JP2002341567A - Electrophotographic cartridge image forming method and image forming device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an image forming method and device capable of obtaining images of a high gradation and high resolution. SOLUTION: The image forming device having at least a photoreceptor, toners and an exposure device has a photosensitive layer containing an oxytitanium phthalocyanine and is characterized in the that the oxytanium phthalocyarsine has a distinct diffraction peak at a Bragg angle (2q±0.2) 27.3 deg. in the X-ray diffraction by a Cukα ray and that the volume average grain size (Dv) of the toners is 3 to 8 μm and the relation between the volume average grain size (Dv) and a number average grain size (Dn) is 1.0<=Dv/Dn<=1.3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to an image forming method and an image forming apparatus. More specifically, the present invention relates to an image forming method and apparatus suitable for a printer and an electrophotographic copying machine.

[0002]

2. Description of the Related Art With the rapid spread of copiers and printers using electrophotography, the demand for high-definition images has increased in recent years. In order to improve a high-definition image, in particular, gradation and resolution, it is conceivable to increase the number of dots during image exposure. For this purpose, the beam diameter is reduced and the number of output pulses is increased. However, in such high-density recording, the time required for exposing one dot is reduced. In such a case, the photosensitivity of the conventional photoreceptor is insufficient, and the reproducibility of one dot is deteriorated, so that the gradation and the resolving power are not improved. In order to solve this problem, it is conceivable to increase the light energy itself, but this causes a problem such as light fatigue in the photosensitive layer.

As a method for solving the above-mentioned problem, Japanese Patent Laid-Open Publication No. Hei 3-37678 discloses that the Bragg angle 2θ of X-ray diffraction for CuKα characteristic X-ray (wavelength 1.541 °) is 2
A method is disclosed in which a crystalline oxytitanyl phthalocyanine having a strong peak at 7.2 ± 0.2 ° is used as a photoconductive substance of a photosensitive layer. By using this oxytitanyl phthalocyanine, high sensitivity and high γ can be obtained. It has been shown that a photoreceptor exhibiting sufficient photo-responsiveness can be realized, and that when this photoreceptor is used, sufficient dot reproducibility can be realized even when the exposure time of each dot is short at high density recording. .

This publication discloses that a toner having an average particle diameter of 8 μm or less is used in combination, but in practice, the above-mentioned problem is not always sufficiently solved if the toner has only a small particle diameter. Not done. That is, even with a small particle size toner,
Depending on the particle size and the particle size distribution of the toner, the fluidity of the toner is deteriorated, and the toner having a non-uniform colorant and a charge control agent is mixed. In this case, the adhesion to the latent image is not uniform. Therefore, the latent image may not be able to be faithfully reproduced.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art.
That is, an object of the present invention is to provide a developing method capable of obtaining an image having excellent fine line reproducibility and gradation.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in view of the above problems, and as a result, have found that the above problems can be solved by a combination of a specific electrophotographic photosensitive member and a toner, and have reached the present invention.

That is, the gist of the present invention is to provide at least a photoconductor,
In an image forming apparatus provided with a toner and an exposure device, the photoconductor contains oxytitanium phthalocyanine having a clear diffraction peak at a Bragg angle (2θ ± 0.2) of 27.3 ° in X-ray diffraction using CuKα radiation. The toner has a photosensitive layer in which a charge generation layer and a charge transfer layer are laminated. The toner has a volume average particle diameter (Dv) of 3 to 8 μm, and has a volume average particle diameter (Dv) and a number average particle diameter (Dn). Relationship with
An image forming apparatus is characterized in that 1.0 ≦ Dv / Dn ≦ 1.3.

Another gist of the present invention is to provide an image forming method using at least a photoreceptor, an exposure device, and an image forming device provided with a toner, in X-ray diffraction by CuKα radiation, the Bragg angle (2θ ± 0). .2) A photoreceptor having a photosensitive layer in which a charge generation layer containing an oxytitanium phthalocyanine having a clear diffraction peak at 27.3 ° and a charge transfer layer is subjected to digital image exposure using the exposure apparatus. Forming an electrostatic latent image on the photoreceptor, and in developing the electrostatic latent image, the volume average particle diameter (Dv) is 3 to 8
μm, volume average particle diameter (Dv) and number average particle diameter (D
The present invention resides in an image forming method characterized by using a toner in which the relationship of n) satisfies 1.0 ≦ Dv / Dn ≦ 1.3.

Another aspect of the present invention is that the volume average particle diameter (Dv) is 3 to 8 μm, and the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.0 ≦ Dv. / Dn ≦
A charge generation layer and a charge transfer layer containing a toner of 1.3 and oxytitanium phthalocyanine having a clear diffraction peak at a Bragg angle (2θ ± 0.2) 27.3 ° in X-ray diffraction by CuKα radiation And an electrophotographic cartridge provided with the photosensitive member.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, an outline of an image forming method and an image forming apparatus used in the present invention will be described for an electrophotographic recording apparatus using a non-magnetic one-component toner which is an example of a full-color image forming method. However, the present invention is not limited to this example. FIG. 1 is a schematic diagram of a main part configuration of an embodiment of an electrophotographic recording apparatus used in the present invention.
It has a transfer device 5, a cleaning device 6, and a fixing device 7.

The photosensitive member 1 is formed of a conductor such as aluminum, for example, and has a photosensitive layer formed by coating a photosensitive conductive material on the outer peripheral surface. A charging device 2, an exposure device 3, a developing device 4, a transfer device 5, and a cleaning device 6 are arranged along the outer peripheral surface of the photoreceptor 1, respectively. The charging device 2 includes, for example, a well-known scorotron charger, a roller charger, and the like, and uniformly charges the surface of the photoconductor 1 to a predetermined potential. The photoconductor is preferably provided in a cartridge (photoconductor cartridge) together with the charging device, and is preferably incorporated in the image forming apparatus. By doing this,
When the photoconductor or the charging device is deteriorated, it can be easily replaced.

The exposure device 3 applies LE to the photosensitive surface of the photosensitive member 1.
D, which forms an electrostatic latent image on the photosensitive surface of the photoconductor 1 by performing exposure with a laser beam or the like. The developing device 4 includes an agitator 42, a supply roller 43, a developing roller 44, and a regulating member 45, and stores the toner T therein. If necessary, the developing device may be provided with a replenishing device (not shown) for replenishing the toner, and the replenishing device can replenish the toner from a container such as a bottle or a cartridge.

The supply roller 43 is made of a conductive sponge or the like, and is in contact with the developing roller 44. The developing roller 44 is disposed between the photoconductor 1 and the supply roller 43. The developing roller 44 is in contact with the photoconductor 1 and the supply roller 43, respectively. The supply roller 43 and the developing roller 44 are rotated by a rotation drive mechanism. The supply roller 43 carries the stored toner and supplies it to the developing roller 44. Developing roller 44
Carries the toner supplied by the supply roller 43 and contacts the surface of the photoconductor 1.

The developing roller 44 is made of iron, stainless steel,
It is made of a metal roll of aluminum, nickel, or the like, or a resin roll in which a metal roll is coated with a silicon resin, a urethane resin, a fluororesin, or the like. The surface of the developing roll is
If necessary, the surface may be smoothed or roughened. It is preferable that the developing device is incorporated in the image forming apparatus as a toner cartridge having a toner.
This facilitates toner replenishment.

The regulating member 45 is formed of a resin blade such as a silicone resin or a urethane resin, a metal blade such as stainless steel, aluminum, copper, brass, phosphor bronze, or the like, or a metal blade coated with a resin. The regulating member 45 contacts the developing roller 44,
A predetermined force is applied to the developing roller 44 side by a spring or the like (a general blade linear pressure is 5 to 500 g / cm), and a function of imparting charge to the toner by frictional charging with the toner as necessary is provided. You may.

The agitator 42 is rotated by a rotary drive mechanism, and agitates the toner and conveys the toner to the supply roller 43 side. A plurality of agitators may be provided with different blade shapes, sizes, and the like.

The transfer device 5 includes a transfer charger, a transfer roller, a transfer belt, and the like, which are arranged to face the photosensitive member 1. The transfer device 5 applies a predetermined voltage value (transfer voltage) having a polarity opposite to the charged potential of the toner, and transfers the toner image formed on the photoconductor 1 to the recording paper P. Note that, depending on the image forming apparatus, there are a case where the toner image on the photoconductor is directly transferred to the recording paper P and a case where the toner image is transferred to the recording paper P via an intermediate transfer belt (not shown).

The cleaning device 6 comprises a cleaning member such as a urethane blade or a fur brush.
The cleaning device removes the residual toner attached to the photoreceptor 1 and collects the residual toner. In some image forming apparatuses, a cleaning device is not provided.

The fixing device 7 comprises an upper fixing member 71 and a lower fixing member 72, and has a heating device 73 inside the upper or lower fixing member. As the fixing member, a known heat fixing member such as a fixing roll obtained by coating a metal tube such as stainless steel or aluminum with silicon rubber, a fixing roll coated with Teflon (registered trademark) resin, and a fixing sheet can be used. Further, a releasing agent such as silicone oil may be supplied to the fixing member to improve the releasing property. Further, a mechanism for forcibly applying pressure to the upper fixing member and the lower fixing member by a spring or the like may be employed.

When the toner transferred onto the paper P passes between the upper fixing member 71 and the lower fixing member 72 heated to a predetermined temperature, the toner is heated to a molten state, cooled after passing through, and recorded. The toner is fixed on the paper P.

In the electrophotographic developing apparatus configured as described above, an image is recorded as follows. That is, first, the surface (photosensitive surface) of the photoconductor 1 is charged to a predetermined potential (for example, −600 V) by the charging device 2. continue,
The charged photosensitive surface of the photoreceptor 1 is exposed by the exposure device 3 in accordance with an image to be recorded, and an electrostatic latent image is formed on the photosensitive surface. Then, the developing device 4 develops the electrostatic latent image formed on the photosensitive surface of the photosensitive member 1.

In the developing device 4, the toner supplied by the supply roller 43 is thinned by the developing blade 45, and has a predetermined polarity (here, the same polarity as the charging potential of the photoreceptor 1 and a negative polarity). After being triboelectrically charged, it is carried on the developing roller 44, transported, and brought into contact with the surface of the photoconductor 1.

From the developing roller 44, a toner image corresponding to the electrostatic latent image is formed on the surface of the photosensitive member 1 by a so-called reversal developing method. Then, the toner image is transferred to the sheet P by the transfer device 5. Thereafter, the toner remaining on the photosensitive surface of the photoconductor 1 without being transferred is removed by the cleaning device 6. The final image is obtained by passing the toner on the recording paper P through the fixing device 7 and thermally fixing the toner.

Next, an example of a tandem type electrophotographic recording apparatus using a non-magnetic one-component toner as a full color will be described. FIG. 2 is a schematic diagram of a main structure of a full-color tandem system, which includes a photosensitive member 1, a charging device 2, an exposure device 3, a black developing device 4k, a cyan developing device 4c, a yellow developing device 4y, a magenta developing device 4m, and a transfer device 5. , And a fixing device 7, and a cleaning device is omitted here. A full-color image can be obtained by superimposing each of magenta, yellow, cyan, and black toners in multiple layers and adjusting the color to a desired color.

In the case of the tandem system, it is better that the color developing section is located before the black developing section so that color mixture due to reverse transfer of black toner is reduced, and that the black developing section is located behind the color developing section. Reduces the color mixture due to photoconductor fog of the color toner when forming an image in a single color of black only, and speeds up the black image formation by conveying the recording paper by short-passing the color developing section. It is preferable because it is possible.

When the image forming method of the present invention is applied to full-color image formation, such a cyan, magenta, and yellow color developing section is located at a front position, and a black developing section is located after a color developing section. Suitable for tandem type. The order in which the cyan, magenta, and yellow color developing units are located can be freely changed as needed.

[0027] The toner used in the present invention contains at least a binder resin and a colorant.
Waxes and other additives can be included. As the method for producing the toner used in the present invention, a method for increasing the accuracy of a classifier in a toner produced by a conventional kneading / pulverizing method, and a method for producing a toner by a wet polymerization method such as a suspension polymerization method, an emulsion polymerization / aggregation method, etc. However, in order to efficiently prepare the toner of the present invention, it is preferable to use a wet polymerization method. Furthermore, in order to achieve a suitable particle size distribution of the toner of the present invention, an emulsion polymerization / aggregation method is particularly preferred. The emulsion polymerization / aggregation method has an advantage that the circularity of the toner can be appropriately controlled.

The binder resin used for the toner can be selected from a wide range including those conventionally known. Preferably, a styrene-based polymer such as a styrene-acrylate copolymer, a styrene-methacrylate copolymer, or an acrylic copolymer of these resins, a saturated or unsaturated polyester-based polymer, and an epoxy-based polymer are exemplified. be able to. Further, the binder resin is not limited to being used alone, and may be used in combination of two or more kinds.

The colorant may be an inorganic pigment, an organic pigment, an organic dye, or a combination thereof. Specific examples of these include carbon black,
Aniline blue, phthalocyanine blue, phthalocyanine green, hansa yellow, rhodamine dye, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye,
Any known dyes and pigments such as disazo and condensed azo dyes can be used alone or in combination. In the case of a full-color toner, it is preferable to use benzidine yellow, a monoazo-based, condensed azo-based dye and pigment as yellow, quinacridone and monoazo-based dye and pigment as magenta, and phthalocyanine blue as cyan, respectively.

Of these, cyan colorants include C.I.
I. Pigment Blue 15: 3, and C.I. I. Pigment yellow 74, C.I. I. Pigment Yellow 93 and C.I. I. Pigment Red 238, C.I. I. Pigment Red 26
9, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 12
2 is preferably used. The amount of the colorant added is preferably in the range of 2 to 25 parts by weight based on 100 parts by weight of the binder resin.

The toner used in the present invention has a charge amount,
A charge control agent may be added for imparting charge stability.
As the charge control agent, a conventionally known compound is used.
Examples thereof include metal complexes of hydroxycarboxylic acids, metal complexes of azo compounds, naphthol compounds, metal compounds of naphthol compounds, nigrosine dyes, quaternary ammonium salts, and mixtures thereof. The addition amount of the charge control agent is preferably in the range of 0.1 to 5 parts by weight based on 100 parts by weight of the binder resin.

