JPH05119534A - Charge donating material - Google Patents

Abstract

PURPOSE:To give proper charge to a toner and to form picture excellent in fine line reproducibility and gradation property without deterioration of performance for long-term use by incorporating a specified calixarene compd. into a charge donating material. CONSTITUTION:The charge donating material contains calixarene compd. expressed by formula I. In formula I, R is hydrogen atom, alkyl group, unsatd. alkyl group, carboxyalkyl group or its salt, acyl group, or aromatic hydrocaton group, R1-R3 are independently hydrogen atom, halogen atom, alkyl group, alkoxy group, aromatic hydrocarbon group, hydroxyl group, carboxyl group, amino group which may have substitutent of alkyl group and/or acyl group, nitro group, sulfon group, sulfoaminde group, carbamoyl group, cyano group, lower alkylcarboxylic acid ester, or acyl group. n is an integer 4-10. Thereby, rising of charges in the toner and stability of electrification can be improved.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a charge imparting material which contributes to charge imparting to toner in an electrophotographic copying process.

[0002]

2. Description of the Related Art Toner is given a positive or negative charge in advance according to the polarity of an electrostatic latent image to be developed. In order to give an electric charge to the toner, it is possible to use only the triboelectric chargeability of the resin which is a component of the toner, but since the toner charge amount is small in this method, the image obtained by development is easily fogged. It becomes unclear. Therefore, in order to impart a desired triboelectric charge amount to the toner, charge control agents such as dyes and pigments that enhance the charging property are added.

However, in order to impart chargeability to the toner by adding these additives, these additives must be exposed on the toner surface to some extent. Therefore, these additives fall off from the toner surface due to friction between toners, collision with a carrier, friction with an electrostatic latent image holding member, etc., and a carrier, an electrostatic latent image holding member such as a photosensitive belt or a drum. Contamination such as occurs. As a result, the charging property is deteriorated, and as the developing operation is repeated, the deterioration progresses, the image density decreases, the reproducibility of fine lines decreases, and the fog increases.

In view of such circumstances, the improvement of the charge imparting property to the toner is not achieved only by the additive of the toner, but a conveying member such as a sleeve, a doctor blade or a carrier which comes into contact with the toner during the developing process. , A regulating member or a friction member (hereinafter, referred to as "charge-giving material" including these, contacting with the toner in the developing step or prior to this, to give the toner a charge necessary for the development or to supplement the charge. It is also proposed to improve the property of imparting charge to the toner by means of the materials and members that can be imparted to the toner.

In the method of positively imparting the electric charge to the toner by the electric charge-imparting material, it is almost unnecessary to add the additive for improving the charging characteristic to the toner.
Essential improvements can be made to the above problems.

However, the charge-imparting material such as the carrier, sleeve, doctor blade, etc. must not only have a strong charge-imparting ability, but must also withstand the friction with the toner and be durable. For example, it is desirable that the carrier be used without being replaced for a long period of time, and the sleeve is required to have the same level of durability as the developing device main body.

In recent years, there has been a demand for downsizing of the developing device in order to downsize the copying machine, reduce the cost, and increase the number of colors. Further, from the aspect of maintenance-free, unitization of the developing device is desired. From these requirements, a one-component developing system in which a thin toner layer is formed on a developing sleeve and brought into contact with a photoconductor to develop is attracting attention. However, as compared with the two-component developing method in which the toner is mixed and stirred with a carrier to charge, the toner is charged only at the moment when it passes between the layer thickness regulating blade and the sleeve, so that a sufficient toner charge amount cannot be uniformly obtained. It was difficult. In order to solve these drawbacks, a method of coating the surface of the layer thickness regulating blade with a strongly charged resin has been considered. Further, it has been proposed to include a charge control agent in the resin coating layer in order to improve the chargeability, but it has not been possible to sufficiently achieve the rise of charge and the stabilization of charge. The purpose of the present invention is to improve the rise and stabilization of these charges.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to provide a charge-providing material that solves the above-mentioned problems, and an object thereof is to provide a charge-providing material that imparts an appropriate charge to a toner. To provide. A further object of the present invention is to provide a charge-imparting material that does not deteriorate in performance after long-term use. A further object of the present invention is to provide a charge imparting material that can contribute to image formation with excellent fine line reproducibility and gradation.

