JP2003207925A - Toner for non-magnetic one-component contact development and image forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner for non-magnetic one-component contact development excellent in not only fixing characteristic such as fixing property at low tempera ture, offset resistance and transmittance in fixing an OHT image but also restraint of fogging, filming, dripping and fusion on a photoreceptor, and making the fixing property compatible with developing property. <P>SOLUTION: The toner used for non-magnetic one-component contact development is the toner incorporating at least binding resin, a colorant, and a release agent, and an unfixed image is formed with the toner. Assuming that the elution amount of wax in the case of immersing the unfixed image in hexane under the environment of 23°C and 60%RH is C(N) and that in the case of immersing the unfixed image formed with the toner in hexane under the environment of 23°C and 60%RH after heating it at 100°C for two minutes is C(H), relation of 1.10≤C(H)/C(N)≤5.00 holds. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-magnetic one-component contact developing toner used in electrophotography, an electrostatic recording method or a toner jet method, and an image forming method using the non-magnetic one-component contact developing toner. Regarding

[0002]

2. Description of the Related Art Conventionally, a large number of electrophotographic methods are known, but generally, a photoconductive substance is used and an electric latent image is formed on an image bearing member (photoreceptor) by various means. Then, the latent image is developed with toner to make it a visible image, and the toner image is transferred to a transfer material such as paper, if necessary, and then the toner image is fixed on the transfer material by heat / pressure. To obtain a copy.

As a method of visualizing an electric latent image, a magnetic two-component developing system comprising a magnetic toner and a carrier, a non-magnetic two-component developing system comprising a non-magnetic toner and a carrier, and a non-magnetic toner to which external additive particles are externally added. The non-magnetic one-component developing method using only the magnetic field and the magnetic one-component developing method using the magnetic toner are generally widely used.

On the other hand, in the electrophotographic industry, the image resolution of printers and the like has been increased to 1200 and 2400 dpi. Accordingly, the developing system of the printer device is also required to have higher definition. Further, in the copying machine as well, the functions and the digitalization are progressing, and the high resolution and the high definition are required as in the printer device.

Further, in recent years, with the spread of copying machines and printers using the electrophotographic method including general households, there is an increasing demand for inexpensive and compact copying machines or printers. .

Therefore, the developing system has been improved in order to meet these demands, and the non-magnetic one-component contact developing system which is easy to meet the demands for high resolution and high definition among various developing systems is preferable. Used.

In the one-component developing method, when the photoconductor and the toner carrier are separated from each other, the lines of electric force are concentrated on the edge portion of the electrostatic latent image on the photoconductor, and the toner is developed along the lines of electric force. Therefore, the image quality is likely to deteriorate due to the edge effect in which the toner is unevenly developed at the edge portion of the image.

Therefore, the edge effect is prevented by bringing the photoconductor and the toner carrier very close to each other, but the gap between the photoconductor and the toner carrier is mechanically set, that is, the toner layer on the toner carrier is formed. It is difficult to set the gap smaller than the thickness of the.

Therefore, the edge effect can be prevented by using the one-component contact developing method in which the toner bearing member is pressed against the photosensitive member to perform the development. However, if the toner carrier surface moving speed is the same as the photosensitive member surface moving speed, a satisfactory image cannot be obtained when the latent image on the photosensitive member is visualized. Therefore, in the one-component contact developing method, by making the surface moving speed of the toner carrier different from the surface moving speed of the photosensitive member, a part of the toner on the toner carrier is removed from the latent image on the surface of the photosensitive member. It is developed and stripped of another portion of the toner resulting in a developed image without edge effects that is very true to the latent image. Further, this non-magnetic one-component contact developing method is considered to be easier to downsize, simplify, and lighten the developing device, as compared with the two-component developing method,
Copiers and printers using electrophotography have great merits for their widespread use, including in general households.

In such a contact one-component developing method, it is indispensable to rub the surface of the photosensitive member with the toner and the toner carrying member. For this reason, the toner deteriorates due to long-term use, and the fluidity and the uniform charging of the toner occur. As a result, the fog is reduced, the fog is increased and the transfer efficiency is lowered, which is not preferable. In addition, toner is a friction charging member, a developing roller,
It is not preferable because it is likely to be fused or filmed on the photoconductor or the like and the image quality is deteriorated. Further, even if the toner is insufficiently charged due to the toner carrier rubbing the surface of the photoreceptor, the toner easily adheres to the surface of the photoreceptor if it is charged to a certain extent, so that the image quality is deteriorated in image formation such as fluffing. This may cause it to be undesirable.

Regarding the non-magnetic one-component contact developing method, JP-A-9-127720 and JP-A-9-190006.
In the publication, a method of externally adding a metal salt compound is disclosed, but when an image evaluation is actually carried out for this as well,
Fog and transfer residue are still at an insufficient level.

In EP 886187A1, fine dots are defined because the average particle size and shape factor on the toner particles of the external additive contained in the toner having a specific circularity distribution and a specific weight average particle size are within a specific range. It is described that a high quality image faithfully reproduced is obtained, the mechanical stress in the developing device is high, and the toner deterioration hardly occurs.

However, the above-mentioned prior art has a point to be further improved in terms of suppressing fog when contact development is carried out.

Furthermore, a copier or printer
For the desire to be cheap and small,
It is necessary to improve not only the developing method but also the fixing method, and for that reason, simplification of the fixing method and reduction of power consumption are essential in designing a copying machine or printer.

The fixing method using a heat roll is most commonly used as a method for fusing and fixing the toner on the paper, but usually, a means for supplying oil to the heat roll is used for the purpose of preventing offset to the heat roll. There is provided means for separating the fixed image from the fixing roller for the purpose of preventing winding at the time of fixing. In simplifying the fixing method, a toner capable of obtaining a good fixed image without using such a means, having excellent fixing strength on a transfer material and excellent separability from a fixing roller is required.

Further, in order to reduce power consumption, electrophotographic toner used in a copying machine or a printer is required to have a low fixing temperature.

To date, proposals have been made to improve the molecular weight and molecular weight distribution of the binder resin in response to the above requirements. For example, a method has been studied in which a resin having a low molecular weight and a narrow molecular weight distribution is used as a binder resin to lower the fixing temperature, and a resin which is melted sharply during fixing to make the image surface smooth. However, when the molecular weight is lowered, the melting point is lowered, but the internal cohesive force is also lowered, so that there is a problem that it is difficult to peel from the fixing roll during melting.

Therefore, in response to the above request, Japanese Patent Laid-Open No.
As described in Japanese Patent Laid-Open No. 6-87051, a method has been studied in which a release agent is added to toner to facilitate peeling from a fixing roll, and some success has been achieved in terms of releasability from the fixing roll. However, not all toner characteristics are satisfactory in the simplified fixing method. The reason for this is that it is difficult to control the distribution and dispersion state of the release agent contained in the toner to the optimum state. In order to satisfy the releasability from the fixing roll, the amount of the release agent added to the toner is preferably 1 to 20% by mass, and the higher the amount of the release agent, the higher the release property. However, especially when the amount of the release agent added is large, for example, when the toner is prepared by the kneading and pulverization method,
When the distribution and dispersion state of the release agent is not controlled to an optimum state and the wax generally used as the release agent is exposed on the toner surface with the pigment at a high concentration,
The powder fluidity and thermal agglomeration deteriorate. Therefore, when the toner is actually used, problems such as blocking, filming, and fusion occur in terms of developability.

As a means for overcoming the drawbacks of the toner to which such a wax is added, JP-A-60-222868, JP-A-61-1114247, and JP-A-59-1.
There is a toner in which a wax as described in Japanese Patent No. 62562 is encapsulated in a toner particle by a capsule type structure. Such a capsule structure toner can reduce the proportion of low molecular weight components such as wax exposed on the surface, and the problems such as blocking and filming described above are relatively small. However, in many cases, such a toner having no surface wax does not always have sufficient releasability from the fixing roll. In order to obtain sufficient separability from the heat roll at the time of fixing, it is necessary to instantly form a release layer of molten wax between the surface of the heat roll and the melted toner layer, but if the wax is completely enclosed There is a problem that it takes time for the molten wax to diffuse to the interface inside the resin to be adhered, and the release layer is not formed instantaneously.

As a means for overcoming the problems relating to both the developability and the fixability at low energy in the non-magnetic one-component contact developing method as described above, JP-A 06-2820 is known.
Japanese Patent Publication No. 99 discloses a method of combining resin particles having a low softening point and resin particles having a high softening point, but it describes that both fixing at low energy and cleaning property are compatible with each other. There is no description.

Further, Japanese Patent Laid-Open No. 2000-147827 discloses a method of incorporating a wax ester containing an oxyacid ester into a toner composition containing a polyester resin having an acid value defined, but fixing with low energy. However, there is no description about fluffing, cleaning property, or maintaining transparency during fixing of OHT image.

[0022]

SUMMARY OF THE INVENTION An object of the present invention is to fix an image formed using an image forming method by non-magnetic one-component contact development at a low fixing temperature,
Peelability from the fixing roller at the time of fixing, offset resistance,
A non-magnetic single component that is compatible not only with fixing characteristics such as transparency when fixing an OHT image in color toners, but also with respect to suppression of fogging, filming, fluffing, and fusion to a photoconductor, and that is compatible with both fixability and developability. To provide a toner for contact development and an image forming method.

[0023]

SUMMARY OF THE INVENTION The present invention is a toner used for non-magnetic one-component contact development, wherein the toner contains at least a binder resin, a colorant and a release agent, and An unfixed image is created with the toner,
When the unfixed image is immersed in hexane at 23 ° C. and 60% RH, the wax elution amount is C
(N), the unfixed image produced by the toner is heated to 100 ° C.
After heating for 2 minutes at 23 ° C. and 60% RH, the wax elution amount when immersed in hexane is C
(H), the relationship of 1.10 ≦ C (H) / C (N) ≦ 5.00 holds, and relates to a non-magnetic one-component contact developing toner, and image formation using this toner. Regarding the method.