It is preferable to add wax to the toner used in the present invention in order to impart releasability from a fixing roller or the like. Any wax can be used as long as it has a releasing property. Specifically, olefin waxes such as low molecular weight polyethylene, low molecular weight polypropylene, and copolymerized polyethylene; paraffin wax; ester waxes having a long-chain aliphatic group such as behenyl behenate, montanic acid ester, and stearyl stearate; Vegetable waxes such as castor oil carnauba wax; ketones having a long-chain alkyl group such as distearyl ketone; silicones having an alkyl group; higher fatty acids such as stearic acid; long-chain aliphatic alcohols such as eicosanol; Examples thereof include carboxylic acid esters or partial esters of polyhydric alcohols obtained from polyhydric alcohols and long-chain fatty acids; higher fatty acid amides such as oleic amide and stearic acid amide; low molecular weight polyesters and the like.

In order to improve the fixability among these waxes, the melting point of the wax is preferably 30 ° C. or more,
0 ° C. or higher is more preferable, and 50 ° C. or higher is particularly preferable.
Further, the temperature is preferably 100 ° C. or lower, more preferably 90 ° C. or lower, and particularly preferably 80 ° C. or lower. If the melting point is too low, the wax is likely to be exposed on the surface after fixing and sticky,
If the melting point is too high, the fixability at low temperatures is poor. Further, as the compound type of the wax, an ester wax obtained from an aliphatic carboxylic acid and a monohydric or polyhydric alcohol is preferable.
Those having 0 to 100 are more preferable, and those having 30 to 60 carbon atoms are particularly preferable.

Among the esters of a monohydric alcohol and an aliphatic carboxylic acid, particularly preferred compounds include behenyl behenate and stearyl stearate. Also,
Among the esters of polyhydric alcohols and aliphatic carboxylic acids, particularly preferred compounds include pentaerythritol stearic acid ester and its partial ester, glycerin montanic acid ester and its partial ester.

The above waxes may be used alone or as a mixture. Further, the melting point of the wax compound can be appropriately selected depending on the fixing temperature at which the toner is fixed. The amount of the wax used is usually 0.1 to 4 in the toner.
0% by weight, preferably 1 to 40% by weight, more preferably 2 to 35% by weight, particularly preferably 5 to 30% by weight.

Next, a wet polymerization method will be described as a preferred method for producing the toner used in the present invention.

In the emulsion polymerization / aggregation method, a colorant dispersion, a charge control agent dispersion, a wax dispersion and the like are mixed with a dispersion of polymer primary particles, and the temperature, salt concentration, pH and the like are appropriately controlled. These are aggregated to produce a toner.

The emulsifier used in the emulsion polymerization includes at least one emulsifier selected from a cationic surfactant, an anionic surfactant and a nonionic surfactant. Specific examples of the cationic surfactant include dodecyl ammonium chloride, dodecyl ammonium bromide, dodecyl trimethyl ammonium bromide, dodecyl pyridinium chloride, dodecyl pyridinium bromide, hexadecyl trimethyl ammonium bromide, and the like. Specific examples of the anionic surfactant include fatty acid soaps such as sodium stearate and sodium dodecanoate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, sodium lauryl sulfate and the like. Further, specific examples of the nonionic surfactant include polyoxyethylene dodecyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene sorbitan monooleate ether, and monodecanoyl. And sucrose. Among these surfactants, alkali metal salts of linear alkylbenzene sulfonic acids are preferred.

In the suspension polymerization method, a colorant,
A charge controlling agent, wax and the like are mixed and subjected to a dispersion treatment using a disperser such as a disperser, and the monomer composition after the dispersion treatment is dispersed in a water-miscible medium using an appropriate stirrer. After granulating to a diameter, the polymerizable monomer is polymerized to produce a toner.

When a suspension stabilizer is used, it is preferable to select a suspension stabilizer which is neutral or alkaline in water and can be easily removed by acid washing after polymerization. Further, it is preferable to select a toner capable of obtaining a toner having a narrow particle size distribution. Suspension stabilizers that satisfy these requirements include calcium phosphate, tricalcium phosphate, magnesium phosphate, calcium hydroxide, magnesium hydroxide and the like. Each can be used alone or in combination of two or more. These suspension stabilizers can be used in an amount of 1 to 10 parts by weight based on the radical polymerizable monomer.

As the polymerization initiator used in the emulsion polymerization / aggregation method and the suspension polymerization method, known polymerization initiators can be used alone or in combination of two or more. For example, potassium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobisiso (2,4-dimethyl) valeronitrile, benzoyl peroxide, lauroyl peroxide, or a redox initiator is used. You can do it. Among these, a redox initiator is preferable in the emulsion polymerization / aggregation method, and an azo initiator is preferable in the suspension polymerization method. A toner having a capsule structure may be prepared by adding a polymer emulsion, a colorant dispersion, a charge control agent dispersion, a wax dispersion, and the like to the toner surface after the toner is manufactured by the above method.

Next, the emulsion polymerization / aggregation method, which is the most preferable method for producing the toner of the present invention, will be described in more detail. When a toner is produced by an emulsion polymerization / aggregation method, it usually has a polymerization step, a mixing step, an aggregation step, and a washing / drying step. That is, the dispersion containing the polymer primary particles obtained by emulsion polymerization is mixed with each dispersion such as a colorant, a charge control agent, and wax, and the primary particles in the dispersion are aggregated to obtain a volume average particle size of 3%. To about 8 μm, and, if necessary, resin fine particles and the like are adhered thereto, and if necessary, the particle aggregates or the particle aggregates to which the resin fine particles are adhered are fused, and the toner thus obtained is obtained. Washing particles,
Dry to obtain product toner particles.

Primary Polymer Particles The primary polymer particles used in the emulsion polymerization / aggregation method preferably have a glass transition temperature (Tg) of 40 to 80 ° C.
And the average particle size is usually from 0.02 to 3 μm. The polymer primary particles are obtained by emulsion polymerization of a monomer.

In the emulsion polymerization, a monomer having a Bronsted acidic group (hereinafter, may be simply referred to as an acidic group) or a Bronsted basic group (hereinafter, may be simply referred to as a basic group) may be used. Is added, and a monomer having neither a Bronsted acidic group nor a Bronsted basic group (hereinafter, may be referred to as another monomer) causes polymerization to proceed. At this time, the monomers may be added separately, or a plurality of monomers may be mixed in advance and added. Further, the monomer composition can be changed during the addition of the monomer. Further, the monomer may be added as it is, or may be added as an emulsified liquid which is previously mixed and adjusted with water or an emulsifier. As the emulsifier, one or a combination of two or more of the above surfactants is selected.

Examples of the monomer having a Bronsted acidic group used in the present invention include monomers having a carboxyl group such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, and cinnamic acid, and sulfonic acid groups such as sulfonated styrene. And monomers having a sulfonamide group such as vinylbenzenesulfonamide.

Examples of the monomer having a Brönsted basic group include aromatic vinyl compounds having an amino group such as aminostyrene, nitrogen-containing heterocyclic-containing monomers such as vinylpyridine and vinylpyrrolidone, dimethylaminoethyl acrylate, and diethylamino. (Meth) acrylic acid esters having an amino group such as ethyl methacrylate;

The monomer having an acidic group and the monomer having a basic group may each be present as a salt with a counter ion. The blending ratio of the monomer having a Bronsted acidic group or a Bronsted basic group in the monomer mixture constituting the polymer primary particles is preferably 0.05% by weight or more, more preferably 1% by weight or more. And it is preferably at most 10% by weight, more preferably at most 5% by weight. Among monomers having a Bronsted acidic group or a Bronsted basic group, acrylic acid or methacrylic acid is particularly preferred.

Other comonomers include styrene,
Methyl styrene, chlorostyrene, dichlorostyrene,
pt-butylstyrene, pn-butylstyrene, p
Styrenes such as -n-nonylstyrene, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, hydroxyethyl acrylate, ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, (Meth) acrylates such as propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, hydroxyethyl methacrylate, ethylhexyl methacrylate, acrylamide, N-propylacrylamide, N, N-dimethylacrylamide, N, N- Examples thereof include dipropylacrylamide, N, N-dibutylacrylamide and acrylamide. Can be mentioned. Among them, styrene, butyl acrylate and the like are particularly preferable.

Further, when a cross-linking resin is used for the polymer primary particles, a polyfunctional monomer having radical polymerizability is used as a cross-linking agent shared with the above-mentioned monomers, for example, divinylbenzene, hexanediol diacrylate, Examples include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol dimethacrylate, neopentyl glycol acrylate, diallyl phthalate, and the like. It is also possible to use a monomer having a reactive group in the pendant group, for example, glycidyl methacrylate, methylolacrylamide, acrolein and the like.

A radically polymerizable difunctional monomer is preferred, and divinylbenzene and hexanediol diacrylate are more preferred. The blending ratio of such a polyfunctional monomer in the monomer mixture is preferably at least 0.005% by weight, more preferably at least 0.1% by weight, particularly preferably at least 0.3% by weight. Preferably 5% by weight or less, more preferably 3% by weight or less,
It is particularly preferably at most 1% by weight.

These monomers are used singly or as a mixture. In this case, the polymer has a glass transition temperature of 40.
~ 80 ° C is preferred. Glass transition temperature 80
If the temperature exceeds 100 ° C., the fixing temperature may become too high, or the OHP transparency may deteriorate. On the other hand, if the glass transition temperature of the polymer is lower than 40 ° C., the storage stability of the toner may deteriorate. is there.

The polymerization initiator may be added to the polymerization system at any time before, simultaneously with, or after addition of the monomer.
You may combine these addition methods as needed.
In the emulsion polymerization, a known chain transfer agent can be used if necessary. Specific examples of such a chain transfer agent include t-dodecylmercaptan, 2-mercaptoethanol, diisopropylxanthogen, and Carbon chloride, trichlorobromomethane, and the like. The chain transfer agent may be used alone or in combination of two or more kinds, and is used in an amount of 0 to 5% by weight based on the polymerizable monomer. Emulsion polymerization is
Mix the above monomers with water, in the presence of a polymerization initiator,
The polymerization is carried out, and the polymerization temperature is usually 50 to 150 ° C, preferably 60 to 120 ° C, and more preferably 70 to 100 ° C.

The volume average particle diameter of the polymer primary particles thus obtained is generally in the range of 0.02 μm to 3 μm, preferably 0.05 μm to 3 μm, more preferably 0.1 μm to 3 μm.
μm to 2 μm, particularly preferably 0.1 μm to 1 μm
m. The average particle size can be measured using, for example, UPA. When the particle size is smaller than 0.02 μm, it is difficult to control the agglomeration rate, which is not preferable. Also,
If it is larger than 3 μm, the particle size of the toner obtained by agglomeration tends to be large, which is unsuitable for producing a toner of 3 to 8 μm.

In the colorant emulsion polymerization / aggregation method, a dispersion of primary polymer particles and colorant particles are mixed to form a mixed dispersion, which is then aggregated to form a particle aggregate. The emulsion is preferably used in the form of an emulsion after emulsification in water in the presence of an emulsifier (the above-mentioned surfactant). The volume average particle size of the colorant particles is preferably 0.01 to 3 μm. The amount of the colorant used is usually 1-2 parts per 100 parts by weight of the polymer primary particles.
It is 5 parts by weight, preferably 3 to 20 parts by weight.

In the wax emulsion polymerization / aggregation method, it is preferable to use a wax which has been dispersed in the presence of an emulsifier (the above-mentioned surfactant) to form an emulsified wax fine particle dispersion. The wax is present in the agglomeration step. For example, the wax fine particle dispersion is co-aggregated with the polymer primary particles and the colorant particles. In some cases, a polymer primary particle containing the above is prepared and this and the colorant particles are aggregated. Of these, in order to uniformly disperse the wax in the toner, it is preferable that the wax fine particle dispersion is present at the time of preparing the above-mentioned polymer primary particles, that is, at the time of polymerizing the monomer.

The average particle diameter of the wax fine particles is 0.01 μm.
m to 3 μm, more preferably 0.1 to 2 μm
m, especially those having a diameter of 0.3 to 1.5 μm are preferably used. The average particle size is, for example, LA-500 manufactured by Horiba.
Can be measured. When the average particle size of the wax emulsion is larger than 3 μm, it tends to be difficult to control the particle size during aggregation, and when the average particle size of the emulsion is smaller than 0.01 μm, a dispersion is prepared. Difficult to do.

As a method for incorporating a charge control agent in the emulsion polymerization / aggregation method, a charge control agent can be used as a seed simultaneously with wax when preparing polymer primary particles, or a charge control agent can be used as a monomer or wax in a monomer or wax. Suitable for use as a toner by dissolving or dispersing it, or by aggregating primary particles of the charge control agent simultaneously with the primary particles of the polymer and the colorant to form a particle aggregate, or by aggregating the primary particles of the polymer and the colorant. After the particles have a suitable particle size, the particles can be aggregated by adding primary particles of the charge control agent. In this case, the charge control agent is also dispersed in water using an emulsifier (the above-described surfactant), and has an average particle size of 0.01 to 3 μm.
It is preferably used as an emulsion of m (primary particles of a charge control agent).

Mixing Step In the aggregating step of the production method of the present invention, the above-mentioned particles of the compounding components such as the polymer primary particles, the colorant particles, and, if necessary, the charge controlling agent and the wax are mixed simultaneously or sequentially. However, dispersions of the respective components, that is, a polymer primary particle dispersion, a colorant particle dispersion, a charge control agent dispersion, and a wax fine particle dispersion are prepared beforehand. It is preferable to obtain a mixed dispersion by mixing. Further, it is preferable that the wax is contained in the toner by using polymer primary particles encapsulated in the polymer primary particles, that is, polymer primary particles obtained by emulsion polymerization using the wax as a seed. In this case, the polymer primary particles are used. It is possible to use the wax encapsulated in and the wax fine particles not encapsulated in combination, but it is more preferable to use substantially the entire amount of the wax in the form encapsulated in the polymer primary particles. is there.

Aggregation Step In a preferred embodiment of the present invention, the above-mentioned polymer primary particles, colorant primary particles and, if necessary, charge control agent fine particles, wax fine particles and other internal additives are emulsified to form an emulsion, These are coagulated to form a particle aggregate. Among the components that perform aggregation, the charge control agent dispersion may be added during the aggregation step or may be added after the aggregation step. Here, in the aggregation step, there are 1) a method of performing aggregation by heating in a stirring tank, and 2) a method of performing aggregation by adding an electrolyte.