[0009]

The present invention has the following general formula:
[I];

[Chemical 2] The present invention relates to a charge-imparting agent containing a calixarene compound represented by

In the general formula [I], R is a hydrogen atom, C ₁ -C
_{12 represents} an alkyl group or an unsaturated alkyl group, a carboxyalkyl group such as carboxymethyl group or a salt thereof, an acyl group such as acetyl group, or an aromatic hydrocarbon group such as phenyl group; R ₁ , R ₂ and R ₃ Are each independently a hydrogen atom, a halogen atom such as a fluorine atom or a chlorine atom, a C _{1 to} C ₁₈ alkyl group, an alkoxy group such as a methoxy group, an aromatic hydrocarbon group such as an aryl group, a hydroxyl group, a carboxyl group. Selected from the group consisting of acyl groups such as an amino group optionally substituted with an alkyl group and / or an acyl group, a nitro group, a sulfone group, a sulfamido group, a carbamoyl group, a cyano group, a lower alkylcarboxylic acid ester, and an acetyl group. To be done. n is 4 to 1
Represents an integer of 0. ]

The calixarene compound of the present invention can be obtained, for example, from CD Gutsche (Accounts of Chemical Research, 1983).
(16) From page 161 to page 170), the following reaction formula:

[Chemical 3] Can be easily synthesized by reacting the phenol derivative represented by the general formula [II] with formaldehyde directly or in the presence of an inorganic strong alkaline catalyst using a suitable solvent. .. The calixarene compound represented by the general formula [III] represents a compound in which R is a hydrogen atom in the general formula [I].
II] can be obtained by carrying out a substitution reaction using an alkylating agent, a phenylating agent, a halogenated alkylcarboxylic acid or the like.

Specific examples of the calixarene compound represented by the general formula [I] obtained as described above are shown below, but the present invention is not limited to these compounds.

[0013]

[Chemical 4]

[0014]

[Chemical 5]

[0015]

[Chemical 6]

[0016]

[Chemical 7]

[0017]

[Chemical 8]

[0018]

[Chemical 9]

[0019]

[Chemical 10]

[0020]

[Chemical 11]

[0021]

[Chemical 12]

[0022]

[Chemical 13]

The charge imparting member functions to impart an appropriate charge to the toner, and blades, sleeves, carriers and the like are known. The calixarene represented by the general formula [I] may be directly contained in the charge imparting material, or a resin coat layer containing the calixarene may be provided on the surface of the charge imparting material. By doing so, an appropriate electric charge can be applied to the toner. When the blade or sleeve is treated with calixarene represented by the general formula [I], it is particularly useful as a blade or sleeve used in the one-component developing method.

There are various one-component developing methods, but in principle, it is provided between a photosensitive drum on which an electrostatic latent image on which toner is transferred is formed and a toner container containing one-component toner. Drum-shaped sleeve (toner conveying member) is arranged,
A blade (toner layer thickness regulating member) that also functions as a toner charging member is pressed onto this toner conveying member, and the toner is made thinner by the toner layer thickness regulating member as the toner conveying member moves. At the same time, the electrostatic latent image on the photoconductor is visualized by being charged to the required polarity and the amount of electric charge necessary for development, supplied to the photoconductor drum, and electrostatically adsorbed.

The blade is usually phosphor bronze, stainless steel,
Metals such as aluminum and iron, or resins such as urethane, nylon, Teflon, silicon, polyacetal, polyester, polyethylene, styrene, acryl, styrene-acryl, melamine and epoxy, or ethylene propylene rubber, fluororubber, polyisoprene rubber, etc. It is made of various synthetic rubbers, natural rubber, etc., and is pressed in line contact with the sleeve surface. In the present invention, such a blade surface is coated with a resin layer containing a calixarene compound represented by the general formula [I]. When the blade is made of resin, calixarene may be contained in the blade.

The binder used when the coating layer containing the compound of the present invention is provided on the blade is not particularly limited as long as it is commonly used as a binder in ordinary hard coating. However, for example, a thermoplastic resin such as styrene resin, (meth) acrylic resin, olefin resin, amide resin, polycarbonate resin, polyether, polysulfone, polyester resin, silicone resin, polyacetal resin, or the like, or Thermosetting resins such as epoxy resin, urea resin, urethane resin, and their copolymers and polymer blends are used.

Furthermore, after the compound shown in the present invention is dispersed in a metal alkoxide such as Si, Ti, Fe, Co, Al, etc., it is shown in the present invention by coating the sleeve surface with this as a binder and heat treatment. A ceramic hard coating layer containing the compound may be formed.

