JP4209337B2 - Friction charging member - Google Patents

Description

  The present invention relates to a developer (toner) used for developing an electrostatic latent image in electrophotography, electrostatic recording, etc., with respect to a developer carrier such as a carrier and a developing sleeve, and a developer layer thickness such as a doctor blade. The present invention relates to a frictional charge imparting member such as a regulating member.

In an electrophotographic image forming process, an electrostatic latent image is formed on a photoreceptor made of an inorganic or organic material, and this is developed with toner, transferred to paper or a plastic film, and fixed to obtain a visible latent image. The photosensitive member has a positive charging property and a negative charging property depending on its configuration. When the printed part is left as an electrostatic charge image by exposure, the photosensitive member is developed with a reverse sign charging toner. On the other hand, in the case of performing reverse development by removing the charge from the printing portion, development is performed with the same sign charging toner.
As a method for retaining the charge in the toner, a method utilizing the triboelectric charging property of the binder resin of the toner and a method of adding a charge control agent to the toner are generally used.

  In the case of a method for maintaining the charge of the toner by utilizing the triboelectric charging property of the toner binder resin, the characteristics required for the binder resin are sufficient triboelectric chargeability, anti-offset property and fixing property in the fixing process. It is required to charge at the same time. However, generally binder resins with good fixing properties tend to be inferior in tribocharging. In recent years, methods for fixing toner with low energy include glass point transfer (Tg) of the binder resin and a method of increasing the proportion of the low molecular weight resin in the binder resin. There was a tendency for chargeability to be inferior.

On the other hand, a method of adding a charge control agent to the toner to improve the triboelectric chargeability of the toner is such that the charge control agent exposed on the toner surface layer falls off or peels off the toner, and the carrier, drum, blade, developing sleeve, and other members Contamination occurs.
As a result, the chargeability decreases, and problems such as a decrease in image density, a decrease in reproducibility, and fogging occur as the number of copies increases.

Accordingly, a method has been proposed in which triboelectric charge is obtained by bringing various members into contact with the toner, instead of solving the charge imparting to the toner with only the charge control agent and the binder resin.
The main frictional charging member is a carrier in a two-component developer, a developing sleeve, a developer layer thickness regulating blade, etc. in a one-component developer, and a developer supplying member, respectively. , Stirring members, conveying screws, and the like.

  It is known that a developer layer thickness regulating member (regulating blade) used for a one-component developer imparts frictional charge to the toner by contacting the blade when the toner passes between the blades. As such, an elastomer such as metal or urethane resin is used. It is known to use a silicone-based elastomer for positively charged toners, and a nylon-based elastomer for negatively charged toners on the surface layer of a member that comes into contact with the toner to impart charge to the toner. Yes.

In addition, it is known that the developing sleeve also carries a toner on the surface thereof to carry a toner, so that a triboelectric charge is given to the toner, and a method of coating the surface of the developing sleeve with a resin that easily gives the triboelectric charge of the toner is also known. ing.
The blades and the surface layer of the developing sleeve are coated with a resin. In order to further impart a triboelectric charge to the toner, a method of dispersing chargeable particles on the surface layer of a member such as a blade has been proposed.

In the carrier that is a frictional charge imparting member used in the two-component developer, iron powder or ferrite has been used. Recently, iron powder or ferrite is used as a core material, and acrylic resin, fluorine resin, silicone resin, phenol resin. In many cases, a carrier coated with a resin such as is used.
Although these resin-coated carriers are coated with a resin, a method of dispersing chargeable particles on the surface layer of the carrier has been proposed in order to further impart a triboelectric charge to the toner.

Patent Document 1 discloses a frictional charge imparting member in which a phenoxyacetic acid derivative is dispersed as chargeable particles on the surfaces of the blade, sleeve, and carrier.
However, the phenoxyacetic acid derivative has a tendency to sublime or decompose at high temperatures, and heat resistance is required for use as a frictional charge imparting member such as a carrier that locally becomes high temperature due to friction.
Further, a two-component toner in which the effect of imparting triboelectric charge is insufficient and the toner is triboelectrically charged with a carrier in which the phenoxyacetic acid derivative is dispersed on the surface, and a sleeve or blade in which the phenoxyacetic acid derivative is dispersed on the surface. Even in the one-component toner that is friction-charged using the toner, there is a drawback that the toner is not sufficiently charged.

