a developer support. The layer regulating member is surface-coated with a nitrogen atom-containing material. The developer is a one-component developer consisting of toner particles containing a bonding resin and a colorant and an additive containing a titanium compound surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound. When the amount of the alkylalkoxysilane compound based on 100 pts.wt. titanium compound is presented by (a) (pts.wt.), the amount (b) (pts.wt.) of the fluorine-containing silane compound is in the range of 0.01a<=b<=0.5a.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method and an image forming apparatus, and more particularly, to a method in which a developer formed in a thin layer on a developer carrying member is transported to a developing section, and the latent image holding member The present invention relates to an image forming method including a step of developing an electrostatic latent image and an image forming apparatus used in the method.

[0002]

2. Description of the Related Art In recent years, the electrophotographic dry development system has been using not only an electrostatic copying machine but also a printer, a facsimile, or a multifunction machine having both a copying machine, a printer and a facsimile. In particular, recently, there is a demand for ecological measures such as miniaturization, weight reduction, resource saving and recycling. To cope with this, improvements and new developments of an image forming method and an image forming apparatus used therein are being made. At present, dry development methods in various electrostatic copying methods that have been put into practical use include:
A two-component developing method using a carrier such as toner and iron powder and a one-component developing method using no carrier are known.

The two-component developing system is currently the most widely used system. However, since only the toner is consumed and the concentration ratio of the toner in the developer decreases, the mixing ratio with the carrier is kept constant. Therefore, there is a disadvantage that a device such as a controller is required for that, and the developing device becomes large. Therefore, the one-component developing method using no carrier does not have the above-mentioned disadvantages, and is advantageous in reducing the size and weight of the apparatus.

[0004] The one-component developing system is classified into a magnetic one-component developing system using a magnetic toner and a non-magnetic one-component developing system using a non-magnetic toner. In the magnetic one-component developing method, a magnetic toner is held on a developer carrying member provided with a magnetic field generating means such as a magnet inside, and a thin layer of the magnetic toner is formed using an elastic blade such as silicone rubber to form an electrostatic latent image. A toner is developed by attaching toner to an electrostatic latent image on an image carrier, and has been put to practical use in recent years because of easy control of toner conveyance and low internal contamination of a copying machine, a printer, and the like. . However, since the magnetic toner used in the magnetic one-component developing system contains a black or brown colored magnetic material such as magnetite therein, there is a drawback that it cannot cope with full color, which has been increasingly required in the market in recent years.

On the other hand, in the non-magnetic one-component developing method, a non-magnetic toner is supplied onto a developer carrier by a toner supply roller and an agitator adjacent to the developer carrier, and a toner layer is formed by a layer regulating blade. The development is performed by attaching toner to the electrostatic latent image on the latent image holding member to perform development. Since the toner does not require a colored magnetic material, it is a development method suitable for colorization. Further, since no magnet is used for the developer carrying member, it is possible to reduce the weight and cost, and in recent years, it has begun to be used in small full-color printers and the like.

Incidentally, the one-component developing system does not have a stable toner charging / transporting means such as a carrier as compared with the two-component developing system, so that stricter characteristics are required for the toner. In particular, since the non-magnetic one-component developing method has no magnetic force for toner conveyance / layer formation, it is necessary to hold the toner on the developer carrier mainly by electrostatic force, and the toner is charged more quickly and uniformly. Is required. Further, the non-magnetic one-component toner is charged mainly by contact friction with the blade / sleeve, but if the toner component is contaminated on those charging members, the charge deteriorates like a two-component developer carrier. In addition, a decrease in density due to a decrease in charge, fogging of a background portion, and contamination of the inside of the apparatus occur, and in particular, when toner components adhere to the blade portion, streak-like image quality defects occur.

Therefore, in order to maintain the durability of the non-magnetic one-component toner, in addition to the above-described high charging ability and high charging speed, characteristics such as low adhesion are strongly required. In particular, in recent years, there has been an increasing demand for higher image quality such as color, and attempts have been made to achieve high image quality by reducing the particle size of the toner. Is increased, and the above-mentioned defects appear remarkably.

Further, in addition to these characteristics relating to toner development, various characteristics are required for toners in recent years in order to reduce the size and weight of the apparatus, to improve image quality, and to support ecological aspects. For example, contact type bias rolls and the like are becoming the mainstream for charging the photoconductor and transferring toner for the purpose of preventing ozone generation in place of conventional corotrons. In order to prevent fusion, high transfer efficiency / high cleaning properties are required.
In order to prevent the central transfer development of characters by the contact type transfer roll, the toner is required to have good adhesion / aggregation characteristics, fluidity, and the like.

Conventionally, as a developer carrying member, a metal sleeve such as aluminum or SUS, or a silicone rubber or NB
An elastic sleeve or the like in which a conductive agent such as carbon is dispersed in R, EPDM, or the like is used. As a layer regulating member, an elastic blade such as urethane rubber or silicone rubber, SU
Metal blades such as S and phosphor bronze are used. However, since these charging members themselves have low charging ability, not only is it difficult to adjust the initial toner charge,
Due to toner deterioration due to long-term use and contamination of charging members,
Low-charge toner and reverse-polarity toner increased, and fog and low image density problems were likely to occur.

In order to solve these problems, various methods have been proposed in which a material having a charge polarity opposite to that of the toner is used on the surface of the charging member to impart strong charge to the toner. However, according to this method, although the initial charging characteristics of the toner are improved and good image quality is obtained, the toner and the additives of the toner are electrostatically charged on the charging member, particularly the surface of the layer regulating member by continuous use. It is easy to adhere, not only hinders charging of the toner, but also prevents uniform layer formation,
There is a problem that streaks on an image are likely to occur. Especially in the case of non-magnetic one-component development in which the toner does not contain a magnetic substance,
This problem was a major obstacle.

Further, in the one-component developing system, the fluidity and fluidity have been conventionally increased in order to stabilize the charging and conveyance of the toner.
Means for adding an inorganic oxidized fine powder such as silica to a toner has been used for the purpose of improving the chargeability. However,
In the case of generally used silica-based fine powder, the effect of improving the fluidity of the toner is particularly excellent, but the negative polarity is strong, especially under low temperature and low humidity, because the charge of the negatively chargeable toner is excessively increased. Even if a positive charge such as treatment with a nitrogen-containing compound is applied, it is not suitable for a positively charged toner, and furthermore, under high temperature and high humidity, water is taken in and the chargeability is reduced. Will occur. As a result, the transferability and chargeability of the toner onto the developer carrying member cannot be optimized under both high temperature, high humidity and low temperature and low humidity, and image density reproduction failure, background fog, toner There has been a problem that it may fall off and further cause in-flight contamination and the like. For example, JP-A-46-5782,
JP-A-48-47345, JP-A-48-4734
No. 6, JP-A-59-34539 and JP-A-59-34539.
JP-A-198470 and JP-A-59-231550 disclose that the surface of silica fine particles is subjected to a hydrophobic treatment. However, the use of these inorganic fine powders alone does not provide a sufficient effect particularly on the charging property.

As a method for alleviating the negative chargeability of toner particles, a method of externally adding silica fine particles surface-treated with an amino-modified silicone oil (Japanese Patent Laid-Open No. 64-733)
No. 54) and a method of externally adding silica fine particles surface-treated with aminosilane and / or amino-modified silicone oil (JP-A-1-237561). However, in the treatment with these amino compounds,
In particular, although an excessive increase in the charge of the negatively chargeable toner under low temperature and low humidity can be suppressed, the environmental dependency of the silica fine powder itself cannot be sufficiently improved. Further, as described above, particularly in the non-magnetic one-component developing system, the charging speed of the developer is required to be high. However, if an amount of the developer having sufficient fluidity is added, the high resistance of the silica fine powder is increased. ,
Defects such as high chargeability, slow charge speed, etc., the distribution of charge on the developer carrier is wide, and even if the charge amount is in a suitable range, there are many reverse polarity toners. It also causes reverse polarity fog and toner cloud (dirt in the machine). As described above, the silica fine particles are subjected to a hydrophobic treatment, a treatment for alleviating negative chargeability, and the like.
At present, it has not been possible to improve the environmental dependence of charging, charging speed, and poor charging distribution of silica.