When performing aggregation by heating, the aggregation temperature is specifically in the temperature range of 5 ° C. to Tg (where Tg is the glass transition temperature of the primary polymer particles), and Tg−10.
C. to Tg-5 C. are preferred. Within the above temperature range, the toner can be aggregated to a preferable toner particle size without using an electrolyte. When performing aggregation by heating,
When the aging step is performed subsequent to the aggregation step, the heat of the aggregation step and the aging step are continuously performed and the boundary may be ambiguous, but the temperature is kept in a temperature range of Tg-20 ° C to Tg for at least 30 minutes. If there is a step to perform, this is regarded as an aggregation step. The aggregation temperature is preferably maintained at a predetermined temperature for at least 30 minutes to obtain toner particles having a desired particle size. The temperature may be raised at a constant rate up to a predetermined temperature, or may be raised stepwise. The retention time is T
The temperature is preferably from 30 minutes to 8 hours, more preferably from 1 hour to less than 4 hours, in the range of g-20 ° C to Tg. By doing so, a toner having a small particle size and a sharp particle size distribution can be obtained.

When the electrolyte is added to the mixed dispersion to effect aggregation, either an organic salt or an inorganic salt may be used, but a monovalent or divalent or higher polyvalent metal salt is preferably used. Can be Specifically, NaCl, KCl,
LiCl, Na ₂ SO ₄ , K ₂ SO ₄ , Li ₂ SO ₄ , MgC
l ₂ , CaCl ₂ , MgSO ₄ , CaSO ₄ , ZnSO ₄ ,
Al ₂ (SO ₄ ) ₃ , Fe ₂ (SO ₄ ) ₃ , CH ₃ COON
a, C ₆ H ₅ SO ₃ Na and the like. Of these,
An inorganic salt having a divalent or higher polyvalent metal cation is more preferable.

The amount of the electrolyte to be added varies depending on the type of the electrolyte, but usually 0.05 to 25 parts by weight based on 100 parts by weight of the solid component of the mixed dispersion. Preferably 0.1 to 15 parts by weight, more preferably 0.1 to 10 parts by weight
Parts by weight. When the amount of the electrolyte added is significantly smaller than the above range, the progress of the agglutination reaction is slowed down and the
Problems tend to occur, such as fine powder having a particle size of not more than μm remaining or an average particle size of the obtained particle aggregate being not more than 3 μm. Further, when the amount of the electrolyte added is significantly larger than the above range, the aggregation tends to be rapid and difficult to control, and coarse particles of 25 μm or more are mixed in the obtained particle aggregate, or the shape of the aggregate is distorted. It tends to cause problems such as irregular shapes. Temperature when adding electrolyte is 5 ° C ~
Tg is preferable, and it is more preferable to heat to Tg-10 ° C to Tg-5 ° C.

Other Ingredients Next, in the present invention, it is preferable to form toner particles by coating (adhering or fixing) resin fine particles as necessary on the surface of the particle aggregate after the above-mentioned aggregation treatment. . When the above-described charge control agent is added after the aggregation treatment, resin fine particles may be added after the charge control agent is added to the dispersion containing the particle aggregate.

The resin fine particles are used as an emulsion dispersed in water or a liquid mainly composed of water by an emulsifier (the above-mentioned surfactant). The resin fine particles used for the outermost layer of the toner do not contain wax. preferable. As the resin fine particles, preferably, the volume average particle size is from 0.02 to
Those having a size of 3 μm, more preferably 0.05 to 1.5 μm, obtained by polymerizing a monomer similar to the monomer used for the above-mentioned polymer primary particles can be used. When the toner is formed by coating the particle aggregate with resin fine particles, the resin used for the resin fine particles is preferably cross-linked.

Aging Step In the emulsion polymerization / aggregation method, in order to increase the stability of the particle aggregate (toner particles) obtained by aggregation, Tg + 20 ° C.
It is preferable to add a ripening step of causing fusion between aggregated particles in the range of Tg + 80 ° C. (where Tg is the glass transition temperature of the primary polymer particles). In the aging step, it is preferable to maintain the temperature in the above-mentioned temperature range for 1 hour or more. By adding the aging step, the shape of the toner particles can be made nearly spherical, and the shape can be controlled. This aging step is usually performed for 1 hour to 24 hours, preferably 1 hour to 10 hours. Although the particle aggregate before the aging step is considered to be an aggregate due to electrostatic or other physical aggregation of the primary particles, after the aging step, the polymer primary particles constituting the particle aggregate are fused to each other. And
Preferably it is substantially spherical. In addition, according to such a method for producing a toner, various shapes such as a grape type in which primary particles are aggregated, a potato type in which fusion has progressed halfway, a spherical shape in which fusion has further progressed, and the like according to purposes. A toner can be manufactured.

Washing / Drying Step The particle aggregate obtained through each of the above-mentioned steps is subjected to solid-liquid separation according to a known method, and the particle aggregate is recovered. After drying, the desired toner particles can be obtained. In this manner, a toner having a relatively small volume average particle diameter of 3 to 8 μm can be manufactured. Moreover, the toner thus obtained has a sharp particle size distribution and is suitable as a toner for developing an electrostatic image for achieving high image quality and high speed.

A known external additive may be added to the toner used in the present invention to control fluidity and developability.
As the external additive, various kinds of inorganic oxide particles such as silica, alumina, titania and the like (which may be subjected to a hydrophobic treatment if necessary), vinyl polymer particles and the like can be used. The amount of the external additive is preferably in the range of 0.05 to 5 parts by weight based on the toner particles.

The toner used in the present invention can be applied to a two-component developer, a magnetic one-component developer such as a magnetite-containing toner, and a non-magnetic one-component developer. When used as a two-component developer, known carriers such as iron powder-based, ferrite-based, and magnetite-based carriers or resin coatings on their surfaces are used as carriers for forming the developer by mixing with the toner. Or a magnetic resin carrier can be used.

As the coating resin for the carrier, generally known styrene resins, acrylic resins, styrene acrylic copolymer resins, silicone resins, modified silicone resins, fluorine resins, etc. can be used. It is not limited. The average particle size of the carrier is not particularly limited, but preferably has an average particle size of 10 to 200 μm. These carriers are preferably used in an amount of 5 to 100 parts by weight based on 1 part by weight of the toner.

As a method for measuring the particle size of the toner,
A commercially available particle size measuring apparatus can be used, but typically, a precision particle size distribution measuring apparatus manufactured by Beckman Coulter KK Coulter Counter Multisizer II
Is used. The toner used in the present invention has a volume average particle size (Dv) of 3 to 8 μm. Volume average particle size is 4 ~
8 μm is preferred, and 4-7 μm is more preferred. If the volume average particle diameter is too large, it is not suitable for forming a high-resolution image, and if it is too small, handling as a powder becomes difficult.

Further, the toner having a sharp particle size distribution tends to have uniform chargeability. In particular,
In the image forming method and apparatus of the present invention, the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.0.
≦ Dv / Dn ≦ 1.3 is used. Dv /
The value of Dn is preferably 1.25 or less,
The following are more preferred. Further, the lower limit of Dv / Dn is 1, which means that all particle diameters are equal, which is difficult to manufacture.
5 or more is more preferable.

It is preferable that the toner has few fine particles (fine powder). When the number of fine particles is small, the fluidity of the toner is improved, and the chargeability is likely to be uniform. For measuring fine particles, for example, a flow particle image analyzer FPIA-2000 manufactured by Sysmex Corporation is preferably used. In the present invention, it is preferable to use a toner whose measured value (number) of particles of 0.6 μm to 2.12 μm by a flow type particle image analyzer is 15% or less of the total number of particles. This means that the number of fine particles is less than a certain amount, but the number of particles of 0.6 μm to 2.12 μm is 1
0% or less is more preferable, 5% or less is particularly preferable,
% Is most preferred. Further, there is no particular lower limit of the fine particles, and it is most preferable that the fine particles do not exist at all. However, this is difficult in production and is usually 0.05% or more, preferably 0.1%.
1% or more.

Further, as other indices of the toner having a small amount of fine powder, the following can be mentioned. 1) In the toner,
Those having a particle size of 40% or less of the volume average particle size are 9.0
It is preferably at most a number%, more preferably at most 8.0 number%. 2) The toner having a particle size of 55% or less of the volume average particle size is preferably 5.0% by volume or less,
More preferably, it is 4.0 volume% or less. 3) The number of toner particles having a particle size of 55% or less of the volume average particle size is preferably 20% by number or less.
More preferably, it is not more than a number%.

The shape of the toner is preferably as close to a sphere as possible. Specifically, as a method of quantifying the shape of the toner, the toner is measured with a flow particle image analyzer FPIA-2000 manufactured by Sysmex Corporation,
When the circularity corresponding to the cumulative particle size value at 50% of the value obtained from the following formula (I) is defined as 50% circularity,
Those having a 50% circularity in the range of 0.9 to 1 are preferred.

[0075]

## EQU00002 ## Circularity = perimeter of circle having the same area as particle projection area / perimeter of particle projection image (I)

The 50% circularity of the toner indicates the degree of unevenness of the toner particles, and is 1 when the toner is perfectly spherical. As the surface shape becomes more complicated, the value of the circularity decreases. The closer to the spherical shape, the less the localization of the charge amount in the individual particles occurs, and the more easily the developability becomes uniform. Therefore, the 50% circularity of the toner is more preferably 0.92 or more,
0.95 or more is particularly preferred. Further, since it is difficult to produce a perfect sphere in production, it is preferably 0.995 or less, more preferably 0.99 or less.

Next, the photosensitive member used in the present invention will be described. The photoreceptor used in the present invention, on a conductive support,
It has at least a photosensitive layer. The photosensitive layer is preferably a laminated type in which a charge generation layer and a charge transfer layer are laminated. The charge generation layer and the charge transfer layer may be provided on the conductive support in the order of the charge transfer layer and the charge transfer layer, or may be provided in the order of the charge transfer layer and the charge transfer layer. Of these, it is preferable to adopt a configuration in which a charge transfer layer is laminated on a charge generation layer. In addition, a layer for improving electric characteristics and mechanical characteristics, such as an intermediate layer such as an adhesive layer and a blocking layer, and a protective layer may be provided. In the case of a photoconductor in which a charge generation layer and a charge transfer layer are provided in this order on a support, the intermediate layer is usually between the support and the charge generation layer, and the protective layer is usually
Provided on the charge transfer layer.

As the conductive support, any of those used for known electrophotographic photosensitive members can be used. Specific examples include metal drums and sheets of aluminum, stainless steel, copper, and the like, and laminates and vapor-deposits of these metal foils. Further, plastic films, plastic drums, paper, paper tubes, and the like, which have been subjected to a conductive treatment by applying a conductive substance such as metal powder, carbon black, copper iodide, and a polymer electrolyte together with a suitable binder, may be mentioned. Further, a plastic sheet or drum containing a conductive substance such as a metal powder, carbon black, or carbon fiber to become conductive may be used. Further, plastic films and belts which have been subjected to conductive treatment with a conductive metal oxide such as tin oxide or indium oxide may be used. When used in a small and high-speed electrophotographic apparatus, the conductive support is preferably cylindrical (drum-shaped), and in this case, the inner diameter of the drum is usually 10 to 40 mm, preferably 13 to 35 m.
m, more preferably 16 to 30 mm. Further, in the case of a small-sized device, it is particularly preferable that the length is 13 to 25 mm. The above-described small-diameter drum is particularly advantageous in the case of a color electrophotographic apparatus, in which a photoconductor is used for each of the four color toners of cyan, magenta, yellow, and black.

A blocking layer is provided between the conductive support and the charge generation layer, if necessary. As the blocking layer, an alumite layer, an undercoat layer (also referred to as an intermediate layer) made of a resin, or a combination of these layers is used. Is used.

When an alumite layer is provided, an aluminum substrate is used as a conductive support, and the aluminum substrate is first degreased by various degreasing and washing methods such as acid, alkali, organic solvent, surfactant, emulsion, and electrolysis. Is preferred. Next, anodizing treatment is performed in an acidic bath such as chromic acid, sulfuric acid, oxalic acid, boric acid, and sulfamic acid, preferably in a sulfuric acid bath, to form an anodized film (alumite layer). The average thickness of the anodic oxide coating is usually 1
-20 μm, preferably 1-7 μm.

The obtained anodic oxide coating can be used as it is, but is poor in weather resistance because it is porous.
Since corrosion and the like are likely to occur, it is preferable to perform a treatment for sealing the holes, that is, a sealing treatment. As such a sealing treatment, for example, a low-temperature sealing treatment in which the anodized film formed as described above is immersed in an aqueous solution containing nickel fluoride as a main component, or an aqueous solution containing nickel acetate as a main component, for example. A high-temperature sealing treatment or the like to be immersed inside is performed. The alumite layer formed as described above is immersed in water, washed with water flow, spraying water, brush-like, foam-like, washed by physical contact with a cloth-like rubbing material, or a combination thereof. A cleaning process is performed, and then a drying process such as air drying or heat drying is performed.

When an undercoat layer is provided on a conductive support, examples of the binder resin include polyvinyl methyl ether, poly-N-vinyl imidazole, polyethylene oxide, ethyl cellulose, methyl cellulose, ethylene-acrylic acid copolymer, and polyamide. , Casein, gelatin, polyethylene, polyester, phenolic resin, vinyl chloride-vinyl acetate copolymer, epoxy resin, polyvinylpyrrolidone, polyvinylpyridine, polyurethane,
Resin materials such as polyglutamic acid, polyacrylic acid, and polyamide resin can be used. Among them, a polyamide resin having excellent adhesion to a supporting substrate and low solubility in a solvent used for a charge generation layer coating solution is preferred.

