JPH10115947A - Nonmagnetic one-component developer and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonmagnetic one-component developer and an image forming method using the developer, capable of stabilizing the electrostatic charge and transfer of a toner over a long period of time, and giving stable image density. SOLUTION: This nonmagnetic one-component developer consists of toner particles contg. a bonding resin, an electrostatic charge controlling agent and a colorant and an additive. The electrostatic charge controlling agent contains a salicylic acid-metal complex compd. and the additive is a titanium compd. obtd. by allowing TiO(OH)2 to react with a silane compd. or silicone oil. The TiO(OH)2 is preferably produced by a wet method. The bonding resin is preferably polyester resin especially having 90-120 deg.C softening point and 60-70 deg.C glass transition temp.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-magnetic one-component developer and a non-magnetic one-component image forming apparatus. More specifically, an image forming method using a non-magnetic one-component image forming apparatus including a step of forming a thin layer of a developer on a developer carrying member, transporting the thin layer to a developing unit, and developing an electrostatic latent image on the latent image holding member And a developer used in the apparatus.

[0002]

2. Description of the Related Art In recent years, not only an electrostatic copying machine but also a multifunction machine having a copying machine, a printer, a facsimile and the like has been used in the electrophotographic dry developing system in addition to an electrostatic copying machine. In particular, as a recent trend, there is a demand for stronger ecological measures such as downsizing, measurement, resource saving and recycling. To cope with this, improvements and new developments of an image forming method and a developer used therein have been made. At present, as a dry developing method in various electrostatic copying methods that are in practical use, a two-component developing method using a carrier such as toner and iron powder and a developing method using a one-component developer without using a carrier are known. I have.

[0003] The two-component development system is the most widely used system, but has the disadvantage that the toner particles adhere to the carrier surface to deteriorate the developer and the image quality cannot be maintained for a long period of time. Therefore, a toner concentration control system for maintaining a constant toner concentration ratio in the developer and a mixing device for mixing the developer and the toner newly added in the developer are required.
There is a disadvantage that the developing device is enlarged. Therefore, as a developing method, there is an increasing demand for a one-component developing method, which is characterized in that the developing device is small and light in weight and the toner density control system has no trouble, and the developing method is now becoming the mainstream.

[0004] The one-component toner development system is classified into a magnetic one-component development system using a magnetic toner and a non-magnetic one-component development system using a non-magnetic toner. The magnetic one-component developing method holds and develops a magnetic toner using a developer carrier having a magnetic field generating means such as a magnet therein, and the toner transport control is easy, such as a copying machine and a printer. In recent years, many of these have been put to practical use because of their low internal contamination. However, the magnetic toner used in the magnetic one-component developing method has black, such as magnetite, inside thereof.
In addition, since it contains a colored magnetic material of tea, there is a serious drawback that full color can not be achieved, which has been increasingly required in the market in recent years. Further, the magnetic one-component developing device must include a magnet inside the developing roll, and therefore, there is a limit to downsizing of the developing roll, and there is also a limit to downsizing of the developing device due to this. is there.

On the other hand, the non-magnetic one-component developing system does not use a magnetic material for the toner, so that a color image can be formed.
Since no magnet is used for the developer carrier, the weight is reduced,
It can be reduced in size and cost, and has recently begun to be put into practical use as a small full-color printer.

However, in the two-component developing system, there is a stable charging and conveying member called a carrier, and in the magnetic one-component developing system, there is a stable conveying and layer forming means of the magnetic force of a magnet roll. Since there is no such a stable charging and conveying means, it is necessary to stably supply and hold the toner on the developer carrier only by electrostatic force, and to charge and develop the toner. At present, it is significantly inferior to the two-component developing system and the magnetic one-component developing system in terms of maintenance. In particular, in a full-color copying machine / printer using four-color development of yellow, magenta, cyan, and black, more precise control of the development amount is required.
Corresponding to the increase in speed, toners are required to have increasingly strict characteristics (rapid and uniform charging, better fluidity, etc.).

Conventionally, a charge control agent has been added to the inside of the toner in order to stabilize the charge and conveyance of the toner. Typical negative charge control agents include metal-containing azo dyes and metal-containing salicylic acid compounds, and positive charge control agents include quaternary ammonium salts. The addition of these charge control agents is certainly effective and indispensable in terms of maintaining quick and uniform toner charging over a long period of time. However, depending on the combination with other additives (particularly, fine particle external additives for imparting fluidity), these charge control agents may not be able to exhibit their performance sufficiently.

That is, conventionally, in order to stabilize the charge and conveyance of the toner, an inorganic oxide fine powder such as silica has been added to the toner for the purpose of improving the fluidity and the chargeability. However, in the case of a silica fine powder generally used, the effect of improving the fluidity of the toner is particularly excellent, but the negative polarity is strong, and the charge of the negatively chargeable toner is excessively increased particularly at low temperature and low humidity. Even if positive charging such as nitrogen compound treatment is performed, it is not suitable for positively charged toner.Furthermore, under high temperature and high humidity, water is taken in and the chargeability is reduced, causing a large difference in chargeability between the two. And the effect of adding the charge control agent to the base toner cannot be sufficiently exhibited. That is, it is impossible to optimize the toner transportability and chargeability on the developer carrying member under both high temperature, high humidity, and low temperature and low humidity conditions, resulting in poor image density reproduction, background fog, and toner drop. In addition, there is a problem that contamination in the machine is caused. It has been proposed to use a surface-treated inorganic fine powder for the purpose of improving these.

For example, JP-A-46-5782, JP-A-48-47345, and JP-A-48-47346.
JP, JP-A-59-34539 and JP-A-59-34539.
JP-A-198470 and JP-A-59-231550 describe that the surface of silica fine particles is subjected to a hydrophobic treatment. However, mere use of these inorganic fine powders does not provide a sufficient effect on the charging property, and the effect is particularly small in the case of using a polyester resin as the binder resin. (In cases where sufficient chargeability can be imparted at high temperature and high humidity, excessive charge is imparted at low temperature and low humidity, the transport amount on the developer carrier becomes excessive, and the broadening of the charge becomes severe, In particular, the degree of developability decreases and the degree of fogging becomes severe.)

As a method of alleviating the negative chargeability of toner particles, a method of externally adding silica fine particles surface-treated with the above-mentioned amino-modified silicone oil (Japanese Patent Application Laid-Open No.
No. 4-73354) and a method of externally adding silica fine particles surface-treated with aminosilane and / or amino-modified silicone oil (Japanese Patent Laid-Open No. 1-237561).
It has been known. However, although treatment with these amino compounds can suppress an excessive increase in charge of the negatively chargeable toner, particularly at low temperature and low humidity, it cannot sufficiently improve the environmental dependency of the silica fine powder itself. In other words, even under high temperature and high humidity, similar charge neutralization occurs, so that environmental dependency is not improved as usual,
Background fog and image density decrease due to poor charging are caused.