In order to uniformly disperse the calixarene compound of the present invention in the coating layer, the particle size of the calixarene compound is 10 μm or less, preferably 3 μm or less.
The amount of the calixarene compound represented by the general formula [I] used is 0.01 to 20 with respect to 100 parts by weight of the coating resin.
Parts by weight, preferably 0.1 to 10 parts by weight. By doing so, the toner rises well and a stable charge amount is given. The same content may be used when forming the ceramic hard coating layer.

As a coating method, a solution in which a predetermined amount of the calixarene compound of the present invention is dissolved or dispersed in the above resin solution dissolved and / or uniformly dispersed in a suitable solvent is placed on a blade by a known method, for example, It can be applied and dried by spraying, dipping, blade method, etc.
The thickness is 1 to 500 μm, preferably 1 to 200 μm, and more preferably 10 to 100 μm. When the thickness is less than 0.1 μm, it is difficult to control the uniform film thickness and form a uniform coating surface, and when the thickness is more than 500 μm, the adhesion with the toner layer thickness controlling member deteriorates.

When a ceramic material is used as the coating material, the usual thermal evaporation method, sputtering method, ion plating method, chemical vapor deposition method, sol-gel method, spray method, dipping method, blade method, etc. A known method is used. The film thickness also corresponds to the case of the resin layer, but a film thickness of 0.5 to 10 μm is preferable.

Further, the sleeve of the toner conveying member constitutes the outer periphery of the conductive cylindrical roller made of aluminum, phosphor bronze, stainless steel, iron or the like, and is conventionally a cylindrical conductive rubber or a metal cylindrical conductive thin film. (Ni, Al, Ti, Cr,
Mo, W, brass, brass, stainless steel, Co-Al
₂ O ₃ , Pb-TiO ₂ , Pb, TiC, etc.) or a cylindrical resin film (polycarbonate, nylon, polyester, polyethylene, polyurethane, fluororesin) or the like is used.

The sleeve of the present invention is one in which the surface of a conventional conveying member is further coated with a resin layer containing the calixarene compound of the present invention, or when a resin film or rubber is used as a material, it should be coated. However, the calixarene compound of the present invention is contained therein. At this time, the content of the calixarene compound, the coating method, and the like may be the same as those described for the blade.

In order to further improve the stability of the toner charge rise and the toner charge amount, it is advantageous to give unevenness to the blade and sleeve surfaces. Such irregularities can be formed by adding the calixarene, but from the viewpoint of imparting irregularities, it is effective to use various fine particles together with the control agent.

The fine particles that can be used in the present invention can generally be used, for example, by the blow-off method with the charge polarity as a guide, and inorganic substances, organic substances and mixtures thereof can be used. For example, as various fine particles, benzoguanamine resin particles, melamine resin fine particles, glass beads, nylon beads, epoxy resin, phenol resin, amino acrylic resin, fluorine resin, silicon resin, polyester resin, polyethylene resin, fluorine Acrylic resin etc. and inorganic and organic fillers
Further, those obtained by subjecting these particles to a treatment such as a coupling agent to make them hydrophobic are used.

The surface roughness is 1/10 to the average particle diameter of the toner.
The thickness is preferably 8/10, and is usually 0.5 to 10 μm, preferably 1 to 5 μm. Surface roughness is 10 μm
If it is larger, the toner enters the concave portion of the surface layer of the toner conveying member, and the probability of contact of the film thickness regulating member with the toner decreases, so that it becomes difficult to convey the toner and it is difficult to form a uniform thin film of the toner, and the uniform charging property to the toner Is difficult to assign. When the surface roughness is smaller than 0.1 μm, the effect due to the surface irregularities is reduced, that is, the effect on the uniform chargeability of the toner and the formation of a uniform thin film is reduced.

In the present invention, the surface roughness means the ten-point average roughness (Rz) as shown below. The ten-point average roughness is the height of the summit from the highest to the fifth peak measured in the direction of longitudinal magnification from a straight line that does not cross the cross-section curve and is parallel to the average line in the part where the reference length is extracted from the cross-section curve. The difference between the average value and the average value of the elevations of the valley bottom from the deepest to the fifth is expressed in micrometers (μm). The ten-point average roughness can be calculated by "Equation 1", and its conceptual understanding is shown in FIG.