The charge generating layer contains at least a binder polymer and a charge generating agent. In the present invention, oxytitanium phthalocyanine is used as the charge generating agent. This may contain an organic photoconductive compound, a dye, an electron-withdrawing compound, and the like, if necessary. As the binder used for the charge generation layer, styrene,
Polymers and copolymers of vinyl compounds such as vinyl acetate, vinyl chloride, acrylates, methacrylates, vinyl alcohol and ethyl vinyl ether, polyvinyl acetal, polycarbonate, polyester, polyamide, polyurethane, cellulose ester, cellulose ether, phenoxy resin , Silicon resin, epoxy resin and the like. Of these, polymers and copolymers of vinyl compounds and polyvinyl acetals are preferred.
The ratio of the oxytitanium phthalocyanine as the charge generating agent to the binder polymer is not particularly limited, but is generally 5 to 500 parts by weight, preferably 20 to 300 parts by weight, per 100 parts by weight of the oxytitanium phthalocyanine. Use

One of the features of the present invention resides in that a specific crystalline oxytitanium phthalocyanine is used as a charge generating agent. The crystalline oxytitanium phthalocyanine used in the present invention has a clear diffraction peak at a Bragg angle (2θ ± 0.2) 27.3 ° in X-ray diffraction using CuKα ray. The X-ray diffraction is measured by a general Bragg-Brentano concentration method. Also, the diffraction intensity is usually expressed in cps.

The crystalline oxytitanium phthalocyanine is disclosed in, for example, FIG. 2 of JP-A-62-67094 (referred to as type II in the same publication) and JP-A-2-82.
No. 56 of FIG. 1, FIG. 1 of JP-A-64-17066, FIG. 1 of JP-A-63-20365, Journal of the Society of Electrophotographic Photography, Vol. 92 (1990), No. 3. 250
２５258 (referred to as Y-type in the same publication). In the present specification, the crystalline oxytitanium phthalocyanine used in the present invention will be referred to as a Y-type according to the name given in academic publications. The Y-type is distinguished from the α-type and β-type because it is characterized by showing the maximum diffraction peak at 27.3 ° according to the Bragg-Brentano concentration method. For example, the crystal forms described in JP-A-3-128973 and JP-A-3-269064 also differ in crystallinity, but are considered to be Y-type. In the case of a Y-type peak other than 27.3 °, the peak intensity ratio may change due to its crystallinity, or the peak may become broad and the peak top position may shift (this is because the crystal is Not strong), typically 7.
The peaks are shown at 4 °, 9.7 ° and 24.2 °. Recently, X-ray diffraction by the transmission method, which has minimized the crystal orientation, has been performed, and a capillary is used as a sample holder. Angle (2θ ± 0.2) 21.3
°, 18.9 °, 7.6 °, and 5.8 ° show peaks.
This is due to 27.3 °, 24.2 ° and 9.
7 ° and 7.4 ° respectively. In the high-resolution X-ray diffraction, the peak corresponding to 9.7 ° is decomposed into two or more peaks.

In the present invention, a charge generating agent other than Y-type oxytitanium phthalocyanine may be mixed and used for the purpose of adjusting sensitivity and the like.
The charge generating substance is α-type oxytitanium phthalocyanine,
If only a titanium-containing phthalocyanine compound such as β-oxytitanium phthalocyanine is mixed, the proportion of the Y-type oxytitanium phthalocyanine in the charge generating agent is usually 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight. % Or more is more preferable. Further, if it is mixed with a charge generating agent other than the titanium-containing phthalocyanine compound, the proportion of the Y-type oxytitanium phthalocyanine in the charge generating agent is usually 40% by weight or more, and 60% by weight.
It is preferably at least 80% by weight, more preferably at least 80% by weight.

The charge generation layer has a thickness of 0.05 to 5 μm,
Preferably it is 0.1 to 2 μm. Charge carriers are injected from the charge generation layer. The charge transfer layer contains a carrier transfer medium (charge transfer agent) having high carrier injection efficiency and transfer efficiency.

The charge transfer layer contains at least a binder and a charge transfer agent, and if necessary, various additives such as an antioxidant, a sensitizer, a plasticizer, a fluidity-imparting agent, and a crosslinking agent. May be included. As the charge transfer agent, poly-N-vinylcarbazole, a polymer compound having a side chain of a heterocyclic compound or a condensed polycyclic aromatic compound such as polystyrylanthracene, and a low-molecular compound such as pyrazoline, imidazole, oxazole, Heterocyclic compounds such as oxadiazole, triazole and carbazole, triarylalkane derivatives such as triphenylmethane, triarylamine derivatives such as triphenylamine, phenylenediamine derivatives, N-phenylcarbazole derivatives, stilbene derivatives, hydrazone compounds In particular, a compound having a large electron donating property substituted by an electron donating group such as a substituted amino group or an alkoxy group, or an aromatic ring group having such a substituent is exemplified. Of these, compounds represented by formula (III), formula (IV), formula (V) or formula (VI) are preferred.

[0089]

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In the general formula (III), X is a divalent residue which may have a substituent, Ar is an aryl group which may have a substituent, and R is a substituent which has a substituent. Also good aryl,
Represents alkyl, fused polycyclic, or heterocyclic. General formula (II
In I), a more preferred structure is that X is -O-,-
S -, - SO ₂ -, a divalent organic residue which may have a substituent, Ar is phenyl group which may have a substituent,
R is a phenyl group or a naphthyl group which may have a substituent. More preferably, X is a methylene group which may have a substituent, Ar is a phenyl group which may have a substituent, and R is a paratolyl group which may have a substituent.

[0091]

Embedded image (In the general formula (IV), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a substituent. Represents an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted amino group, which may be the same or different from each other, and k, l, m, n, o, and p are 0 ~ respectively
Represents an integer of 4, and represents a plurality of R's in the case of an integer of 2 or more
⁴¹ each to R ^46, may be the same or different.
In the general formula (IV), X ¹¹ is the following general formula (IV-a)
And X ¹² represents a hydrogen atom or the following general formula (IV-b). )

[0092]

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(In the general formulas (IV-a) and (IV-b), i is 0 to
Represents an integer 2, h represents an integer of 0 to 2, R ^47,
R ⁴⁸ , R ⁴⁹ , R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ each have a hydrogen atom, an alkyl group which may have a substituent, and a substituent. Represents an optionally substituted alkoxy group, an optionally substituted aryl group, or an optionally substituted heterocyclic group, which may be the same or different. Furthermore, a pair consisting of R ⁵⁰ and R ⁵¹ , or R ⁵⁵ and R
^The pair consisting of ⁵⁶ may be fused to form a carbocyclic or heterocyclic group. However, a pair consisting of R ⁵⁰ and R ⁵¹ or R ⁵⁵ and R
^{In the} pair consisting of ⁵⁶ , when either one is a hydrogen atom or an alkyl group, the other is an aryl group or a heterocyclic group. When i = 2, each R ⁴⁷ and R ⁴⁸ may be the same or different, and when h = 2, each R ⁴⁷ and R ^48
55 and R ⁵⁶ may be the same or different. X ¹¹ and X ¹²
May be the same or different. )

[0094]

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(In the general formula (V), Ar ¹ represents a benzene ring optionally having a substituent, a naphthalene ring optionally having a substituent, or a biphenyl ring optionally having a substituent. And Ar ^{2 to} Ar ³ each independently represent an aromatic ring which may have a substituent. N represents 1 or 2.) In the general formula (V), Ar ¹ represents a substituent Represents a benzene ring, which may have a substituent, a naphthalene ring which may have a substituent, or a biphenyl ring which may have a substituent. Good biphenyl rings are preferred. As the substituent, a halogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, an alkylthio group having 3 or less carbon atoms, a cyano group, and a nitro group are preferable. Among them, a methyl group, a fluorine atom, and a chlorine atom are preferable. Atoms are more preferred. However, an unsubstituted aromatic ring is most preferred.

Ar ^{2 to} Ar ³ each independently represent an aromatic ring which may have a substituent. Examples of the aromatic ring include:
Any of an aromatic hydrocarbon or an aromatic heterocycle may be used,
Specific examples include a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a pyridine ring, a pyrrole ring, a furan ring, a thiophene ring, a benzofuran ring, a fluorene ring, and a benzothiophene ring. Of these, a benzene ring, a naphthalene ring and a thiophene ring are preferred. Also,
Examples of the substituent on the aromatic ring include a halogen atom, an alkyl group having 4 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, an alkylthio group having 3 or less carbon atoms, a cyano group, a nitro group, or a compound represented by the following general formula (V The substituent represented by -a) is preferred.

[0097]

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(In the general formula (Va), Ar ⁴ represents a halogen atom or a phenyl group which may be substituted with an alkyl group. R ⁶¹ and R ⁶² each independently represent a hydrogen atom or Represents a methyl group, and n represents 1, 2 or 3.)

[0099]

Embedded image (In the formula (VI), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ are each independently an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or Represents an aralkyl group which may have a substituent.) The alkyl group is preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and the aryl group is a phenyl group, a naphthyl group, a thienyl group, or a furyl group. Preferably, the aralkyl group is a benzyl group, a phenethyl group, a thienylmethyl group, or a furylmethyl group. The substituent on the alkyl group is preferably a halogen atom, an alkoxy group having 3 or less carbon atoms, or an alkylthio group having 3 or less carbon atoms, and the substituent on the aryl group and the aralkyl group is preferably a halogen atom, 4 carbon atoms. The following alkyl groups, alkoxy groups having 3 or less carbon atoms, alkylthio groups having 3 or less carbon atoms, cyano groups, and nitro groups are preferred.

In addition, the following formula (VII), formula (VIII), formula (IX), or formula (X), formula (XI)
Compounds having an atomic group represented by are also preferably used.

[0101]

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Specific examples of preferred charge transfer agents are shown below.

[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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Further, a binder polymer is used in the charge transfer layer as needed. As the binder polymer, a polymer having good compatibility with the above-described charge transfer agent and not causing crystallization or phase separation of the carrier transfer medium after forming the coating film is preferable.Examples thereof include styrene, vinyl acetate, and chloride. Vinyl, acrylic acid ester, methacrylic acid ester, polymers and copolymers of vinyl compounds such as butadiene, polyvinyl acetal, polycarbonate, polyester, polyarylate, polysulfone, polyphenylene oxide, polyurethane, cellulose ester, cellulose ether, phenoxy resin,
Silicon resin, epoxy resin and the like can be mentioned.

The preferred binder resin depends on the type of the charge transfer agent, but preferably contains polycarbonate or polyarylate. As the polyarylate, those containing a structural unit represented by the following general formula (XII) are preferable.

[0114]

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(In the formula (XII), Ar ¹ and Ar ² each independently represent a benzene ring which may have a substituent,
X is a divalent aliphatic hydrocarbon group which may have a substituent, a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or Represents an optionally substituted biphenyl ring. R ¹ and R ² each independently represent an aryl group which may have a substituent, an acyloxy group which may have a substituent, an arylsulfoxy group which may have a substituent, R ¹ and R ² may be connected to each other to form a cyclic structure. When the polyarylate having the structural unit of the formula (XII) is used as the binder, in particular, abrasion resistance, toner transferability,
Excellent releasability. When this polyarylate is used as a binder for the charge transfer layer, preferable charge transfer agents include A-10, A-13, A-14, B-1, and B-.
2, B-3, B-4, B-5, C-4, and C-6.

In the formula (XII), Ar ¹ and Ar ² each independently represent a benzene ring which may have a substituent,
As the substituent, a halogen atom, a cyano group, a nitro group,
A hydrocarbon group, a hydrocarbon group substituted with a halogen atom, an alkoxy group, an alkoxy group substituted with a halogen atom,
Alkylthio groups are preferred, of which methyl, cyclohexyl, phenyl and allyl groups are more preferred. Further, the benzene ring is also preferably unsubstituted. Preferred substituents for X are a halogen atom, a cyano group, a nitro group, a hydrocarbon group, a hydrocarbon group substituted with a halogen atom, an alkoxy group, an alkoxy group substituted with a halogen atom, and an alkylthio group. Of these, a fluorine atom, a chlorine atom, a bromine atom, a methyl group, a methoxy group, a trifluoromethyl group, and a trifluoromethoxy group are more preferred. Further, X is preferably unsubstituted.

As the polycarbonate, those containing structural units represented by the following formulas (XIII), (XIV), (XV) or (XVI) are preferred.

[0118]

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(In the formula (XIII), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group, and R ⁵ and R ⁶ are linked to each other. R ⁷ and R ⁸ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aralkyl group, and R ⁹ and R ¹⁰ are each independently do it,
It represents a hydrogen atom or an alkyl group which may have a substituent. When a polycarbonate having the structural unit of the formula (XIII) is used, the abrasion resistance, the transferability of the toner, and the releasability are particularly excellent.

In the formula (XIII), R^FiveAnd R⁶As preferred
New ones are hydrogen atoms or alkyl groups having 8 or less carbon atoms.
The substituent of the alkyl group includes a halogen atom,
Cyano group, nitro group, alkoxy group having 5 or less carbon atoms, charcoal
And an alkylthio group having a prime number of 5 or less. Also, R⁷
And R⁸Are preferably a hydrogen atom and a carbon number of 8 or less.
A lower alkyl group or an aralkyl group having 10 or less carbon atoms.
As a substituent of the alkyl group, R ^ThreeAnd R^Fourin the case of
Is the same as Also, R⁹And R^TenPreferred as
Is a hydrogen atom, an alkyl group having 8 or less carbon atoms,
As a substituent of the alkyl group, R⁷And R⁸Is the same as
is there.

[0121]

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(In the formula (XIV), Z represents an aliphatic hydrocarbon ring having 5 to 8 carbon atoms which may have a substituent.) A polycarbonate having a structural unit of the formula (XIV) was used. In this case, it is particularly excellent in abrasion resistance, transferability of toner, and releasability, and is advantageous in production. When this polycarbonate is used as a binder for the charge transfer layer, preferable charge transfer agents are A-8, A-10, and A-1.
3, A-14, B-1, B-2, B-3, B-4, B-
5, C-1, C-4, C-6, D-2, and D-3. In the formula (XIV), preferred as Z are a cyclopentane ring, a cyclohexane ring, a cycloheptane ring,
Dimethylcyclopentane ring, methylcyclohexane ring,
It is a dimethylcyclohexane ring, and a cyclohexane ring is particularly preferred.

[0123]

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(In the formula (XV), R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group which may have a substituent. R ¹³ and R ¹⁴ each independently represent hydrogen may have an atom or a substituent represents an alkyl group, R ¹³ and R ¹⁴ may have a linked cyclic structure .R ¹⁵
And R ¹⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent. However, this excludes the case where all of R ^{11 to} R ¹⁴ are the same substituent and both R ¹⁵ and R ¹⁶ are hydrogen atoms. Here, x: y = 1: 9 to 9: 1. The use of a polycarbonate having the structural unit of the formula (XV) is particularly advantageous in that it has excellent electrical properties and has a wide range of solvent solubility. When this polycarbonate is used as a binder for the charge transfer layer, preferable charge transfer agents include A-8, A-10, A-13, and A-13.
-14, B-1, B-2, B-3, B-4, B-5, C
-1, C-4, C-6, D-2 and D-3.