[0024]

DETAILED DESCRIPTION OF THE INVENTION As a result of intensive studies made by the present inventors, not only the toner characteristics, in particular, the fixing characteristics at low temperature and the releasability from the fixing roller at the time of fixing, and the offset resistance, Fog, filming, fluffing,
In order to solve the problem of achieving both fixability and developability, which is excellent in suppressing fusion to the photoconductor, the distribution and dispersion of the release agent contained in the toner should be optimized. The inventors have found that control is important and have completed the present invention.

That is, the toner of the present invention is a toner containing at least a binder resin, a colorant and a release agent, and has a proper affinity for wax as a binder and a colorant in the preparation of the toner by a pulverization method. By adjusting the melt-kneading conditions and cooling conditions of the melt-kneaded product, by controlling the dispersion and distribution state of the wax from the affinity with the binder and the colorant, and also by controlling the hardness of the binder, Not only controlling the viscoelasticity of the binder by controlling the crushing method at the time of crushing and the dispersion and distribution state of the wax when made into toner, but also the wax is distributed to some extent near the surface of the toner particles, and the dispersion state In order to optimize the stress applied to the toner at the time of classification, by controlling so that it is in an appropriate state, and further optimizing the classification method. To maintain the surface condition of the toner in an optimum state, and to adjust the amounts of the cross-linking agent and the wax in the production by the polymerization method, and to adjust the type and amount of the monomer and the colorant to be appropriate for the wax. Adjust to have affinity, stirring time with an attritor,
Not only controlling the viscoelasticity of the binder, but also controlling the viscoelasticity of the toner particles by adjusting the polymerization temperature to an appropriate level and adjusting the conditions for adding the wax, monomer, charge control agent, etc. used for toner preparation. The wax is distributed to some extent in the toner, and is controlled and controlled so that it is in an appropriate state even in its dispersed state, and by further optimizing the drying method, it is contained in the toner in the process of removing water and other contained substances during drying. By controlling the distribution of the low molecular weight substance and the structural state of the binder,
When the wax contained in the toner was immersed in hexane under a temperature environment of ℃
(N), after heating the toner at 100 ° C. for 2 minutes, 2
When the wax contained in the toner was immersed in hexane in an environment of 3 ° C., the elution amount of the wax contained in the toner into hexane was C.
When it is (H), the non-magnetic one-component contact developing toner is characterized in that the relationship of 1.10 ≦ C (H) / C (N) ≦ 5.00 is established.

When C (H) / C (N) is less than 1.10, a large amount of wax may be exposed on the surface of the toner. In this case, due to charging failure during development. Fogging, filming, further fluffing, and fusion on the photosensitive member may cause problems in terms of developability, such being undesirable. Second, it is possible that the wax diffuses slowly from the inside of the toner to the interface at the time of fixing, and in this case, the peeling layer from the fixing roller does not form rapidly between the fixing roller and the toner because of the peeling layer from the fixing roller.
There is a problem in fixability such as offset resistance.
Further, if the fixing temperature is lowered to avoid them, the transparency of the color toner at the time of fixing cannot be maintained.

If C (H) / C (N) is more than 5.00, a problem occurs that the resulting image is glaring due to the wax, and the quality is deteriorated particularly when the image is characters. Not preferable. Further, particularly in the image formation on the OHT with the color toner, there is a problem that the release layer of the wax on the fixed image lowers the transparency of the image, which is not preferable.

A method for preparing a wax extract by immersing the toner in a solvent and a method for quantifying the extract in the present invention will be described below. Measuring device: Gas Chromatography GC System
m HP6890 (manufactured by HP) Used column: HP-1 (capillary column) inner diameter of 0.
32 mm, length 30 m, film thickness 0.25 μm (manufactured by HP) Measurement conditions: Injector injection amount: 2.0 μl Injection port: Front pulsed split gas: He Heater: 325 ° C. Pressure: 5.2 psi Total flow: 8. Pulse at 3 ml / min injection: 40 psi until 0.50 mi
n Split ratio: 5.1: 1 Split flow rate: 4.9 ml / min Gas saver: 100 ml / min @ 2.00 min ・ Column mode: Constant flow inlet: Front detector: Back outlet: Atmospheric pressure He flow rate pressure: 5 .2 psi Flow rate: 1.0 ml / min Average linear velocity: 18 cm / sec ・ Oven

[0029]

[Table 1] Oven setting value: 50 ° C Oven configuration: Maximum value: 330 ° C Equilibrium: 2.00min ・ Detector: FID back heater: 325 ° C H ₂ flow rate: 30ml / min Air flow rate: 400ml / min Makeup flow rate: He 25

Sample preparation method: using the prepared toner
Commercially available PIXEL CP6 as an image forming device
The fixing device of 60-A (made by Canon Inc.) was removed.
An unfixed image is produced on the surface of transfer paper by an image forming device.
To do. However, the transfer mass of the solid image part on the transfer paper (M
/ S): 0.65 mg / cm ² Solid image size: 2cm x 5cm Transfer paper: 75 g paper made by Xerox Co., Ltd. Xerox 402
4 DP Paper

The unfixed image thus produced is cut into a margin of 2 to 3 mm and cut into strips to prepare the following two types (I and II) of samples. I: The above unfixed image is transferred to the oven TAH-21P (THO
2 at 100 ° C with MAS SCIENTIFIC)
Heated for two minutes II: Unfixed image as it is (no heating) 17 g of hexane is weighed out in a 30 ml screw tube. Each of the sample images prepared in the hexane-containing screw tube is dipped, sealed and left to stand. Take a sample image from the screw tube after 1 hour, close the lid of the screw tube and shake well. afterwards,
Return the sample image that was taken out to the screw tube, seal, and let it stand. (The sample image that has been immersed for 1 hour is immersed in the screw tube containing the original solvent.) After further immersing for 1 hour (total immersion for 2 hours), the sample image is taken out, shaken well and then the extracted solution is added. sampling. The extract sampled in 1 is quantified by gas chromatography to calculate C (H) / C (N).

In the quantification, a sample for a calibration curve was prepared, and a calibration curve was prepared from the peak area of the main peak of wax. Further, regarding the measurement sample, the unfixed image formed by the toner was immersed in hexane under an environment of 23 ° C., and C (N) was determined by a calibration curve from the peak area of the main peak of the wax in the extract, The unfixed image produced with the toner was heated at 100 ° C. for 2 minutes and then immersed in hexane under an environment of 23 ° C. to obtain C (H) from the peak area of the main peak of the wax in the extract obtained by a calibration curve. Then, C (H) / C (N) was calculated. Hexane was used as the solvent used to extract the wax because the wax is soluble and the binder is almost insoluble. Further, in the case of a toner containing two or more kinds of wax, hexane is used for each wax to calculate the elution amount of each wax, and {(total of C (H) of each wax) / (each wax C (N) total)} to C (H)
Calculated as the value of / C (N). The method for quantifying the wax in the extract may be changed to a column of an appropriate type depending on the type of wax, and it is not necessary to limit the method to the gas chromatography described above, and a suitable method may be used. Other quantitative analysis devices such as liquid chromatography may be used instead of gas chromatography as long as the type of column and measurement conditions are set.

As a method for producing the toner particles of the present invention, for example, a resin, a release agent, a colorant, a charge control agent and the like are melt-kneaded by using a pressure kneader, an extruder or a roll mill, and then cooled and solidified. , Mechanically or in a jet stream to collide with a target to finely pulverize to a desired toner particle size and classify to obtain a toner, including a pulverization method, a suspension polymerization method, a dispersion polymerization method, an emulsion polymerization or dispersion method. A conventionally known manufacturing method such as a method of aggregating resin particles produced by polymerization to obtain a toner can be used.

Examples of the wax component functioning as a releasing agent used in the toner of the present invention include plant waxes such as carnauba wax and rice wax, petroleum waxes such as paraffin wax, polyolefin wax and microcrystalline wax, and Fischer-Tropish. Examples of the wax include polymethylene wax, polyethylene wax, polypropylene wax, amide wax, higher fatty acid, long chain alcohol, ketone, ether, ester wax and derivatives thereof such as graft compounds and block compounds. It is preferable that the removed DSC endothermic curve has a sharp maximum endothermic peak.

More preferably used waxes include linear alkyl alcohols having 15 to 100 carbon atoms, linear fatty acids, linear acid amides, linear esters, and montan derivatives. Further, it is also preferable that impurities such as liquid fatty acid have been previously removed from these waxes.

Further, particularly preferred waxes include ester waxes containing an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkylcarboxylic acid having 15 to 45 carbon atoms as a main component. preferable.

The release agent used in the present invention has a DSC endothermic curve of 40 to 140 ° C. (more preferably 45 ° C.).
It is preferable to have an endothermic main peak in the region of 120 ° C. Furthermore, the half-value width of the endothermic main peak is 10
A substance having a low softening point, which has a sharp melting point and is within the range of 0 ° C (more preferably within the range of 5 ° C), is preferable. In the DSC endothermic curve, when the peak top temperature of the endothermic main peak is the melting point, the melting point is preferably 60 to 120 ° C.

The amount of the wax added to the toner particles of the present invention depends on the average dispersed diameter of the finely divided wax, but usually 0.1 to 40% by mass can be used, but it is 1 to 20.
The range of mass% is more preferable. If it is less than 1% by mass, sufficient releasability from the fixing roller cannot be obtained, and if it exceeds 20% by mass, filming on the photoconductor or the charging member becomes remarkable, which is not preferable.

