JP2002091079A - Toner and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner showing good low temperature fixing property, high temperature offset resistance and cold offset resistance, free from contamination of a rotary pressurizing member and having excellent developing property and storage property in a fixing device using an electromagnetic induction method. SOLUTION: The toner is used for the image forming method by which an image is formed on a recording material by using (i) a magnetic field generating means 3, (ii) a rotary heating member 1 having at least a heat generating layer 11 which generates heat by electromagnetic induction and a release layer 12 and (iii) a rotary pressurizing member 2 forming a nip with the rotary heating member, and by heating and fixing a toner image 8 on the recording material while pressing the rotary heating member through the recording material 16. The toner contains at least a binder resin, coloring agent and wax, and the binder resin contains a mixture of polyester resin ad hybrid resin having vinyl polymer units and polyester units.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a toner used in an image forming method such as electrophotography, electrostatic recording, electrostatic printing, and toner jet, and an image forming method using the toner.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, US Pat.
Numerous methods are known as described in Japanese Patent Publication No. 297691, Japanese Patent Publication No. 42-23910 and Japanese Patent Publication No. 43-24748.

Generally, a photoconductive material is used to form an electric latent image on a photoreceptor, and then toner is transferred to the latent image, and then fixed by heating, pressure, heating pressure or solvent vapor. To obtain a copy. The toner remaining on the photoreceptor without being transferred is cleaned by various methods, and the above steps are repeated. Examples of this type of image forming apparatus include a copying machine, a printer, and a facsimile machine.

Conventionally, various methods and apparatuses have been developed for the process of fixing a toner image to a sheet such as paper. The most common method at present is a pressure heating method using a heat roller.

In the pressure heating method using a heating roller, the fixing is performed by allowing the toner image surface of the sheet to be fixed to pass through the surface of the heat roller, which is formed of a material having releasability from the toner, under pressure. It is what you do.

According to this method, since the surface of the heat roller and the toner image of the sheet to be fixed come into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing is quickly performed. And is very effective in a high-speed electrophotographic copying machine.

However, in the above method, since the surface of the heat roller and the toner image come into contact with each other under pressure in a molten state, a part of the toner image adheres to and transfers to the surface of the fixing roller, and is transferred again to the next sheet to be fixed. As a result, an offset phenomenon may occur, and the sheet to be fixed may be soiled. Preventing toner from adhering to the surface of the heat fixing roller is one of the essential conditions of the heat roller fixing method.

Heretofore, vinyl resins such as polyester resins and styrene resins have been mainly used as toner resins. Polyester resins originally have excellent low-temperature fixability, but have the disadvantage that offset phenomena are likely to occur at high temperatures.

If the viscosity is increased by increasing the molecular weight of the polyester resin in order to compensate for this drawback, not only the low-temperature fixability is impaired, but also the pulverizability during the production of the toner is deteriorated. Is also inappropriate.

Also, vinyl copolymers such as styrene resins are excellent in pulverizability at the time of toner production and easy in high molecular weight. Lowering the molecular weight to improve
Blocking resistance and developability will deteriorate.

[0011] In order to make the most of the advantages of these two types of resins and to compensate for the drawbacks, several methods of mixing and using these resins have been studied. For example, JP-A-54-1
Japanese Patent No. 14245 discloses a toner containing a resin obtained by mixing a polyester resin and a vinyl copolymer. However, since the polyester resin and the vinyl copolymer are inherently poorly compatible, it is difficult to satisfy all of the low-temperature fixing property, the high-temperature offset resistance, and the blocking resistance unless the compounding ratio is appropriate. . In addition, the dispersibility of the coloring agent, wax and the like added during the production of the toner becomes insufficient, so that a problem is likely to occur in the developability. In particular, in recent years, this problem is remarkable in a toner in which fine particles are advanced.

JP-A-56-116043 and JP-A-58-159546 disclose toners characterized by containing a polymer obtained by polymerizing a monomer in the presence of a polyester resin. Have been. JP-A-58-1
JP-A-02246 and JP-A-1-156759 disclose toners characterized by containing a polymer obtained by polymerizing a vinyl copolymer in the presence of an unsaturated polyester resin. JP-A-2-881 discloses a toner containing a polymer obtained by esterifying an acid value-containing styrenic resin and a polyester resin. In these methods, although the compatibility between the polyester resin and the vinyl copolymer is improved, it is difficult to uniformly disperse the wax added during the production of the toner. There still remains a problem to be improved in developability.