Further, the non-magnetic one-component toner is a carrier for two-component development, and the magnetic force of a magnet roll in a magnetic one-component developer is used to stably transport the toner. It needs to be stably supplied and held on the body, and charged and developed. For this reason, it is necessary to perform contact frictional charging in a short time and space between the developer carrier (sleeve) and the charging blade. Become. However, the toner to which silica fine particles are externally added generally has a slow charge rise regardless of whether the toner is a two-component toner or a magnetic one-component toner. , Reverse polarity fog, and toner cloud (dirt in the machine).

Further, the silica fine powder has high resistance, high chargeability,
This is mainly due to the slow charge speed, etc., and the distribution of charge on the developer carrier is widened.Also, even if the charge amount falls within an appropriate range, there are also many disadvantages such as the presence of a large number of toners of opposite polarity. Causes fogging and toner cloud (dirt in the machine).

As described above, even if the silica fine particles are subjected to a hydrophobic treatment, a treatment for alleviating the negative charging property, etc., it is necessary to improve the environmental dependence of the charging, the charging speed, and the poor charging distribution of the silica. It has not been reached yet. In addition, when the inorganic oxide added for the purpose of charging and fluidity is a commonly used titania, the charge rises quickly with respect to silica, and the charge distribution becomes sharp because of the low resistance of the titania. It has the characteristic of. However, in the case where titania is added, the charge of the toner is reduced, so that even if a charge control agent is added to the base toner, a sufficiently high charge cannot be imparted, resulting in a decrease in the transport amount and a decrease in the charge. , The density reproducibility is reduced, and background fog is apt to occur.

For the purpose of improving the chargeability, a two-component system
Regardless of the one-component system, a method of externally adding hydrophobic titanium oxide to a toner has been proposed. (Japanese Patent Laid-Open No. 58-216252)
JP, JP-A-60-123862, JP-A-60-123682
The hydrophobic titanium oxide is obtained by treating the surface with a silane compound, a silane coupling agent, silicone oil, or the like. With this method,
Certainly, the chargeability can be improved with respect to untreated hydrophilic titania, and it is used for two-component toners and magnetic one-component toners. In, the charge level can be improved to some extent by the type and amount of the treating agent, but the charge level is not yet at a satisfactory level, and there is a limit in environmental dependency. In addition, by increasing the hydrophobicity of the titanium oxide with the treatment agent, the charge level and environmental dependency are certainly better than the conventional hydrophilic titanium oxide. In fact, the speed and sharpness of the charge distribution are greatly inferior to conventional titanium oxide.

Titanium oxide is obtained mainly by extracting titanium oxide crystals from ilmenite ore by a sulfuric acid method or a hydrochloric acid method. Since titanium oxide is purified by a wet method and obtained by heating and firing, titanium oxide is obtained. Naturally, chemical bonds resulting from dehydration condensation also exist, and it is not easy to re-disperse such aggregated particles using existing techniques. That is, the titanium oxide taken out as fine powder is secondary,
Secondary aggregation was formed, and the effect of improving the fluidity of the toner was significantly inferior to that of silica. In recent years, in particular, the demand for high image quality such as color has been increasing in the market, and attempts have been made to achieve high image quality by reducing the particle size of the toner. This phenomenon is remarkable, and this phenomenon is remarkable. Further, titanium oxide which has been conventionally used has a drawback that it does not firmly adhere to the toner surface and is easily peeled off from the toner surface, probably because of its large specific gravity with respect to silica. For this reason, long-term charging stability accompanied by sleeve contamination is inferior, and contamination of the photoreceptor is easily caused, which causes image quality deterioration and image quality defects.

Attempts have been made to add hydrophobic titanium oxide and hydrophobic silica in combination in order to achieve both improvement in fluidity and environmental dependency of charging. According to this method, although the respective disadvantages of the hydrophobic silica and the hydrophobic titanium oxide are temporarily suppressed, either of the additives is easily affected by the dispersion state. In particular, considering the maintainability, it is difficult to stably control 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 the respective disadvantages over a long period of time.

Next, a method of adding hydrophobic amorphous titanium oxide to a toner has been proposed. (JP-A-5-20
No. 4183, JP-A-5-72797) Amorphous titanium oxide can be obtained by hydrolyzing a metal alkoxide or a metal halide by using a CVD method. (Chemical Engineering Transactions (Vol. 18, No. 3
However, although the titanium oxide obtained by the hydrolysis method can improve both the charging characteristics and the toner fluidity, it has a large amount of adsorbed water inside the particles, so that the It remains on the photoreceptor by itself. That is, the adhesive force between the amorphous titanium oxide and the photoreceptor is strong, and only the adherence remains on the photoreceptor without being transferred, causing defects such as white spots on an image or scratching on the photoreceptor with hard titanium oxide during cleaning. Have.

On the other hand, in a method of purifying titanium oxide by a wet method, a silane compound is hydrolyzed in an aqueous medium, the surface of the titanium oxide is treated, and the titanium oxide is taken out in a state where aggregation is suppressed. Has been proposed. (JP-A-5-188633)

When the silane compound treatment is carried out by this method, the number of aggregated particles is reduced as compared with the conventional method of hydrophobizing titanium oxide. That is, although the fluidity of the toner is improved, the charge level of the negatively charged toner is improved. The environment dependency is no different from the conventional one, and the desired high negative charging property and the environment dependency are not sufficient, and further, the charging speed (admix property of the additional toner) and the charge distribution are adversely affected.

Further, when these inorganic oxides are added to the surface of the toner, stress is applied to the toner by the layer forming member or the like due to long-term continuous use, and toner filming / fusion to the layer forming member occurs, Since the toner charging property changes due to peeling or embedding of the agent, it becomes difficult to maintain stable toner charging and conveyance for a long period of time.
In order to solve these problems, Japanese Patent Application Laid-Open No. 6-95429 is disclosed.
JP, JP-A-6-102699, JP-A-6-266
In 156 and the like, it is proposed to use a specific binder resin to prevent embedding of an external additive. Also, JP-A-6-51561, JP-A-6-208242, JP-A-6-208242
In -250442 and the like, it is proposed to use a specific charge control agent and an external additive. However, none of these effects is sufficient. Particularly in a full-color developing system in which four colors are superimposed, it is necessary to more precisely control the amount of toner development. Challenges still remain in the transition.

[0021]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and aims to solve the problems. That is, a first object of the present invention is to provide a non-magnetic one-component developer capable of stabilizing toner charging and conveyance for a long period of time and obtaining a stable image density. A second object of the present invention is to provide a non-magnetic one-component developer which does not easily cause problems such as low developability and fog over a long period of time. Further, a third object of the present invention is to provide a non-magnetic one-component developer in which problems of filming and fusion do not easily occur for a long period of time. Further, a fourth object of the present invention is to provide an image forming method using the above-described non-magnetic one-component developer.