As the binder resin of the toner according to the present invention,
There is no particular limitation, and resins generally used as toner resins can be used. Specifically, a homopolymer of styrene and its substitution products such as polyester resin, polystyrene and polyvinyltoluene; styrene-propylene copolymer, styrene-vinyltoluene copolymer,
Styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-dimethylamino acrylate Ethyl copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-dimethylaminoethyl methacrylate copolymer, styrene-vinyl methyl ether copolymer Copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Styrenic copolymers such as Polymethyl methacrylate, polybutyl methacrylate, polyvinyl acetate, polyethylene,
Examples thereof include polypropylene, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, epoxy resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, paraffin wax, and carnauba wax. These can be used alone or in combination.

As the colorant used in the toner according to the present invention, carbon black as a black colorant, and a yellow / magenta / cyan colorant shown below, which is toned in each color, are used.

As the yellow colorant, condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
Compounds represented by azo metal complexes, methine compounds and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 109, 110,
111, 128, 129, 147, 168, 180 etc. are used suitably.

As the magenta colorant, a condensed azo compound, a diketopyrrolopyrrole compound, an anthraquinone, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazolone compound, a thioindigo compound, and a perylene compound are used. Specifically, C.I.
I. Pigmentlet 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
22, 144, 146, 166, 169, 177, 18
4, 185, 202, 206, 220, 221, 254
Is particularly preferable.

As the cyan colorant used in the present invention, copper phthalocyanine compounds and their derivatives, anthraquinone compounds, basic dye lake compounds and the like can be used.
Specifically, C.I. I. Pigment Blue 1, 7, 15,
15: 1, 15: 2, 15: 3, 15: 4, 60, 6
2, 66 and the like can be used particularly preferably.

These colorants can be used alone or in the form of a mixture, or in the state of a solid solution.

In the case of color toner, the colorant of the present invention is
It is selected from the viewpoints of hue angle, saturation, lightness, weather resistance, OHP transparency, and dispersibility in toner. The amount of the colorant added is
It is used by adding 1 to 20 parts by mass to 100 parts by mass of the resin.

In the present invention, when the toner is obtained by the polymerization method, it is necessary to pay attention to the polymerization inhibitory property and the water phase transfer property of the colorant. Preferably, surface modification of the colorant,
For example, it is better to perform a hydrophobic treatment with a substance that does not inhibit polymerization. Especially, dyes and carbon black are
Since many of them have polymerization inhibitory properties, caution is required when using them. As a preferred method of surface-treating the colorant, a method of polymerizing the polymerizable monomer in the presence of these colorants in advance is mentioned, and it is preferable to add the obtained colored polymer to the monomer composition. . Further, the carbon black may be subjected to a treatment similar to the above-mentioned colorant, or a graft treatment with a substance that reacts with the surface functional group of the carbon black, such as polyorganosiloxane.

A charge control agent can be used in the toner of the present invention, if necessary.

The charge control agent used in the present invention includes
Although known compounds can be used, a charge control agent which is colorless and has a high charging speed of the toner and which can stably maintain a constant charge amount is particularly preferable.

Specific compounds include negative compounds such as salicylic acid, naphthoic acid, dicarboxylic acids, metal compounds of their derivatives, polymeric compounds having sulfonic acid and carboxylic acid in the side chains, boron compounds, urea compounds, and silicon. Compounds, currys arenes and the like can be used, and as a positive system, quaternary ammonium salts, polymer type compounds having the quaternary ammonium salt in the side chain, guanidine compounds, imidazole compounds and the like are preferably used. Furthermore, a suitable combination of these can be preferably used.

Further, metal soap, an inorganic or organic metal salt can be used in combination with the above charge control agent. Such metal soaps include aluminum tristearate, aluminum distearate, barium, calcium, lead and zinc stearate, or cobalt,
Manganese, lead and zinc linolenate, aluminum,
Calcium, cobalt octanoate, calcium and cobalt oleate, zinc palmitate, calcium, cobalt, manganese, lead and zinc naphthenates,
Calcium, cobalt, manganese lead and zinc resinates and the like can be used. Further, as the inorganic and organic metal salts, for example, the cationic component in the metal salt is selected from the group consisting of metals of Group Ia, Group IIa, and Group IIIa of the periodic table, and the anionic property of the acid is selected. Is a salt selected from the group consisting of halogens, carbonates, acetates, sulphates, borates, nitrates, and phosphates.

The charge control agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin. However, the addition of the charge control agent is not essential in the present invention, and when the two-component developing method is used, triboelectric charging with the carrier is utilized, and the blade member is used even when the non-magnetic one-component blade coating developing method is used. It is not always necessary to include a charge control agent in the toner by positively utilizing triboelectric charging with the sleeve member.

The toner of the present invention has an average circularity of 0.95.
0 or more and less than 0.990 (preferably 0.965 or more and 0.9.
(Less than 990) and the standard deviation of circularity is less than 0.05, excellent fixability is exhibited in the examples of the present invention. Average circularity less than 0.950 and circularity standard deviation 0.05
In the above case, since the shape of the toner particles is non-uniform, the transfer efficiency is lowered, and further, the heat and pressure at the time of fixing are not evenly transferred, so that the melting of the binder and the wax becomes non-uniform, so that especially at low temperature. The fixability is poor in the area. When the average circularity is 0.990 or more, when the toner remaining on the image carrier after the transfer is removed, the fluidity of the toner is too good to pass through between the cleaning member and the image carrier, resulting in poor cleaning. There is a problem that occurs. Further, in fixing, particularly in pressure fixing, it is difficult to be destroyed by pressure, and fixing failure is likely to occur. Also, the average particle size is 5.0 μm or more 1
When the thickness is less than 2.0 μm, it is easy to regulate the toner layer on the toner carrier by the frictional charging member, which is preferable.

The weight average particle diameter of the toner can be measured by various methods such as Coulter Counter TA-II type or Coulter Multisizer (manufactured by Coulter Co.).
In the present invention, a Coulter counter TA-II type (manufactured by Coulter, Inc.) is used, an interface (manufactured by Nikkaki) for outputting number distribution and volume distribution and a PC9801 personal computer (manufactured by NEC) are connected, and the electrolytic solution is a primary chloride. Prepare a 1% aqueous NaCl solution with sodium. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used.
As a measuring method, 0.1 to 5 ml of a surfactant, preferably an alkylbenzene sulfonate as a dispersant is added to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolytic solution in which the sample was suspended was subjected to a dispersion treatment for about 1 to 3 minutes by an ultrasonic disperser, and the Coulter Counter TA-II type 100 was used as an aperture.
The volume distribution and the number distribution were calculated by measuring the volume and number of the toner having a particle size of 2 μm or more using a μm aperture.
Then, the volume-based weight-average particle diameter (D4: the median value of each channel is used as the representative value of the channels) determined from the volume distribution according to the present invention was determined.

The average sphericity and the circularity standard deviation are measured by a circle equivalent diameter-circularity scattergram based on the number of toner particles measured by a flow type particle image measuring device, and in the present invention, "FPIA". -1000 "(manufactured by Toa Medical Electronics Co., Ltd.) was used for the measurement, and the following formula was used for calculation. Circularity = Circular length having the same projected area as the particle image / Perimeter of the particle projected image Average circularity = Total circularity of each particle / Total number of particles Circularity standard deviation = {Σ (Circularity of each particle− Average circularity)
² / total number of particles} ^1/2

Here, the "particle projection area" is the area of the binarized toner particle image. As a specific measuring method, 10 ml of ion-exchanged water from which impure solids and the like have been removed in advance is prepared in a container, and a surfactant as a dispersant,
Preferably after adding the alkylbenzene sulfonate,
Furthermore, 0.02 g of a measurement sample is added and uniformly dispersed. As means for dispersing, ultrasonic disperser "UH-50 type"
(Manufactured by SMT) with a 5Φ titanium alloy chip attached as a vibrator, dispersion treatment is performed for 5 minutes,
Use this as the dispersion liquid for measurement. At that time, the temperature of the dispersion is 40
Cool appropriately so that the temperature does not exceed ℃.

To measure the shape of the toner, the flow type particle image measuring device was used, and the toner particle concentration at the time of measurement was 3000.
The concentration of the dispersion liquid is readjusted to be about 10,000 particles / μl, and 1,000 or more toner particles are measured. After the measurement, the circularity of the toner is obtained using this data.

As a method of controlling the shape factor of the toner particles of the present invention, for example, a method of producing toner by controlling the spheroidizing condition when spheronizing the toner particles produced by a pulverizing method, and Examples thereof include a method of controlling the polymerization conditions when manufacturing toner particles by a polymerization method such as emulsion polymerization, suspension polymerization, and dispersion polymerization, and manufacturing a toner.

As a method of spheroidizing the toner particles produced by the pulverization method, a resin, a release agent, a colorant, a charge control agent, etc. are uniformly dispersed by using a pressure kneader, an extruder or a media disperser. After that, the target is collided mechanically or under a jet stream to be finely pulverized to a desired toner particle size. After that, hot water bath method, hot air flow method,
The toner particles are spheroidized by a mechanical impact method or the like, and a particle size distribution is adjusted through a classification step. The shape factor of the toner particles can be adjusted by appropriately controlling the processing conditions such as the processing temperature, the processing time, and the processing energy when the spheroidizing process is performed. Especially in the method of mechanically spheronizing toner particles produced by the pulverization method, not only the spherical coefficient is adjusted, but also the mechanical impact causes the binder to cover the release agent exposed on the surface of the toner particles. As a result, the release agent is distributed in the vicinity of the toner surface, and the effect of contributing to both the fixing property and the developing property can be seen.