JP-A-4-338973 discloses a toner using two types of polyester resins having different softening points, and JP-A-8-166688 discloses a toner using two types of polyester resins having different molecular weights. . However, in all cases, the high-temperature offset resistance is within the range of the polyester resin and is a problem to be improved.

In JP-A-8-44108,
Disclosed is a toner using two types of hybrid resins having different softening points obtained by performing an addition polymerization reaction with a vinyl resin monomer and a polycondensation reaction with a polyester resin monomer in parallel. Also, JP-A-8-547
No. 54 discloses a toner using a resin obtained by mixing a polyester resin and a hybrid resin obtained by performing an addition polymerization reaction with a vinyl resin monomer and a polycondensation reaction with a polyester resin monomer in parallel. are doing. In these methods, the balance between the crosslinking on the low molecular weight side and the crosslinking on the high molecular weight side of the toner is not good, and there is still a problem to be improved in low-temperature fixability, wax dispersion and long-term developability.

As described above, as a method of fixing a visible image of toner on a recording material, a heating roller maintained at a predetermined temperature and a rotary pressing member having an elastic layer and pressed against the heating roller are used. A hot roll fixing method in which a recording material holding an unfixed toner visible image is heated and pressed while nipping and transporting the recording material is often used. However, hot roll fixing has the following points to be improved. (1) The wait time (time during which the image forming operation is prohibited) until the heat roller reaches a predetermined temperature is long. (2) The heating roller is maintained at an appropriate temperature in order to prevent defective fixing due to fluctuations in the temperature of the heating roller due to the passage of a recording material or other external factors, and to prevent an offset phenomenon to the heating roller. There is a need to. For this purpose, the heat capacity of the heating roller or the heating element must be increased, which requires a large amount of electric power. (3) Since the temperature of the heating roller is high and the ambient temperature is also high, the recording material and the toner on the recording material are cooled slowly after the recording material is discharged through the heating roller. The state of high performance is maintained, and a paper jam may occur due to an offset to the roller or a recording material wound around the roller.

In order to solve such a problem, Japanese Patent Publication No. 7-8
No. 2250, Japanese Patent Publication No. Hei 8-12454-8-1246
No. 1, Japanese Patent Publication No. 8-12476, Japanese Patent Publication No. 8-1
No. 6804, Special Registration No. 2660075, Special Registration No. 27
No. 46475, Special Registration No. 2774536, Special Registration No. 277
No. 4537, Special Registered Patent No. 282156, and the like, a visible image of toner is applied to a recording material by pressing a heating member fixed and supported against the heating member and bringing the recording material into close contact with the heating member via a film. A heat fixing method characterized by performing heat fixing with a pressure member and a toner used in the heat fixing method are disclosed. However, further energy savings,
Shortening of the wait time is required.

JP-A-9-204110, JP-A-9-204110
JP-A-319242, JP-A-10-48868, JP-A-10-161444, and the like include a film having a conductive portion, a support member that supports the film, and a magnetic flux generating unit that generates a magnetic flux. An electromagnetic induction type fixing device is disclosed in which an eddy current is generated in the film by a magnetic flux generated by the magnetic flux generating means, and an image on a recording material is heated by heat of the film generated by the eddy current.

This fixing method enables energy saving, shortening of the wait time, and non-uniformity of the fixing temperature in the recording material and little fixing non-uniformity (gloss difference) of the fixed image, thereby enabling high-quality or color image fixing.

However, the pressure on the recording material is more limited than other fixing systems, and the performance required for the toner has been enhanced.

As one of the problems, there is a problem in that the toner is accumulated on the pressure member of the fixing device, and the accumulated toner mass is discharged onto the image to cause image defects such as black spots, which is a problem of the rotation pressure member stain. . This problem has become evident because the wait time is greatly reduced by this fixing method.

Further, it has been found that in this fixing method, when halftone is output, a cold offset is likely to occur, and this becomes a serious problem when the process speed is increased.