[0022]

Means for Solving the Problems The inventors of the present invention have conducted sincere studies to solve the above-mentioned problems, and as a result, have found that toners containing binder resin, a charge controlling agent and a colorant, and an additive are used. In the magnetic one-component developer, the charge control agent contains a metal salicylate complex, and the additive is TiO (OH)
_{By using a} titanium compound obtained by the reaction of ₂ with a silane compound or a titanium compound obtained by a reaction of TiO (OH) ₂ with a silicone oil, a stable image free from problems such as density change, fogging and filming can be obtained. The present invention was found to be obtained over a long period of time, and the present invention was completed.

Further, the image forming method of the present invention comprises the step of forming a latent image on a latent image carrier, and the step of developing the latent image using development on a developer carrier. A non-magnetic one-component developer is used as the developer.

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The non-magnetic one-component developer of the present invention is used in an image forming method including a step of forming a latent image on a latent image carrier and a step of developing the latent image using development on the developer carrier. Particularly suitable for an image forming apparatus having a latent image forming step, a developing step, a transferring step of transferring a toner image on a latent image holding member to a transferring member, and a fixing step of thermally fixing the toner image on the transferring member. Used, especially yellow, magenta, cyan,
It is used in a full-color developing device using four-color black toner.

In the latent image forming step, a conventionally known method can be applied, and an electrostatic latent image is formed on a latent image holding member such as a photosensitive layer or a dielectric layer by an electrophotographic method or an electrostatic recording method. 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.
The cylindrical holder can be obtained by a known manufacturing method such as extruding aluminum or an aluminum alloy and then working the surface.

In the developing step, the toner carrier (developing roll)
On the rotating cylinder, a thin layer of toner is formed with an elastic blade or the like and transported to development, and the developing unit and the latent image holding body holding the electrostatic latent image are brought into contact with the developing unit or a certain gap is formed. The electrostatic latent image is developed with toner while applying a bias between the developing roll and the latent image holding member. Examples of the toner carrier used in the present invention include: an elastic sleeve such as silicon rubber; a sleeve from which a metal such as aluminum, SUS, and nickel or a ceramic is drawn; and an oxidized or metalized substrate surface for controlling toner transportability and chargeability. The surface treatment such as plating, polishing, and blasting, and coating with resin are used. Particularly, when a sleeve from which a metal or ceramic such as aluminum, SUS, nickel or the like is drawn is used, the effect of the present invention is remarkable. Becomes The formation of the toner layer on the developing roll is performed by bringing an elastic blade into contact with the sleeve surface. As the material of the elastic blade, a rubber elastic material such as silicone rubber or urethane rubber is preferably used, and an organic or inorganic material may be added or dispersed in the elastic material in order to control the toner charge amount.

As a method of developing the four-color toner, a developing device for the four-color toner is arranged around the photoconductor, and the charging / exposure of the photoconductor and the development of the electrostatic latent image are repeated for each color toner for four cycles. , And charging of four-color toner in one cycle /
A method of performing exposure / development includes a method in which a developing machine for four-color toner is arranged on each of four photoconductors, and charging, exposure, and development of the four-color toner are performed in each of the photoconductors and the developing machine.
As a method of superimposing the four color toners, a method of transferring the toner image formed on the photoreceptor one by one onto a transfer drum around which a transfer paper is wound and superimposing the toner image, and a method of transferring the toner image formed on the photoreceptor to the transfer material After transferring the color toner image on the transfer body and superimposing the color toner image on the transfer body,
After the color toner images are superimposed on the photoreceptor, they are collectively transferred onto transfer paper.

As the transfer means, a known type such as a contact type in which a transfer roller, a transfer belt / drum or the like is brought into pressure contact with the latent image holding member, and a non-contact type using a corotron can be used. From the viewpoint of preventing ozone generation and the like, a contact type is preferred.

In the cleaning step, toner remaining on the latent image holding member without being transferred in the transfer step is removed by a cleaner. As the cleaning means in the present invention,
Known ones such as blade cleaning or roller cleaning can be used. Blade cleaning is
Elastic rubber such as silicone rubber or urethane rubber is used.

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 generally used.

The developer used in the present invention comprises toner particles containing at least a binder resin, a colorant and a charge control agent, and an additive. The charge control agent comprises a salicylic acid metal complex compound, and the additive is at least a titanium compound or a T compound obtained by reacting TiO (OH) ₂ with a silane compound.
It consists of a product obtained by reacting iO (OH) ₂ with silicone oil.

The TiO (OH) ₂ is produced by a wet method, and is preferably a titanium compound having a specific gravity of 2.8 to 3.6. When the specific gravity of the titanium compound is smaller than 2.8, the separation of the titanium compound from the toner surface is reduced, but the reaction between the processing agents is increased, so that the processing agent is easily peeled off from the titanium compound, and filming on the photosensitive material is performed. And toner contamination failure due to sleeve contamination. If the specific gravity of the titanium compound is greater than 3.6, the processing agents do not easily react with each other and the processing agent does not peel off. However, the titanium compound itself is easily peeled off from the toner and the photosensitive material is liable to adhere.

In general, the production method of titanium oxide by a usual wet method is produced through a chemical reaction in a solvent, and can be divided into a sulfuric acid method and a hydrochloric acid method. When the sulfuric acid method is simplified, the following reaction proceeds in a liquid phase, and insoluble TiO (OH) ₂ is produced by hydrolysis. 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

The wet hydrochloric acid method is similar to the dry method.
To produce titanium tetrachloride by chlorination. Then dissolved in water
And hydrolyzed while adding a strong base to form TiO (O
H) _TwoIs produced. Briefly, it is as follows. TiCl_Four+ H_TwoO → TiOCl_Two+ 2HCl TiOCl_Two+ 2H_TwoO → TiO (OH)_Two+2 HCl

In the usual titanium oxide production process, washing with water and filtration are repeated thereafter, followed by firing to obtain titanium oxide. Further, if necessary, a treatment such as a silane compound is performed after pulverization and pulverization. However, the conventional production of titanium oxide has a serious disadvantage that particles are sintered in the sintering process due to the strength of bonding between Tis, and many agglomerations are generated. Many solutions have been devised to solve this serious drawback, such as enhanced wet pulverization and treatment agent treatment before drying, but it has not been possible at present to disintegrate this agglomeration into primary particles. Even if this titanium oxide is applied to an additive of a toner, even if the coverage on the toner is combined with silica particles, fluidity comparable to that of silica cannot be obtained, and furthermore, it is thought that the aggregation causes the photosensitive material scratches, Filming will occur. Further, the amount of the treated titanium oxide of the conventional production method that can be treated in the treatment of the silane compound is limited. Generally, increasing the amount of the silane compound increases the charge-imparting ability, but the ability is saturated at a treatment amount of about 15 to 20% of the amount of titanium oxide. Therefore, even if the amount of the coupling agent is increased in order to impart high charge, not only high charge is not obtained, but also a further increase in agglomerated particles due to the reaction between the excess coupling agent and the case where the toner is added to the toner. This leads to a decrease in charging speed, a broadening of charging distribution, and the like.
As described above, the conventional titanium oxide is not at a level that satisfies all of the requirements for the large number of aggregated particles, high charging ability, low charging speed, and charging distribution.