On the other hand, as a method for preventing the character dropout phenomenon due to the contact-type transfer roll, it has been proposed to add silica fine powder treated with silicone oil to the toner. Certainly, although this method can improve the void phenomenon of characters, as described above, it is not possible to improve the charge distribution of the toner, and at present it is difficult to achieve compatibility with fog, toner cloud, and the like.

On the other hand, when the inorganic oxide added for the purpose of improving charging and fluidity is titania which is generally used, the charging speed is higher than that of silica and the low resistance of the titania may cause the charging. It has the characteristic that the distribution becomes sharp. Further, these additions suppress the charge-up of the developer and have an effect of suppressing the ghost phenomenon.
However, when titania is added, high charge cannot be imparted to the toner, and the toner is liable to cause a decrease in the transport amount due to continuous use, a decrease in density reproducibility due to a decrease in the charge, a background fog, and an in-machine stain.

For the purpose of improving the chargeability, a method has been proposed in which hydrophobic titanium oxide is externally added to a toner (JP-A-58-216252, JP-A-60-12386).
No. 2, JP-A-60-238847). Hydrophobic titanium oxide can be obtained by treating the surface with a silane compound, a silane coupling agent, silicone oil, or the like. By this method, it is possible to increase the chargeability of untreated hydrophilic titania, but in the case of one-component toner, although the charge level can be improved to some extent by the type and amount of the processing agent, the chargeability of the toner can be improved. The levels are not yet at a satisfactory level, and there are limits to environmental dependencies. In addition, by increasing the hydrophobicity of titanium oxide with the treatment agent, the charge level and environmental dependency are certainly better than the conventional hydrophilic titanium oxide, but the charging speed of titanium oxide is conversely improved. In fact, the speed and sharpness of the charge distribution are greatly inferior to conventional titanium oxide.

Therefore, in order to achieve both improvement in fluidity and environmental dependency of electrification, it has been attempted to add hydrophobic titanium oxide and hydrophobic silica in combination (Japanese Patent Application Laid-Open No. 60-136).
755). This technique temporarily suppresses the respective disadvantages of hydrophobic silica and hydrophobic titanium oxide, but is susceptible to the effect of either additive depending on the dispersion state. In particular, when considering the maintainability, it is difficult to stably suppress the dispersion structure on the toner surface, and the characteristics of hydrophobic silica or hydrophobic titanium oxide tend to appear due to stress on the sleeve. That is, it has been difficult to stably control each of the defects for a long period of time.

Therefore, in a method of purifying titanium oxide by a wet method, the silane compound is hydrolyzed in an aqueous medium, the surface of the titanium oxide is treated, the titanium oxide is taken out in a state where aggregation is suppressed, and added to the toner. (Japanese Patent Laid-Open No. 5-188633). When the silane compound treatment is performed by this method, the amount of aggregated particles is reduced as compared with the conventional method of hydrophobizing titanium oxide. In other words, although the fluidity of the toner is improved, the charge level and environmental dependency of the negatively charged toner are improved. Is not any different from the conventional one and is not sufficient in the intended high negative chargeability and environmental dependency, and further has an adverse effect on the charging speed and charge distribution.

JP-A-59-52255 proposes adding hydrophobic titanium oxide treated with an alkyl trialkoxysilane to a toner. Although the electrophotographic properties of the toner are improved by mixing the hydrophobic titanium oxide and the toner particles, the surface activity of the titanium oxide is originally smaller than that of silica, and the degree of hydrophobicity is reduced to a target level. Cannot be enhanced,
Alternatively, if the treatment amount is increased in order to increase the degree of hydrophobicity, or if a measure is taken to lengthen the treatment time, aggregated particles in which the titanium oxide particles are united at the stage of the treatment may occur, or the hydrophobicity may be non-uniform. There was a tendency to be.

Next, there has been proposed a method of adding hydrophobic amorphous titanium oxide to a toner (Japanese Patent Laid-Open No. 5-20).
No. 4,183, JP-A-5-72797). Amorphous titanium oxide can be obtained by hydrolyzing a metal alkoxide or a metal halide using a CVD method (Chemical Engineering Transactions, Vol. 18, No. 3, No. 30).
3-307 (1992)). However, although titanium oxide obtained by such a hydrolysis method can achieve both improvement in charging characteristics and toner fluidity, it has a large amount of adsorbed water inside the particles, and therefore, the titanium oxide itself is transferred to the photosensitive member during transfer. Will remain. That is, since amorphous titanium oxide has a strong adhesive force to the photoreceptor, only the titanium oxide remains on the photoreceptor without being transferred, and white spots on an image or hard titanium oxide damage the photoreceptor surface during cleaning. And the like.

[0020]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned conventional problems and achieve the following objects. That is, an object of the present invention is to provide an image forming method which is not easily influenced by environment such as temperature and humidity, stabilizes charging and conveyance of toner for a long period of time, and can obtain stable image density. Another object of the present invention is to provide an image forming method in which low developability, no fogging, etc. appear for a long period of time, good cleanability, and filming and fusion hardly occur. Still another object of the present invention is to provide an image forming apparatus capable of stably obtaining excellent image quality over a long period of time.

[0021]

Means for solving the above problems are as follows. That is, <1> a latent image forming step of forming an electrostatic latent image on a latent image holding member, and the latent image using a developer thinly formed by a layer regulating member in contact with a developer carrying member; And a developing step of developing an electrostatic latent image on the holding member, wherein the layer regulating member is surface-coated with a material containing a nitrogen atom, and the developer contains a binder resin and a colorant. Toner particles, and an additive containing a titanium compound, and the titanium compound is surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound, and 100 parts by weight of the titanium compound, When the treatment amount of the alkylalkoxysilane compound is a (parts by weight),
An image forming method, wherein the processing amount b (parts by weight) of the fluorine-containing silane compound is a one-component developer represented by the following formula. 0.01a≤b≤0.5a <2> Latent image forming means for forming an electrostatic latent image on the latent image holding member, and development in which a thin layer is formed by a layer regulating member abutting on the developer carrying member Developing means for developing an electrostatic latent image on the latent image holding member using an agent; transferring means for transferring an image developed on the latent image holding member to a transfer member; Fixing means for thermally fixing the image, wherein the layer regulating member is surface-coated with a material containing a nitrogen atom, and the developer contains a binder resin and a colorant. Toner particles, and an additive containing a titanium compound, and the titanium compound is surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound, based on 100 parts by weight of the titanium compound,
In the surface treatment, when the treatment amount of the alkylalkoxysilane compound is a (parts by weight), the treatment amount b (parts by weight) of the fluorine-containing silane compound is a one-component developer represented by the following formula. An image forming apparatus according to claim 1. 0.01a ≦ b ≦ 0.5a

[0022] The means for solving the above-mentioned problems are preferably as follows. That is, it is preferable that the titanium compound is surface-treated with an alkylalkoxysilane compound and then surface-treated with a fluorine-containing silane compound.
In addition, it is preferable that the treatment amount of the alkylalkoxysilane compound in the surface treatment is 20 to 80 parts by weight and the treatment amount of the fluorine-containing silane compound is 1 to 40 parts by weight with respect to 100 parts by weight of the titanium compound. .
Further, the former aspect in which the fluorine-containing silane compound is represented by the following formula (1) or (2) is preferable. _{C n F 2n + 1 CH 2} CH 2 Si (CH 3) p X 3-P (1) ( wherein, X represents a hydrolyzable group, n represents 1, 4, 6, 8
Or 10 and p represents 0 or 1. _{) C m F 2m + 1 -Ph} -CH 2 CH 2 Si (CH 3) q Y 3-q (2) ( wherein, Ph represents a phenylene group, Y represents a hydrolyzable group, m is 1 , 4, 6, or 8, and q represents 0 or 1.) In addition, an embodiment in which the titanium compound is metatitanic acid is preferable. It is preferable that the surface-treated titanium compound has a hydrophobicity of 50 to 80%.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. [Image Forming Method] The image forming method of the present invention comprises at least a latent image forming step of forming an electrostatic latent image on a latent image holding member;
A developing step of developing an electrostatic latent image on the latent image holding member using a developer formed in a thin layer by a layer regulating member abutted on a developer carrying member. Accordingly, the method may include a transfer step of transferring the image developed on the latent image holding member to a transfer member, a fixing step of thermally fixing the image transferred on the transfer member, and the like. The image forming method of the present invention uses a specific layer-regulating member as the layer-regulating member used in the developing step, and uses a specific one-component developer as the developer. By using them in combination, the object of the present invention can be achieved for the first time.