JP-A-7-140725

  An object of the present invention is to provide a heat-providing charge imparting member having an excellent charge imparting effect.

The present invention relates to a friction for imparting a triboelectric charge to a developer (toner) used in an image forming apparatus used for developing an electrostatic latent image in the field of electrophotography, electrostatic recording material and the like. In the charging member,
1. The present invention relates to a frictional charge imparting member comprising a compound represented by the following general formula (1) on the surface.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group or a fluorine-substituted alkoxy group. X ₂ represents a hydrogen atom, a halogen atom, a halogenated alkyl group or a halogenated alkoxy group. In the formula, R represents hydrogen. Represents an atom, a carboxymethyl group, or a 1-carboxyethyl group.)

The present invention also provides:
2. A frictional charge imparting member characterized by containing a compound represented by the following general formula (2) on the surface is preferable.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. In the formula, X ₂ represents a hydrogen atom, a halogen atom, a halogenated alkyl group, or a halogenated alkoxy group. R represents a hydrogen atom, a carboxymethyl group, or a 1-carboxyethyl group.)

The present invention also provides:
3. A triboelectric charge imparting member characterized by containing a compound represented by the following general formula (3) on the surface is further preferred.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. In the formula, R represents a hydrogen atom, a carboxymethyl group, or a 1-carboxyethyl group.)

Further, the present invention is the frictional charge imparting member according to any one of 1 to 3, wherein the frictional charge imparting member is a carrier particle.
Furthermore, the present invention is the frictional charge imparting member according to any one of 1 to 3, wherein the frictional charge imparting member is used in a developing device.

The frictional charge imparting member of the present invention has good heat resistance and can sufficiently withstand even when used as a frictional charge imparting member on a carrier or the like that locally becomes high temperature due to friction.
Further, the frictional charge imparting member of the present invention has a sufficient imparting effect with respect to the frictional charge imparting effect required to charge the toner.

Next, the present invention will be described in more detail with reference to preferred embodiments.
In the method for producing a phenylbenzamide compound having a hydroxyl group at the terminal where R in the general formula (1), general formula (2), and general formula (3) used in the present invention is a hydrogen atom, aniline having a substituent is toluene, It dissolves in a solvent such as xylene and ethylbenzene, and preferably, a reaction reagent such as phosphorus trichloride is added dropwise while maintaining at 0 to 50 ° C., more preferably 0 to 30 ° C., and preferably 30 minutes to 2 hours after the completion of the addition. Is stirred at a temperature of 0 to 50 ° C., more preferably 20 to 30 ° C., p-hydroxybenzoic acid is added, the temperature is raised, and the mixture is stirred at reflux for 1 to 6 hours. The reaction solution is cooled, an alkali agent such as sodium hydroxide is added, and stirring is preferably performed in a suspended state at 40 to 80 ° C., more preferably at 50 to 60 ° C. for 30 minutes to 2 hours. An acid such as hydrochloric acid is added to the solution, and the precipitated solid is collected by filtration, dried, and recrystallized with a mixed solvent of toluene-methanol. The preferable addition amount of p-hydroxybenzoic acid with respect to 1 mol of aniline having a substituent is 1.00 to 1.30 mol, and more preferably 1.05 to 1.10 mol.

  The method for producing a phenylbenzamide compound having a carboxymethoxy group at the terminal where R in the general formula (1), general formula (2), and general formula (3) used in the present invention is a carboxymethyl group or a 1-carboxyethyl group, Although not particularly limited, after dissolving the phenylbenzamide compound having a hydroxyl group at the terminal obtained by the above method in a solvent and capturing potassium acid and the like in order to capture the acid generated in the reaction, methyl bromoacetate, bromoacetic acid Ethyl, tert-butyl bromoacetate, benzyl bromoacetate, methyl chloroacetate, ethyl chloroacetate, isopropyl chloroacetate, butyl chloroacetate, tert-butyl chloroacetate, benzyl chloroacetate, methyl 2-bromopropionate, 2-bromopropionic acid Ethyl, butyl 2-bromopropionate, tert-butyl 2-bromopropionate , Methyl 2-chloropropionate, ethyl 2-chloropropionate or the like is added, and the reaction temperature is appropriately selected depending on the solvent used, but stirring is carried out at 50 to 130 ° C. for 1 to 8 hours. Is removed, concentrated, and recrystallized with a solvent such as toluene. In order to hydrolyze the ester, the obtained crystals are dissolved in alcohol such as methanol, dioxane or the like, and an aqueous solution such as sodium hydroxide, potassium hydroxide or lithium hydroxide is added, preferably 5 to 80 ° C., more preferably Is stirred at 5 to 20 ° C. for 30 minutes to 2 hours, then the solvent is distilled off, neutralized with hydrochloric acid or the like, and the precipitated solid is collected by filtration, washed and dried, and the terminal has a carboxymethoxy group-terminated phenyl. A benzamide compound can be obtained.