However, the titanium compound in the present invention is
It is produced by reacting a silane compound or silicone oil with TiO (OH) ₂ produced in the above-mentioned wet process and drying it. Therefore, the particles do not pass through the baking process of several hundred degrees, so that strong bonds between Tis are not formed, there is no aggregation, and the particles can be taken out in a substantially primary particle state. Further, the titanium compound in the present invention is TiO (O
Since the silane compound or silicone oil is directly reacted with H) ₂ , the amount that can be treated can be increased.
That is, the conventional treated titanium oxide has a low limit value of the treatment amount contributing to the charging ability, but the titanium compound used in the present invention has a high limit value and depends on the particle size of the raw material, Approximately three times the amount of conventional products (about 50 to
70%). Therefore, the charge of the toner can be controlled by the treatment amount of the silane compound, and the charge ability that can be provided can be greatly improved as compared with the conventional titanium oxide. Furthermore, since the excess silane compound is reduced, that is, the reaction between the silane compounds is small, even when the treatment amount is increased, high charge can be obtained without sacrificing the charge speed and charge distribution. Further, the titanium compound of the present invention hardly transfers to the sleeve, and there is no transfer of the processing agent, that is, there is little contamination of the sleeve. Therefore, the toner charge on the developer carrier does not change for a long time. Further, there is no adhesion on the photosensitive material, and there is no image quality defect for a long time. This is because the specific gravity is 2.8 to 3.6, which is lighter than other titanium oxides, so that the adhesion on the toner surface is strong, and there is no detachment from the toner even for long-term use. This is because there is little transfer of the treating agent due to a small reaction between the silane compounds to be treated (which is firmly attached to the drug substance).

In the present invention, the titanium compound used has a resistance of 10 ⁸ Ω · cm to 10 ¹² Ω · cm as a toner charge distribution control for improving fog and developability. Resistance is 1
If it is less than 0 ⁸ Ω · cm, the chargeability of the toner is reduced, fogging and toner scattering are likely to occur. If it exceeds 10 ¹² Ω · cm, the charge distribution of the toner becomes broad and fog or high Adhesion of the charged toner to the developer carrying member tends to cause two-layer formation of the toner.

The titanium compound used in the present invention has an average primary particle diameter of 100 nm or less, preferably 1 nm or less.
Those having a range of 0 nm to 70 nm are used. If the average primary particle size is larger than 100 nm, sufficient fluidity cannot be imparted to the toner, and the titanium compound is easily released from the toner, and filming and comet on the photoreceptor easily occur. On the other hand, if it is smaller than 10 nm, the particle agglomeration is so severe that the dispersibility on the toner surface is deteriorated, and sufficient chargeability and fluidity cannot be obtained.

As the silane compound used in the present invention, any of chlorosilane, alkoxysilane, silazane, and a special silylating agent can be used. Specifically, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, tetramethoxysilane, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, tetraethoxysilane, methyl Triethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, diphenyldiethoxysilane, isobutyltrimethoxysilane, decyltrimethoxysilane, hexamethyldisilazane, N, O- (bistrimethylsilyl) acetamide, N, N-bis ( Trimethylsilyl)
Urea, tert-butyldimethylchlorosilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, β- (3.4 epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxy Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, and the treating agent in the present invention includes the above-mentioned treating agents. It is not limited to compounds.

The amount of the above treatment depends on the primary particle size of the TiO (OH) ₂ raw material.
The amount of the silane compound is in the range of 5 to 80 parts by weight, more preferably 10 to 50 parts by weight, based on 100 parts by weight of the raw material of H) ₂ . If the treatment amount is less than 5 parts by weight, the function of the silane compound to be treated is not exhibited, and the treatment amount is
When the amount exceeds the weight part, the excess silane compound turns into oil and causes a problem in toner fluidity.
However, the treatment with the silane compound is aimed at imparting a high charge to the toner, improving the environment dependency, improving the fluidity of the toner, and reducing the interaction of the photosensitive material. , TiO (OH)
_It must be adjusted appropriately in consideration of the particle size of the bulk material of ₂ .

In the present invention, the titanium compound is T
iO (OH) ₂ , especially TiO (O)
H) It can also be obtained by reacting ₂ with silicone oil or silicone varnish. As the silicone oil used in the present invention, those represented by the general formula (1) are preferable.

[0042]

Embedded image (Wherein, R represents an alkyl group having 1 to 3 carbon atoms, R ′ represents an alkyl group, a halogen-modified alkyl group, a phenyl group, a modified phenyl group, and R ″ represents an alkyl group having 1 to 3 carbon atoms or an alkoxy group. Represents a group, and m and n represent integers.)

Examples of these silicone oils include dimethyl silicone oil, alkyl-modified silicone oil, α-methyl sulfone-modified silicone oil,
Chlorophenyl silicone oil, fluorine-modified silicone oil, amino-modified silicone oil and the like can be mentioned.

The amount of the additive (titanium compound) to be added to the toner varies depending on the particle size of the toner, the composition of the developer carrying member, and the like.
0 parts by weight, more preferably 0.2 to 2.0 parts by weight. When the amount is less than 0.1 part by weight, the fluidity of the toner cannot be obtained.
In the fixing step, the fixing temperature is increased and the fixing strength is lowered, and the light transmittance of a full-color image is lowered to hinder the color development.

In the present invention, in addition to the titanium compound, other fluidizing agent fine particles may be externally added in combination with the titanium compound for the purpose of assisting appropriate fluidity and charging property of the developer. Examples of the fluidizing agent fine particles used include inorganic fine powders such as silica and alumina, organic fine powders such as fatty acids or their derivatives and metal salts, and fine resin powders such as a fluororesin, an acrylic resin and a styrene resin. Among them, silica fine particles are most preferably used. The fine particle silica used is one whose surface has been subjected to a hydrophobic treatment with a silane coupling agent or silicone oil in order to improve chargeability and environmental stability. Among them, silica treated with silicone oil is preferable from the viewpoints of environmental stability, toner cohesion, and low adhesion to a photosensitive material.