As a method for producing toner particles by a polymerization method, a releasing agent, a colorant, a charge control agent, a polymerization initiator and other additives are added to a polymerizable monomer, and a homogenizer / ultrasonic disperser or the like is used. The monomer composition that has been uniformly dissolved or dispersed by the above method is dispersed by a homomixer or the like in an aqueous phase containing a dispersion stabilizer. The granulation is stopped when the droplets of the monomer composition have the desired toner particle size. After that, stirring may be performed to the extent that the particle state is maintained and the particles are prevented from settling due to the action of the dispersion stabilizer. Polymerization temperature is 40 ° C or higher, generally 5
Polymerization is performed by setting the temperature at 0 to 90 ° C. Further, for the purpose of obtaining a predetermined molecular weight distribution, the temperature may be raised in the latter half of the polymerization reaction, and further in the latter half of the reaction in order to remove unreacted polymerizable monomer, by-products, or after the reaction. Part of the aqueous medium may be distilled off. After the reaction is completed, the produced toner particles are collected by washing and filtration and dried. In the suspension polymerization method, water is usually added in an amount of 300 to 100 parts by mass of the monomer composition.
It is preferable to use 3000 parts by weight as the dispersion medium.

The shape factor of the toner particles can be controlled by controlling the kind and amount of the dispersion stabilizer, the stirring conditions, the pH of the aqueous layer and the polymerization conditions, and the molecular weight of the additive when the toner particles are produced by the above-mentioned polymerization method. Can be adjusted.

In the present invention, when the toner particles are obtained by the suspension polymerization method, the polymerizable monomer is styrene, o (m-, p-)-methylstyrene, m (p-)-.
Styrene-based monomers such as ethylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, (meth)
Octyl acrylate, Dodecyl (meth) acrylate,
(Meth) acrylic acid ester-based monomers such as stearyl (meth) acrylate, behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate Body; ene-based monomers such as butadiene, isoprene, cyclohexene, (meth) acrylonitrile, and acrylic acid amide are preferably used. These are published alone or generally in the Polymer Handbook, Second Edition II.
I-P139-192 (John Wiley & Son)
The product has a theoretical glass transition temperature (Tg) of 40
The monomers are appropriately mixed and used so as to show -80 ° C.
If the theoretical glass transition temperature is lower than 40 ° C., problems occur in terms of storage stability of toner and durability stability of developer,
On the other hand, if it exceeds 80 ° C., the fixing point is increased, which is not preferable.

Further, in the method of obtaining toner particles by using the suspension polymerization method, it is particularly preferable to add the polar resin at the same time from the viewpoint of allowing the polymerization reaction of the polymerization monomer to be carried out without hindrance. Examples of the polar resin used in the present invention include copolymers of styrene and (meth) acrylic acid, copolymers of styrene and unsaturated carboxylic acid esters, nitrile monomers such as acrylonitrile, vinyl chloride and the like. Halogen-based monomers, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, other unsaturated dibasic acids and unsaturated dibasic acid anhydrides, polymers such as nitro-based monomers, or these monomers A copolymer with a styrene-based monomer, a maleic acid copolymer, a polyester resin or an epoxy resin is preferably used. It is particularly preferable that the polar resin does not contain an unsaturated group capable of reacting with the monomer in the molecule. The addition amount of these polar polymers and / or copolymers is preferably 0.1 to 10 mass% of the polymerizable monomer.

As the polymerization initiator used in the present invention, for example, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile,
1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-
Azo-based polymerization initiators such as dimethyl valeronitrile and azobisisobutyronitrile; benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-
Peroxide type polymerization initiators such as dichlorobenzoyl peroxide and lauroyl peroxide are used.

When the melt index (MI) of the toner of the present invention is in the range of 1.0 to 25 g / 10 minutes, it exhibits excellent fixability in the examples of the present invention. Toner MI
Is less than 1.0, it is disadvantageous from the viewpoint of simplifying the fixing method and reducing the power consumption because the pressure from the fixing roller and the heating required at the time of fixing must be high temperature and high pressure. Further, if it exceeds 25, the internal cohesive force decreases,
Offset resistance deteriorates, which is not desirable.

The melt index here is the flow test method for thermoplastics of Japanese Industrial Standards JIS K7.
Using the apparatus described in No. 210, measurement is performed by the manual cutting method under the following measurement conditions. At this time, the measured value is converted into a 10-minute value. Measurement temperature: 135 ° C. Load: 2.16 kg (21.2 N) Sample filling amount: 5-10 g

The additives used for the purpose of imparting various properties used in the present invention are, from the viewpoint of durability when added to the toner,
The particle diameter is preferably 1/10 or less of the weight average diameter of the toner particles. The particle size of the additive means the average particle size thereof obtained by observing the surface of the toner particles with an electron microscope. As the additives for the purpose of imparting these characteristics, for example, the followings are used, but are not particularly limited.

1) As fluidity imparting agents: metal oxides (silica, hydrophobic silica, silicon oxide, aluminum oxide, titanium oxide, etc.), carbon black, carbon fluoride, etc. It is more preferable that each is subjected to a hydrophobic treatment. Furthermore, it is more preferable that the silicone oil is subjected to a hydrophobic treatment.

2) As abrasives: metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts ( Calcium sulfate, barium sulfate, calcium carbonate, etc.) are preferred.

3) As lubricants: fluorine resin powder (vinylidene fluoride, polytetrafluoroethylene, etc.),
Fatty acid metal salts (zinc stearate, calcium stearate, etc.) and the like are preferable.

4) As the charge controllable particles, metal oxides (tin oxide, titanium oxide, zinc oxide, silicon oxide, aluminum oxide, etc.), carbon black and the like are preferable.

These additives are preferably used in an amount of 0.1 to 10 parts by mass (preferably 0.1 to 5 parts by mass) per 100 parts by mass of the toner. These additives may be used alone or in combination.

Next, the image forming method of the present invention will be described below with reference to the accompanying drawings.

In FIG. 1, 100 is a developing device and 109
Is a photoconductor, 105 is a transfer target such as paper, 106 is a transfer member, 107 is a fixing pressure roller, 108 is a fixing heating roller, and 110 is a primary charging member that contacts the photoconductor 109 to perform direct charging. Show.

A bias power source 115 is connected to the primary charging member 110 so as to uniformly charge the surface of the photoconductor 109.

The developing device 100 contains the toner 104, and is provided with a toner carrier 102 which comes into contact with the photoconductor 109 and rotates in the direction of the arrow. Further, the developing blade 101 for regulating the toner amount and imparting the charge, and the toner 104
The toner carrier 102 and the toner carrier 10
Also provided is an application roller 103 that rotates in the direction of the arrow in order to impart charge to the toner by friction with 2. A developing bias power source 117 is connected to the toner carrier 102. A bias power source (not shown) is also connected to the coating roller 103, and a voltage is applied to the negative side of the developing bias when the negative charging toner is used, and to the positive side of the developing bias when the positive charging toner is used. Is set.

A transfer bias power source 116 having a polarity opposite to that of the photosensitive member 109 is connected to the transfer member 106.

Here, the photoconductor 109 and the toner carrier 10
The length in the rotation direction at the contact portion of 2, the so-called developing nip width, is preferably 0.2 mm or more and 8.0 mm or less.
If it is less than 0.2 mm, the amount of development is insufficient to obtain a satisfactory image density, and the transfer residual toner is not sufficiently collected. 8.0
If it exceeds mm, the toner supply amount becomes excessive,
The fog suppression is apt to deteriorate, and the abrasion of the photoconductor is also adversely affected.

As the toner carrier, a so-called elastic roller having an elastic layer on its surface is preferably used.

The hardness of the material of the elastic layer used is
Those having a temperature of 30 to 60 degrees (asker-C / load of 1 kg) are preferably used.

The resistance of the toner carrier is preferably in the range of about 10 ² to 10 ⁹ Ωcm in terms of volume resistance value. 1
When it is lower than 0 ² Ωcm, for example, when there is a pinhole on the surface of the photoconductor 10 ⁹ , an overcurrent may flow.
On the other hand, when it is higher than 10 ⁹ Ωcm, toner charge-up due to triboelectric charging is apt to occur and the image density is apt to be lowered.

The toner coat amount on the toner carrier is 0.
1 to 1.5 mg / cm ² is preferable. 0.1 mg / cm ²
If less than 1.5mg, it is difficult to obtain sufficient image density, and 1.5mg
If it is more than / cm ^2, it becomes difficult to uniformly triboelectrically charge all the individual toner particles, which causes deterioration of fog suppression. Furthermore, 0.2-0.9 mg / cm ² is more preferable.

The toner coating amount is controlled by the developing blade 101, which is in contact with the toner carrier 102 via the toner layer. The contact pressure at this time is preferably 4.9 to 49 N / m (5 to 50 gf / cm). If it is less than 4.9 N / m, it becomes difficult to control the toner coat amount and to make uniform triboelectrification.
It causes deterioration of fog control. On the other hand, when it is higher than 49 N / m, the toner particles are excessively loaded, and the deformation of the particles and the fusion of the toner to the developing blade or the toner carrier are likely to occur, which is not preferable.

The free end of the regulating member may have any shape. For example, in addition to a linear cross section, an L-shaped bent near the tip or a spherical bulge near the tip. The thing etc. are used suitably.

As the toner coat amount regulating member, a rigid metal blade or the like may be used in addition to the elastic blade for applying the toner under pressure.

For the elastic regulating member, it is preferable to select a friction charging series material suitable for charging the toner to a desired polarity, such as silicone rubber, urethane rubber, NB.
Rubber elastic bodies such as R, synthetic resin elastic bodies such as polyethylene terephthalate, and metal elastic bodies such as stainless steel, steel and phosphor bronze can be used. Further, it may be a complex thereof.

Further, when durability is required for the elastic regulating member and the toner carrier, it is preferable that the elastic metal member is laminated with resin or rubber so as to contact the sleeve abutting portion, or coated.