[0037]

[Equation 1] [In the formula; R ₁ ', R ₃ ', R ₅ ', R ₇ ', R ₉ ': Elevation R ₂ ', R ₄ 'of the highest to fifth peaks of the extracted portion corresponding to the reference length L. , R ₆ ′, R ₈ ′, R ₁₀ ′: Elevation of the valley bottom from the deepest to the 5th part of the extracted portion corresponding to the reference length L] In the present invention, the reference length (L) is specified in particular. Unless otherwise specified, the one in Table 1 below is used.

[0038]

[Table 1]

As such a ten-point average measuring device, for example, a stylus type surface roughness profile measuring device Surfcom 550A (manufactured by Tokyo Seimitsu Co., Ltd.) can be used.

1 and 2 show an example of a schematic structure of an example of a developing device equipped with the above-mentioned blade and sleeve.
The developing device (1) shown in FIG. 1 is arranged on the side of the photosensitive drum (7) which is rotationally driven in the direction of the arrow (a). The developing roller (3) has a structure in which a sleeve (8) is coated on a conductive roller such as aluminum, and a developing bias voltage is applied to the roller. Therefore, the sleeve is provided with appropriate conductivity. The sleeve of the present invention described above is applied as this sleeve. further,
It is desirable to give unevenness to the surface of the sleeve.

The developing roller (3) is rotatably supported and is drivingly connected to a driving source (not shown).
The outer peripheral surface is in contact with the periphery of the photoconductor drum (7), and the blade (4) for regulating the toner layer thickness is press-contacted to the obliquely upper portion on the back side. The above-mentioned member containing calixarene is used. ing. It is preferable to use those having irregularities. The member of the present invention may be used for both the blade (4) and the sleeve, or only one of them may be used.

The agitator (5) rotates in the direction of the arrow (c) to feed the toner to the surface of the developing roller (3), and the toner should pass through the pressure contact portion between the developing roller (3) and the blade (4). By this, the surface of the sleeve (8) is uniformly applied in a thin layer and triboelectrically charged.

Next, the developing device shown in FIG. 2 will be described. In FIG. 2, the developing device (1) is arranged on the side of the photosensitive drum (7) which is rotationally driven in the direction of arrow (a).
The elastic drive roller (10) has a structure in which a conductive member such as aluminum is covered with an elastic member such as rubber, and a developing bias voltage is applied to the roller. Therefore, the upper rubber elastic member has an appropriate conductivity. The thin film member (11) is composed of an elastic drive roller (1
(0) is an endless one having a slightly longer circumference than that of (0) and is mounted on the elastic drive roller (10). For the thin film member (11), a sleeve of the present invention comprising a resin containing a calixarene compound or a resin coating layer is used. Elastic drive roller (10) equipped with thin film member (11)
Is rotatably supported and is connected to a drive source (not shown). At both ends of the drive roller (10),
A sleeve guide (9) for bringing the thin film member (11) into close contact with the outer peripheral surface of the elastic drive roller (10) is interposed. Therefore, the portion of the thin film member (11) that comes into contact with the sleeve guide (9) is in close contact with the outer peripheral surface of the drive roller (10), and the front surface portion of the elastic drive roller (10) is surrounded by the peripheral surface of the elastic drive roller (10). The surplus portion of the thin film member (11) formed slightly longer than the length is concentrated, and the thin film member (11) and the elastic drive roller (1
0) and the outer peripheral surface of the thin film member (11) covering the space (S) is in contact with the peripheral surface of the photoconductor drum (7). The coefficient of friction between the outer peripheral surface of the elastic drive roller (10) and the inner peripheral surface of the thin film member (11) is μ1, and the thin film member is
When the coefficient of friction between the outer peripheral surface of (11) and the inner surface of the sleeve guide (9) is μ2, the relationship of μ1 >> μ2 is given. Therefore, when the elastic drive roller (10) rotates in the direction of the arrow (b), the thin film member (11) follows in the same direction, and the outer surface of the thin film member (11) covering the space portion (18) becomes appropriate. The surface of the photosensitive drum (7) is rubbed with the nip width.

A blade (12) having a metal round bar (16) at its tip is attached to the back surface of a supporting member (17) provided on the upper part of the elastic drive roller (10). Is in pressure contact with the elastic drive roller (10) obliquely above the back side via a thin film member (11). The metal round bar attached to the tip of the blade (12) is made of a resin or a resin coat layer containing a calixarene compound represented by the general formula [I]. The thin film member (11) and the metal round bar
The member of the present invention may be used for both of (16) or only one of them.