In the formula (XV), R ¹¹ and R ¹² are preferably a hydrogen atom or an alkyl group having 8 or less carbon atoms, and the substituent of the alkyl is not highly reactive at normal temperature and normal pressure. And specific examples thereof include a halogen atom, a cyano group, a nitro group, an alkoxy group having 5 or less carbon atoms, and an alkylthio group having 5 or less carbon atoms. Preferred as R ¹³ and R ¹⁴ are a hydrogen atom or an alkyl group having 8 or less carbon atoms, and the substituents of the alkyl group are the same as those of R ¹¹ and R ¹² . Preferred as R ¹⁵ and R ¹⁶ are a hydrogen atom or an alkyl group having 8 or less carbon atoms.
For R ¹¹ and R ¹² is the same as.

[0126]

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(In the formula (XVI), R ³ and R ⁴ are each independently
Represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group. When a polycarbonate having the structural unit of the formula (XVI) is used, the abrasion resistance, the transferability of the toner, and the releasability are particularly excellent. In the formula (XVI), R ³ and R ⁴ are preferably a hydrogen atom or an alkyl group having 8 or less carbon atoms, and the substituent of the alkyl group is preferably not highly reactive at normal temperature and normal pressure. Specifically, a halogen atom, a cyano group, a nitro group, an alkoxy group having 5 or less carbon atoms,
The following alkylthio groups are mentioned.

When the charge transfer agent is a high molecular compound, it is not necessary to use a binder polymer, but mixing may be carried out to improve flexibility. In the case of a low-molecular compound, a binder polymer is used for film-forming properties, and the amount of use is usually 50 to 100 parts by weight of the charge transfer agent.
It is in the range of 1000 parts by weight, preferably 100 to 500 parts by weight. In addition to the above, various additives for improving the mechanical strength and durability of the coating film can be used in the charge transfer layer. Examples of such additives include well-known plasticizers, various stabilizers, flowability-imparting agents, and crosslinking agents. The thickness of the charge transfer layer is generally 10 to 60 μm, preferably 15 to 45 μm, and more preferably 27 to 40 μm.

The above-mentioned undercoat layer, charge generation layer and charge transfer layer are dissolved or dispersed in an appropriate solvent depending on the binder and the components used, and are spray-coated, spiral-coated, ring-coated, dip-coated. Provided by law. In the case of the dip coating method, the total solid concentration is preferably 25 to
A coating solution having a viscosity of 40%, preferably 50 to 300 centipoise, more preferably 100 to 200 centipoise, is prepared. As a drying method after the application, a hot air dryer, a steam dryer, an infrared dryer, a far infrared dryer, or the like can be used.

Next, as an exposure apparatus for performing exposure for forming a latent image on the photoreceptor, an apparatus for performing digital exposure is used. In consideration of the absorbance of the above-mentioned Y-type oxytitanium phthalocyanine, 500 to 850 nm is used. Is preferable. More specifically, 5
Around 32 nm, around 635 nm, around 650 nm, 78
An exposure apparatus that emits a laser beam near 0 nm or 830 nm is preferable.

When an image is formed using the above-mentioned toner and the photosensitive member, when a toner having Dv of 3 to 8 μm and a value of Dv / Dn of 1.0 or more and 1.3 or less is used, Since the uniformity of toner adhesion on the latent image is improved,
A high-gradation, high-resolution latent image can be faithfully reproduced.

Further, since such toner has a uniform particle shape, localization of the charge amount within the individual particle due to the difference in particle shape is unlikely to occur. It is considered that the latent image is faithfully reproduced because it adheres to the surface with almost uniform force.

Further, by using the above oxytitanium phthalocyanine as a charge generating substance of the photoreceptor, the photoreceptor has high sensitivity and high γ, and the photoreceptor has sufficient photoresponsiveness. Even when the number of dots increases and the exposure time of each dot decreases, development can still be performed with a sufficient toner density. Further, the present invention can be effectively applied to a smaller, faster, and higher-resolution image forming apparatus. Therefore, the image forming method of the present invention is particularly effective when forming an image having a resolution of 600 dpi or more, and more preferably 1200 dpi or more. When the rotation speed of the electrophotographic photosensitive member is 1.5 times / sec. It is particularly effective, and is particularly effective when the inner diameter of the electrophotographic photosensitive member is 35 mm or less.

[0134]

The present invention will be described in detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In the following examples, “parts” means “parts by weight”. The average particle size, weight average molecular weight, glass transition point (Tg), and 50% circularity were measured by the following methods.

Volume average particle size, number average particle size: LA-500 manufactured by Horiba, and Microtrac UPA (ul) manufactured by Nikkiso Co., Ltd.
tra particle analyzer) and a Coulter Counter Multisizer II (Coulter Counter).

Weight average molecular weight (Mw): Measured by gel permeation chromatography (GPC) (apparatus: GPC apparatus HLC-8020 manufactured by Tosoh Corporation, column: PL-gel Mixed-B 10 μm manufactured by Polymer Laboratory,
(Solvent: THF, sample concentration: 0.1 wt%, calibration curve: standard polystyrene)

Glass transition temperature (Tg): Measured by DSC7 manufactured by PerkinElmer (heated from 30 ° C. to 100 ° C. in 7 minutes, rapidly cooled from 100 ° C. to −20 ° C., and then cooled from −20 ° C. to 100 ° C.)
The temperature was raised in 12 minutes, and the value of Tg observed during the second temperature increase was used).

The number of particles having a particle size of 0.6 to 2.12 μm: measured by a flow type particle image analyzer FPIA-2000 manufactured by Sysmex Corporation. Proportion of particle size of 55% or less of volume average particle size, ratio of 40% or less of volume average particle size: Measured by Coulter counter.

50% circularity: The toner was measured with a flow particle image analyzer FPIA-2000 manufactured by Sysmex Corporation, and the circularity corresponding to the cumulative particle size value at 50% of the value obtained from the following equation was used. Circularity = Perimeter of a circle with the same area as the projected area of the particle / Perimeter of the projected image

Examples A1 to A3, Comparative Examples B1 to B3 [Production of toner for development-1 (TA1)] (Wax dispersion-1) 68.33 parts of demineralized water, ester mixture mainly composed of stearic acid ester of pentaerythritol (Unistar H-476, manufactured by NOF Corporation) 30 parts,
Sodium dodecylbenzenesulfonate (Neogen SC,
1.67 parts of Daiichi Kogyo Seiyaku, active ingredient 66%)
The mixture was emulsified by applying high-pressure shear at 90 ° C. to obtain a dispersion of fine particles of ester wax. The average particle size of the ester wax fine particles measured by LA-500 was 340 nm.

(Polymer Primary Particle Dispersion-1) A reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries (volume: 60 liter, inner diameter: 40)
0 mm), 28 parts of a wax dispersion liquid, 1.2 parts of a 15% neogen SC aqueous solution, and 393 parts of demineralized water were charged, and heated to 90 ° C. under a nitrogen stream, 1.6 parts of an 8% hydrogen peroxide aqueous solution, 8 parts of ascorbic acid 1.6 parts of an aqueous solution were added. Thereafter, a mixture of the following monomers / emulsifier aqueous solution was added over 5 hours from the start of the polymerization, and the aqueous initiator solution was added over 6 hours from the start of the polymerization.
Minutes.

[0142]

[Table 1] [Monomers] Styrene 79 parts (5530 g) Butyl acrylate 21 parts Acrylic acid 3 parts Bromotrichloromethane 0.45 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.9 parts [Emulsifier aqueous solution] 15% Neogen SC aqueous solution 1 Part Demineralized water 25 parts [Initiator aqueous solution] 8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF is 12
7,000, the average particle diameter measured by UPA was 220 nm, and Tg was unclear.

(Resin Particle Dispersion-1) Reactor equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries (volume: 60 liters, inner diameter: 400 mm)
5 parts of 15% neogen SC aqueous solution and 372 parts of demineralized water were charged, and the temperature was increased to 90 ° C. under a nitrogen stream, and 1.6% of an 8% aqueous hydrogen peroxide solution was added.
And 1.6 parts of an 8% aqueous ascorbic acid solution. Thereafter, a mixture of the following monomers and an aqueous solution of an emulsifier was added over 5 hours from the start of the polymerization, and an aqueous solution of the initiator was added over 6 hours from the start of the polymerization, and the mixture was further maintained for 30 minutes.

[0145]

[Table 2] [Monomers] Styrene 88 parts (6160 g) Butyl acrylate 12 parts Acrylic acid 2 parts Bromotrichloromethane 0.5 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.4 parts [Emulsifier aqueous solution] 15% Neogen SC aqueous solution 2.5 Part Demineralized water 24 parts [Initiator aqueous solution] 8% hydrogen peroxide aqueous solution 9 parts 8% ascorbic acid aqueous solution 9 parts

After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF is 54,
000, average particle diameter measured by UPA was 83 nm, and Tg was 85 ° C.

(Colorant Fine Particle Dispersion-1) C.I. I. Pigment Blue 15: 3 aqueous dispersion (EP-700 Blue GA, manufactured by Dainichi Seika, solid content 35%) The average particle size measured by UPA was 150 nm.

[0148]

Table 3 Production of toner for development-1 Polymer primary particle dispersion-1 103 parts (2773 g: as solid) Resin fine particle dispersion-1 5 parts (as solid) Colorant fine particle dispersion-1 6.7 parts 0.5% of 15% Neogen SC aqueous solution (as solid content)

Using the above-mentioned components, a toner was manufactured according to the following procedure. A polymer primary particle dispersion and a 15% aqueous solution of neogen SC were charged into a reactor (volume: 60 liters, anchor blade with baffle), mixed uniformly, and then a colorant fine particle dispersion was added, followed by uniform mixing. While stirring the obtained mixed dispersion, an aqueous solution of aluminum sulfate was added dropwise (0.6 part as a solid content). Thereafter, with stirring, the temperature was raised to 50 ° C over 25 minutes, held for 1 hour, and further maintained at 60 ° C for 15 minutes.
And held for 1 hour and 35 minutes. A resin fine particle dispersion and an aqueous solution of aluminum sulfate (0.07 part as solids) were added in this order, and the temperature was raised to 62 ° C. over 5 minutes and maintained for 30 minutes. After adding a 15% aqueous solution of Neogen SC (3 parts as a solid content), the temperature was raised to 96 ° C. over 50 minutes and maintained for 3 hours. Then cool down,
The toner was obtained by filtration, washing with water and drying.

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred, and a developing toner (T
A1) was obtained. Evaluation of Toner-1 The volume average particle diameter of the developing toner (TA1) measured by a Coulter counter is 7.2 μm, the ratio of particles having a particle diameter of 5 μm or less is 2.5%, the ratio of particles having a particle diameter of 15 μm or more is 0.8%, and the particle diameter is 0. .6
The ratio of the number of particles having a particle size of ~ 2.
The ratio of the particle diameter of 12% by number and 40% or less of the volume average particle diameter was 1.37% by number. Dv / Dn = 1.13
And the 50% circularity was 0.95.

[Production of developing toner-2 (TA2)] (Wax dispersion liquid-2) 68.33 parts of demineralized water, an ester mixture mainly composed of behenyl behenate (Unistar M-2222S)
L, Nippon Oil & Fats) and ester mixture mainly composed of stearyl stearate (Unistar M9676, Nippon Oil & Fats) 7: 3
And 1.67 parts of sodium dodecylbenzenesulfonate (Neogen SC, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., active ingredient 66%) were mixed and emulsified by applying high-pressure shear at 90 ° C. to obtain a dispersion of ester wax fine particles. Was. The average particle size of the ester wax fine particles measured by LA-500 was 340 nm. (Polymer primary particle dispersion liquid-2) Wax dispersion liquid in a reactor (volume: 60 liters, inner diameter: 400 mm) equipped with a stirrer (three blades), a heating / cooling device, a concentrating device, and a device for charging raw materials and auxiliaries. -Charge 28 parts, 1.2 parts of 15% neogen SC aqueous solution and 393 parts of demineralized water, raise the temperature to 90 ° C under a nitrogen stream, and add 1.6 parts of 8% aqueous hydrogen peroxide and 1.6 parts of 8% ascorbic acid aqueous solution. did. Thereafter, a mixture of the following monomers and an aqueous solution of an emulsifier was added over 5 hours from the start of the polymerization, and an aqueous solution of the initiator was added over 6 hours from the start of the polymerization, and the mixture was further maintained for 30 minutes.

[0152]

[Table 4] [Monomers] Styrene 79 parts Butyl acrylate 21 parts Acrylic acid 3 parts Bromotrichloromethane 0.45 parts 2-mercaptoethanol 0.01 parts Hexanediol diacrylate 0.9 parts [Emulsifier aqueous solution] 15% Neogen SC aqueous solution 1 part Demineralized water 25 parts [Initiator aqueous solution] 8% Hydrogen peroxide aqueous solution 9 parts 8% Ascorbic acid aqueous solution 9 parts

After the completion of the polymerization reaction, the mixture was cooled to obtain a milky white polymer dispersion. The weight-average molecular weight of the polymer soluble in THF is 14
The average particle size measured by 8,000 and UPA was 207 nm, and Tg was 55 ° C. (Resin Particle Dispersion-2) The same as Resin Particle Dispersion-1 was used. (Colorant fine particle dispersion liquid-2) C.I. I. Pigment Yellow 74, 20 parts, polyoxyethylene alkyl phenyl ether, 7 parts, and deionized water, 73 parts, were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle size measured by UPA was 211 nm. (Charge control agent fine particle dispersion liquid-2) 4,4'-methylenebis [2-
[N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] (Compound CCA-1 having the following structure) 20 parts, alkylnaphthalenesulfonate 4 parts, and demineralized water 76 parts are dispersed by a sand grinder mill and charged. A control agent fine particle dispersion was obtained. The average particle size measured by UPA was 200 nm.