Further, an organic substance or an inorganic substance may be added to the elastic regulating member, and may be melt-mixed or dispersed. For example, metal oxides, metal powders, ceramics, carbon allotropes, whiskers, inorganic fibers, dyes, pigments,
The chargeability of the toner can be controlled by adding a surfactant or the like. In particular, when the elastic body is a molded body such as rubber or resin, silica, alumina, titania, tin oxide, zirconia oxide, fine powder of metal oxide such as zinc oxide,
It is also preferable to include carbon black, a charge control agent generally used in toner, and the like.

Further, by applying a DC electric field and / or an AC electric field to the regulating member, the uniform thin layer coating property and the uniform charging property are further improved due to the effect of loosening the toner, and a sufficient image density is obtained. Achieved and good quality images can be obtained.

In FIG. 1, the primary charging member 110 uniformly charges the photoconductor 109 rotating in the direction of the arrow.

The primary charging member used here is a cored bar 110b at the center and a conductive elastic layer 110 having its outer periphery formed.
and a is a charging roller having a basic configuration. The charging roller 110 is brought into contact with the entire surface of the electrostatic latent image carrier with a pressing force, and is rotated by the rotation of the electrostatic latent image carrier 109.

A preferable process condition when the charging roller is used is that the contact pressure of the roller is 4.9 to 490.
The applied voltage is N / m (5 to 500 gf / cm), and the applied voltage may be a DC voltage or a DC voltage superposed with an AC voltage. The applied voltage is not particularly limited. It is preferably used, and the voltage value in this case is in the range of ± 0.2 to ± 5 kV.

Other charging means include a method using a charging blade and a method using a conductive brush. These contact charging means, compared to non-contact corona charging,
It is effective in that high voltage becomes unnecessary and the generation of ozone is reduced. The material of the charging roller and the charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), etc. can be applied.

After the primary charging step, an electrostatic latent image corresponding to the information signal is formed on the photoconductor 109 by the exposure 123 from the light emitting element, and the electrostatic latent image is formed by the toner at the position where it abuts on the toner carrier 102. Develop and visualize. Furthermore, in the image forming method of the present invention, particularly by combining with a developing system in which a digital latent image is formed on a photoconductor, it is possible to faithfully develop a dot latent image without disturbing the latent image. . The visible image is the transfer member 106.
Is transferred to the transfer target 105 by the heating roller 108.
And the pressure roller 107 to fix the toner and obtain a permanent image. As the heating / pressurizing fixing means, a heating roller having a heating roller having a heating element such as a halogen heater as shown here and an elastic pressure roller pressed against the heating roller with a pressing force as a basic constitution may be used. A method of heating and fixing with a heater through a film is also used.

On the other hand, the untransferred toner remaining on the photoconductor 109 without being transferred is collected by the cleaner 138 having a cleaning blade that is in contact with the surface of the photoconductor 109, and the photoconductor 109 is cleaned.

Next, a full-color image forming method will be described with reference to FIG. 2 in which toner images of respective colors are formed in a plurality of image forming sections and are sequentially transferred onto the same transfer material.

Here, the first, second, third and fourth image forming sections 29a, 29b, 29c and 29d are arranged in parallel, and each image forming section has its own electrostatic latent image holding member, It has so-called photosensitive drums 19a, 19b, 19c and 19d.

The photosensitive drums 19a to 19d are provided with latent image forming means 23a, 23b, 23c and 23d on the outer peripheral side thereof.
Developing units 17a, 17b, 17c and 17d, transfer discharging units 24a, 24b, 24c and 24d, and cleaning units 18a, 18b, 18c and 18d are arranged.

With this structure, first, the latent image forming means 23a forms a latent image of, for example, a yellow component color on the original image on the photosensitive drum 19a of the first image forming section 29a. The latent image is made into a visible image by the developer having the yellow toner of the developing means 17a, and is transferred to the recording material S as a transfer material at the transfer portion 24a.

While the yellow image is being transferred onto the transfer material S as described above, a latent image of a magenta component color is formed on the photosensitive drum 19b in the second image forming section 29b, and then the magenta of the developing means 17b is formed. A developer having toner makes a visible image. This visible image (magenta toner image)
When the transfer material S, which has been transferred by the first image forming section 29a, is carried into the transfer section 24b, the transfer material S is transferred onto a predetermined position of the transfer material S in an overlapping manner.

Thereafter, the third and fourth steps are performed in the same manner as described above.
The cyan and black images are formed by the image forming units 29c and 29d, and the cyan color and the black color are transferred to the same transfer material S in an overlapping manner. When such an image forming process is completed, the transfer material S is conveyed to the fixing unit 22 and the image on the transfer material S is fixed. As a result, a multicolor image can be obtained on the transfer material S. The photosensitive drums 19a, 19b, 19 that have completed the transfer
c and 19d are cleaning parts 18a, 18b, 18
Residual toner is removed by c and 18d, and the toner is provided for the subsequent latent image formation.

In the image forming apparatus, the conveyor belt 25 is used to convey the recording material S as the transfer material. In FIG. 2, the transfer material S is conveyed from the right side to the left side, and the conveyance is performed. In the process, each image forming unit 29a, 29
b, 29c and 29d, each transfer portion 24a, 24
It passes through b, 24c, and 24d and undergoes transcription.

In this image forming method, a transport belt using a mesh of Tetron (registered trademark) fiber and a polyethylene terephthalate resin, a polyimide resin, as a transport means for transporting the transfer material, from the viewpoint of ease of processing and durability. A conveyor belt using a thin dielectric sheet such as urethane resin is used.

When the transfer material S passes through the fourth image forming portion 29d, an AC voltage is applied to the static eliminator 20, the transfer material S is neutralized and separated from the belt 25, and then the fixing device 22 is attached.
Then, the image is fixed, and the sheet is discharged from the discharge port 26.

In this image forming method, each image forming portion is provided with an independent electrostatic latent image holding member, and the transfer material is a belt type conveying means, and each electrostatic latent image holding member is sequentially transferred. It may be configured to be sent to the transfer section of.

Further, in this image forming method, an electrostatic latent image holding member common to the image forming portion is provided, and the transfer material is a drum type conveying means, and the transfer portion of the electrostatic latent image holding member is used. It may be configured to be repeatedly sent to each color to be transferred.

However, since this transport belt has a high volume resistance, as in the color image forming apparatus,
In the process of repeating transfer several times, the conveyance belt increases the charge amount. Therefore, uniform transfer cannot be maintained unless the transfer current is sequentially increased for each transfer.

Since the toner of the present invention is excellent in transferability,
Even if the charge of the conveying means is increased each time the transfer is repeated, the transferability of the toner in each transfer can be made uniform by the same transfer current, and a high quality image of high quality can be obtained.

The fixing property is evaluated in a low temperature and low humidity environment (10 ° C.,
The commercially available PIXEL CP660-A (manufactured by Canon Inc.) at 15% RH) was modified as shown in FIG. 2, and the process speed was further modified to 100 mm / s. Was completely acclimated to the low temperature and low humidity environment, the temperature of the fixing device was set to 170 ° C., 200 sheets were continuously printed out, and the 200th sheet of the printed image was used for evaluation of the fixing property . The fixing property was evaluated by applying a load of 50 g / cm ² (4.9 kPa) to the fixed image and applying the sillbon paper (Lenz Cleaning Pa).
per “dasper” Ozu Paper Co. L
It was rubbed with td) and evaluated by the rate of decrease in density before and after rubbing.
Plain paper for copiers (9
0 g / m ² ) was used. Therefore, as the value of the reduction rate of the reflection density after rubbing (image density reduction rate) is larger, the rate of peeling of the image due to rubbing is higher, and the toner fixability is worse. When the decrease rate was 10% or less, there was no practical problem.

Offset resistance is measured in a low temperature and low humidity environment (10
CIX, 15% RH) commercially available PIXEL CP660-
A (made by Canon Inc.) was modified as shown in Fig. 2 and the process speed was modified to 100 mm / s, and the stains on the back side of the image samples from the initial stage to the durability of 100 sheets were observed and the number of generated sheets was observed. Counted. The number of occurrences of 3 or less was regarded as practically no problem.

Fog is measured in a low temperature and low humidity environment (10
CIX, 15% RH) commercially available PIXEL CP660-
A (made by Canon Inc.) was modified as shown in Fig. 2 and the process speed was modified to 100 mm / s, and the fog amount of the image sample at the durability 5000th from the initial stage was measured by Tokyo Denshoku REFLECT METER. MODEL
It was measured using TC-6DS. The amount of fog was calculated by the following formula. The smaller the number, the less fog. A fog amount of less than 2.0% was regarded as practically no problem.

Fog amount (%) = (whiteness before printout)-(whiteness of non-image forming portion (white background portion) of recording material after printing)

Filming is performed in a hot and humid environment (30 ° C.,
A commercially available PIXEL CP660-A (manufactured by Canon Inc.) was modified at 80% RH) as shown in FIG. 2 and a process speed was modified to 100 mm / s, and a durability test was conducted to start filming. The number of sheets was evaluated. When the number of sheets starting to be generated was 2000 or more, there was no problem in practical use.

The fluff is removed in a hot and humid environment (30 ° C., 80
% RH), the commercially available PIXEL CP660-A (manufactured by Canon Inc.) was modified as shown in FIG. 2, and the endurance test was carried out by modifying the process speed to 100 mm / s. Was evaluated. When the number of sheets starting to be generated was 2000 or more, there was no problem in practical use.

The fusing onto the photoconductor is carried out under a low temperature and low humidity environment (10
CIX, 15% RH) commercially available PIXEL CP660-
A (manufactured by Canon Inc.) was modified as shown in FIG. 2 and further modified with a process speed of 100 mm / s to carry out a durability test, and evaluation was made based on the number of sheets where fusion on the photosensitive member started to occur. When the number of sheets starting to be generated was 2000 or more, there was no problem in practical use.