(Latent Image Forming Step) In the latent image forming step, a conventionally known method can be applied, and the latent image forming step is performed on a latent image holding member such as a photosensitive layer or a dielectric layer by electrophotography or electrostatic recording. An electrostatic latent image is formed. As the photosensitive layer of the latent image holding member used in the present invention, a known layer such as an organic or amorphous silicon can be used. When the latent image holding member is cylindrical, the latent image holding member can be obtained by a known manufacturing method such as extruding aluminum or an aluminum alloy and then processing the surface. Further, a belt-shaped latent image holding member can be used.

(Developing Step) In the developing step, a thin layer of toner is formed on a rotating cylindrical body of a developer carrying member (hereinafter, sometimes referred to as a “developing roll”) by a layer regulating member, and the toner is formed up to a developing nip. The developing roller and the latent image holding member that holds the electrostatic latent image are conveyed or arranged in the developing section with a contact or a fixed gap therebetween, and statically applied while applying a bias between the developing roll and the latent image holding member. The electrostatic latent image is developed using toner. As a method for supplying the toner onto the developer carrying member, there is a method in which a urethane sponge, a toner supply roll such as a conductive polypropylene or an acrylic brush or the like is pressed against the developer carrying member.

The developer carrying member includes an elastic sleeve such as silicone rubber, a sleeve from which a metal or ceramic such as aluminum, SUS, nickel or the like is pulled out, and an oxidation of the surface of the base for controlling the transportability and chargeability of the toner. Alternatively, a metal coating, polishing, blasting or other surface treatment, or a resin coating of acrylic, phenol, or the like, or a polymer coating layer in which a charge control agent, a conductive agent, a lubricant, or the like is dispersed, is coated on these substrates. And a rigid sleeve such as a plastic sleeve obtained by integrally molding them.

As the layer regulating member, an elastic blade such as silicone rubber or urethane rubber, SUS, Al plate,
A conventionally known blade such as a metal braid such as phosphor bronze or the like is used, which is coated with a material containing a nitrogen atom. The toner layer regulation is performed by bringing the layer regulation member into contact with the surface of the developer carrying member. In the present invention, coating the surface of the layer regulating member with a material containing a nitrogen atom not only imparts good chargeability to the toner, but also allows the toner and toner additives to remain in the layer regulating member even during long-term use. It is difficult to adhere and adhere to the surface of the film, so that good layer formation and chargeability can be continuously obtained. The reason for this is that a material containing nitrogen atoms having a positive polarity opposite to that of the toner is applied to the surface of the layer regulating member so that the toner has a sufficient negative charge during frictional charging with the toner. Because you can do it. Accordingly, adhesion of the low-charge toner to the layer regulating member due to stagnation can be prevented, and stable image quality can be obtained even during long-term use.

Here, the use of a material containing a nitrogen atom makes it possible to impart appropriate charge to the toner in both high-temperature, high-humidity and low-temperature, low-humidity environments, compared to a coating agent containing other atoms. Because you can. However, in the case of a coating agent that does not contain nitrogen atoms and has a high charge-imparting property, electrostatic adhesion to the layer regulating member occurs due to charge-up of the toner under low temperature and low humidity, and conversely, the charge imparting that does not contain nitrogen atoms With a coating agent having low properties, dirt of the toner under high temperature and high humidity and fogging of the photoreceptor occur. On the other hand, although the coating agent containing a nitrogen atom has the above-described excellent effects, the problem that the charge-up property of charging under high temperature and high humidity is low only by coating the layer regulating member with the coating agent still remains. Have been. Although the reason for this is not clear, it is considered that the toner tends to absorb moisture under the condition of high humidity, thereby lowering the initial charge.

Therefore, in the present invention, in order to exhibit the effect of imparting charge by nitrogen atoms, the developer used is as follows:
A toner particle containing a binder resin and a colorant, and an additive containing a titanium compound, wherein the titanium compound is surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound, and the titanium compound is 100 parts by weight. On the other hand, when the treatment amount of the alkylalkoxysilane compound in the surface treatment is a (parts by weight), the treatment amount b (parts by weight) of the fluorine-containing silane compound is 0.0.
By using the one-component developer represented by 1a ≦ b ≦ 0.5a, it was possible to solve the problem that the charge-up property of charging under high temperature and high humidity was low. As will be described later, the one-component developer makes it possible to impart good fluidity and hydrophobicity to the toner, thereby improving the charge-up property of the nitrogen-containing coating agent under high temperature and high humidity. Was low, and stable electrification could be maintained even when used for a long time.

Here, the material containing a nitrogen atom is, for example, a compound having an amino group, an amide group, a nitro group, an imino group or the like, or an azine containing a nitrogen atom in a ring (diazine, triazine, tetrazine). Are preferred,
In order to coat the surface of the layer regulating member, a resin-like material is more preferable, and examples thereof include polyimide, polyamide, polybenzimidazole, urea, melamine, polyacrylamide, and nylon. Melamine is particularly preferred from the viewpoints of heat resistance, water resistance, mechanical strength and the like. These may be used alone or in combination of two or more.

Further, these resins containing a nitrogen atom include those having a releasability, such as silicone resins and fluororesins.
Alternatively, a material having excellent mechanical properties such as polyether sulfone, polyphenylene oxide, phenol, polyester, styrene resin, and acrylic resin may be used in combination. At this time, the content of the resin containing a nitrogen atom is preferably 10% by weight or more of the total resin amount, and 15% by weight.
More preferably, it is the above. If the amount of the resin containing a nitrogen atom is less than 10% by weight of the total amount of the resin, it may be difficult to impart sufficient negative chargeability to the toner.

A coating solution obtained by dissolving the resin containing a nitrogen atom with a suitable solvent is coated on the surface of the layer regulating member. The solvent is not particularly limited, and a conventionally known solvent can be used. Specifically, methanol, ethanol, isopropyl alcohol, butanol, toluene, tetrahydrofuran, tetramethoxyfuran, methyltrichlorosilane, methyltrimethoxysilane and the like are preferably exemplified. The concentration of the coating solution,
Although it is not particularly limited as long as the object of the present invention can be achieved, 20 to 80% by weight is preferable, and 40 to 60% by weight is more preferable.

The coating method is not particularly limited, and a conventionally known coating method can be used. Specifically, preferred examples include spray coating, dip coating, spin coating, and flow coating. The coating layer formed by applying the coating liquid on the surface of the layer regulating member has a thickness of 0.1 mm.
It is preferably from 0.5 to 20 μm, more preferably from 0.1 to 10 μm. When the film thickness is less than 0.05 μm, the wear of the coat layer is increased due to friction with the toner, and the durability may be reduced. On the other hand, when the film thickness is more than 20 μm, the toner may be charged. The application tends to decrease, and the mechanical strength tends to decrease, so that it may be difficult to form a stable layer.

(Transfer Step) In the transfer step, a transfer roller, a transfer belt, or the like is pressed against the latent image holding member to transfer a toner image to the transfer member, or a non-contact transfer type using a corotron to transfer the toner image to the transfer member. A known method such as a method of transferring a toner image to a belt-like or cylindrical intermediate transfer body once and then transferring the toner image to a transfer body is used, but a contact type is generally used to reduce the size of the apparatus. Have been.