The solvent used when the phenylbenzamide compound having a hydroxyl group at the terminal is reacted can be appropriately selected other than the solvent that adversely affects the reaction. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone 3-methyl-2-pentanone, 4-methyl-2-pentanone, 2-methyl-3-pentanone, 2,4-dimethyl-3-pentanone, 2-hexanone, 3-hexanone, 3-methyl-2-hexanone 5-methyl-2-hexanone, 2-methyl-3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 6-methyl-2-heptanone, 2-methyl-3 -Heptanone, 5-methyl-3-heptanone, 2-methyl-4-heptanone, 3-methyl-4-hept Ketones such as tanone, 2-octanone, 3-octanone, 4-octanone, aliphatic ethers such as ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, methyl butyl ether, methyl isoamyl ether, ethyl propyl ether, ethyl butyl ether , Aromatic ethers such as anisole, phenyl ether and benzyl ether, and cyclic ethers such as dioxane.
In addition, the hydrogen bromide generated in the reaction and the base used for capturing hydrogen chloride are not particularly limited as long as they capture the acid generated without adversely affecting the reaction, but sodium carbonate, calcium carbonate, Examples thereof include magnesium carbonate, potassium carbonate, sodium hydrogen carbonate and the like, but potassium carbonate is preferable.

  The aniline having a substituent used for producing the phenylbenzamide compound used in the present invention is a compound represented by the formula (4),

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. X ₂ represents a hydrogen atom, a halogen atom, a halogenated alkyl group, or a halogenated alkoxy group.)

  Specific examples include 4-fluoroaniline, 3-chloro-4-fluoroaniline, 4-trifluoromethoxyaniline, 3,4-difluoroaniline, 4-trifluoromethylaniline, 3-trifluoromethyl-4-fluoroaniline. 2,4-difluoroaniline and the like.

  Next, specific examples of the phenylbenzamide compound of the general formula (1) used in the present invention are listed in Tables 1 and 2, but the present invention is not limited to the described compounds.

The compound used for imparting triboelectric chargeability to the member is an active ingredient of a phenylbenzamide compound represented by general formula (1), preferably general formula (2), more preferably general formula (3). The phenylbenzamide compounds represented by the general formulas (1) to (3) may be used alone or in combination of two or more. Since the phenylbenzamide compound that imparts triboelectric chargeability has better heat resistance than conventional phenoxyacetic acid compounds, the compound is stable against local heat generation due to friction when used in triboelectric charging members. In addition, the effect of imparting electrification is also excellent.
In addition, the phenylbenzamide compound used in the present invention does not necessarily exclude the inclusion of other substances such as aniline or p-hydroxybenzoic acid having a small amount of substituent as an unreacted raw material or moisture.

The method for allowing the compound represented by any one of the general formulas (1) to (3) to be contained on the surface is not particularly limited. For example, a coating solution containing the phenylbenzamide compound represented by the above general formulas (1) to (3) is applied to the base material of the friction charge imparting member by a method such as a dipping method, a spray method, or a coating method and dried. Then, the frictional charge imparting member of the present invention can be obtained. Or the method etc. which disperse | distribute the phenylbenzamide compound represented by the said General Formula (1) thru | or (3) to resin, and make it coat | cover with the well-known method to the base material of a friction charge provision member etc. are mentioned.
Further, the compound represented by the general formulas (1) to (3) can be dispersed and contained in a moldable resin by a known method, and then molded into a sleeve, a doctor blade or the like. .
As the resin that can be used for coating as described above or a resin that can be molded as a base material for a frictional charge imparting member such as a sleeve, generally known resins can be used. For example, styrene resin, vinyl resin, acrylic resin, epoxy resin, polyester resin, polyethersulfone resin, polycarbonate resin, polyphenylene oxide resin, polyamide resin, fluororesin, alkyd resin, phenol resin, melamine resin, polyimide resin, A thermoplastic resin such as a urea resin, a silicone resin, or a polyurethane resin, or a photocurable resin can be used.