[0154]

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[0155]

Table 5 Production of toner for development-2 Polymer primary particle dispersion-2 105 parts (as solids) Resin fine particle dispersion-1 5 parts (as solids) Colorant fine particles dispersion-2 6.7 parts (solids) 2) 2 parts (as solid content)

Using each of the above components, a toner was manufactured according to the following procedure. A polymer primary particle dispersion and a colorant fine particle dispersion were charged into a reactor (volume: 1 liter, anchor wing with baffle) and uniformly mixed. While stirring the obtained mixed dispersion, an aqueous solution of aluminum sulfate was added dropwise (0.6 part as a solid content). Thereafter, with stirring, the temperature was raised to 51 ° C. over 25 minutes and maintained for 1 hour, and further raised to 59 ° C. over 8 minutes and maintained for 40 minutes. Charge control agent fine particle dispersion, resin fine particle dispersion, aluminum sulfate aqueous solution (as solid content
0.07 parts), and the temperature was raised to 61 ° C. over 15 minutes and maintained for 30 minutes. 15% Neogen SC aqueous solution (3.8 parts as solid content)
Was added and the temperature was raised to 96 ° C. over 30 minutes and maintained for 4 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner. To 100 parts of this toner, 0.6 part of silica subjected to a hydrophobic surface treatment was mixed and stirred to obtain a developing toner (TA2).

Evaluation of Toner-2 The volume average particle diameter of the developing toner (TA2) measured by a Coulter counter was 7.5 μm, the ratio of particles having a particle diameter of 5 μm or less was 1.6%, the ratio of particles having a particle diameter of 15 μm or more was 0.7%, Particle size 0.6
The ratio of the number of particles of .about.2.12 μm is 0.46%, and the ratio of the particle size of 55% or less of the volume average particle size is 0.26 vol% and
The ratio of 8 number% and the particle diameter of 40% or less of the volume average particle diameter was 1.29 number%. Dv / Dn = 1.14
And the 50% circularity was 0.96.

[Production of Developing Toner-3 (TA3)] (Wax Dispersion-3) A product prepared in the same manner as the wax dispersion-2 was used. The average particle size of the ester wax fine particles measured by LA-500 was 340 nm. (Polymer Primary Particle Dispersion-3) Wax Fine Particle Dispersion-
The polymer was prepared in the same manner as in Polymer Primary Particle Dispersion-2 using No.3. The weight average molecular weight of the polymer soluble in THF is 119,000, the average particle diameter measured by UPA is 189 nm, Tg
Was 57 ° C. (Resin Fine Particle Dispersion-3) The same as Resin Fine Particle Dispersion-1 was used. (Colorant fine particle dispersion liquid-3) C.I. I. Pigment Red
20 parts of 238 (compound of the following formula (A)), 2.5 parts of an alkylbenzene sulfonate and 77.5 parts of deionized water were dispersed in a sand grinder mill to obtain a colorant fine particle dispersion. The average particle size measured by UPA was 181 nm.

[0159]

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[0160]

(Table 6) (Charge Control Agent Fine Particle Dispersion-3) The same as Charge Control Agent Fine Particle Dispersion-2 was used. Production of toner for development-3 Polymer primary particle dispersion-3 104 parts (as solids) Resin fine particle dispersion-16 parts (as solids) Colorant particle dispersion-3-3 6.7 parts (as solids) Charge Control agent fine particle dispersion-2 2 parts (as solid content) 15% Neogen SC aqueous solution 0.65 parts (as solid content)

Using each of the above components, a toner was produced according to the following procedure. A polymer primary particle dispersion and a 15% aqueous solution of neogen SC were charged into a reactor (volume: 1 liter, anchor wing with baffle), uniformly mixed, and then a colorant fine particle dispersion was added and uniformly mixed. While stirring the obtained mixed dispersion, an aqueous solution of aluminum sulfate was added dropwise (0.8 part as a solid content). Then take 15 minutes with stirring 51
° C and maintained for 1 hour, and further raised to 59 ° C over 6 minutes and maintained for 20 minutes. Charge control agent fine particle dispersion, resin fine particle dispersion, aluminum sulfate aqueous solution (solid content of 0.09
Parts) and kept at 59 ° C. for 20 minutes. 15% Neogen S
After the addition of the C aqueous solution (3.7 parts as a solid content), the temperature was raised to 95 ° C. over 25 minutes, and the 15% neogen SC aqueous solution (0.7 parts as a solid content) was further added and maintained for 3.5 hours. Thereafter, the mixture was cooled, filtered, washed with water, and dried to obtain a toner.

To 100 parts of this toner, 0.6 part of hydrophobic surface-treated silica was mixed and stirred, and a developing toner (T
A3) was obtained. Evaluation of Toner-3 The volume average particle size of the developing toner (TA3) measured by a Coulter counter is 7.8 μm, the ratio of the volume particle size of 5 μm or less is 2.1%, the ratio of the volume particle size of 15 μm or more is 2.1%, and the particle size. The ratio of the number of particles of 0.6 to 2.12 μm is 0.80%, the ratio of the particle size of 55% or less of the volume average particle size is 0.51% by volume,
The ratio of the particle size of 40% or less of the volume average particle size was 1.85% by number. Also, Dv / Dn = 1.15 and 50
The% circularity was 0.97.

(Production example 1 of photoreceptor) (alumite layer)
An aluminum cylinder having a length of 340 mm and a thickness of 1 mm was treated with a degreasing agent, NC- # 30 (manufactured by Kizai Co., Ltd.) at 30 g /
Degreasing and washing were performed in an aqueous solution at 60 ° C. for 5 minutes. Subsequently, after rinsing with water, it was immersed in 7% nitric acid at 25 ° C. for 1 minute. After further washing with water, anodic oxidation was carried out at a current density of 1.2 A / dm ^{2 in} a 180 g / l sulfuric acid electrolytic solution (dissolved aluminum concentration: 7 g / l) to form an anodized film having an average film thickness of 6 μm. Next, after washing with water, it was immersed in a 10 g / l aqueous solution of a high-temperature sealing agent Top Seal DX-500 (manufactured by Okuno Pharmaceutical Co., Ltd.) containing nickel acetate as a main component at 95 ° C. for 30 minutes to perform a sealing treatment. Subsequently, after washing with water, the entire surface of the coating film was reciprocated three times using a polyester sponge to carry out rubbing washing. Then, it was washed with water and dried.

(Undercoat layer) Titanium oxide manufactured by Ishihara Sangyo Co., Ltd., product name: TTO-55N (crystal rutile primary particle size: 0.03-0.05 μm), mixed alcohol (methanol / 1-propanol = 70 / 30) was dispersed in a ball mill for 16 hours. The titanium oxide dispersion obtained here was added to a mixed alcohol (methanol / 1-propanol = 70/30) solution of the following polyamide resin (PA-1). Finally, a dispersion having a solid content concentration of 16% with a titanium oxide / nylon ratio of 1/1 (weight ratio) was prepared and used as a dispersion for the undercoat layer.

[0165]

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The above drum (aluminum cylinder)
Was applied by dip coating to the undercoat layer dispersion, and an undercoat layer was provided so that the dry film thickness was 0.75 μm (charge generation layer). Β-oxytitanium phthalocyanine (β-TiOP)
Preparation of c) 97.5 g of phthalodinitrile was converted to α-chloronaphthalene 7
50 ml of titanium tetrachloride 2 under a nitrogen atmosphere.
2 ml are added dropwise. After dropping, the temperature is increased and 200
After reacting at ~ 220 ° C for 3 hours, it is allowed to cool, and
The mixture was filtered while hot at 30 ° C., and washed with 200 ml of α-chloronaphthalene heated to 100 ° C. 200ml of N-
The hot suspension washing treatment (100 ° C., 1 hour) with methylpyrrolidone was performed three times. Subsequently, the resultant was washed with 300 ml of methanol at room temperature, and further washed three times with 500 ml of methanol for 1 hour while hot. According to the X-ray diffraction of the oxytitanium phthalocyanine thus obtained, the black angle (2θ ± 0.
In 2 ゜), there is no substantial peak from 4 ゜ to 8 ゜, and 9.
3 ゜, 10.6 ゜, 13.2 ゜, 15.1 ゜, 15.7
゜, 16.1 ゜, 20.8 ゜, 23.3 ゜, 26.3
{27.1} have clear diffraction peaks, of which 2
The peak at 6.3 ° is the strongest. Therefore, it is identified as a β-type crystal.

Production of Y-type oxytitanium phthalocyanine (Y-type TiOPc) The β-type oxytitanium phthalocyanine obtained as described above was subjected to a grinding treatment for 20 hours in a sand grind mill, and subsequently 400 ml of water, The solution was placed in a suspension of 40 ml of orthodichlorobenzene and heat-treated at 60 ° C. for 1 hour. According to X-ray diffraction (Bragg-Brenter concentration method) of the oxytitanium phthalocyanine thus obtained, it was determined that the oxytitanium phthalocyanine had a black angle (2θ ± 0.2 °) of 27.
The peak was maximum at 3 ° and showed a sharp peak.

When the Y-type oxytitanium phthalocyanine thus obtained was subjected to transmission X-ray diffraction at 1.2085 ° using a capillary as a sample holder, a Bragg angle (2θ ± 0.2 °) of 21.3 was obtained. ° (1
00) (However, the values in parentheses indicate a peak intensity at 21.3 ° of 10).
Relative intensity when 0), 18.9 ° (13), 1
4.1 ° (12), 11.8 ° (14), 11.1 °
(11), 9.2 ° (11), 7.6 ° (36), 7.
A diffraction peak was observed at 4 ° (25) and 5.8 ° (8). The measuring device was a multiple detector X-ray powder diffractometer. Details of the device were published by High Energy Physics Laboratory.
"Radiation Powder Diffraction Experiment Station (BL-4B) Design Report, (1995), KEK Report
94-11 ". The measurement conditions are a step angle of 0.005 °, 4.5 seconds / step, and a wavelength for d value calculation = 1.2085 °.

Preparation of Coating Solution for Charge Generating Layer and Coating 10 parts of Y-type TiOPc obtained in the above manufacturing example was
In addition to 150 parts by weight of methoxy-4-methylpentanone-2, pulverization and dispersion treatment was performed with a sand grind mill. In addition, polyvinyl butyral (Electrical Chemical Industry Co., Ltd.)
Made, 5% of trade name Denka Butyral # 6000C)
100 parts of a 1,2-dimethoxyethane solution and 5 of phenoxy resin (PKHH, manufactured by Union Carbide Co.)
100 parts of a 1,2-dimethoxyethane solution were mixed to prepare a binder solution. Pigment dispersion liquid 1 prepared earlier
To 60 parts by weight, 100 parts by weight of a binder solution and an appropriate amount of 1,2-dimethoxyethane were added to finally prepare a dispersion having a solid content of 4.0%. The dispersion thus obtained was further applied by dip coating on the aluminum drum to which the undercoat layer had been applied to form a charge generation layer having a thickness of 0.2 μm.

(Charge Transfer Layer) Then, 45 parts of the following charge transfer material (TAPC), 100 parts of a polycarbonate resin represented by the following structural formula (m: n = 51: 49, viscosity average molecular weight 30,000), 4-methyl-2,6-
16 parts of di-t-butylphenol and 0.03 part of silicone oil (manufactured by Shin-Etsu Silicone, KF-96) were dissolved in a mixed solvent of 170 parts of dioxane and 400 parts of tetrahydrofuran to prepare a coating solution. Then, a charge transfer layer was provided on the aluminum drum coated with the undercoat layer and the charge generation layer by dip coating so that the film thickness after drying at 125 ° C. for 20 minutes was 20 μm. This is designated as photoconductor "PC-A1".

[0171]

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[0172]

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(Production of Photoreceptor-2) Production example of the above photoreceptor up to the production of an alumite layer, an undercoat layer and a charge generation layer
The same as in Example 1. (Charge Transfer Layer) Next, 60 parts of the charge transfer material of the structural formula (D-2), 100 parts of a polycarbonate resin represented by the following structural formula, 6 parts of 4-methyl-2,6-di-t-butylphenol, and A coating liquid was prepared by dissolving 0.03 part of silicone oil (KF-96, manufactured by Shin-Etsu Silicone) in a mixed solvent of 170 parts of dioxane and 400 parts of tetrahydrofuran. Then, a charge transfer layer was provided on the aluminum drum coated with the undercoat layer and the charge generation layer by dip coating so that the film thickness after drying at 125 ° C. for 20 minutes was 20 μm. This is called photoconductor "PC-A
2 ".

[0174]

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(Production Example 3 of Photoreceptor) A photoreceptor was manufactured in the same manner as in Production Example 1 up to the production of an alumite layer, an undercoat layer, and a charge generation layer. (Charge Transfer Layer) The charge transfer material of the structural formula (B-5)
Part of a polyester represented by the following structural formula [100 parts of a 7: 3 copolymer polyester resin of (P-1) and (M-1) (viscosity average molecular weight 33,000)], 4-methyl-2,
8 parts of 6-di-t-butylphenol and silicone oil as a leveling agent (KF-9, manufactured by Shin-Etsu Silicone)
6) 0.03 part was dissolved in a mixed solvent of 170 parts of dioxane and 400 parts of tetrahydrofuran to prepare a coating solution. This was further applied by dip coating on an aluminum drum coated with the undercoat layer and the charge generation layer, at 125 ° C.
The charge transfer layer was provided so that the film thickness after drying for 20 minutes was 20 μm. This is designated as photoconductor "PC-A3".

[0176]

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(Production Example 4 of Photoreceptor) The alumite layer was
The photoconductor was manufactured in the same manner as in Manufacturing Example-1. A charge generation layer was provided on the alumite layer in the same manner as in Production Example 1 of the photoreceptor, without providing the undercoat layer. (Charge Transfer Layer) The charge transfer material of the structural formula (B-5)
Part and a polycarbonate resin represented by the following structural formula (m: n = 51: 49, viscosity average molecular weight 31,400)
100 parts, 8 parts of 4-methyl-2,6-di-t-butylphenol, and 0.03 part of silicone oil (KF-96 manufactured by Shin-Etsu Silicone) are dissolved in a mixed solvent of 170 parts of dioxane and 400 parts of tetrahydrofuran, A coating solution was prepared. Then, a charge transfer layer was provided on the aluminum drum coated with the undercoat layer and the charge generation layer by dip coating so that the film thickness after drying at 125 ° C. for 20 minutes was 20 μm. This is called photoconductor "PC-A
4 ".