A rear part of the developing tank (2) is a toner storage tank (15), and an agitator (14) is provided in the toner storage tank (15) so as to be rotatable in the direction of arrow (c).
(14) moves the toner stored in the toner storage tank (15) in the direction of the arrow (c) and prevents blocking of the toner. The toner used is a non-magnetic one-component toner.

The operation of the developing device having the structure shown in FIG. 2 will be described below. While the elastic drive roller (10) and the agitator (14) are rotating in the directions of the arrows (b) and (c) by a drive source (not shown), the toner in the toner storage tank (15) is agitated. The arrow after receiving the stirring action of (14)
It is forcibly moved in the direction (c). On the other hand, the elastic drive roller (1
The thin film member (11) is driven by the direction of arrow (b) due to the frictional force with the thin film member (11).
It receives a conveying force in the direction of arrow (b) due to contact with (11) and electrostatic force. The toner is a thin film member.
(11) and a metal rod (16) at the tip of the blade (12) are taken in by a wedge-shaped take-in portion (13),
When reaching the pressure contact portion of the blade (12), the thin film member (11) is uniformly applied in a thin film form and frictionally charged.

The toner held on the thin film member (11) is
When the thin film member (11) driven by the elastic drive roller (10) is moved to the portion (developing area (X)) facing the photoconductor drum (7), the surface potential and elasticity of the photoconductor drum (7) change. A toner image is formed by adhering to the electrostatic latent image formed on the surface of the photoconductor drum (7) based on the voltage difference from the bias voltage applied to the drive roller (10).

Here, the thin film member (11) in contact with the photosensitive drum (7) is elastically driven by the elastic drive roller (10) through the space (S).
Since it is not in contact with the photosensitive drum (7), the thin film member (11) contacts the photosensitive drum (7) softly and evenly with a proper nip width, so that the electrostatic latent image on the photosensitive drum (7) has a uniform toner. Form an image. In addition, even if there is a speed difference between the peripheral speed of the photoconductor drum (7) and the speed of the thin film member (11), the toner image once formed on the photoconductor drum (7) is not destroyed. Absent. The toner that has passed through the developing area (X) is continuously conveyed in the direction of the arrow (b) together with the thin film member (11), and again at the pressure contact portion of the toner layer thickness regulating member (12), the surface of the thin film member (11). A uniform thin layer of charged toner is formed thereon, and the above-described operation is repeated thereafter.

The present invention can also be applied to a carrier constituting a two-component developer as an auxiliary means for imparting a charge to the toner. The carrier is not particularly limited, but in general, a carrier such as a binder-type carrier obtained by mixing iron powder or ferrite carrier coated with resin or fine powder such as iron powder or ferrite with resin, kneading and crushing. Often used. In addition, a carrier of the type in which the surface of the magnetic material is coated with polymer fine particles, or various types of organic or inorganic fine particles such as polymer fine particles and magnetic powder, and a surface-modified carrier can be exemplified.

The calixarene compound represented by the general formula [I] is contained in the resin layer around the magnetic substance of the carrier or in the polymer fine particles. The content should be appropriately selected depending on the type of carrier, magnetic powder, etc., but in the case of a binder type carrier, the calixarene compound of the general formula [I] is added in an amount of 0.01 to 100 parts by weight of the binder resin. Two
0 parts by weight, preferably 0.1 to 10 parts by weight are used. Two
If the amount is more than 0 parts by weight, charging stability becomes poor during printing. In the case of the surface-modified carrier and the resin-coated carrier, 0.0001 is added to 100 parts by weight of the carrier core material.
-10 parts by weight, preferably 0.01-5 parts by weight may be used.

As a method for manufacturing the carrier, a known method may be applied, and the calixarene compound of the general formula [I] may be contained in the coat layer on the surface of the magnetic material. Specifically, for example, in order to coat the carrier core material particles with a resin to form a coat layer, the resin is dissolved in a solvent in the same manner as in the production of a known coated carrier, and the resulting solution is sprayed onto the carrier. It is sprayed on the core particles and dried, or the carrier core material and polymer particles are mechanically mixed using a blender mill, a Henschel mixer, etc., and a coating layer of particles is formed mechanochemically on the surface of the carrier core material. Then, there is a method of melting and solidifying by heating and melting. The calixarene compound may be dissolved and / or uniformly dispersed in a resin dissolved in a solvent to form a coat layer, or may be mechanochemically formed with polymer particles. Further, after forming the resin coat layer, calixarene can be further processed by a mechanochemical method to be manufactured.