These hydrophobic silicas have a BET specific surface area of 2
0 to 300 m2 / g, preferably 30 to 200 m2 / g
g, more preferably 40 to 120 m2 / g. When the BET is 20 m2 / g or less, the BET easily separates from the toner surface, and the photosensitive material tends to film or comet.

These fine powders are used in an amount of 0.1 to 3 parts by weight, preferably 0.3 to 1.5 parts by weight, based on 100 parts by weight of the toner. If the amount of external addition is less than 0.1 part by weight, the toner surface coverage by the fine powder is low, so that a sufficient effect cannot be provided. On the other hand, if the external addition amount is more than 3 parts by weight, not only the fine powder adheres to the photoreceptor to cause comet and filming, but also the environmental stability is deteriorated.

The binder resin used in the toner of the present invention includes styrenes such as styrene and chlorostyrene, monoolefins such as ethylene, propylene, butylene and isobutylene, vinyl acetate, vinyl propionate, vinyl benzoate and vinyl butyrate. Such as vinyl esters, methyl acrylate, ethyl acrylate, butyl acrylate,
Octyl acrylate, dodecyl acrylate, phenyl acrylate, methyl methacrylate, ethyl methacrylate,
Α such as butyl methacrylate, dodecyl methacrylate, etc.
-Homopolymers and copolymers such as esters of methylene aliphatic monocarboxylic acids, 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 Coalescence can be exemplified.

Particularly typical binder resins include polystyrene, styrene-alkyl acrylate copolymer, styrene-alkyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, and styrene-maleic anhydride. Copolymers, polyethylene, polypropylene, and further include polyester, polyurethane, epoxy resin, silicone resin, polyamide, modified rosin, paraffin wax, and the like.
As a full-color toner, a polyester resin is preferable in terms of color development / image strength, and a softening point of 9 is particularly preferable in terms of charge / layer formation maintenance in non-magnetic one-component development.
A polyester resin at 0 to 120 ° C, preferably 95 to 115 ° C is used.

The softening point referred to here is a flow tester (manufactured by Shimadzu Corporation, nozzle 1 × 1 mm, load 10 kg)
10 ⁴ Pas (10 ⁵ poi)
Refers to the temperature in se). When the softening point is lower than 90 ° C., the fixing temperature is lowered, and the surface properties of the fixed image become uniform, so that the color developability is improved. However, problems such as offset to the heat roll at a high temperature and a decrease in image strength are likely to occur. In addition, when the toner is repeatedly used, streaks and poor charging are likely to occur due to fusion of the toner to the developer carrier and the layer forming blade. When the softening point is higher than 120 ° C., toner fusion to the developer carrier and the layer forming blade is small, and the development maintaining property is stabilized, but the low-temperature fixing property is deteriorated, so that the coloring property and OHP are deteriorated.
Light transmittance becomes a problem.

The glass transition temperature of the polyester resin is from 60 to 75 ° from the viewpoint of improving development maintenance by preventing fusion of the toner to the developer carrier and the layer forming blade, and at the same time, fixing, blocking and image strength. C, preferably 6
Those having a temperature of 2 to 70 ° C are used. Here, the glass transition temperature is determined from a shoulder value in a DSC curve measured using a differential scanning calorimeter DSC-50 (manufactured by Shimadzu Corporation, heating rate 10 ° C./min., Reference material alumina). . If the glass transition temperature of the polyester resin is lower than 60 ° C., blocking occurs, and the storage characteristics deteriorate. If it exceeds 70 ° C., the fixability decreases.

As the composition of the polyester resin in the present invention, generally known monomer compositions can be used. For example, as the acid component, phthalic acid, terephthalic acid, isophthalic acid, fumaric acid, maleic acid, and the like, and as the alcohol component, ethylene glycol, propylene glycol, glycerin, bisphenol A, and the like. A polyester resin containing terephthalic acid or the like and an aromatic dialcohol such as bisphenol A as a main component is preferable.

As the colorant of the toner used in the present invention,
Carbon black, aniline blue, calcoil blue, chrome yellow, ultramarine blue, ポ ン upon oil red, quinoline yellow, methylene blue chloride, copper phthalocyanine, malachite green oxalate, lamp black, rose bengal, C.I. I. Pi
gment Red 48: 1, C.I. I. Pigmen
t Red 122, C.I. I. Pigment Red
57: 1, C.I. I. Pigment Yellow
97, C.I. I. Pigment Yellow 12,
C. I. Pigment Yellow 17, C.I.
I. Pigment Blue 15: 1, C.I. I. P
15: 3, etc., and these may be directly dispersed in the binder resin by a kneading machine. However, in order to improve the dispersion in the resin and improve the color developing property, a master batch method or a flushing method is used. Coloring materials can also be used.

In the developer used in the present invention,
A release agent may be added for the purpose of improving gross and offset properties. The release agent is preferably a paraffin having 8 or more carbon atoms, polyolefin, or the like. Examples thereof include paraffin wax, paraffin latex, microcrystalline wax, and the like, and polypropylene, polyethylene, and the like. These may be used alone or in combination.
The addition amount is preferably in the range of 0.3 to 10% by weight.

Further, the toner of the present invention contains a salicylic acid metal complex compound as a charge control agent. Examples of these charge control agents include those having the structure shown in the following (Chemical Formula 2). When these are contained in toner particles and the above-mentioned titanium compound is added, the charge control agent on the sleeve during continuous use is reduced. The toner charge amount and the transport / layer formation state are greatly stabilized, and the environment dependence of charging is reduced.

[0056]

Embedded image

Among these charge control agents, a metal complex of salicylic acid containing Zn, B, and Cr elements shown in Chemical formula 3 is preferable in view of sharpness of charge distribution and admixability, and more particularly, salicylic acid containing Zn element. Metal complex compounds are preferred. These charge control agents are used in an amount of 0.1 to 10% by weight, preferably 1 to 7% by weight, based on the resin. If the amount of the charge control agent relative to the resin is less than 0.1% by weight, the charge maintaining property cannot be obtained. If the amount exceeds 10% by weight, the offset and the image strength are reduced, and a fixing failure occurs.

[0058]

Embedded image

The volume average particle diameter of the toner used in the present invention is preferably 3 to 13 μm, and more preferably 5 to 10 μm. 3μ volume average particle size
If it is less than m, the fluidity is remarkably deteriorated, so that the layer cannot be formed properly, causing fogging or dirt. Is more likely to occur.

The toner used in the present invention can be produced by any known method, but a kneading and pulverizing method is particularly preferable. That is, the binder resin and the colorant, the charge control agent and the like are melted and kneaded in a kneader such as a kneader or an extruder, and after cooling, pulverized by a jet mill or a mechanical pulverizer and the like, and air classification is performed. A method of adding and mixing is preferable.