[0178]

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(Production Example 5 of Photoconductor) Production Example of Photoconductor
In the same manner as in No. 4, a charge generation layer was provided on the alumite layer. (Charge Transfer Layer) The charge transfer material of the structural formula (A-13)
5 parts and 35 parts of the charge transfer material (B-2), 100 parts of a polycarbonate resin (Iupilon Z-400, manufactured by Mitsubishi Gas Chemical Co., Ltd.) represented by the following structural formula, 4-methyl-
8 parts of 2,6-di-t-butylphenol and silicone oil as a leveling agent (manufactured by Shin-Etsu Silicone, K
F-96) was dissolved in a mixed solvent of 110 parts of toluene and 450 parts of tetrahydrofuran to prepare a coating solution. This was further applied by dip coating on the aluminum drum coated with the undercoat layer and the charge generation layer to form a 125
The charge transfer layer was provided so that the film thickness after drying at 20 ° C. for 20 minutes was 20 μm. This is designated as photoconductor "PC-A5".

[0180]

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(Production Example 6 of Photosensitive Member) (Comparative photosensitive member: β
(Type TiOPc was used) The photoreceptor was manufactured in the same manner as in Production Example-4 except that β-type was used instead of Y-type as oxytitanium phthalocyanine. This is called the photoconductor
B1 ”.

(Production example of photoconductor-7) (Comparative photoconductor: β
A photoreceptor was manufactured in the same manner as in Photoreceptor Production Example-6, except that in Production Example-6 of the photoreceptor, an aluminum substrate having a diameter of 30 mm and a length of 243 mm was used. This is designated as photoconductor "PC-B2".

Example A1 Color laser printer Color manufactured by Casio
A cyan toner (TA1) is placed in a developing tank of Pagepresto N4-612II, and a photoconductor (PC-A
1: Y-type oxytitanium phthalocyanine) was attached, and a thin line image was formed in a vertical direction and a horizontal direction of 2 dots on and 2 dots off at an exposure density of 600 dpi.

Comparative Example B1 A fine line image was formed in the same manner as in Example A1, except that a genuine N4-612II cyan toner (hereinafter referred to as toner (TB1); produced by a kneading / pulverizing method) was used as the toner. did. The volume average particle diameter (Dv) of TB1 is 9.10 μm, Dv / Dn = 1.24, the 50% circularity is 0.93, and the ratio of the number of particles having a particle diameter of 0.6 to 2.12 μm is 4.8. %Met.

The fine line images obtained in Example A1 and Comparative Example B1 were read with a digital microscope manufactured by KEYENCE CORPORATION, and analyzed with Winloop software of Mitani Corporation to obtain image densities. The value of the image density is raw data calculated by the software through image analysis, and the larger the value, the higher the image density. FIG. 3 is a graph showing an image analysis result of a thin line image drawn in a vertical direction, and FIG. 4 is a graph showing an image analysis result of a thin line image drawn in a horizontal direction. FIG.
In the (vertical direction), both the toners TA1 and TB1 have substantially the same peak and valley shape and substantially the same resolution, but in FIG.
In the case of using No. 1, it was found that the shapes of peaks and valleys were clearly reproduced, and high resolution was exhibited.

Reference Example Laser printer Docuprin manufactured by Xerox
t At P1202, a photoreceptor (PC-B2: using β-type oxytitanium phthalocyanine) is attached, and the toner TA1 or TB1 is put in the developing tank, and the vertical direction of 2 dots on and 2 dots off at an exposure density of 600 dpi And a thin line image was formed in the horizontal direction. The image analysis was performed in the above Example A1.
5 (image analysis result of a thin line image drawn in the vertical direction) and FIG. 6 (image analysis result of a thin line image drawn in the horizontal direction). From these results, it was found that the toner in both the vertical and horizontal directions was
It can be seen that the resolution is similar.

That is, when a high-sensitivity photoreceptor containing Y-type oxytitanium phthalocyanine is used, a high-resolution image can be reproduced when the particle size is small and the particle size distribution is sharp. It has been shown that the performance of the sensitivity photoreceptor is particularly exhibited.

Comparative Example B2 An image was formed in the same manner as in Comparative Example B1, except that the kneaded / crushed yellow toner (TB2) genuine N4-612 was used instead of the cyan toner (TB1). Was performed, the result equivalent to Comparative Example B1 was obtained. The volume average particle diameter (Dv) of TB2 is 9.18 μm, Dv / Dn = 1.25, the 50% circularity is 0.93, and the ratio of the number of particles having a particle diameter of 0.6 to 2.12 μm is 1
3.7%.

Comparative Example B3 Image formation was performed in the same manner as in Comparative Example B1, except that the cyan toner (TB1) was replaced by a genuine N4-612 kneaded / crushed magenta toner (TB3). , The same results as in Comparative Example B1 were obtained. The volume average particle diameter (Dv) of TB3 is 9.16 μm, Dv / Dn = 1.32, the 50% circularity is 0.93, and the ratio of the number of particles having a particle diameter of 0.6 to 2.12 μm is 1.
It was 5.8%.

Example A2 An image was formed in the same manner as in Example A1, except that yellow toner (TA2) was used in place of the cyan toner (TA1). An image having the same resolution as that of is obtained.

Example A3 An image was formed in the same manner as in Example A1, except that magenta toner (TA3) was used in place of the cyan toner (TA1). An image having the same resolution as that of is obtained.

Example A5 In Example A1, the photoconductor (PC-A1) was replaced with a photoconductor (PC-A1).
By forming an image in the same manner as in Example A1 except that the photoconductor (PC-A2) is used, an image having the same resolution as that in Example A1 can be obtained.

Example A6 In Example A1, instead of the photoconductor (PC-A1),
By forming an image in the same manner as in Example A1 except that the photoconductor (PC-A3) is used, an image having the same resolution as that in Example A1 is obtained.

Example A7 In Example A1, the photoconductor (PC-A1) was replaced with a photoconductor (PC-A1).
By forming an image in the same manner as in Example A1 except that the photoconductor (PC-A4) is used, an image having the same resolution as that in Example A1 can be obtained.

Example A8 In Example A1, instead of the photoconductor (PC-A1),
By forming an image in the same manner as in Example A1 except that the photoconductor (PC-A5) is used, an image having the same resolution as that in Example A1 is obtained.

Examples A9 to A14, Comparative Examples B4 and B5 [Production of toner for development-4 (TA4 to TA9)] (Preparation of colorant dispersion) i) Colorant dispersion A I. Pigment Red 48: 2 50 g and demineralized water 1
50 g and 7.6 g of an alkylbenzene sulfonate were added, and the mixture was subjected to a dispersion treatment with a sand grinder mill for 6 hours to obtain a colorant dispersion having an average particle size of 0.20 μm. ii) Colorant dispersion B C.I. I. Pigment Blue 15: 360 (160 g), desalted water (130 g) and polyoxyethylene alkylphenyl ether (10 g) were added, and the mixture was dispersed in a sand grinder mill for 6 hours to obtain a colorant dispersion B having an average particle size of 0.15 μm. iii) Colorant dispersion C C.I. I. Pigment Yellow 74 to 40 g, 1 desalinated water
46 g and polyoxyethylene alkylphenyl ether 14 g were added, and the mixture was subjected to a dispersion treatment with a sand grinder mill for 6 hours to obtain a colorant dispersion C having an average particle size of 0.30 μm.

Iv) Colorant Dispersion D To 40 g of carbon black (MA100, manufactured by Mitsubishi Chemical),
146 g of demineralized water and 14 g of polyoxyethylene alkylphenyl ether were added, and the mixture was dispersed with a sand grinder mill for 6 hours, and a colorant dispersion D having an average particle size of 0.30 μm was obtained.
I got

(Synthesis of Polymer Emulsion) 2.2 kg of an ester wax emulsion having a solid content of 30% and 26 kg of demineralized water were placed in a reactor and heated to 90 ° C., and 6 g of dodecylbenzenesulfonate, 5 kg of styrene, and n-butyl were added. 1.3 kg of acrylate, 186 g of acrylic acid, 25 g of divinylbenzene, 31 g of trichlorobromomethane, 656 g of 8% aqueous hydrogen peroxide solution, 65% of 8% aqueous ascorbic acid solution
6 g were added. The reaction was continued at 90 ° C. for 7 hours to obtain an emulsion (polymer primary particle dispersion) composed of a styrene acrylic polymer.

(Preparation of Charge Control Agent Dispersion) 4,4'-Methylenebis [2- [N- (4-chlorophenyl) amide] -3-hydroxynaphthalene] (CCA-1)
To 40 g, 160 g of demineralized water and 8 g of an alkylnaphthalene sulfonate as a dispersant were added and subjected to a dispersion treatment for 2 hours by a sand grinder mill to obtain a charge control agent dispersion.

(Production of Toner) a) Toner (TA4) To 300 g of the polymer emulsion, 19 g of the colorant dispersion A and 1.8 g of the charge control agent dispersion were mixed and stirred. While the stirring was continued, 79.4 g of 0.5% Al ₂ (SO ₄ ) ₃ was added thereto, the temperature was raised from 25 ° C. to 60 ° C. over 2 hours, and the stirring was continued. Add 2 g of dodecylbenzenesulfonate and add 98 g
C. and the stirring was continued for 6 hours. The obtained particles were repeatedly subjected to suction filtration and washing with water, followed by air-drying to obtain 60 g of a magenta toner. When the particle diameter of the obtained particles was measured using a Coulter counter, the volume average diameter was 7.6.
μm, and the number average diameter was 6.7 μm. Volume average particle size /
The value of the number average particle size was 1.13, and the particle size distribution was excellent. Also, when the circularity and the number ratio of particles of 0.6 to 2.12 μm were measured using FPIA-2000, the 50% circularity was 0.99 and 0.6 to
The number ratio of 2.12 μm particles was 6%. 100 parts of toner is treated with 1 part of hydrophobically treated silica
Was added and mixed and stirred to form a developing toner (this was TA4
And).

B) Toner (TA5) Except that the colorant dispersion B was used instead of the colorant dispersion A used in the toner (TA4), the toner (TA5)
When manufactured in the same manner as in 4), the volume average diameter was 7.3 μm,
57 g of a cyan toner having a number average diameter of 6.3 μm was obtained. The value of volume average diameter / number average diameter is 1.16.
Met. The 50% circularity is 0.99, 0.6 to
The number ratio of 2.12 μm particles was 4%. An external addition process was performed in the same manner as the toner (TA4) to obtain a developing toner (this is referred to as TA5).

C) Toner (TA6) The toner (TA6) was replaced with the colorant dispersion C instead of the colorant dispersion A used in the toner (TA4).
When manufactured in the same manner as in 4), the volume average diameter was 7.5 μm,
57 g of a yellow toner having a number average diameter of 6.3 μm was obtained. The value of volume average diameter / number average diameter is 1.1.
Nine. The 50% circularity is 0.99, 0.6 to
The number ratio of the 2.12 μm particles was 3%. An external addition process was performed in the same manner as the toner (TA4) to obtain a developing toner (this is referred to as TA6).

D) Toner (TA4) Toner (TA4) except that colorant dispersion D was used instead of colorant dispersion A used in toner (TA4).
As a result, 57 g of a black toner having a volume average diameter of 7.5 μm and a number average diameter of 6.2 μm were obtained. In addition, the value of volume average diameter / number average diameter was 1.21. The 50% circularity is 0.98, 0.6 to 2.
The number ratio of 12 μm particles was 4%. Toner (T
An external addition process was performed in the same manner as in A4) to obtain a developing toner (this is referred to as TA7).

E) Toner (TA8) The toner (TA4) was manufactured in the same manner as the toner (TA4) except that the stirring time at 98 ° C. was changed from 6 hours to 1 hour. 3
μm, 59 g of magenta toner having a number average diameter of 6.4 μm
I got it. The value of volume average diameter / number average diameter is
1.15. The 50% circularity is 0.93,
The number ratio of particles of 0.6 to 2.12 μm was 7%. An external addition process was performed in the same manner as the toner (TA4) to obtain a developing toner (this is referred to as TA8). f) Toner (TA9) In the production of the above-mentioned toner (TA4), the temperature is from
Except for changing the temperature rise time to 2 ° C. from 2 hours to 30 minutes, the same production as for the toner (TA4) was carried out to obtain 60 g of a magenta toner having a volume average particle diameter of 7.5 μm and a number average particle diameter of 6.2 μm. Was completed. In addition, the value of volume average diameter / number average diameter was 1.21. The 50% circularity is 0.
98, the number ratio of particles of 0.6 to 2.12 μm is 16%
Met. An external addition process was performed in the same manner as the toner (TA4) to obtain a developing toner (referred to as TA9).

G) Toner (TB4) (Comparative Toner) Polyester resin (Tg = 60 ° C., Sp = 135 ° C., 1
% Crosslinking) in 94 parts of C.I. I. Pigment Blue 15: 3, 10 parts of a masterbatch of the polyester resin containing 40% of 4,4'-methylenebis [2
-[N- (4-Chlorophenyl) amide] -3-hydroxynaphthalene] (the above-mentioned CCA-1), 1 part of the mixture was kneaded, then pulverized and classified. The volume average diameter of the obtained toner was 7.8 μm, and the number average diameter was 5.8 μm. The value of volume average diameter / number average diameter was 1.34. To 100 parts of this toner, 1 part of silica having been subjected to hydrophobic surface treatment was added and mixed and stirred to obtain a toner for comparative development. (This is called TB4)

(Evaluation method) Toners (TA4 to TA9) and photoconductors (PC-A1, PC-B) obtained as described above
1) is a Color Pagepres made by CASIO.
The image was mounted on an oN4-612II and an image was formed at an exposure density of 600 dpi, and the following items were evaluated. The results are shown in Table 2.

A gradation roller was connected to a print roller having an image mode in which the image density could be determined in ten levels based on the area ratio of halftone dots, and the number of levels in which the printed image could be determined was evaluated. The larger the stage that can be determined, the higher the gradation. -Resolution-1 As a print image, exposure is performed so as to draw 6, 9, and 12 equally spaced vertical lines per 1 mm, and an image is formed.
The number of vertical lines per mm was visually evaluated to determine how many lines could be used. The higher the number, the higher the definition.

Resolution-2 Evaluation was made based on the reproducibility of an isolated dot having a diameter of 50 μm on the printed image. A: Very good reproducibility B: Good C: Insufficient resolution

[0209]

[Table 7]

[0210]

As described above, according to the present invention, a high-gradation, high-resolution image can be formed by using the above-mentioned specific titanyl phthalocyanine for the photoreceptor and combining it with the particle size distribution of the toner.