(Cleaning Step) The cleaning step is a step of removing the toner remaining on the latent image holding member without being transferred in the transfer step by a cleaner. However, when there is little untransferred toner, the cleaner-less operation is possible. . In the case of having a cleaning step, known ones such as blade cleaning, brush cleaning and roller cleaning may be mentioned. Elastic rubber such as silicone rubber or urethane rubber is used for blade cleaning.

(Fixing Step) In the fixing step, the toner image transferred to the transfer member is fixed by a fixing device. As a fixing means, a heat fixing method using a heat roll is preferably exemplified.

(One-Component Developer) The one-component developer used in the present invention comprises toner particles containing at least a binder resin and a colorant, and an additive containing a titanium compound. , An alkylalkoxysilane compound and a fluorine-containing silane compound. -Titanium compound- Hereinafter, the titanium compound before the surface treatment is referred to as "pre-treatment titanium compound", and the titanium compound after the surface treatment is referred to as "post-treatment titanium compound". The treated titanium compound used in the present invention has a specific gravity of 2.0 to 5.0,
Those having a degree of hydrophobicity of 50 to 80% are preferable, and specific gravity is 3.
It is more preferably from 0 to 4.5 and having a hydrophobicity of 55 to 75%, particularly preferably having a specific gravity of 3.5 to 4.0 and having a hydrophobicity of 60 to 70%. The degree of hydrophobicity is 50
%, The charge amount is significantly reduced particularly during initial and long-term storage under high humidity, and the device may be complicated due to the need for a mechanism for accelerating charging on the device side. On the other hand, if the degree of hydrophobicity exceeds 80%, it becomes difficult to control the charging of the titanium compound itself, and as a result, the toner may be charged up particularly under low humidity.

The specific gravity of the titanium compound after the treatment was measured using a Le Chatelier pycnometer in accordance with JIS-K-0061, 5-2-1. The operation method is as follows. (1) Put about 250 ml of water into a Lucheterie pycnometer,
Adjust so that the meniscus is at the scale position. (2) The specific gravity bottle is immersed in a thermostatic water bath, and the liquid temperature is 20.0 ± 0.
When the temperature reaches 2 ° C., the position of the meniscus is accurately read on the scale of the pycnometer (accuracy: 0.025 ml). (3) Approximately 100 g of a sample is weighed to the order of 1 mg, and its mass is represented by W. (4) Place the weighed sample in a pycnometer to remove bubbles. (5) The specific gravity bottle is immersed in a constant temperature water bath, and the liquid temperature is adjusted to 20.0 ±
Keep the temperature at 0.2 ° C and read the position of the meniscus accurately on the scale of the pycnometer (accuracy 0.025 ml). (6) The specific gravity is calculated by the following equation. D = W / (L2-L1) S = D / 0.9982 [where D: density of sample (20 ° C.) (g / cm ³ ),
S: specific gravity of sample (20/20 ° C.), W: apparent mass of sample (g), L1: meniscus reading (20 ° C.) (ml) before placing sample in pycnometer, L2: sample of pycnometer Of the meniscus (20 ° C.) (ml) after placing in the jar. Note that 0.9982 in the above formula means the density of water at 20 ° C. (g / cm ³ ).

The degree of hydrophobicity of the titanium compound after the treatment was measured by a methanol titration test. The operation method is as follows. (1) 0.2 g of the test silica fine powder is added to 50 ml of water in a 250 ml Erlenmeyer flask. (2) Titrate the methanol from the buret until the entire amount of silica is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed by the suspension of the entire amount of the fine silica powder in the liquid, and the degree of hydrophobicity is expressed as the percentage of methanol in the liquid mixture of methanol and water at the end point.

In the treatment amount of the alkylalkoxysilane compound and the fluorine-containing silane compound used for the surface treatment, the treatment amount of the alkylalkoxysilane compound is a (parts by weight) with respect to 100 parts by weight of the titanium compound before treatment.
It is necessary that the treatment amount b (parts by weight) of the fluorine-containing silane compound satisfies 0.01a ≦ b ≦ 0.5a. As a result, the cohesiveness of the titanium compound can be reduced, good fluidity and hydrophobicity can be imparted to the toner, and a stable charge can be maintained even when used for a long time. By treating the alkoxysilane compound and the fluorine-containing silane compound, it is possible to solve the problem of fog on the photoreceptor under high temperature and high humidity and low concentration under low temperature and low humidity, and obtain good image quality without the influence of environmental differences. Can be.

The treatment amount b (parts by weight) of the fluorine-containing silane compound preferably satisfies 0.03a ≦ b ≦ 0.25a, and more preferably satisfies 0.05a ≦ b ≦ 0.20a. . When the treatment amount b (parts by weight) of the fluorine-containing silane compound is less than 0.01 a (parts by weight), the effect of imparting charge of fluorine atoms contained in the fluorine-containing silane compound and the low surface energy effect are sufficiently exhibited. However, sufficient charge cannot be obtained under high temperature and high humidity, fog occurs on the photoreceptor, and if used for a long time, streak-like image quality degradation due to toner blade contamination occurs, and furthermore, Background fogging, which is considered to be due to low chargeability, occurs. On the other hand, when the treatment amount b (parts by weight) of the fluorine-containing silane compound exceeds 0.5a (parts by weight),
The hydrophobization of the titanium compound by the alkylalkoxysilane compound is insufficient, or the aggregation of the excess fluorine-containing silane compound may cause a problem in the fluidity of the toner, and the excess of the fluorine-containing silane compound Due to the charging effect, problems such as insufficient density at low temperature and low humidity occur.

Hereinafter, a method for producing titanium oxide, which is one of preferred specific examples of the titanium compound before treatment used in the present invention, will be described. In general, the production method of titanium oxide by an ordinary wet method is a method of producing titanium oxide by a chemical reaction in a solvent, and is divided into a sulfuric acid method and a hydrochloric acid method. Among them, in the sulfuric acid method, the following reaction proceeds in a liquid phase, and insoluble TiO (OH) ₂ is obtained by hydrolysis, which is washed with water, filtered, and calcined at 400 to 1000 ° C. ₂ is obtained. FeTiO ₃ + 2H ₂ SO ₄ → FeSO ₄ + TiOSO ₄ + 2H ₂ O TiOSO ₄ + 2H ₂ O → TiO (OH) ₂ + H ₂ SO ₄ TiO (OH) ₂ → TiO ₂ + H ₂ O (fired)

In the hydrochloric acid wet method, chlorination is first performed in the same manner as in the dry method to produce titanium tetrachloride, which is then dissolved in water and hydrolyzed while adding a strong base to the TiO ( OH) ₂ is obtained, washed with water, filtered, and then calcined at 400 to 1000 ° C. to obtain TiO ₂ . This is represented by the following chemical formula. TiCl ₄ + H ₂ O → TiOCl ₂ + 2HCl TiOCl ₂ + 2H ₂ O → TiO (OH) ₂ + 2HCl TiO (OH) ₂ → TiO ₂ + H ₂ O (fired)

Titanium oxide has three crystal forms: rutile type, anatase type, and itatanite. However, itatasite is unstable and difficult to synthesize as compared to the other two forms. Therefore, the form taken up as titanium oxide is anatase type generated at a relatively low temperature, rutile type generated at a high temperature, or water of TiO ₂ .nH ₂ O generated and separated in the process of synthesizing these two types. It is a compound having a composition equivalent to a sum. Note that n often has a fraction of 2 or less, and the value differs depending on the adjustment conditions. In particular, n
= 2 when α or orthotitanic acid, n = 1 when β
Or metatitanic acid. As the titanium compound before treatment, all of these titanium compounds and a mixture thereof can be used, but it is more preferable to use metatitanic acid. This is because metatitanic acid has lower cohesiveness than other titanium oxides, and does not cause re-aggregation due to the treatment of the silane compound. In addition, metatitanic acid has a high surface activity and is advantageous for the reaction because it contains more Ti-OH groups that can react with the silane compound, and can be uniformly treated with a small amount of a treating agent, and has a high hydrophobicity. It is because it can raise.