The cleaning property is (30
Commercially available PIXEL Commercially available PIXE at ℃, 80% RH)
The LCP660-A (made by Canon Inc.) was modified as shown in FIG. 2 and the process speed was modified to 100 mm / s, and 10,000 sheets were continuously printed out, and the cleaning property and the image quality were visually evaluated. . (Good cleaning is indicated by ◯, and poor cleaning is indicated by x, in which the elasticity of the blade is lowered, and black horizontal stripes are generated in the image due to the toner slipping through.)

The image quality is in a high temperature and high humidity environment (30 ° C., 80 ° C.).
At which the commercial PIXEL CP660-A (manufactured by Canon Inc.) was modified as shown in FIG. 2, was further remodeled process speed 100 mm / s at% RH), 75 g / m ²
The E character was printed out at a printing rate of 2% using the transfer paper of No. 1 and the image was visually evaluated. A: Excellent, no glare B: Good, glare is slight C: Yes, some glare D: No, some glare

The transparency of the transparency sheet image is a commercially available PI under the environment of a temperature of 23 ° C. and a humidity of 65% RH.
XEL CP660-A (made by Canon Inc.) was modified as shown in FIG. 2 and the process speed was modified to 50 mm / s, and the transparency sheet (CG37) was used.
(3: 00: 3M) was developed and transferred at a development contrast of 320 V to obtain a fixed image having gradation.

The image density of the obtained fixed image is 0.4 to 0.
The transmittance at 6 points was measured.

The transmittance was measured by Shimadzu self-spectrophotometer UV.
2200 (manufactured by Shimadzu Corporation) was used for measurement. Then, the transparency of the transparency sheet alone is set to 100.
%, And the transmittance at the maximum absorption wavelength at 600 nm was measured.

The following criteria were used for evaluation. A: Transmittance of 80% or more B: Transmittance of 65% or more and less than 80% C: Transmittance of 50% or more and less than 65% D: transmittance is less than 50%

[0121]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention.

<Example 1> Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C, molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Paraffin wax (mp 75 ° C.) 1.5 parts by mass Low molecular weight ethylene propylene copolymer (mp 140 ° C.) 2.5 parts by mass First, the above materials are mixed in a Henschel mixer, and then the kneaded product is melt-kneaded by a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part.
Melt-kneading with a three-roll mill was repeated twice at 20 ° C. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill, crushed by a fine crusher using a jet stream, and further an air stream utilizing the Coanda effect. By classifying using a type classifier, negatively chargeable triboelectric cyan toner particles having a weight average particle size of 7.5 μm were obtained. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 2 Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Yellow 17 5 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by mass Paraffin wax (mp 75 ° C.) 1.5 parts by mass Low molecular weight ethylene propylene copolymer (mp 140 ° C.) 2 0.5 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded by a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part, and the kneaded product is further heated at 120 ° C.
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, classification was performed using an airflow classifier utilizing the Coanda effect to obtain negatively charged triboelectrically chargeable black toner particles having a weight average particle diameter of 7.5 μm. M of the obtained toner
The results obtained for I, weight average particle size, average circularity, and circularity standard deviation are shown in Table 2 below.

To 100 parts by mass of the yellow toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-
0.3 part by mass of Al metal complex was externally added and mixed by a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 3 Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Red 122 5 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by mass Paraffin wax (mp 75 ° C.) 1.5 parts by mass Low molecular weight ethylene propylene copolymer (mp 140 ° C.) 2 0.5 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded by a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part, and the kneaded product is further heated at 120 ° C.
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, classification was carried out using an airflow classifier utilizing the Coanda effect to obtain negatively charged triboelectrically chargeable black toner particles having a weight average particle size of 7.5 μm. M of the obtained toner
The results obtained for I, weight average particle size, average circularity, and circularity standard deviation are shown in Table 2 below.

To 100 parts by mass of the magenta toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-
0.3 part by mass of Al metal complex was externally added and mixed by a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 4 Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C., molecular weight: Mw 37000) 100 parts by mass carbon black 10 parts by mass monoazo metal complex (negative charge controlling agent) 1 Parts by mass paraffin wax (mp 75 ° C.) 1.5 parts by mass low molecular weight ethylene propylene copolymer (mp 140 ° C.) 2.5 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product Is melt-kneaded at 125 ° C. by a three-roll mill, and the kneaded product is discharged from the kneaded product discharging section.
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, classification was performed using an airflow classifier utilizing the Coanda effect to obtain negatively charged triboelectrically chargeable black toner particles having a weight average particle diameter of 7.5 μm. M of the obtained toner
The results obtained for I, weight average particle size, average circularity, and circularity standard deviation are shown in Table 2 below.

To 100 parts by mass of the black toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-
0.3 part by mass of Al metal complex was externally added and mixed by a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 5 Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Paraffin wax (mp 75 ° C.) 2.5 parts by mass Low molecular weight ethylene propylene copolymer (mp 140 ° C.) ) 1.5 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded by a three-roll mill at 125 ° C, the kneaded product is discharged from the kneaded product discharging part, and the kneaded product is further heated at 120 ° C.
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, classification was carried out using an airflow classifier utilizing the Coanda effect to obtain negatively charged triboelectric toner particles having a weight average particle size of 7.7 μm. MI of the obtained toner
The results obtained for the weight average particle size, average circularity, and standard deviation of circularity are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 6 Styrene-n-butyl acrylate-hydroxyethyl acrylate-octyl acrylate copolymer (Tg 62.8 ° C., molecular weight: Mw 57000) 100 parts by mass Styrene-methacrylic acid-methyl methacrylate copolymer ( Tg 63.1 ° C., molecular weight: Mw 52000) 1.5 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkyl salicylic acid 3.0 parts by mass Paraffin wax (mp 75 ° C.) 2 parts by mass Low molecular weight ethylene propylene co-weight Combined (mp 140 ° C.) 2 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded with a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part, and further Kneaded product at 120 ℃
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, classification was performed using an airflow classifier utilizing the Coanda effect to obtain triboelectric triboelectric particles having negative chargeability and having a weight average diameter of 7.2 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 7 Styrene-n-butyl acrylate-octyl acrylate copolymer (Tg 57.5 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by mass Paraffin wax (mp 75 ° C.) 2 parts by mass Low molecular weight ethylene propylene copolymer (mp 140 ° C.) 2 Parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded at 125 ° C. by a three-roll mill, and the kneaded product is discharged from the kneaded product discharging part, and the kneaded product is further heated at 120 ° C.
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Furthermore, after spheroidizing with a hybridizer (manufactured by Nara Machinery Co., Ltd.), it is further classified with an airflow classifier utilizing the Coanda effect to give a triboelectrifying triboelectric cyanide having a weight average diameter of 7.3 μm. Toner particles are obtained. Processing conditions such as processing temperature, processing time, and processing energy when performing this spheroidizing treatment were controlled appropriately. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 8 Styrene-n-butyl acrylate-hydroxyethyl acrylate-octyl acrylate copolymer (Tg 61.5 ° C., molecular weight: Mw 53000) 100 parts by mass Styrene-methacrylic acid-methyl methacrylate copolymer ( Tg 62.4 ° C., molecular weight: Mw 51000) 0.5 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 1 part by mass Paraffin wax (mp 75 ° C.) 2 parts by mass Low molecular weight ethylene propylene copolymer ( m.p. 140 ° C.) 2 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded by a three-roll mill at 125 ° C. and the kneaded product is discharged from the kneaded product discharging part, and the kneaded product is further mixed. To 120 ° C
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Furthermore, after spheroidizing with a hybridizer (manufactured by Nara Machinery Co., Ltd.), it is further classified with an airflow classifier utilizing the Coanda effect to give a triboelectrifying triboelectric cyanide having a weight average diameter of 7.3 μm. Toner particles are obtained. Processing conditions such as processing temperature, processing time, and processing energy when performing this spheroidizing treatment were controlled appropriately. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 9 Styrene-n-butyl acrylate-hydroxyethyl acrylate-octyl acrylate copolymer (Tg 62.2 ° C., molecular weight: Mw 54000) 100 parts by mass Styrene-methacrylic acid-methyl methacrylate copolymer ( Tg 63.1 ° C., molecular weight: Mw 52000) 1 part by mass C.I. I. Pigment Blue 15:35 5 parts by weight Monoazo metal complex (negative charge control agent) 1 part by weight Aluminum compound of dialkylsalicylic acid 1.7 parts by weight Paraffin wax (mp 75 ° C.) 2 parts by weight Low molecular weight ethylene propylene co-weight Combined (mp 140 ° C.) 2 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded with a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part, and further Kneaded product at 120 ℃
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Furthermore, after spheroidizing with a hybridizer (manufactured by Nara Machinery Co., Ltd.), it is further classified with an airflow classifier utilizing the Coanda effect to give a triboelectrifying triboelectric cyanide having a weight average diameter of 7.3 μm. Toner particles are obtained. Processing conditions such as processing temperature, processing time, and processing energy when performing this spheroidizing treatment were controlled appropriately. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Example 10 Styrene-n-butyl acrylate-hydroxyethyl acrylate-octyl acrylate copolymer (Tg 61.5 ° C., molecular weight: Mw 53000) 100 parts by mass Styrene-methacrylic acid-methyl methacrylate copolymer ( Tg 62.4 ° C., molecular weight: Mw 51000) 0.7 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkyl salicylic acid 1.2 parts by mass Paraffin wax (mp 75 ° C.) 2 parts by mass Low molecular weight ethylene propylene co-weight Combined (mp 140 ° C.) 2 parts by mass After mixing the above materials with a Henschel mixer, the kneaded product is melt-kneaded with a three-roll mill at 125 ° C., and the kneaded product is discharged from the kneaded product discharging part, and further Kneaded product at 120 ℃
The melt-kneading with a three-roll mill was repeated twice. Further, the kneaded product was melt-kneaded at 135 ° C. by a twin-screw kneading extruder. The resulting kneaded product is rapidly cooled to a predetermined temperature, left at room temperature and gradually cooled, then roughly crushed by a cutter mill and crushed by a fine crusher using a jet stream,
Further, after spheroidizing with a hybridizer (manufactured by Nara Machinery Co., Ltd.), it is further classified with an airflow classifier utilizing the Coanda effect to give a triboelectrifying triboelectric cyanide having a weight average diameter of 7.4 μm. Toner particles are obtained. Processing conditions such as processing temperature, processing time, and processing energy when performing this spheroidizing treatment were controlled appropriately. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