  The proportion of the phenylbenzaldehyde compound represented by any one of the general formulas (1) to (3) dispersed in the resin is preferably 1 to 80 parts by mass with respect to 100 parts by mass of the resin. If the amount is less than 1 part by mass, the charge imparting property is hardly improved by addition, and if it exceeds 80 parts by mass, the coating strength tends to decrease.

  The carrier core material used in the present invention is not particularly limited. For example, (1) magnetic iron oxide such as magnetite, maghemite and ferrite, and iron oxide containing other metal oxides. Or (2) metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, Alloys with metals such as tungsten and vanadium. (3) and mixtures thereof are used. (4) Furthermore, ceramic particles such as glass and silicon carbide, resin powder, resin powder containing a magnetic substance, and the like can be given.

Specific examples of magnetic iron oxide include iron trioxide (Fe ₃ O ₄ ), iron sesquioxide (γ-Fe ₂ O ₃ ), zinc oxide zinc (ZnFe ₂ O ₄ ), and iron yttrium oxide (Y ₃ Fe). ₅ O ₁₂ ), iron cadmium oxide (CdFe ₂ O ₄ ), iron gadolinium oxide (Gd ₃ Fe ₅ O ₁₂ ), iron oxide copper (CuFe ₂ O ₄ ), lead iron oxide (PbFe ₂ O ₄ ), nickel iron oxide (NiFe ₂ O ₄ ), iron neodymium (NdFe ₂ O ₄ ), iron barium oxide (BaFe ₂ O ₄ ), magnesium iron oxide (MgFe ₂ O ₄ ), iron manganese oxide (MnFe ₂ O ₄ ), iron lanthanum oxide (LaFeO ₃ ) and the like.

Moreover, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements and mixtures thereof can be used.
Illustratively, the different elements include lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, Examples include gallium. Specific examples include manganese-zinc ferrite, nickel-zinc ferrite, manganese-magnesium ferrite, lithium ferrite, and copper-zinc ferrite.
As the heterogeneous elements, magnesium, aluminum, silicon, phosphorus, and zirconium are preferable, and these may be incorporated into the iron oxide crystal lattice, or may be incorporated into the iron oxide as an oxide, It may exist on the surface as an oxide or hydroxide.

  The base material of the developer layer thickness regulating member that can be used in the present invention is not particularly limited, and examples thereof include metals or alloys such as iron, stainless steel, nickel, and aluminum, and non-metallic materials such as ceramics, plastics, and rubber. In many cases, these materials are processed into a plate shape and used, but a roll shape may be used. Further, a rubber plate can be attached to a metal base, or an elastomer material can be attached to a portion of the metal elastic plate that contacts the sleeve.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, these do not limit this invention at all. (Hereafter, all parts are parts by mass)

[Production Example 1] (Production of Compound No. 1 in Table 1)
Dissolve 23 parts of 4- (trifluoromethoxy) aniline in 173 parts of toluene, add dropwise 13 parts of phosphorus trichloride while maintaining the temperature at 30 ° C. or lower, and stir at room temperature (26 ° C.) for 1 hour after completion of the dropwise addition. 19 parts of p-hydroxybenzoic acid was added, and the mixture was stirred at 110 ° C. under reflux for 4 hours. The reaction solution was cooled, 100 parts of 25% aqueous sodium hydroxide solution was added while maintaining the temperature at 50 ° C. or lower, and the suspension was stirred at 50 ° C. for 1 hour. After cooling, 200 parts of 2 mol / l hydrochloric acid was added to the aqueous layer, and the precipitated solid was collected by filtration, dried, and recrystallized with a toluene-methanol mixed solvent to obtain 29 parts of white crystals.
The melting point of this product was 201.7 ° C.
About this product, the structure of N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1) was confirmed from the results of IR measurement and NMR measurement.

[Production Example 2] (Production of Compound No. 2 in Table 1)
After dissolving 18 parts of N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1) in 192 parts of 4-methyl-2-pentanone and adding 25 parts of potassium carbonate, 2-bromopropion 14 parts of ethyl acid was added and stirred at 100 ° C. for 3 hours. After cooling the reaction solution, it was washed once with water, twice with hydrochloric acid and twice with water, concentrated and recrystallized with toluene to give 2- {4- [N- (4-trifluoro) as white crystals. 21 parts of methoxyphenyl) carbamoyl] phenoxy} propionic acid ethyl ester were obtained.
The obtained white crystals were dissolved in 222 parts of dioxane, 161 parts of 1 mol / l sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. After stirring, dioxane was distilled off, 150 parts of 2 mol / l hydrochloric acid was slowly added dropwise and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed with water and then dried to obtain 20 parts of white crystals.
The melting point of this product was 212.3 ° C.
About this product, the structure of 2- {4- [N- (4-trifluoromethoxyphenyl) carbamoyl] phenoxy} propionic acid (Compound No. 2) was confirmed from the results of IR measurement and NMR measurement.