The additives such as the titanium compound in the present invention are added to and mixed with the toner particles. The mixing can be performed by, for example, a V-type blender, a Henschel mixer, a Loedige mixer or the like.

At this time, if necessary, other additives may be added in combination. Examples of these additives include fine particles such as magnetite and cerium oxide as abrasives, organic fine particles such as polystyrene / polymethyl methacrylate having relatively large particle diameters as developing / transfer aids, and inorganic fine particles such as titanium oxide. And cleaning aids such as polyvinylidene fluoride fine particles. Further, if necessary, coarse particles of the toner may be removed using a vibration sieving machine, a wind sieving machine, or the like.

The charge amount of the toner used in the present invention was measured by using a blow-off charge amount measuring device manufactured by Toshiba Chemical Company.
m of iron powder and 1.2 g of toner were measured after stirring for 60 seconds with a Turbula mixer. The measurement environment was at a temperature of 22 ° C /
The test was performed at a humidity of 55% RH. The particle size of the toner used in the present invention is a particle size analyzer TA manufactured by Coulter Counter Co., Ltd.
-II, measured at an aperture diameter of 100 μm.

The specific gravity of the titanium compound used in the present invention was determined using a Le Chatelier pycnometer according to JIS-K-0061,
It was measured according to 5-2-1. The operation is as follows.
Pour approximately 250 ml of water into a Lucheterie pycnometer and adjust so that the meniscus is at the scale position. The pycnometer is immersed in a thermostatic water bath, and when the liquid temperature reaches 20.0 ± 0.2 ° C., the position of the meniscus is accurately read on the scale of the pycnometer. (Accuracy: 0.025 ml) Approximately 100 g of sample
Is weighed to the order of 1 mg, and its mass is referred to as W. Place the weighed sample in a pycnometer to remove bubbles. The pycnometer is immersed in a thermostatic water bath, the liquid temperature is maintained at 20.0 ± 0.2 ° C., and the position of the meniscus is accurately read on the scale of the pycnometer. (Accuracy 0.025ml)

The specific gravity is calculated by the following method. D = W / (L ₂ −L ₁ ) 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) L ₁ : Reading of meniscus before putting sample in pycnometer (2
0 ° C) (ml) L ₂ : Meniscus reading after placing the sample in a pycnometer (2
0 ° C) (ml) 0.9982: density of water at 20 ° C (g / c)
m ³ )

[0066]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In the following description, all “parts” mean “parts by weight” unless otherwise specified.

In the present invention, titanium oxide produced by a wet method, that is, a sulfuric acid method and a hydrochloric acid method are applied. The titanium oxide used in the examples uses ilmenite as an ore, and is dissolved in sulfuric acid to separate iron components. Hydrolysis of TiOSO ₄ to T
The wet sedimentation method that produces iO (OH) ₂ was used. The key technologies in this adjustment are hydrolysis and dispersion adjustment for nucleation and washing with water. In particular, pH adjustment (neutralization of acid) in the dispersion treatment and adjustment of the slurry concentration determine the primary particles of the titanium compound later. And requires a high level of control.

Preparation of External Additive A 100 parts by weight of TiO (OH) ₂ produced by the above-mentioned method is mixed with 50 parts by weight of isobutyltrimethoxysilane, and heated to react. After that, it was washed with water, filtered, dried at 120 ° C., and soft agglomeration was removed with a pin mill. The particle size was 30 nm, the specific gravity was 3.1, and the resistance was 5.8 × 10 ¹⁰ Ω
-Cm of titanium compound A was obtained.

Adjustment of External Additive B The same procedure as for External Additive A was used except that 40 parts by weight of isobutyltrimethoxysilane was mixed instead of adjusting the pH and dispersion for adjusting the particle size, and the specific gravity was 3 nm. 1.1, a titanium compound B having a resistance of 9.8 × 10 ⁹ Ω · cm.

Adjustment of External Additive C A particle diameter of 70 nm, a specific gravity of 3.1 and a resistance of 8.5 × 10 were obtained in the same manner as for the external additive B, except that the pH adjustment and the dispersion adjustment for adjusting the particle size were changed. ⁹ Ω · cm of titanium compound C was obtained.

Preparation of External Additive D Except that isobutyltrimethoxysilane was replaced with decyltrimethoxysilane, the particle size was 30 nm, the specific gravity was 3.4, and the resistance was 8.0 × 10 ^{10 in the} same manner as for External Additive A. An external additive D of Ω · cm was obtained.

Preparation of External Additive E The TiO (OH) ₂ prepared by the above method was washed with water, filtered, and calcined to obtain titanium oxide having a particle size of 30 nm. Thereafter, the mixture is pulverized with a jet mill to have a specific gravity of 3.9 and a resistance of 6.0.
An external additive E of × 10 ⁶ Ω · cm was obtained.

Preparation of external additive F External additive E was dispersed in methanol, and 100 weight of external additive E was added.
Parts by weight to 40 parts by weight of isobutyltrimethoxysilane
Mixed with a sand grinder, wet kneaded, and then kneaded.
The solvent was removed while stirring at, and dried to a specific gravity of 3.9.
Anti 3.0 × 10 ⁹An external additive F of Ω · cm was obtained.

Preparation of External Additive G The TiO (OH) ₂ prepared by the above method was washed with water, filtered, and calcined to obtain titanium oxide having a particle size of 30 nm. Thereafter, the mixture was dispersed again in water, wet-pulverized with a sand grinder, mixed with 40 parts by weight of isobutyltrimethoxysilane in water, stirred, dried, and pulverized with a jet mill to obtain a specific gravity of 3.9. An external additive G of 4.2 × 10 ⁹ Ω · cm was obtained.

Production of Toner Particle 1 92 parts of polyester resin (terephthalic acid / bisphenol A propylene oxide adduct Mw = 11000, Mn = 3300, Tg = 67 ° C., softening point = 97 ° C.) Phthalocyanine pigment (C.I. Pigment Blue 15: 3) 5 parts Charge control agent Example 1 (1) Zn salicylic acid complex compound 3 parts After mixing the above materials with a Henschel mixer, melt-kneading with an extruder, cooling, and then pulverizing with a jet mill. Classified by a classifier, the average particle size is 9.0.
μm cyan toner particles 1 were obtained.

Production of Toner Particles 2 I. Pigment Red 57: 1, except that the amount was 5 parts, and the average particle size was 9.1 μm.
Magenta toner particles 2 were obtained.

Production of Toner Particles 3 I. Pigment Yellow 17 was changed to 5 parts, and the average particle size was changed to 9.2 μm in the same manner as in the toner particle 1.
m yellow toner particles 3 were obtained.