Specific equipment therefor is an autoclave Piraflow equipped with a stirrer (manufactured by Front Sangyo Co., Ltd.), an impact type reformer combined with thermal treatment (eg Nara Hybridizer).
(Nara Machinery Co., Ltd.), Ong Mill (manufactured by Hosokawa Micron Co., Ltd.), Spiral coater (manufactured by Okada Seiko Co., Ltd.) and the like. Hereinafter, the present invention will be described with reference to examples.

(Production Example A of blade surface coating layer)
On the surface of the phosphor bronze metal blade shown in FIG. 1, 3 parts by weight of the compound [5] of the present invention was added with a silicone hard coating liquid (Tosgard 510; manufactured by Toshiba Silicone Co.) with a solid content of 10
What was evenly dispersed in 0 part by weight was uniformly coated by a spray method, air-dried for 30 minutes, and then 15
A blade A having a silicone resin coating layer having a film thickness of 5 μm was obtained by heating and curing at 0 ° C. for 1 hour.

(Blade surface coating layer production example B)
On the surface of the phosphor bronze metal blade shown in FIG. 2, 5 parts by weight of the compound [13] of the present invention is uniformly dispersed in 10 parts by weight of a solid content of a heat-crosslinking acrylic coating solution (Paraloid AT-50; manufactured by Rohm & Haas). The resulting mixture is uniformly coated by a spray method, air-dried for 30 minutes, and then 1
A blade B having an acrylic coating layer with a film thickness of 5 μm was obtained by heat curing at 20 ° C. for 1 hour.

(Blade surface coating production example C) A blade surface coating layer production example A was prepared by the same method except that the coating solution was changed to a polyester resin (Byron 200; manufactured by Toyobo Co., Ltd.) toluene solution. A blade C having layers was obtained.

(Production Example D of blade surface coating layer)
Blade surface coating layer A blade having a silicone resin coating layer with a film thickness of 5 μm in the same manner as in Production Example A except that 3 parts by weight of Spiron Black TRH (manufactured by Orient Chemical Industry Co., Ltd.) was added instead of the compound [5]. I got D.

(Sleeve Surface Coating Production Example A) 3 parts by weight of the compound [20] of the present invention was uniformly dispersed in a silicone hard coating solution on the surface of the aluminum sleeve shown in FIG. Was evenly coated, air dried for 30 minutes, and then heat-cured at 150 ° C. for 1 hour to obtain a sleeve A having a silicone resin coating layer with a film thickness of 5 μm.

(Leave surface coating production example B) FIG.
On the surface of a 40 μm nickel endless belt sleeve obtained by the nickel electroforming method shown in FIG.
9 parts of 3] are evenly dispersed in a silicone hard coating solution, which is evenly applied to the surface of the sleeve by a spray method and air-dried for 30 minutes.
By heat-curing for 1 hour, a sleeve B having a silicone resin coating layer having a film thickness of 6 μm was obtained.

(Sleeve Surface Coating Production Example C) In the sleeve surface coating Production Example A, the compound [2
[0] was added in place of 3 parts by weight of Spiron Black TRH (manufactured by Orient Chemical Industry Co., Ltd.) to obtain a sleeve C having a silicone resin coating layer with a thickness of 6 μm by the same method.

(Embodiment 1) A copying machine having a one-component developing system was prepared by modifying the copying machine EP-50 (manufactured by Minolta Camera Co., Ltd.) and installing the developing machine having the structure shown in FIG. Obtained. Using the toner A prepared as described below in this copying machine, initial image evaluation and printing durability test were conducted, and various image evaluations shown below were conducted. The results are summarized in "Table 2".

(Production of Toner A) Component by weight: Styrene-n-butyl methacrylate copolymer 100: Carbon black (MA # 8 manufactured by Mitsubishi Kasei) 8: Oxidized polypropylene (Viscor TS-200; Sanyo Kasei Co., Ltd.) 2) The above materials were thoroughly mixed with a ball mill, and then kneaded on a three-roll mill heated to 140 ° C. After leaving the mixture to cool,
Coarse pulverization was performed using a phasor mill and fine pulverization was performed using a jet mill. Next, air classification was performed to obtain fine powder having an average particle size of 11 μm. This fine powder is designated as Toner A. Further, 100 parts by weight of the particles obtained here was post-treated with 0.2 part by weight of positively-charged hydrophobic silica.