The titanium compound after treatment used in the present invention is preferably obtained by reacting the silane compound with TiO (OH) ₂ produced in the above wet process and then drying. In this method, since there is no high-temperature sintering step of several hundred degrees, no strong bonding between titanium occurs, there is no agglomeration, the particles can be taken out almost in the form of primary particles, and after this treatment, the titanium compound is Since the silane compound can be directly reacted with TiO (OH) ₂ , it can be treated in a large amount.

The silane compound used in the present invention can be appropriately selected depending on the purpose of surface modification (for example, control of charging characteristics and further stabilization of charging under high humidity) and reactivity of the silane compound. And at least an alkylalkoxysilane compound and a fluorine-containing silane compound. Further, those which do not themselves thermally decompose at the reaction treatment temperature are preferred.

The above-mentioned alkylalkoxysilane compound is volatile, has both a hydrophobic group and a reactive bonding group, and is preferably represented by the following formula (3). C _a H _{2a + 1} -Si- (OC _b H _{2b + 1} ) ₃ (3) In the formula, a is preferably an integer of 4 to 12, more preferably 4 to 8. b is preferably an integer of 1 to 3, and more preferably an integer of 1 to 2.

Specific examples of the alkylalkoxysilane compound include n-butyltrimethoxysilane, iso
-Butyltrimethoxysilane, n-butyltriethoxysilane, iso-butyltriethoxysilane, n-pentyltrimethoxysilane, n-pentyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n- Heptyltrimethoxysilane, n-heptyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane,
Preferred examples include n-nonyltrimethoxysilane, n-nonyltriethoxysilane, n-decyltrimethoxysilane, and n-decyltriethoxysilane.

In the above formula (3), when the number of carbon atoms (a) of the alkyl group is smaller than 4, the treatment becomes easy, but good hydrophobicity may not be obtained. On the other hand, when the carbon number (a) of the alkyl group is larger than 12, the hydrophobicity becomes sufficient,
The coalescence between the fine powders increases, and the fluidity-imparting ability may decrease. In the formula (3), when the number of carbon atoms (b) of the alkoxy group is larger than 3, the reactivity may be reduced and good hydrophobicity may not be obtained.

The amount of the alkylalkoxysilane compound to be treated depends on the primary particle size of the titanium compound before treatment, but is generally 20 to 80 parts by weight based on 100 parts by weight of the titanium compound before treatment. Is preferred, and 30 to 70
A weight part is more preferable, and 40 to 60 weight parts is particularly preferable. When the treatment amount is less than 20 parts by weight, the function of treating the alkylalkoxysilane compound may not be exhibited. On the other hand, when the treatment amount exceeds 80 parts by weight, the excess alkylalkoxysilane compound is turned into oil. As a result, a problem may occur in the fluidity of the toner.

The fluorine-containing silane compound is preferably represented by the following formula (1) or (2). _{C n F 2n + 1 CH 2} CH 2 Si (CH 3) in _p X _3-P (1) formula, X represents a hydrolyzable group, n represents 1, 4, 6, 8 or 10, p Represents 0 or 1. _{C m F 2m + 1 -Ph-} CH 2 CH 2 Si (CH 3) q Y 3-q (2) wherein, Ph represents a phenylene group, Y represents a hydrolyzable group, m is 1,4 , 6 or 8, and q represents 0 or 1. In the formulas (1) and (2), as the hydrolyzable group, any functional group that can be decomposed by water can be used. In particular, a halogen atom such as a chlorine atom, a methoxy group, an ethoxy group and the like can be used. It is preferably an alkoxy group. By treating with the fluorine-containing silane compound, the adhesion of the external additive and / or the toner particles to the blade, which is a charging member, is greatly reduced, and no streak is generated due to poor conveyance, and the concentration reproducibility is excellent for a long time. And good image quality without fogging or the like on the image.

The treatment amount of the fluorine-containing silane compound is as follows:
1 to 40 parts by weight, preferably 3 to 35 parts by weight, more preferably 5 to 40 parts by weight, based on 100 parts by weight of the titanium compound before treatment.
30 parts by weight are particularly preferred. When the processing amount is less than 1 part by weight, if used for a long period of time, the image quality deteriorates in a streak shape due to contamination of the blade of the toner, and further, fogging in the background portion, which is considered to be caused by the low chargeability of the streaks, may occur. is there. On the other hand, when the processing amount is more than 40 parts by weight, the excess fluorine-containing silane compound may aggregate to cause a problem in the fluidity of the toner.

The titanium compound after treatment used as an additive is preferably treated with the fluorine-containing silane compound after the titanium compound before treatment is reacted with the alkylalkoxysilane compound in advance by a wet method. Here, the titanium compound obtained by reacting the alkylalkoxysilane compound with the pre-treatment titanium compound has a low cohesiveness, so that re-aggregation due to the treatment of the fluorine-containing silane compound does not occur. Uniform processing becomes possible. Thereby, the charge distribution of the toner is further sharpened, and over a long period of time,
Background fog on the photoreceptor can also be reduced. In the present invention, among the titanium compounds after treatment, those having an average primary particle diameter of 100 nm or less, preferably 10 to 70 n
m.

In recent years, the demand for higher image quality has been increasing, and the toner tends to have a small particle size. In order to improve transfer failure due to an increase in adhesion due to the small particle size, a large particle size is required. Of silica or titania is used as a second external additive (transfer aid). However, the titanium compound used in the present invention can be used even when such a large particle size transfer aid is added. For example, by using a large particle size titania in combination with the titanium compound after the treatment,
Prevents low electrification, environmental dependency and deterioration of admixability (broadening of electrification distribution due to repeated use over a long period of time) caused by the addition of an external additive, and is further caused by peeling of the treating agent. Good transferability can be obtained without deteriorating the charging ability due to long-term stress.

In the present invention, in addition to the alkylalkoxysilane compound and the fluorine-containing silane compound,
Other silane compounds can be used for the surface treatment of the titanium compound before the treatment, and examples thereof include chlorosilane, silazane, and a special silylating agent. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, hexamethyldisilazane, N, O-bis (trimethylsilyl) acetamide, N, N-bis (trimethylsilyl) urea, tert -Butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the like, but are not limited thereto.

The amount of the titanium compound to be added to the toner particles after the treatment varies depending on the particle size of the toner particles, the composition of the developer carrying member, and the like. 1 to 5.0 parts by weight is preferred, and 0.2
-2.0 parts by weight is more preferred. If the amount is less than 0.1 part by weight, the fluidity of the toner may be insufficient. On the other hand, if the amount exceeds 5.0 parts by weight, the fixing temperature may be increased in the fixing step. In addition to causing a decrease in fixing strength, when used in full color, the color development of the superimposed base color may be hindered due to a decrease in light transmittance.

-Toner Particles- The toner particles used in the present invention contain at least a binder resin and a colorant, and further contain other components as necessary. Examples of the binder resin contained in the toner particles include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene butadiene copolymer, and styrene-maleic anhydride. Known materials such as acid copolymers, polyethylene, polypropylene, polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, and paraffin wax can be used. Among them, styrene-acrylic copolymers and polyesters are preferable. used. Further, with the recent trend toward colorization, a binder resin having a low softening point is often used from the viewpoint of smoothness and transparency of a fixed image, but on the other hand, it is easily fused to a charging member by heat. ,
There is a problem that the chargeability and layer formation of the toner are easily hindered, and the present invention is particularly effective when a binder resin having a softening point of 90 to 120 ° C. and a low softening point is used. The softening point referred to here is a flow tester (manufactured by Shimadzu Corporation, nozzle 1 × 1
mm, load 10 kg) melt viscosity 10 ⁴
It means the temperature at Pa · s (10 ⁵ poise).