<Example 11> Styrene monomer 160 parts by mass n-butyl acrylate monomer 30 parts by mass 2 Ethylhexyl acrylate monomer 10 parts by mass C.I. I. Pigment Blue 15: 3 20 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.35 parts by mass Paraffin wax (mp 75 ° C.) 30 parts by mass or more The mixture was dispersed for 5 hours using an attritor, and then 2,2'-azobis (2,4-
2 parts by mass of dimethylvaleronitrile) and 3 parts by mass of lauroyl peroxide were added to 1 part of water to prepare a monomer composition.
After 200 parts by mass and 7 parts by mass of tricalcium phosphate were mixed into an aqueous solution at 68.5 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer and granulated for 11 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 60 rpm for 10 hours. At that time, 3 hours after the completion of the granulation, 5 parts by mass of a styrene monomer, 5 parts by mass of an octyl acrylate monomer, 10 parts by mass of an ethylhexyl acrylate monomer, 2 parts by mass of paraffin wax and 2,2′- Stirring 0.3 parts by mass of azobis (2,4-dimethylvaleronitrile) at a liquid temperature of 70 ° C. was continuously added dropwise, and after 0.5 hours, water 120 was added.
An aqueous solution in which 1 part by mass and 0.5 parts by mass of tricalcium phosphate were mixed was added.

After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, washing and drying were carried out by a high speed fluidized bed drier to obtain cyan toner particles having a weight average particle diameter of 7.4 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and 1.5 parts by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane were mixed with a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner.
The results obtained are shown in Table 2.

<Example 12> Styrene monomer 160 parts by mass n-butyl acrylate monomer 40 parts by mass C.I. I. Pigment Blue 15: 3 20 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.40 parts by mass Paraffin wax (mp 75 ° C.) 30 parts by mass or more The mixture was dispersed for 4.5 hours using an attritor, and then 2,2'-azobis (2,2, which is a polymerization initiator).
4-dimethylvaleronitrile) 2 parts by mass and lauroyl peroxide 3 parts by mass,
After water (1200 parts by mass) and tricalcium phosphate (7.5 parts by mass) were mixed into an aqueous solution at 68.5 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer and granulated for 11 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 60 rpm for 10 hours. At that time, 3 hours after the completion of granulation, 5 parts by mass of a styrene monomer, 3 parts by mass of an n-butyl acrylate monomer, 2 parts by mass of a hydroxyethyl acrylate monomer, an alkylcarboxylic acid of C22 and an alkyl alcohol of C22. And 2 parts by mass of ester wax and 0.3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) stirred at a liquid temperature of 70 ° C. were continuously added dropwise, and then 0.5
After a lapse of time, an aqueous solution obtained by mixing 120 parts by mass of water and 0.5 parts by mass of tricalcium phosphate was added.

After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, washing and drying were carried out by a high-speed fluidized bed drier to obtain cyan toner particles having a weight average particle diameter of 7.2 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and 1.5 parts by mass of silica (specific surface area 200 m ^{2 /} g) which was hydrophobized with hexamethyldisilazane were mixed with a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner.
The results obtained are shown in Table 2.

Example 13 Styrene Monomer 160 parts by mass n-Butyl Acrylate Monomer 40 parts by mass C.I. I. Pigment Blue 15: 3 20 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.45 parts by mass Paraffin wax (mp 75 ° C.) 30 parts by mass or more The mixture was dispersed for 4.5 hours using an attritor, and then 2,2'-azobis (2,2, which is a polymerization initiator).
4-dimethylvaleronitrile) 2 parts by mass and lauroyl peroxide 3 parts by mass,
After water (1200 parts by mass) and tricalcium phosphate (7.5 parts by mass) were mixed into an aqueous solution at 68.5 ° C., the mixture was stirred at 12,000 rpm with a TK homomixer and granulated for 11 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 60 rpm for 10 hours. At that time, 3 hours after the completion of granulation, 5 parts by mass of a styrene monomer, 3 parts by mass of an n-butyl acrylate monomer, 2 parts by mass of a hydroxyethyl acrylate monomer, an alkylcarboxylic acid of C22 and an alkyl alcohol of C22. And 2 parts by mass of ester wax and 0.3 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) stirred at a liquid temperature of 70 ° C. were continuously added dropwise, and then 0.5
After a lapse of time, an aqueous solution obtained by mixing 120 parts by mass of water and 0.5 parts by mass of tricalcium phosphate was added.

After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, the particles were washed and dried with a high speed fluidized bed drier to obtain cyan toner particles having a weight average particle diameter of 7.3 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and 1.5 parts by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane were mixed with a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner.
The results obtained are shown in Table 2.

<Example 14> Styrene monomer 160 parts by mass n-butyl acrylate monomer 40 parts by mass C.I. I. Pigment Blue 15: 3 20 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.40 parts by mass Ester wax of C22 alkylcarboxylic acid and C22 alkyl alcohol (Mp 75 ° C.) A mixture of 30 parts by mass or more was dispersed for 4.5 hours using an attritor, and then 2,2′-azobis (2,2, which is a polymerization initiator).
4-dimethylvaleronitrile) 2 parts by mass and lauroyl peroxide 3 parts by mass,
After water (1200 parts by mass) and tricalcium phosphate (7 parts by mass) were mixed into an aqueous solution at 68.5 ° C., the mixture was stirred with a TK homomixer at 12,000 rpm and granulated for 11 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 60 rpm for 10 hours. At that time, 3 hours after the completion of granulation, 5 parts by mass of a styrene monomer, 3 parts by mass of an n-butyl acrylate monomer, 2 parts by mass of a hydroxyethyl acrylate monomer, an alkylcarboxylic acid of C22 and an alkyl alcohol of C22. 2 parts by weight of ester wax and 2,2′-azobis (2,4
-Dimethylvaleronitrile) 0.3 parts by mass at a liquid temperature of 70 ° C.
Was continuously added dropwise after 0.5 hour,
An aqueous solution obtained by mixing 120 parts by mass of water and 0.5 parts by mass of tricalcium phosphate was added.

After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, the particles were washed and dried with a high-speed fluidized bed drier to obtain cyan toner particles having a weight average particle diameter of 6.8 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and 1.5 parts by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane were mixed with a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner.
The results obtained are shown in Table 1.

<Example 15> Styrene monomer 160 parts by mass n-butyl acrylate monomer 40 parts by mass C.I. I. Pigment Blue 15: 3 20 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.40 parts by mass Ester wax of C22 alkylcarboxylic acid and C22 alkyl alcohol (Mp 75 ° C.) A mixture of 30 parts by mass or more was dispersed for 4.5 hours using an attritor, and then 2,2′-azobis (2,2, which is a polymerization initiator).
4-dimethylvaleronitrile) 2 parts by mass and lauroyl peroxide 3 parts by mass,
After water (1200 parts by mass) and tricalcium phosphate (7 parts by mass) were mixed into an aqueous solution at 68.5 ° C., the mixture was stirred with a TK homomixer at 12,000 rpm and granulated for 11 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 60 rpm for 10 hours. At that time, 3 hours after the completion of granulation, 5 parts by mass of a styrene monomer, 3 parts by mass of an n-butyl acrylate monomer, 2 parts by mass of a hydroxyethyl acrylate monomer, an alkylcarboxylic acid of C22 and an alkyl alcohol of C22. 2 parts by weight of ester wax and 2,2′-azobis (2,4
-Dimethylvaleronitrile) 0.3 parts by mass at a liquid temperature of 70 ° C.
Was continuously added dropwise after 0.5 hour,
An aqueous solution obtained by mixing 120 parts by mass of water and 0.5 parts by mass of tricalcium phosphate was added.