Production of Toner Particles 4 Black toner particles 4 having an average particle size of 9.0 μm were obtained in the same manner as in the case of toner particles 1 except that the colorant was changed to 4 parts of carbon black.

Production of Toner Particles 5 92 parts of polyester resin (terephthalic acid / glycerin / bisphenol A propylene oxide adduct Mw = 18,000, Mn = 3800, Tg = 65 ° C., softening point = 105 ° C.) Phthalocyanine pigment (C Pigment Blue 15: 3) 5 parts Boron salicylic acid complex compound of charge control agent example (3) 3 parts After mixing the above materials with a Henschel mixer, melt kneading with an extruder, cool, and finely pulverize with a jet mill. And further classified by a classifier to obtain an average particle size of 9.0.
μm cyan toner particles 5 were obtained.

Production of Toner Particles 6 I. Pigment Red 122 was changed to 5 parts, and magenta toner particles 6 having an average particle size of 9.0 μm were obtained in the same manner as toner particles 5.

Production of Toner Particles 7 I. Pigment Yellow 17 was changed to 5 parts, and the average particle diameter was changed to 9.2 μm in the same manner as the toner particles 5.
m yellow toner particles 7 were obtained.

Production of Toner Particles 8 Black toner particles 8 having an average particle size of 9.3 μm were obtained in the same manner as the toner particles 5 except that the colorant was changed to 4 parts of carbon black.

(Image Forming Apparatus) FIG. 1 shows an image forming apparatus used for evaluating the image quality of a non-magnetic one-component developer. Around the latent image carrier 1, a developer carrier 2 having four color developers of yellow, magenta, cyan, and black is disposed so as to be spaced from the latent image carrier 1 by 150 μm.
After the latent image holding member 1 is charged by the roller charger 3, it is exposed to laser light to form an electrostatic latent image, and an AC voltage and a DC voltage are applied to the developer carrier 3 and the developer supply roller 4. Develop the electrostatic latent image, and charge / expose /
The development was repeated four cycles. The layer of the developer was formed by bringing a layer-forming blade 5 made of silicone rubber into contact with the developer carrier 2 at a constant linear pressure. To transfer the toner, the transfer paper 7 is wound around the transfer drum 6 to transfer the toner image on the latent image holding member 1 one color at a time.
Superimposed. The fixing was performed by the heat fixing device 8. here,
The peripheral speed of the latent image carrier 1 was 130 mm / s, the peripheral speed of the developer carrier 2 was 200 mm / s, and the blade type cleaner 8 was used for cleaning the untransferred toner on the latent image carrier 1.

Example 1 External additive A: 100 parts by weight of toner particles 1-4:
1.0 parts by weight and 0.8 parts by weight of silica fine particles having a BET specific surface area of 110 m ² / g whose surface was hydrophobized with dimethyl silicone oil were externally added and mixed with a Henschel mixer, and further mixed with a wind sieving machine at 45 μm. Sieved, developer 1
~ 4. The obtained developers 1 to 4 are put into cyan, magenta, yellow and black developing machines of the image forming apparatus shown in FIG. 1 and the evaluation environment is set to 28 ° C. and 85% for every 1000 sheets.
A total of 10,000 print tests were performed in a high-temperature and high-humidity environment of RH and a low-temperature and low-humidity environment of 10 ° C and 30% RH, and high image quality without density unevenness and fog was continuously obtained. Was done. Table 1 shows the results.

Example 2 Developers 5 to 8 were obtained in the same manner as in Example 1 except that the external additive A was replaced with the external additive D. The obtained developer 5
8 was evaluated for image quality in the same manner as in Example 1. As a result, high image quality similar to that in Example 1 was continuously obtained. Table 1 shows the results.
Shown in

Example 3 External additive B: 100 parts by weight of toner particles 1-4:
1.2 parts by weight and 0.6 parts by weight of silica fine particles having a BET specific surface area of 120 m ² / g whose surface was hydrophobized with dimethyldichlorosilane were externally added and mixed with a Henschel mixer, and further mixed with a wind sieve at 45 μm. Sieved, developer 9 ~
12 was obtained. When the image quality of the obtained developers 9 to 12 was evaluated in the same manner as in Example 1, high image quality similar to that in Example 1 was continuously obtained. Table 1 shows the results.

Example 4 External additive C: 100 parts by weight of toner particles 1-4:
1.3 parts by weight were externally added and mixed with a Henschel mixer,
Further, the mixture was sieved with a wind sieving machine at 45 μm, and developer 13 to 1 was used.
6 was obtained. When the image quality of the obtained developers 13 to 16 was evaluated in the same manner as in Example 1, high image quality similar to that in Example 1 was continuously obtained. Table 1 shows the results.

Example 5 External additive A: 100 parts by weight of toner particles 1-4:
1.0 parts by weight and 0.9 parts by weight of silica fine particles having a BET specific surface area of 60 m ² / g whose surface was hydrophobized with dimethyl silicone oil were externally added and mixed with a Henschel mixer, and further mixed with a wind sieve at 45 μm. Sieved, developer 17
~ 20 were obtained. When the image quality of the obtained developers 17 to 20 was evaluated in the same manner as in Example 1, high image quality without density unevenness and fog was continuously obtained. Table 1 shows the results.

Example 6 Toner particles 5 to 8: 100 parts by weight of external additive B:
1.0 parts by weight and 0.8 parts by weight of silica fine particles having a BET specific surface area of 90 m ² / g whose surface was hydrophobized with dimethyl silicone oil were externally added and mixed with a Henschel mixer, and further mixed with a wind sieving machine at 45 μm. Sieved, developer 21
~ 24 were obtained. When the obtained developers 21 to 24 were evaluated for image quality in the same manner as in Example 1, high image quality without density unevenness and fog was continuously obtained. Table 1 shows the results.

Example 7 Developers 25 to 28 were obtained in exactly the same manner as in Example 6, except that the external additive B was replaced with the external additive C. When the image quality of the obtained developers 25 to 28 was evaluated in the same manner as in Example 1, high image quality without density unevenness and fog was continuously obtained until the end. Table 1 shows the results.

Example 8 Toner particles 5 to 8: 100 parts by weight of external additive D:
1.0 parts by weight and 0.7 parts by weight of silica fine particles having a BET specific surface area of 70 m ² / g whose surface was hydrophobized with hexamethylene disilazane were externally added and mixed by a Henschel mixer, and further 45 μm by a wind sieving machine. Sifted with developer 29
~ 32 were obtained. When the image quality of the obtained developers 29 to 32 was evaluated in the same manner as in Example 1, high image quality without density unevenness and fog was continuously obtained until the end. Table 1 shows the results.