The colorants contained in the toner particles include carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, dupont oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, and malachite green oxalate. , Lamp Black, Rose Bengal, CI Pigmen
t Red 48: 1, CI Pigment Red 122, CI Pigment Red 57:
1, CI Pigment Yellow97, CI Pigment Yellow 12, CIP
igment Yellow 17, CIPigment Yellow 180, CIPigme
Known ones such as nt Blue 15: 1 and CI Pigment Blue 15: 3 can be used.

As the magnetic material used for the magnetic toner, any conventionally known magnetic materials can be used. For example, metals such as iron, cobalt, and nickel and alloys thereof, Fe ₃ O ₄ , γ-Fe ₂
Metal oxides such as O ₃ and cobalt-added iron oxide; ferrites such as MnZn ferrite and NiZn ferrite;
These magnetic materials are generally used by adding 30 to 70% by weight.

A releasing agent may be added to the toner used in the present invention for the purpose of improving gloss and offset properties. The release agent is preferably a paraffin having 8 or more carbon atoms, polyolefin, or the like, for example, paraffin wax, paraffin latex, microcrystalline wax, carnauba wax, or the like, or polypropylene, polyethylene, or the like. Can be used.

Further, a charge controlling agent can be added to the toner used in the present invention for the purpose of assisting the charging of the toner. When used as a negatively charged toner, azo complex salt dyes such as chromium and iron, complex compounds of chromium, zinc, aluminum, boron and the like of salicylic acid, and charge control resins can be used.

Further, in the present invention, fine particles of a fluidizing agent are added for the purpose of imparting appropriate fluidity and chargeability to the one-component developer, conductive powder for the purpose of improving charge exchangeability, and cleaning properties. Additives such as lubricants and abrasives may be added for the purpose of improving or preventing toner, external additives, talc from adhering to the photoreceptor, black spots, white spots, whitening, comets, filming and the like. The fluidizing agent fine particles, as an additive,
Hydrophobic silica, hydrophobicized fine particles titanium oxide, inorganic fine powder such as alumina, organic fine powder such as fatty acid or its derivative and metal salt, fluorine resin, resin fine powder such as acrylic resin or styrene resin, cerium oxide, Magnetite and the like can be mentioned, and these can be used alone or in combination.

The particle diameter of the toner used in the present invention is preferably 4 to 12 μm, more preferably 5 to 10 μm in terms of volume average particle diameter. When the volume average particle size is smaller than 4 μm, the fluidity is remarkably deteriorated, so that a layer cannot be formed well and fog and dart are easily caused. Further, the volume average particle size is 12 μm.
If it is larger than m, not only the resolution will be reduced and high image quality will not be obtained, but also the charge per unit weight of the developer will be reduced, so that the layer formation retention will be poor and fog and dirt will easily occur. The toner used in the present invention can be produced by any known method. For example, kneading, pulverization method, that is, after pre-mixing the binder resin and the colorant, the charge control agent, etc., melt kneading with a kneading machine, after cooling, pulverization,
A method of performing classification and adding and mixing external additive fine particles, a polymerized toner by suspension polymerization, emulsion polymerization, or the like is used.

[Image Forming Apparatus] The image forming apparatus of the present invention comprises: a latent image forming means for forming an electrostatic latent image on a latent image holding member;
Developing means for developing an electrostatic latent image on the latent image holding member using a developer formed in a thin layer by a layer regulating member in contact with a developer holding member; and developing on the latent image holding member. Transfer means for transferring the transferred image to a transfer member, and fixing means for thermally fixing the image transferred on the transfer member, wherein the layer regulating member and the developer used are the image of the present invention described above. It is a layer regulating member and a one-component developer used in the forming method. The latent image forming unit, the developing unit, the transferring unit, and the fixing unit in the image forming apparatus of the present invention may be any of conventionally known units, and are not particularly limited.

Hereinafter, the image forming apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the image forming apparatus of the present invention. In one example of the embodiment of the image forming apparatus of the present invention, the photosensitive drum 1 and the developing roll 3
They are arranged so as to have a constant gap. After being charged by the roll charger 2, the photosensitive drum 1 is exposed to laser light to form an electrostatic latent image on the photosensitive drum 1. A thin layer of toner is formed by a layer forming blade 5 which is in contact with the developing roll 3 at a constant linear pressure and is surface-coated with a material containing nitrogen atoms. An AC voltage and a DC voltage are superimposed on the developing roll 3 and the developer supply roll 4,
The electrostatic latent image is developed. The transfer of the toner image is performed by the roll transfer device 6, and the cleaning is performed by the blade type cleaner 7. The peripheral speed of the photosensitive drum 1 is usually about 60 to 80 mm / sec, and the peripheral speed of the developing roll 3 is usually about 90 to 120 mm / sec.

[0066]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the following description, “parts” are used unless otherwise specified.
All mean "parts by weight".

[Preparation of Layer Restriction Member] (Preparation of Layer Restriction Member 1) 120 g of isopropyl alcohol, 20 g of ethanol, and 3 g of ion-exchanged water were placed in a 500 ml flask equipped with a stirrer, a thermometer, and a reflux condenser, and uniformly stirred. Thereafter, 1 g of nitric acid was added, 20 g of ethyl silicate 28 (manufactured by Colcoat) was added, and the mixture was reacted at 30 ° C. for 5 hours with stirring to obtain a partially hydrolyzed alcoholic silica sol. 20 g of this alcoholic silica sol and 8 amino resin 20SE60 (manufactured by Sankyo Chemical)
g was mixed to obtain a layer regulating member coating liquid. This layer-regulating member coating liquid is spray-coated on the surface of a layer-regulating blade made of stainless steel having a thickness of 0.15 mm and a 1-mm-thick urethane rubber stuck to a leaf spring material, and then dried and cured at 100 ° C. for 3 hours. Then, it was left at 25 ° C. for 48 hours to obtain a layer regulating member 1 whose surface was coated with a resin containing a nitrogen atom. The thickness of the coat layer on the surface was about 1.0 μm.

(Preparation of Layer Control Member 2) Nylon Resin CM
15 g of 8000 (manufactured by Toray Industries, Inc.) was dissolved in a mixed solution of 50 g of methanol and 30 g of butanol to obtain a coating solution for a layer regulating member. After dip-coating this layer regulating member coating liquid on a 0.15 mm thick leaf spring material made of stainless steel,
After drying at 00 ° C. for 1 hour, a layer regulating member 2 whose surface was coated with a resin containing a nitrogen atom was obtained. The thickness of the coat layer on the surface was about 1.0 μm.

(Preparation of Layer Control Member 3) Acrylic resin (B
R80) was mixed with 75 g of the MEK solution, and allowed to stand on a wave rotor for 24 hours to obtain a layer-regulating member coating solution. This layer regulating member coating liquid was applied by dip coating on a stainless steel leaf spring material having a thickness of 0.15 mm.
After drying at 0 ° C. for 1 hour, a layer regulating member 3 was obtained. The thickness of the coat layer on the surface was about 1.0 μm.

(Layer regulating member 4) A stainless steel leaf spring material having a thickness of 0.15 mm, to which no coating liquid was applied, was used as the layer regulating member 4.

[Production of Additives for Toner Particles] Ilmenite ore was used as a titanium compound before treatment, and the ilmenite ore was dissolved in sulfuric acid to separate iron components.
₄ was hydrolyzed to form TiO (OH) ₂ using a wet sedimentation method. What is important in this method is hydrolysis, dispersion adjustment / aggregation adjustment, and water washing for generating nuclei. In particular, pH adjustment (acid neutralization) and slurry concentration adjustment in the dispersion treatment / aggregation adjustment are as follows. Since the primary particle diameter of the subsequent titanium compound is determined, a high level of control is required. (Preparation of titanium compound A) TiO (OH) ₂ produced by the above method
To 100 parts, 40 parts of isobutyltrimethoxysilane were mixed and heated and reacted at 60 ° C. Next, the same treatment is performed using 10 parts of a fluorine-containing silane compound (structural formula: CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ), followed by washing with water, filtration, and drying at 120 ° C. By disaggregation, the average primary particle size is 45 nm, the specific gravity is 3.2, and the degree of hydrophobicity is 50.0-5.
2.0% of titanium compound A was obtained.