After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, the particles were washed and dried with a high speed fluidized bed drier to obtain cyan toner particles having a weight average particle diameter of 7.1 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and silica hydrophobized with silicone oil (specific surface area 2
The toner for evaluation was obtained by mixing 1.5 parts by mass of (00 m ² / g) with a Henschel mixer. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Comparative Example 1 Styrene-n-butyl acrylate copolymer (Tg 57.1 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass Paraffin wax (mp 75 ° C.) 1 part by mass After mixing the above materials with a Henschel mixer, 110 ° C.
Melt-kneading with a twin-screw kneading extruder, gradually cooling the kneaded product to room temperature, coarsely crushing with a cutter mill, crushing with a fine crusher using a jet stream, and further classifying with a vibrating screen. As a result, negatively charged triboelectric cyan toner particles having a weight average diameter of 6.5 μm were obtained. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Comparative Example 2 Styrene-n-butyl acrylate copolymer (Tg 57.1 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15: 3 5 parts by weight Monoazo metal complex (negative charge control agent) 1 part by weight Paraffin wax (mp 75 ° C.) 5 parts by weight After mixing the above materials with a Henschel mixer, 110 ° C.
Melt-kneading with a twin-screw kneading extruder, gradually cooling the kneaded product to room temperature, coarsely crushing with a cutter mill, crushing with a fine crusher using a jet stream, and further classifying with a vibrating screen. As a result, negatively charged triboelectric cyan toner particles having a weight average diameter of 7.8 μm were obtained. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Comparative Example 3 Styrene-n-butyl acrylate copolymer (Tg 57.1 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge control agent) 1 part by mass After mixing the above materials with a Henschel mixer, 110 ° C
Melt-kneading with a twin-screw extruder and gradually cooling the kneaded product to room temperature, then roughly crushing with a cutter mill, crushing with a fine crusher using a jet stream, and further classifying with a wind classifier. By doing so, negatively chargeable triboelectric charging black toner particles having a weight average diameter of 7.5 μm were obtained. Furthermore, paraffin wax 1.5 is added to 100 parts of the toner particles.
Part was treated with Hybridizer type I (manufactured by Nara Machinery Co., Ltd.) at 6000 rpm for 2 minutes, and then 1.0 part of styrene-butyl acrylate-acrylic acid copolymer (Tg: 47 ° C.) was further hybridized to the toner particles. Using a Dizer I type (manufactured by Nara Machinery Co., Ltd.), 6000 rpm,
After being treated for 2 minutes, the obtained toner particles were further classified by using a vibrating screen to obtain cyan toner particles having a weight average particle diameter of 7.6 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m ^{2 /} g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Comparative Example 4 Styrene-n-butyl acrylate copolymer (Tg 58.5 ° C., molecular weight: Mw 37000) 100 parts by mass C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by weight Paraffin wax (mp 75 ° C.) 1 part by weight Low molecular weight ethylene propylene copolymer (mp 140 ° C.) 1 Parts by mass After mixing the above materials with a Henschel mixer, 130 ° C
Melt-kneading with a twin-screw extruder and gradually cooling the kneaded product to room temperature, then roughly crushing with a cutter mill, crushing with a fine crusher using a jet stream, and further classifying with a wind classifier. Then, the mixture was further spheroidized by using a hybridizer (manufactured by Nara Machinery Co., Ltd.), and then classified by using a vibrating sieve to obtain triboelectrically-charged cyan toner particles having a negative charge property and a weight average diameter of 7.0 μm. . Processing conditions such as processing temperature, processing time, and processing energy when performing this spheroidizing treatment were controlled appropriately. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

To 100 parts by mass of the cyan toner particles, 1.0 part by mass of silica (specific surface area 200 m2 / g) hydrophobized with hexamethyldisilazane, Mg-A
0.3 parts by mass of the 1-metal complex were externally added and mixed in a Henschel mixer to obtain a toner for evaluation. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

Comparative Example 5 160 parts by mass of styrene monomer 40 parts by mass of n-butyl acrylate monomer 2 parts by mass of unsaturated polyester C.I. I. Pigment Blue 15:35 5 parts by mass Monoazo metal complex (negative charge controlling agent) 1 part by mass Aluminum compound of dialkylsalicylic acid 2 parts by mass Divinylbenzene 0.6 parts by mass Ester wax of C22 alkylcarboxylic acid and C22 alkyl alcohol (Mp 75 ° C.) 20 parts by mass or more of the mixture was dispersed for 3 hours using an attritor, and then the monomer composition containing 3 parts by mass of lauroyl peroxide as a polymerization initiator was added to water. 1200 parts by mass and 7 parts by mass of tricalcium phosphate were added to an aqueous solution at 71.0 ° C., and then TK type homomixer was used to obtain 10,000 parts.
The mixture was stirred at 0 rpm and granulated for 10 minutes. Then, the stirrer was changed from the high speed stirrer to the propeller stirrer, and the polymerization was continued at 50 rpm for 10 hours. After completion of the polymerization, dilute hydrochloric acid was added to remove calcium phosphate. Further, washing and drying were carried out to obtain cyan toner particles having a weight average particle diameter of 7.1 μm. The results obtained for the MI, weight average particle diameter, average circularity, and circularity standard deviation of the obtained toner are shown in Table 2 below.

100 parts by mass of the cyan toner particles and silica hydrophobized with silicone oil (specific surface area 2
The toner for evaluation was obtained by mixing 1.5 parts by mass of (00 m ² / g) with a Henschel mixer. Fixing evaluation and developing property evaluation were performed using this developer and externally added toner. The results obtained are shown in Table 2.

[0167]

[Table 2]

[0168]

As described above, according to the present invention, an image formed by the image forming method by non-magnetic one-component contact development can be fixed at a low fixing temperature, and the fixing roller at the time of fixing can be fixed. In addition to the fixing properties such as peeling resistance from the toner, anti-offset property, and transparency when fixing an OHT image in color toner, it is excellent in fixing property such as fogging, filming, dripping, and fusing to the photoreceptor. It is possible to obtain a toner for non-magnetic one-component contact development which is compatible with developability and an image forming method using the toner.

[Brief description of drawings]

FIG. 1 is a schematic view of an image forming apparatus having a developing device that performs non-magnetic one-component contact development.

FIG. 2 is a schematic diagram of a full-color image forming apparatus having a developing device that performs non-magnetic one-component contact development.

[Explanation of symbols]

17 Development Department 18 Cleaning section 19 Photosensitive drum (latent image carrier) 20 Slow power section 22 Fixer 23 Latent Image Forming Means 24 Transfer Discharge Unit 25 belt 26 outlet 29 Image forming unit S recording material 100 developing device 101 Development blade 102 toner carrier 103 coating roller 104 toner 105 Transferred material such as paper 106 transfer member 107 Pressure roller for fixing 108 Heating roller for fixing 109 photoconductor drum (latent image carrier) 110 Primary charging member 110a conductive elastic layer 110b core metal 115 Bias power supply 116 Bias power supply 117 Bias power supply 123 Exposure from light emitting element 138 cleaner

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 15/01 G03G 9/08 361 15/08 507 15/08 507L (72) Inventor Satoshi Handa 3 Shimomaruko Ota-ku, Tokyo Canon No. 30-2 Canon Inc. (72) Inventor Yuji Moriki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. F-term (reference) 2H005 AA06 AA08 AA15 AA21 CA12 CA14 CB13 DA06 EA03 EA05 EA10 FA07 FB02 2H030 AB02 AD01 BB44 2H077 AD06 BA10 DB14 EA14 EA24 GA13

Claims (14)

[Claims] 1. A toner used for non-magnetic one-component contact development, wherein the toner contains at least a binder resin, a colorant and a release agent, and an unfixed image is formed by the toner. Created, and the unfixed image at 23 ℃,
The amount of wax eluted when immersed in hexane in a 60% RH environment was C (N), and the unfixed image produced by the toner was heated at 100 ° C. for 2 minutes and then at 23 ° C., 6
When the wax elution amount when immersed in hexane in a 0% RH environment is C (H), the relationship of 1.10 ≦ C (H) / C (N) ≦ 5.00 holds. A characteristic non-magnetic one-component contact developing toner. 2. The toner has a weight average particle diameter of 5.0 μm.
It is less than 12.0 μm and the average circularity is 0.950.
It is more than 0.990 and the circularity standard deviation is 0.05.
The toner for non-magnetic one-component contact development according to claim 1, which is less than 1. 3. The toner has a weight average particle diameter of 5.0 μm.
It is less than 12.0 μm and the average circularity is 0.965.
It is more than 0.990 and the circularity standard deviation is 0.05.
The toner for non-magnetic one-component contact development according to claim 1, which is less than 1. 4. The toner at 135.degree. C., load 2160 g
The melt index (M
The toner for non-magnetic one-component contact development according to any one of claims 1 to 3, wherein I) is 1.0 g / 10 minutes or more and 25 g / 10 minutes or less. 5. The non-magnetic single component according to claim 1, wherein at least one of the toners used in the image forming method using a full-color toner consisting of yellow toner, magenta toner, cyan toner, and black toner. Toner for contact development. 6. The wax contained in the toner particles has a melting point of at least 60 ° C. and not more than 120 ° C., a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl having 15 to 45 carbon atoms. The non-magnetic one-component contact developing toner according to claim 1, further comprising an ester wax containing an ester compound with a carboxylic acid as a main component. 7. The toner for non-magnetic one-component contact development according to claim 1, wherein the toner contains an inorganic fine powder treated with silicone oil. 8. A method for forming an image by non-magnetic one-component contact development, wherein the toner forming the toner image is a toner containing at least a binder resin, a colorant and a release agent, and the toner. To produce an unfixed image, and to determine the amount of wax elution when the unfixed image is immersed in a solvent at 23 ° C. and 60% RH, C (N). When the wax elution amount when immersed in a solvent at 23 ° C. and 60% RH after heating at 100 ° C. for 2 minutes is C (H), 1.10 ≦ C (H) / C ( The image forming method is a non-magnetic one-component contact developing toner characterized in that N) ≦ 5.00. 9. The toner has a weight average particle diameter of 5.0 μm.
It is less than 12.0 μm and the average circularity is 0.950.
It is more than 0.990 and the circularity standard deviation is 0.05.
9. The image forming method according to claim 8, which is less than 10. 10. The toner has a weight average particle diameter of 5.0 μm.
m or more and less than 12.0 μm, and average circularity is 0.96
5 or more and less than 0.990 and a circularity standard deviation of 0.0
The image forming method according to claim 8, wherein the number is less than 5. 11. The toner at 135 ° C., load 2160 g
The melt index (M
The image forming method according to claim 8, wherein I) is 1.0 g / 10 minutes or more and 20 g / 10 minutes or less. 12. The image forming method according to claim 8, wherein at least one of the toners used in full-color image formation using the yellow toner, the magenta toner, the cyan toner, and the black toner as the toner. 13. The wax contained in the toner particles has a melting point of at least 60 ° C. and 120 ° C.
An ester wax containing an ester compound of a long-chain alkyl alcohol having 15 to 45 carbon atoms and a long-chain alkyl carboxylic acid having 15 to 45 carbon atoms as a main component is contained below. 13. The image forming method according to any one of 12. 14. The toner according to claim 8, wherein the toner contains an inorganic fine powder treated with silicone oil.
14. The image forming method according to any one of 1 to 13.