(Measurement of Particle Size) The particle size of the toner and the carrier which will be described later was measured as follows. Toner average particle size is measured by Coulter Counter II (manufactured by Coulter Counter)
Was used to measure the relative weight distribution by particle size with a 100 μm aber tube. Carrier particle size is
Microtrac model 7995-10SRA (manufactured by Nikkiso Co., Ltd.) was used to determine the average particle size.

(Evaluation) 1) Fogging on image When toner fogging on a white background image was evaluated, a good image with less overall fogging was obtained. This shows that the toner charge amount is sufficiently obtained.

2) Base Fogging After Black Solid Image Using a document whose half surface is black solid, the toner fog on the white background image after copying the half black solid image was evaluated, and it was confirmed whether the black solid image was present or not. No, there was little fogging. This shows that the toner charge amount rises quickly and a good image can be stably obtained regardless of the original.

3) Printing durability test After evaluating the initial image, a printing durability test was performed on 100,000 sheets to visually evaluate the image. As a result, as shown in Table 2, a stable image with less fog was obtained regardless of the number of copies. This shows that the coating layer containing the charge control agent shown in the present invention applied on the blade has sufficient durability. Further, no problem such as toner fusion on the blade occurred.

(Examples 2 to 5 and Comparative Examples 1 to 3) The same evaluation as in Example 1 was carried out by using the developing device constitution shown in Table 2 (the numbers in the table indicate the figure numbers), the blade and the sleeve. went.
The results are summarized in Table 2.

[0067]

[Table 2]

(Production Example A of Carrier) Component by Weight Polyester Resin 100 (Softening Point, 123 ° C .; Glass Transition Point, 65 ° C., AV23, OHV40) Inorganic Magnetic Powder (Toda Kogyo EPT-1000) 500 ・ Carbon black (MA # 8, manufactured by Mitsubishi Kasei Co., Ltd.) 2 The above materials were thoroughly mixed and crushed with a Henschel mixer, and then the cylinder part 180 ° C. and the cylinder head part 17
It was melted and kneaded using an extrusion kneader set to 0 ° C. The kneaded product was cooled and then finely pulverized with a jet mill, and then classified using a classifier to obtain a magnetic carrier having an average particle diameter of 55 μm. The carrier obtained here is called carrier A.

(Production Example B of Carrier) A magnetic carrier B having an average particle diameter of 55 μm was obtained by the same method except that 3 parts by weight of the compound [29] according to the present invention was added to the components of the carrier A.

(Production Example C of Carrier) Silicone resin (SR-2400; manufactured by Toray Silicone Co.) in 2 L of toluene.
A coating solution was prepared by dissolving 150 g, and then core material ferrite F-250HR (average particle size 50 μm; electric resistance 3.5)
0 × 10 ⁷ Ωcm; Nippon Iron Powder Co., Ltd.) 3000 parts by weight with a sprayer SP-40 (Okada Seiko Co., Ltd.) spray pressure 3.
The coated particles were treated for 120 minutes under the conditions of 5 kg / cm, spraying rate of 40 g / min, and temperature of 50 ° C., and the particles thus obtained were removed using a sieve (screen opening: 105 μm) to remove the coated carrier (a). Obtained. 400 parts by weight of the above-mentioned coated carrier (a) and 2 parts by weight of the compound [20] according to the present invention were applied to an Ongmill AM-20F (manufactured by Hosokawa Micron Co.) at a rotation speed of 100.
The carrier particles obtained by treating at 0 rpm for 40 minutes are filtered.
The aggregate was removed by (screen opening; 150 μm) to obtain a carrier. The carrier obtained here is designated as C. Average particle size 52 μm.

(Production Example D of Carrier (Fine Polymer Particles Containing Magnetic Powder)) Parts by Weight Styrene-Acrylic Copolymer Resin (SBM-73F: Sanyo Chemical Industry Co., Ltd.): 100 Magnetic Powder EPT-1000 (Average Particle Size 0 .3 to 0.5 μm): 200-Compound [29] 5 of the present invention The above components are mixed with a Henschel mixer, the resulting mixture is kneaded with a twin-screw extruder, cooled, and then coarsely pulverized. The crushed product is crushed and classified with a jet mill crusher and an air classifier,
Polymer fine particles containing a magnetic powder having an average particle diameter of 3 μm and a charge control agent were obtained. Next, ferrite carrier F-2
Carrier D (average) obtained by treating 5 parts by weight with 100 parts by weight of 50 HR (average particle size 50 μm) (manufactured by Nippon Iron Powder Co., Ltd.) with Ongmill AM-20F (manufactured by Hosokawa Micron Co., Ltd.) at a rotation speed of 1000 rpm for 40 minutes. A particle size of 55 μm) was obtained.