[Production Example 3] (Production Method of Compound No. 12 in Table 2)
20 parts of N- (4-trifluoromethylphenyl) -4-hydroxybenzamide was dissolved in 234 parts of 4-methyl-2-pentanone, 25 parts of potassium carbonate was added, 15 parts of ethyl bromoacetate was added, For 3 hours. The reaction solution is cooled, washed once with water, twice with hydrochloric acid, twice with water, concentrated, and recrystallized with toluene to give 4- [N- (4-trifluoromethylphenyl) as white crystals. 22 parts of carbamoyl] phenoxyacetic acid ethyl ester were obtained.
The obtained white crystals were dissolved in 248 parts of dioxane, 161 parts of 1 mol / l sodium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. After stirring, dioxane was distilled off, 180 parts of 2 mol / l hydrochloric acid was slowly added dropwise and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed with water and then dried to obtain 21 parts of white crystals.
The melting point of this product was 251.2 ° C.
With respect to this product, the structure of 4- [N- (4-trifluoromethylphenyl) carbamoyl] phenoxyacetic acid (Compound No. 12) was confirmed from the results of IR measurement and NMR measurement.

[Comparative manufacturing example]
20 parts of N- (4-trifluoromethylphenyl) -4-hydroxybenzamide is dissolved in 224 parts of 4-methyl-2-pentanone, 30 parts of potassium carbonate is added, and then 17 parts of ethyl 2-bromopropionate is added. And stirring at 100 ° C. for 3 hours. The reaction solution is cooled, washed once with water, twice with hydrochloric acid, twice with water, concentrated, and recrystallized with toluene to give 4- [N- (4-trifluoromethylphenyl) as white crystals. 22 parts of carbamoyl] phenoxypropionic acid ethyl ester were obtained.
The melting point of this product was 153.9 ° C.

[Example 1]
25 parts of N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1) and 50 parts of styrene-acrylic resin are dissolved in 500 parts of toluene-acetone (1: 1), and this is added to a spherical ferrite carrier. 1000 parts (average particle size 100 μm) were coated with a fluidized bed type coating apparatus. Meanwhile, 100 parts of a styrene-acrylic copolymer resin (manufactured by Mitsui Chemicals, trade name CPR-100) is added with 3 parts of low molecular weight polypropylene (trade name Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.) and 5 parts of carbon black, The mixture was melt-mixed with a heating and mixing apparatus (bench kneader) at 150 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. Further, the mixture was finely pulverized with a jet mill and classified to obtain a black toner having a volume average particle size of 9 ± 0.5 μm. 3 parts of this toner was added to 100 parts of the carrier and mixed with a ball mill to obtain a developer. The charge amount of the toner was measured with a blow-off powder charge amount measuring device. The results are shown in Table 3.

[Examples 2-3]
Instead of “N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1)” in Example 1, “2- {4- [N- (4-trifluoromethoxyphenyl) carbamoyl] phenoxy” } Propionic acid (Compound No. 2) ”and 4- [N- (4-trifluoromethylphenyl) carbamoyl] phenoxyacetic acid (Compound No. 12). The developer was prepared by the method and measured with a blow-off powder charge measuring device. The results are shown in Table 3.

[Comparative Example 1]
25 parts of the compound obtained in the comparative production example and 50 parts of styrene-acrylic resin were dissolved in 500 parts of toluene-acrylic (1: 1), and this was added to 1000 parts of a spherical ferrite carrier (average particle size 100 μm). It was coated with a coating device. On the other hand, 100 parts of styrene-acrylic copolymer resin (trade name, CPR-100, manufactured by Mitsui Chemicals), 3 parts of low molecular weight polypropylene (trade name, Viscol 550P, manufactured by Sanyo Chemical Co., Ltd.), and 5 parts of carbon black. In addition, the mixture was melted and mixed with a heating and mixing apparatus (bench kneader) at 150 ° C., and the cooled mixture was coarsely pulverized with a hammer mill. Further, the mixture was finely pulverized with a jet mill and classified to obtain a black toner having a volume average particle size of 9 ± 0.5 μm. 3 parts of this toner was added to 100 parts of the carrier and mixed with a ball mill to obtain a developer. The charge amount of the toner was measured with a blow-off powder charge amount measuring device. The results are shown in Table 3.