[0211]

[Brief description of the drawings]

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

FIG. 2 is a schematic view of main components of an example of a tandem-type full-color image forming apparatus used in the present invention.

FIG. 3 is a graph showing an image analysis result of a thin line image drawn in a vertical direction in Example A1 and Comparative Example B1.

FIG. 4 is a graph showing an image analysis result of a thin line image drawn in the horizontal direction in Example A1 and Comparative Example B1.

FIG. 5 is a graph showing an image analysis result of a thin line image drawn in the vertical direction in the reference example.

FIG. 6 is a graph showing an image analysis result of a thin line image drawn in the horizontal direction in the reference example.

[Explanation of symbols]

 Reference Signs List 1 photoconductor 2 charging device 3 exposure device 4 developing tank 4k black developing tank 4y yellow developing tank 4c cyan developing tank 4m magenta developing tank 5 transfer device 6 cleaning device 7 fixing device 42 agitator 43 supply roller 44 developing roller 45 regulating member 71 upper part Fixing member 72 Lower fixing member 73 Heating device T Toner P Recording paper

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 5/05 101 G03G 5/05 101 5/14 101 5/14 101B 101D 9/08 9/08 365 365 9/087 15/01 J 9/09 21/00 350 15/01 15/04 120 15/04 9/08 384 15/043 381 21/00 350 361 (72) Inventor: Akira Fujii Aoba, Yokohama-shi, Kanagawa Prefecture 1000 Kamoshita-cho, Yokohama Mitsubishi Research Institute Yokohama Research Laboratory F-term (reference) 2H005 AA15 AA21 AB03 AB06 CA14 EA03 EA05 EA07 2H030 AB02 AD01 BB02 BB23 BB38 2H035 CA07 CB03 2H068 AA13 AA42 AA43 AA54 BA12 BB23 FA27 FB11 2H076 AB02 AB09 AB42 DA37 DA39 EA01

Claims (42)

[Claims] 1. An image forming apparatus comprising at least a photoconductor, a toner and an exposure device, wherein the photoconductor is CuKα.
Angle (2θ ± 0.2) in X-ray diffraction by X-ray
A photosensitive layer containing oxytitanium phthalocyanine having a clear diffraction peak at 27.3 °, wherein the volume average particle diameter (Dv) of the toner is 3 to 8 μm, and the volume average particle diameter (Dv) and the number average The relationship with the particle size (Dn) is 1.0
≦ Dv / Dn ≦ 1.3. An image forming apparatus. 2. The volume average particle diameter (Dv) is 3 to 8 μm, and the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.0 ≦ Dv / Dn ≦ 1.3. And a photosensitive member having a photosensitive layer containing oxytitanium phthalocyanine having a clear diffraction peak at a Bragg angle (2θ ± 0.2) of 27.3 ° in X-ray diffraction by CuKα radiation. The image forming apparatus according to claim 1, further comprising a photoreceptor cartridge provided. 3. The volume average particle size (Dv) is 3 to 8 μm, and the relationship between the volume average particle size (Dv) and the number average particle size (Dn) is 1.0 ≦ Dv / Dn ≦ 1.3. And a toner that is
In X-ray diffraction by CuKα ray, Bragg angle (2θ ±
2. The image forming apparatus according to claim 1, further comprising an electrophotographic cartridge provided with a photosensitive member having a photosensitive layer containing oxytitanium phthalocyanine having a clear diffraction peak at 27.3 °. 4. The image forming apparatus according to claim 1, wherein the photosensitive layer is formed by laminating a charge generation layer and a charge transfer layer. 5. The image forming apparatus according to claim 1, wherein the toner contains at least a binder resin and a colorant, and is manufactured by a wet polymerization method. 6. The image forming apparatus according to claim 5, wherein the wax contains 1 to 40% of the toner. 7. The image forming apparatus according to claim 6, wherein the melting point of the wax is 30 to 100 ° C. 8. The image forming apparatus according to claim 6, wherein the wax contains a fatty acid alkyl ester having 10 to 30 carbon atoms. 9. The image forming apparatus according to claim 6, wherein the wax contains a fatty acid ester of a polyhydric alcohol having 15 to 50 carbon atoms. 10. The image forming apparatus according to claim 1, wherein the toner is obtained through a step of aggregating at least polymer primary particles and colorant particles to form a particle aggregate. 11. The image forming apparatus according to claim 10, wherein the toner is obtained through a step of attaching resin fine particles containing no wax to the particle aggregate. 12. The method according to claim 1, wherein the particle aggregate is formed by a method of Tg + 20 ° C. to Tg +
The image forming apparatus according to claim 10, wherein the image forming apparatus is obtained through a step of maintaining the temperature in a temperature range of 80 ° C. (where Tg is a glass transition temperature of polymer primary particles) for 1 hour or more. 13. The method according to claim 1, wherein the toner is prepared by adhering wax-free resin fine particles to the particle aggregate,
The image forming apparatus according to claim 11, wherein the image forming apparatus is obtained through a step of maintaining the temperature in a temperature range of Tg + 80 ° C. (where Tg is a glass transition temperature of primary polymer particles) for 1 hour or more. 14. The image forming apparatus according to claim 10, wherein the polymer primary particles contain wax. 15. The image forming apparatus according to claim 14, wherein the polymer primary particles are obtained by polymerizing a monomer in the presence of emulsified and dispersed wax fine particles. 16. A toner having a volume average particle diameter (Dv) of 4 to 16.
8 μm, and a particle size of 0. 0 by a flow type particle image analyzer.
The image forming apparatus according to claim 1, wherein a measured value (number) of particles having a size of 6 μm to 2.12 μm is 15% or less of the total number of particles. 17. The toner according to claim 1, wherein the toner has a 50% circularity of 0.9 to 1 corresponding to the cumulative particle size at 50% of the value obtained by the following formula (I). Image forming apparatus. ## EQU00001 ## Circularity = perimeter of a circle having the same area as the projected area of the particle / perimeter of the projected image of the particle (I) 18. The image forming apparatus according to claim 1, wherein the photosensitive member has at least a charge generation layer and a charge transfer layer on a cylindrical conductive substrate in this order. 19. The image forming apparatus according to claim 18, wherein the charge transfer layer contains at least a charge transfer agent and a binder resin, and contains a compound represented by the general formula (III) as the charge transfer agent. Embedded image (In the general formula (III), X is a divalent residue which may have a substituent, Ar is an aryl group which may have a substituent, and R may have a substituent. Represents an aryl, an alkyl, a condensed polycyclic ring, or a heterocyclic ring.) 20. The image forming apparatus according to claim 18, wherein the charge transfer layer contains at least a charge transfer agent and a binder resin, and contains a compound represented by the general formula (IV) as the charge transfer agent. Embedded image (In the general formula (IV), R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and a substituent. Represents an optionally substituted alkoxy group, an optionally substituted aryl group, or a substituted amino group, which may be the same or different from each other, and k, l, m, n, o, and p are 0 ~ respectively
Represents an integer of 4, and represents a plurality of R's in the case of an integer of 2 or more
⁴¹ each to R ^46, may be the same or different.
In the general formula (IV), X ¹¹ is the following general formula (IV-a)
And X ¹² represents a hydrogen atom or the following general formula (IV-b). ) (In the general formulas (IV-a) and (IV-b), i represents an integer of 0 to 2, h represents an integer of 0 to 2, R ⁴⁷ , R ⁴⁸ , R ⁴⁹ ,
R ⁵⁰ , R ⁵¹ , R ⁵² , R ⁵³ , R ⁵⁴ , R ⁵⁵ and R ⁵⁶ each represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, Represents an aryl group which may have a group or a heterocyclic group which may have a substituent, and these may be the same or different. Further, the pair consisting of R ⁵⁰ and R ⁵¹ or the pair consisting of R ⁵⁵ and R ⁵⁶ may be fused to form a carbocyclic or heterocyclic group.
However, when one of the pair consisting of R ⁵⁰ and R ⁵¹ or the pair consisting of R ⁵⁵ and R ⁵⁶ is a hydrogen atom or an alkyl group, the other is an aryl group or a heterocyclic group. i =
In the case of 2, each R ⁴⁷ and R ⁴⁸ may be the same or different, and when h = 2, each R ⁵⁵ and R ⁵⁶ may be the same or different. X ¹¹ and X ¹² may be the same or different. ) 21. The image forming apparatus according to claim 18, wherein the charge transfer layer contains at least a charge transfer agent and a binder resin, and contains a compound represented by the general formula (V) as the charge transfer agent. Embedded image (In the general formula (V), Ar ¹ represents a benzene ring which may have a substituent, a naphthalene ring which may have a substituent,
Or represents a biphenyl ring which may have a substituent,
Ar ^{2 to} Ar ³ each independently represent an aromatic ring which may have a substituent. n represents 1 or 2. ) 22. The image forming apparatus according to claim 18, wherein the charge transfer layer contains at least a charge transfer agent and a binder resin, and contains a compound represented by formula (VI) as the charge transfer agent. Embedded image (In the formula (VI), R ⁷¹ , R ⁷² , R ⁷³ and R ⁷⁴ are each independently an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or Represents an aralkyl group which may have a substituent.) 23. The image forming apparatus according to claim 18, wherein the binder resin of the charge transfer layer contains polycarbonate. 24. The image forming apparatus according to claim 23, wherein the polycarbonate resin contains a structural unit represented by the following general formula (XIII). Embedded image (In the formula (XIII), R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group, and R ⁵ and R ⁶ are connected to each other to form a cyclic structure. R ⁷ and R ⁸ are each independently a hydrogen atom,
Represents an alkyl group which may have a substituent or an aralkyl group. R ⁹ and R ¹⁰ each independently represent a hydrogen atom or an alkyl group which may have a substituent. ) 25. The image forming apparatus according to claim 23, wherein the polycarbonate resin contains a structural unit represented by the following general formula (XIV). Embedded image (In the formula (XIV), Z represents an optionally substituted aliphatic hydrocarbon ring having 5 to 8 carbon atoms.) 26. The image forming apparatus according to claim 23, wherein the polycarbonate resin contains a structural unit represented by the following general formula (XV). Embedded image (In the formula (XV), R ¹¹ and R ¹² are each independently, .R ¹³ representing an alkyl group which may have a hydrogen atom or a substituent
And R ¹⁴ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and R ¹³ and R ¹⁴ may be linked to each other to have a cyclic structure. R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or an alkyl group which may have a substituent. However, this excludes the case where all of R ^{11 to} R ¹⁴ are the same substituent and both R ¹⁵ and R ¹⁶ are hydrogen atoms. Here, x: y = 1: 9 to 9: 1. ) 27. The image forming apparatus according to claim 18, wherein the binder resin of the charge transfer layer contains polyarylate. 28. A polyarylate resin represented by the following general formula (XI)
The image forming apparatus according to claim 27, further comprising a structural unit represented by I). Embedded image (In the formula (XII), Ar ¹ and Ar ² each independently represent a benzene ring which may have a substituent, and X represents a divalent aliphatic hydrocarbon group which may have a substituent. R ¹ and R ² each independently represent a benzene ring which may have a substituent, a naphthalene ring which may have a substituent, or a biphenyl ring which may have a substituent. which may have a substituent aryl group, which may have a substituent acyloxy group, which may have a substituent arylsulfoxy group, R ¹ and R ² are linked to each other (A cyclic structure may be formed.) 29. The image forming apparatus according to claim 18, wherein the binder resin of the charge generation layer contains polyvinyl butyral. 30. The image forming apparatus according to claim 18, wherein the photosensitive member has an intermediate layer between the conductive substrate and the charge generating layer. 31. The image forming apparatus according to claim 30, having an alumite layer as an intermediate layer. 32. The image forming apparatus according to claim 30, having an undercoat layer as an intermediate layer, wherein the binder resin of the undercoat layer contains polyamide. 33. The image forming apparatus according to claim 30, wherein the intermediate layer has both an alumite layer and an undercoat layer. 34. The image forming apparatus according to claim 1, wherein the photosensitive member has a drum shape, and has an inner diameter of 10 to 40 mm. 35. The image forming apparatus according to claim 1, wherein the exposure apparatus performs digital image exposure on the photoconductor at a recording dot density of 600 dots / inch or more. 36. The image forming apparatus according to claim 1, wherein the exposure device emits laser light in a range of 500 to 850 nm. 37. The image forming apparatus according to claim 1, further comprising at least four color toners of yellow, magenta, cyan, and black. 38. The image forming apparatus according to claim 37, wherein toners of at least four colors of yellow, magenta, cyan, and black are provided in respective toner cartridges, and the toner cartridges are arranged in a tandem type. 39. An image forming method using at least a photoreceptor, an exposing device, and an image forming device provided with a toner, wherein the X-ray diffraction by CuKα ray has a Bragg angle (2θ ± 0.2) of 27.3 °. A charge generating layer containing oxytitanium phthalocyanine having a clear diffraction peak and a photosensitive member having a photosensitive layer in which a charge transfer layer is laminated are subjected to digital image exposure by the exposure apparatus, and an electrostatic charge is applied on the photosensitive member. In forming a latent image and developing the electrostatic latent image, the volume average particle diameter (Dv) is 3 to 8 μm, and the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is as follows.
An image forming method using a toner satisfying 0 ≦ Dv / Dn ≦ 1.3. 40. The image forming method according to claim 39, wherein the exposure apparatus performs digital image exposure at a recording dot density of 600 dots / inch or more. 41. A volume average particle size (Dv) of 3 to 8 μm
Wherein the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.0 ≦ Dv / Dn ≦ 1.3,
Bragg angle (2θ ±) in X-ray diffraction by CuKα ray
0.2) An electrophotographic cartridge provided with both a charge generation layer containing oxytitanium phthalocyanine having a distinct diffraction peak at 27.3 ° and a photosensitive member having a charge transfer layer laminated thereon. 42. A volume average particle size (Dv) of 3 to 8 μm
Wherein the relationship between the volume average particle diameter (Dv) and the number average particle diameter (Dn) is 1.0 ≦ Dv / Dn ≦ 1.3,
Bragg angle (2θ ±) in X-ray diffraction by CuKα ray
0.2) An electrophotographic cartridge having both a charge generation layer containing oxytitanium phthalocyanine having a clear diffraction peak at 27.3 ° and a photoreceptor having a charge transfer layer laminated thereon. Image forming apparatus.