(Examples 6 to 8 and Comparative Example 4) Predetermined carriers and toner A shown in "Table 3" were used as toner / carrier =
A two-component developer was prepared by mixing in a ratio of 7/93.
Using this developer, in comparison with Examples 6 to 8 and Comparative Example 4, E
Using P-5400 (manufactured by Minolta Camera Co., Ltd.), initial image evaluation (and printing durability test) was performed, and various image evaluations shown in "Table 3" were performed. The results are shown in "Table 3".

[0073]

[Table 3]

1) Charge Amount (Q / M) and Scattering Amount The surface-treated toner A2g and the above carrier
(A to D) To check the rise of the charge amount of the toner when placed in a plastic bottle of 28 g and 50 cc and placed on a rotary stand and rotated at 1200 rpm, the charge amount after stirring for 10 minutes was measured, and at that time, Was investigated. Similarly, the toner and carrier are put in a plastic bottle, and the temperature is 35 ° C. and the relative humidity is 8
Moisture resistance was also measured by measuring the amount of charge and the amount of scattering after storage for 24 hours under 5%.

The amount of scattering is measured by a digital dust meter P5H2 type.
(Shibata Chemical Co., Ltd.). The dust meter and the magnet roll are installed at a distance of 10 cm, 2 g of the developer is set on this magnet roll, and the dust meter generates toner particles that generate dust when the magnet is rotated at 2000 rpm. , And display the count number per minute as cpm. The amount of scattering obtained here is 300 cpm
The following three-level evaluations were conducted, in which the following was ◯, 500 cpm or less was Δ, and x was more than 500 cpm. It is practically usable with a rank or more, but ◯ is preferable. The measurement results of the charge amount and the scattered amount are shown in "Table 3".

2) Fogging on Image As described above, images were printed by using the above copying machine in combination of various toners and carriers. Regarding the fogging on the image, the toner fogging on the white background image was evaluated and ranked. It can be practically used in a rank or more, but is preferably in a rank or more.

3) Printing durability test Using a chart having a B / W ratio of 6% using EP-470, 1
A printing durability test was performed on 0,000 sheets, and images and fogging were evaluated. The results are shown in "Table 3". In the table, ◯ means (practical feasible area), and x means (practical problem area).

4) Humidity resistance test After the EP-470Z device was stored at 35 ° C. and high humidity of 85% (relative humidity) for 24 hours, image evaluation, charge amount and scattering amount measurement were performed.

[0079]

When the calixarene compound represented by the general formula [I] is contained in the charge-imparting agent, the rise of charge of the toner and the stability of the charge are improved, and the toner is given an appropriate charge. it can.

[Brief description of drawings]

FIG. 1 is a schematic view of a developing device including a toner layer thickness regulating member and / or a toner conveying member of the present invention.

FIG. 2 is a schematic view of a developing device including a toner layer thickness regulating member and / or a toner conveying member of the present invention.

FIG. 3 is a diagram for explaining how to obtain a ten-point average roughness.

[Explanation of symbols]

1: Developing device 2: Developing tank 3: Developing roller 4: Blade 5: Agitator 7: Photosensitive drum 8: Sleeve 9: Sleeve guide 10: Drive roller 11: Thin film member 12: Blade
13: Intake unit 14: Agitator 15: Toner storage tank 16: Metal round bar

Claims (4)

[Claims] 1. The following general formula [I]; [Wherein R is a hydrogen atom, an alkyl group, an unsaturated alkyl group, a carboxyalkyl group or a salt thereof, an acyl group,
Or represents an aromatic hydrocarbon group; R ₁ , R ₂ and R ₃ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, a hydroxyl group, a carboxyl group, an alkyl group and Selected from the group consisting of an amino group optionally substituted with an acyl group, a nitro group, a sulfone group, a sulfamido group, a carbamoyl group, a cyano group, a lower alkylcarboxylic acid ester, and an acyl group; n is 4 to 10 Represents the integer. ] A charge-imparting material containing a calixarene compound represented by the following formula. 2. The charge-giving material according to claim 1, wherein the charge-giving agent is a sleeve. 3. The charge-giving material according to claim 1, wherein the charge-giving material is a doctor blade. 4. The charge-giving material according to claim 1, wherein the charge-giving material is a carrier.