[Comparative Example 2]
A developer was prepared in the same manner as in Comparative Example 1 except that the amount of the “compound obtained in Comparative Production Example” described in Comparative Example 1 was changed to “4-fluorophenoxyacetic acid”. The measurement was carried out with a powder charge measuring device, and “4-fluorophenoxyacetic acid” was used as Comparative Example 2. The results are shown in Table 3.

  The frictional charge imparting member of the present invention has good heat resistance (high melting point) and a high charge imparting effect compared to a frictional charge imparting member using a conventional phenoxyacetic acid derivative or the like. In addition, since the compound having a charge-imparting effect (the phenylbenzamide compound used in the present invention) does not contain a metal such as chromium, there is no burden on the environment.

[Example 4]
25 parts of N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1) and 50 parts of silcon resin were dissolved in 500 parts of toluene-acetone (1: 1). This was coated on the toner conveying member by a spray method and dried to prepare a developing portion. On the other hand, 3 parts of low molecular weight polypropylene (manufactured by Sanyo Chemical Co., Ltd., Viscol 550P) and 90 parts of magnetic iron oxide are added to 100 parts of styrene-acrylic copolymer resin (manufactured by Mitsui Chemicals, trade name: CPR-100). The mixture was melt-mixed with a heating and mixing apparatus (bench kneader) at 150 ° C., and the cooled mixture was coarsely pulverized with a hammer mill, then finely pulverized with a jet mill, and classified to obtain a volume average particle size of 9 ± 0.5 μm. Black toner was obtained. To 100 parts of this black toner, 0.2 part of hydrophobic colloidal silka was stirred and mixed with a Henschel mixer to obtain a toner. Put the toner in a developing device of a commercially available magnetic one-component developing type printer (resolution 600 dpi), take out the image, and measure the image density of the solid black portion of the tenth image from the start of printing with a Magbes reflection densitometer. . The results are shown in Table 4.

[Comparative Example 3, Comparative Example 4]
Except that N- (4-trifluoromethoxyphenyl) -4-hydroxybenzamide (Compound No. 1) described in Example 4 was changed to “4-fluorophenoxyacetic acid” and “4-trifluoromethylphenoxyacetic acid”. A developing part was produced in the same manner as in Example 4. An image was produced in the same manner as in Example 4, and the image density of the solid black portion of the tenth image density from the start of printing was measured with a Magbes reflection densitometer, and a sample using “4-fluorophenoxyacetic acid” was used as a comparative example. 3, Comparative Example 4 was prepared using “4-trifluoromethylphenoxyacetic acid”. The results are shown in Table 4.

In Example 4, the image density was in the range of 1.45 to 1.55, which is desirable for a printer, and was good. In Comparative Example 3 and Comparative Example 4, a satisfactory image density could not be obtained.

Claims (5)

A triboelectric charge imparting member comprising a compound represented by the following general formula (1) on the surface.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. In the formula, X ₂ represents a hydrogen atom, a halogen atom, a halogenated alkyl group, or a halogenated alkoxy group. R represents a hydrogen atom, a carboxymethyl group, or a 1-carboxyethyl group.) A triboelectric charge imparting member comprising a compound represented by the following general formula (2) on the surface.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. In the formula, X ₂ represents a hydrogen atom, a halogen atom, a halogenated alkyl group, or a halogenated alkoxy group. R represents a hydrogen atom, a carboxymethyl group, or a 1-carboxyethyl group.) A frictional charge imparting member comprising a compound represented by the following general formula (3) on the surface.

(In the formula, X ₁ represents a fluorine atom, a fluorine-substituted alkyl group, or a fluorine-substituted alkoxy group. In the formula, R represents a hydrogen atom, a carboxymethyl group, or a 1-carboxyethyl group.) The frictional charge imparting member according to any one of claims 1 to 3, wherein the frictional charge imparting member is carrier particles. The frictional charge imparting member according to any one of claims 1 to 3, wherein the frictional charge imparting member is used in a developing device.