(Preparation of Titanium Compound B) In the preparation of the titanium compound A, the addition amount of the isobutyltrimethoxysilane was changed to 50 parts and the addition amount of the fluorine-containing silane compound was changed to 25 parts. A titanium compound B having an average primary particle size of 40 nm, a specific gravity of 3.1 and a hydrophobicity of 50.0 to 52.0% was obtained in the same manner as in A.

(Preparation of Titanium Compound C) In the preparation of the titanium compound A, the addition amount of the isobutyltrimethoxysilane was changed to 70 parts and the addition amount of the fluorine-containing silane compound was changed to 5 parts. A titanium compound C having an average primary particle size of 35 nm, a specific gravity of 3.1 and a hydrophobicity of 57.5 to 60.0% was obtained in the same manner as in A.

(Preparation of Titanium Compound D) In the preparation of the titanium compound A, except that isobutyltrimethoxysilane was replaced with decyltrimethoxysilane, the average primary particle diameter was 30 nm and the specific gravity was 3 0.3, a titanium compound D having a degree of hydrophobicity of 52.5 to 55.0% was obtained.

(Preparation of Titanium Compound E) In the preparation of the titanium compound A, the fluorine-containing silane compound was replaced with another fluorine-containing silane compound (structural formula: C ₈ F ₁₇ CH ₂ CH ₂ Si (OC
Except for replacing H ₃ ) ₃ ), in the same manner as for titanium compound A, the average primary particle size was 40 nm, the specific gravity was 3.2, and the degree of hydrophobicity was 6
5.0-67.5% of titanium compound E was obtained.

(Preparation of Titanium Compound F) The TiO (OH) ₂ produced by the above method was washed with water, filtered, and calcined at 700 ° C.
A titanium oxide having an average primary particle size of 30 nm was obtained. Then, the mixture is pulverized by a jet mill, then dispersed in water, mixed with 100 parts of titania and mixed with 70 parts of isobutyltrimethoxysilane, wet-pulverized with a sand grinder, further stirred with a kneader, and then mixed with a fluorine-containing silane compound (structure Formula: CF ₃ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ) 5 parts were mixed and treated similarly. Thereafter, the resultant was heated and dried to obtain a titanium compound F having a specific gravity of 3.9 and a hydrophobicity of 50.0 to 52.0%.

(Preparation of Titanium Compound G) In the preparation of the titanium compound A, the addition amount of the isobutyltrimethoxysilane was changed to 20 parts and the addition amount of the fluorine-containing silane compound was changed to 60 parts. A titanium compound G having an average primary particle size of 40 nm, a specific gravity of 3.1 and a degree of hydrophobicity of 45.0 to 47.5% was obtained in the same manner as in A.

(Preparation of Titanium Compound H) In the preparation of the titanium compound A, the addition amount of isobutyltrimethoxysilane was changed to 40 parts and the titanium compound A was added except that no fluorine-containing silane compound was added. In a similar manner, a titanium compound G having an average primary particle size of 40 nm, a specific gravity of 3.1 and a hydrophobicity of 50.0 to 52.0% was obtained.

(Preparation of Titanium Compound I) The TiO (OH) ₂ produced by the above method was washed with water, filtered, and calcined at 700 ° C.
Titanium oxide having an average primary particle size of 40 nm was obtained. Thereafter, the mixture is dispersed in toluene, wet-pulverized by a sand grinder, and then mixed with 100 parts of titania and 30 parts of a fluorine-containing silane compound (structural formula: C ₈ F ₁₇ CH ₂ CH ₂ Si (OCH ₃ ) ₃ ).
This is stirred, dried by heating, and further crushed by a jet mill to have a specific gravity of 3.9 and a degree of hydrophobicity of 42.5 to 45.0.
% Of titanium compound I was obtained.

[Production of Toner Particles] Polyester resin: 92 parts (terephthalic acid / bisphenol A ethylene oxide adduct weight average molecular weight Mw: 12000, Tg: 65 ° C.) , Softening point: 100 ° C) Copper phthalocyanine blue pigment: 5 parts Charge control agent: 3 parts (Bontron E84, manufactured by Orient Chemical Industries) The above materials were premixed by a Henschel mixer, and then kneaded by a twin screw extruder at a set temperature of 140 ° C, a screw rotation speed of 300 rpm, and a supply speed of 150 kg / h. After cooling, the mixture was roughly pulverized, finely pulverized by a jet mill, and further classified by an air classifier to obtain toner particles X having a volume average particle diameter D50 of 7.3 μm.

Example 1 100 parts of the toner particles X and 1.0 part of the titanium compound A were mixed using a Henschel mixer, and sieved at 106 μm using a wind sieving machine to produce a one-component developer 1. did. The layer regulating member 1 is attached as the layer forming blade 5 of the image forming apparatus in FIG. 1, and the obtained one-component developer 1 is
8 ℃, 85% RH high temperature and high humidity environment and 10 ℃, 15%
In a low-temperature, low-humidity environment of RH, image formation (print test) of 10,000 sheets was performed, and the following evaluation was performed. Note that the peripheral speed of the photosensitive drum 1 is 60 mm / sec.
The peripheral speed of the developing roll 3 was 90 mm / sec. Alumite was used as a material for the developing roll 3. The evaluation results are shown in Tables 1 and 2.

<Charge Amount> The toner was conveyed onto the sleeve, and the charge amount was measured by the suction travo measurement method under each environment, and the charge amount after 10,000 sheets was similarly measured. <Concentration> The concentration of the solid was measured by a concentration measuring device manufactured by X-rite,
It was measured by X-rite 404A. ≧ 1.3, 1.3> △ ≧ 1.1, × <1.1.

<Fog> P / R: The tape was transferred onto the photoreceptor, and the density was measured with a density measuring device X-rite 404A manufactured by X-rite.
The value of the evaluation was (measured value)-(value of tape only). ○ ≦ 0.02, 0.02 <△ ≦ 0.06, ×> 0.0
6 was evaluated. On paper: The sensitivity was evaluated by observing the background with a 50x loupe.な し Not at all, △ slightly, × fairly evaluated.

<Streaks> The number of streaks generated in an image obtained by developing the entire surface of the toner on A4 paper was measured. ５ 5 or less, # 6 to 10 and × 11 or more.

[Comprehensive charge evaluation] <Environmental difference> Comprehensive evaluation was performed with {initial charge amount (high temperature / high humidity / low temperature / low humidity) + charge amount after running 20,000 sheets (high temperature / high humidity / low temperature / low humidity)} × 1/2. . ≧ 0.7, 0.7> △ ≧ 0.5, × <0.5.

<Maintainability> A comprehensive evaluation was made of {high-temperature and high-humidity charge (after 30,000 sheets, initial) + low-temperature, low-humidity charge (after 10,000 sheets {initial)} × 1/2. ≧≧ 0.8, 0.8> △ ≧ 0.5, × <0.5.

<Charge Distribution> The charge distribution of the toner on the sleeve after copying 30,000 sheets was measured by a charge distribution measuring device, and the value was obtained by dividing the central value of the distribution by the width of the distribution. ≧ 0.6, 0.6> △ ≧ 0.4, × <0.4.

[Comprehensive image quality evaluation] <Density unevenness / transfer failure> The solid density was measured at three points (A4 size) using a density measuring device X-rite 404A manufactured by X-rite.
(Upper part to lower part) was measured and judged. ○ There is no problem at all, △ There is a slight problem, × There is a considerable problem,
XX: Very problematic.