Example 9 100 parts by weight of toner particles 5 to 8: External additive A:
1.0 parts by weight was externally mixed with a Henschel mixer,
Further, the mixture was sieved with a wind sieving machine at 45 μm, and developer 33 to 3 was used.
6 was obtained. When the image quality of the obtained developers 33 to 36 was evaluated in the same manner as in Example 1, high image quality similar to that in Example 1 was continuously obtained. Table 1 shows the results.

Comparative Example 1 Developers 37 to 40 were obtained in the same manner as in Example 1 except that the external additive A was changed to the external additive E. When the image quality of the obtained developers 37 to 40 was evaluated in the same manner as in Example 1, fog was large from the beginning, and the inside of the device due to toner scattering was severe. Table 1 shows the results.

Comparative Example 2 Developers 41 to 44 were obtained in exactly the same manner as in Example 1 except that the external additive A was changed to the external additive F. The image quality of the obtained developers 41 to 44 was evaluated in the same manner as in Example 1.
The density decreased from around the end of the 00 sheet, and fog and toner scattering worsened. Table 1 shows the results.

Comparative Example 3 Developers 45 to 48 were obtained in the same manner as in Example 8, except that the external additive D was changed to the external additive G. The image quality of the obtained developers 45 to 48 was evaluated in the same manner as in Example 1.
The low density, fog, and toner scattering deteriorated after about 00 sheets. Table 1 shows the results.

Comparative Example 4 Developers 49 to 52 were obtained in the same manner as in Example 9 except that the external additive A was changed to the external additive F. The image quality of the obtained developers 49 to 52 was evaluated in the same manner as in Example 1. As a result, fog was severe from the beginning, and the inside of the apparatus due to toner scattering was also severe. Table 1 shows the results.

Comparative Example 5 To 100 parts by weight of toner particles 1 to 4, 1.0 part by weight of silica fine particles having a BET specific surface area of 110 m ² / g whose surface was hydrophobized with dimethyl silicone oil was mixed with a Henschel mixer. Externally added and mixed, and then 45
The mixture was sieved at μm to obtain Developers 53 to 56. When the image quality of the obtained developers 53 to 56 was evaluated in the same manner as in Example 1, fog was severe from the beginning, and streaks were formed on the developing roll after about 500 sheets, and the environmental fluctuation of the density was large. Table 1 shows the results.

Comparative Example 6 A BET specific surface area of 1 to 100 parts by weight of toner particles 5 to 8 whose surface was hydrophobized with dimethyldichlorosilane was 1
1.0 part by weight of 20 m ² / g silica fine particles were externally added and mixed with a Henschel mixer, and further 45 μm with a wind sieving machine.
m to obtain developers 57 to 60. When the image quality of the obtained developers 57 to 60 was evaluated in the same manner as in Example 1, fog was severe from the beginning, streaks were formed on the developing roll after about 500 sheets, and the environmental fluctuation of the density was large.

Evaluation Method <Initial Concentration> X-Rite concentration measuring instrument, X-Ri
In the density measurement by te404A,…... ≧ 1.4, Δ... 1.1 to 1.4, ×... <1.1 <Density maintenance> The density after 10,000 copies was evaluated in the same manner as described above. <Initial fog> Sensitivity was evaluated by observing the background with a magnifier of 50 times. None, slightly, and fairly good were evaluated as ○, Δ, and ×, respectively. <Fog maintenance> Fog after 10,000 copies was evaluated in the same manner as described above. <Concentration environment difference> Concentration difference under high temperature and high humidity environment of 28 ° C and 85% RH and under low temperature and low humidity environment of 10 ° C and 30% RH ○ <0.2, Δ △ 0.2 to 0.4 , ×... ≧ 0.4 <Image streak, toner scattering, filming> Each state was visually evaluated. ○… Not at all, △… Some, ×… Some

[0100]

[Table 1]

[0101]

The non-magnetic one-component developer of the present invention can be used for all of the non-magnetic one-component developers required for the non-magnetic one-component developer, such as charge speed, charge retention, environment dependency, charge distribution, and layer formation retention. In order to satisfy the characteristics, image density fluctuation for a long time, low developing property, fog, in-machine contamination due to toner scattering, photosensitive material filming,
It is possible to obtain excellent image quality that does not cause problems such as scratches.

[Brief description of the drawings]

FIG. 1 is a schematic configuration diagram showing an embodiment of an image forming apparatus suitable for being applied to an image forming method using a non-magnetic one-component developer of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 latent image holder 2 developer carrier 3 roller charger 4 developer supply roller 5 layer forming blade 6 transfer drum 7 transfer paper 8 fixing device 9 cleaner

Continued on the front page (72) Inventor Tetsu Torigoe 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Inside Fuji Xerox Co., Ltd. (72) Inventor Hiroe Okuyama 1600 Takematsu, Minamiashigara-shi, Kanagawa Prefecture Fuji Xerox Co., Ltd. Takahashi 1600 Takematsu, Minamiashigara, Kanagawa Prefecture Fuji Xerox Co., Ltd. (72) Inventor Hiroshi Nakazawa 1600 Takematsu, Minamiashigara, Kanagawa Prefecture Fuji Xerox Co., Ltd.

Claims (9)

[Claims] 1. A non-magnetic one-component developer comprising a binder resin, a toner particle containing a charge control agent and a colorant and an additive, wherein the charge control agent contains a metal complex of salicylic acid. A non-magnetic one-component developer, wherein the agent is a titanium compound obtained by reacting TiO (OH) ₂ with a silane compound or a titanium compound obtained by reacting TiO (OH) ₂ with silicone oil. 2. The non-magnetic one-component developer according to claim 1, wherein the additive has a specific gravity of 2.8 to 3.6. Wherein the TiO (OH) ₂ is a non-magnetic one-component developer according to claim 1, characterized in that the TiO (OH) ₂ made by the wet method. 4. The non-magnetic one-component developer according to claim 1, wherein the binder resin is a polyester resin. 5. The polyester resin has a softening point of 90 ° C.
The non-magnetic one-component developer according to claim 4, wherein the non-magnetic one-component developer has a glass transition temperature of 60 to 70 ° C. 6. The non-magnetic one-component developer according to claim 1, wherein the additive further contains hydrophobic silica particles. 7. The image forming method according to claim 1, wherein the step of forming a latent image on the latent image carrier and the step of developing the latent image using development on a developer carrier are performed. An image forming method, comprising using the non-magnetic one-component developer. 8. An image forming method comprising: forming a latent image on a latent image carrier; and developing the latent image using development on the developer carrier. 8. The image forming method according to claim 7, wherein the developing is performed in a non-contact state, and the non-magnetic one-component developer according to claim 1 is used as the developer. 9. An image forming method comprising: forming a latent image on a latent image carrier; and developing the latent image using development on the developer carrier. ,
The image forming method according to claim 7, wherein the image forming method is performed by pressing a toner supply roll.