<Density Maintainability> The image densities at the initial stage and at the time of 10,000 sheets are measured with a density measuring device X-rite 404 manufactured by X-rite.
A was measured and judged. ○ There is no problem at all, △ There is a slight problem, × There is a considerable problem,
XX: Very problematic.

<Image Quality Defects> Image quality defects caused by damage to the photoreceptor were visually determined. ○ There is no problem at all, △ There is a slight problem, × There is a considerable problem,
XX: Very problematic.

<In-machine contamination> The state of toner scattering due to toner scattering and sleeve streaks was visually determined. ○ There is no problem at all, △ There is a slight problem, × There is a considerable problem,
XX: Very problematic.

Example 2 A one-component developer 2 was prepared in the same manner as in Example 1 except that the titanium compound B was used instead of the titanium compound A, and the same procedure as in Example 1 was carried out except that the developer 2 was used. An image was formed and the same evaluation was performed. Table 1 shows the results
And Table 2.

Example 3 A one-component developer 3 was prepared in the same manner as in Example 1 except that the titanium compound C was used instead of the titanium compound A, and the same procedure as in Example 1 was carried out except that the developer 3 was used. An image was formed and the same evaluation was performed. Table 1 shows the results
And Table 2.

(Example 4) In Example 1, a one-component developer 4 was produced using titanium compound D instead of titanium compound A, and a layer regulating member 2 was used instead of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

(Example 5) In Example 1, a one-component developer 5 was produced by using a titanium compound E in place of the titanium compound A, and a layer regulating member 2 was used in place of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

(Example 6) In Example 1, a one-component developer 6 was produced by using the titanium compound F instead of the titanium compound A, and the layer regulating member 2 was used instead of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

Comparative Example 1 An image was formed in the same manner as in Example 1 except that the layer restricting member 3 was used instead of the layer restricting member 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

Comparative Example 2 An image was formed in the same manner as in Example 1 except that the layer restricting member 4 was used instead of the layer restricting member 1, and the same evaluation was performed. The results are shown in Tables 1 and 2.

(Comparative Example 3) A one-component developer 7 was prepared in the same manner as in Example 1 except that the titanium compound G was used instead of the titanium compound A, and the same procedure as in Example 1 was carried out except that the developer 7 was used. An image was formed and the same evaluation was performed. Table 1 shows the results
And Table 2.

Comparative Example 4 A one-component developer 8 was prepared in the same manner as in Example 1 except that the titanium compound H was used instead of the titanium compound A, and the same procedure as in Example 1 was carried out except that the developer 8 was used. An image was formed and the same evaluation was performed. Table 1 shows the results
And Table 2.

Comparative Example 5 A one-component developer 9 was prepared in the same manner as in Example 1 except that the titanium compound I was used instead of the titanium compound A, and the same procedure as in Example 1 was carried out except that the developer 9 was used. An image was formed and the same evaluation was performed. Table 1 shows the results
And Table 2.

(Comparative Example 6) In Example 1, a one-component developer 7 was produced using the titanium compound G instead of the titanium compound A, and the layer regulating member 3 was used instead of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

Comparative Example 7 A one-component developer 8 was prepared in the same manner as in Example 1 except that the titanium compound H was used instead of the titanium compound A, and the layer regulating member 3 was used instead of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

Comparative Example 8 In Example 1, a one-component developer 9 was produced using the titanium compound I instead of the titanium compound A, and the layer regulating member 3 was used instead of the layer regulating member 1. Other than that, an image was formed in the same manner as in Example 1,
Similar evaluations were made. The results are shown in Tables 1 and 2.

(Comparative Example 9) In Example 1, a one-component developer 10 was produced using amorphous titanium having a particle diameter of 30 nm in place of the titanium compound A, and a layer regulating member was substituted for the layer regulating member 1. Except for using No. 4, image formation was performed in the same manner as in Example 1, and the same evaluation was performed. Table 1 shows the results
And Table 2.

Comparative Example 10 A one-component developer 11 was prepared in the same manner as in Example 1 except that fine particles of silica having a particle diameter of 12 nm treated with silicone oil were used instead of the titanium compound A. The image formation was performed in the same manner as in Example 1 except that the layer regulating member 4 was used instead of, and the same evaluation was performed. The results are shown in Tables 1 and 2.

(Comparative Example 11) In Example 1, a one-component developer 12 was produced using silica fine particles having a particle diameter of 16 nm treated with hexamethyldisilazane in place of the titanium compound A, and the layer was regulated. Except that the layer regulating member 4 was used instead of the member 1, image formation was performed in the same manner as in Example 1.
Similar evaluations were made. The results are shown in Tables 1 and 2.

[0108]

[Table 1]

[0109]

[Table 2]

From the results shown in Tables 1 and 2, Examples 1 to 4 using the layer regulating member surface-coated with the material containing a nitrogen atom specified in the present invention and the one-component developer specified in the present invention are shown. 6 is excellent in all of the evaluation items. On the other hand, it can be seen that Comparative Examples 1 to 5 in which any one of the above is not specified in the present invention are inferior in image quality and the like as compared with the examples. Furthermore, it can be seen that Comparative Examples 6 to 11, both of which are not specified in the present invention, are considerably inferior in image quality and the like as compared with Examples.

[0111]

According to the present invention, it is possible to provide an image forming method which is hardly influenced by the environment such as temperature and humidity, stabilizes the charging and conveyance of the toner for a long time, and can obtain a stable image density. . Further, according to the present invention, it is possible to provide an image forming method in which low developability, no fogging, etc. appear for a long time, good cleaning property, and filming and fusion hardly occur. Further, according to the present invention, it is possible to provide an image forming apparatus capable of stably obtaining excellent image quality over a long period of time.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view illustrating an example of an image forming apparatus of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 photoreceptor drum 2 roll charger 3 developing roll 4 developer supply roll 5 layer forming blade 6 roll transfer unit 7 blade cleaner

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) G03G 15/08 507 G03G 15/08 507L (72) Inventor Yasuhiro Oya 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. (72) Inventor Hirora Okuno 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Yosuke Tsurumi 1600 Takematsu, Minami Ashigara City, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. 1600 Takematsu, Minamiashigara-shi Fuji Xerox Co., Ltd. F-term (reference) 2H005 AA08 CA26 CB07 CB10 DA10 EA07 FA05 2H077 AD02 AD06 AD13 AD16 AD23 AE03 EA11 FA13 GA11

Claims (2)

[Claims] 1. A latent image forming step of forming an electrostatic latent image on a latent image holding member, and the latent image is formed by using a developer thinly formed by a layer regulating member in contact with a developer carrying member. A developing step of developing an electrostatic latent image on the holding member, wherein the layer regulating member is surface-coated with a material containing a nitrogen atom, and the developer contains a binder resin and a colorant. Toner particles, comprising an additive containing a titanium compound, and the titanium compound is surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound,
With respect to 100 parts by weight of the titanium compound, the treatment amount of the alkylalkoxysilane compound in the surface treatment is a
(Parts by weight), wherein the processing amount b (parts by weight) of the fluorine-containing silane compound is a one-component developer represented by the following formula: 0.01a ≦ b ≦ 0.5a 2. A latent image forming means for forming an electrostatic latent image on a latent image holding member, and the latent image using a developer thinly formed by a layer regulating member in contact with a developer carrying member. Developing means for developing the electrostatic latent image on the holding member, transfer means for transferring the image developed on the latent image holding member to a transfer member, and fixing for thermally fixing the image transferred on the transfer member Means, wherein the layer regulating member is surface-coated with a material containing a nitrogen atom, and the developer is a toner particle containing a binder resin and a colorant; and a titanium compound. And the titanium compound is surface-treated with an alkylalkoxysilane compound and a fluorine-containing silane compound,
With respect to 100 parts by weight of the titanium compound, the treatment amount of the alkylalkoxysilane compound in the surface treatment is a
(Parts by weight) wherein the processing amount b (parts by weight) of the fluorine-containing silane compound is a one-component developer represented by the following formula. 0.01a ≦ b ≦ 0.5a