[0022]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner which solves the above-mentioned problems and an image forming method using the toner.

That is, an object of the present invention is to provide a low-temperature fixing property and a high-temperature offset resistance in a fixing device of an electromagnetic induction type, and to provide a long-term developing property and storage property that do not cause contamination of a rotating pressure member and cold offset. An object of the present invention is to provide an excellent toner and an image forming method using the toner.

[0024]

The present invention provides (i) a magnetic field generating means, (ii) a rotary heating member having at least a heat generating layer and a release layer that generate heat by electromagnetic induction, and (iii)
The toner image on the recording material is heated and fixed by pressing the rotation heating member and the rotation pressing member forming the nip through the recording material to form a fixed image on the recording material. Which comprises at least a binder resin, a colorant and a wax, wherein the binder resin is a polyester resin and a hybrid resin having a vinyl polymer unit and a polyester unit. And a toner having a mixture of

Further, the present invention is an image forming method for forming a fixed image on a recording material by heating and fixing a toner image on the recording material by a heating and pressing means. A binder resin, a colorant, and a wax, wherein the binder resin has a mixture of a polyester resin and a hybrid resin having a vinyl polymer unit and a polyester unit, and the heating and pressurizing unit includes
(I) a magnetic field generating means, (ii) a rotary heating member having at least a heat generating layer and a release layer that generate heat by electromagnetic induction, and (iii) a rotary pressing member forming a nip with the rotary heating member. The present invention relates to an image forming method for forming a fixed image on a recording material by heating and fixing a toner image on the recording material while pressing the rotary heating member via the recording material.

[0026]

DESCRIPTION OF THE PREFERRED EMBODIMENTS "Rotating pressure member stain" means that a relatively small number of prints of about 5 or less are printed in a low-temperature environment by 10 to 2 times.
It has been found that such a situation is likely to occur if printing is continued at intervals of 0 minutes or more. The mechanism of this phenomenon is considered as follows.

In the fixing device of the electromagnetic induction type, the temperature of the rotary heating member rises quickly and printing is performed in a very short preheating time as compared with the hot roll fixing type. Since the time for transmitting heat to the pressure member is short and the surface temperature of the rotary pressure member does not rise so much, the temperature difference from the heated rotary heating member becomes very large. For this reason, the toner slightly offset from the toner image on the recording material to the rotating heating member, after the recording material has passed through the fixing unit, has a low temperature at the nip portion between the rotating heating member and the rotating pressing member. Move to If there is an interval of 10 to 20 minutes or more before the next print, in a low-temperature environment, the surface temperature of the rotary pressing member falls to near the temperature in the initial state again. A similar phenomenon is repeated by printing about 5 or less sheets,
The toner is accumulated on the surface of the rotating pressure member.

When a certain amount of toner is accumulated and the toner mass adheres to the surface of the rotating pressure member, the accumulated toner mass separates from the surface of the rotating pressure member and moves to the rotating heating member or performs recording. It transfers directly to the material and causes image defects such as black spots.

When about 10 or more prints are made at once or when printing is performed without time delay, the surface of the rotary pressing member is sufficiently heated to increase the temperature. Even if the difference becomes small and the toner is offset from the toner image on the recording material to the rotary heating member, the toner does not transfer to the rotary pressing member, and the toner is gradually discharged from the rotary heating member onto the recording material. It is considered that no image defect occurs.

The term "toner slightly offset from the rotary heating member" is different from a so-called cold offset or high-temperature offset, and is mostly an electrostatically offset toner. It has been experimentally found that there is basically no relationship with the fixing performance such as the offset property. Therefore, in order to improve the contamination of the rotating pressure member from the toner side, it is necessary to design the toner from a viewpoint different from the fixing performance.

As another problem in the fixing device used in the present invention, there is a problem that a cold offset is apt to occur when a halftone image is printed. Occasionally, the toner developed on the recording material is weakly pressed against the recording material at the nip portion of the fixing device. In particular, in a halftone image, the amount of toner developed on the recording material is small, and it is considered that this occurs because it is difficult to obtain an adhesive force between the toners in the surface direction of the recording material.

The inventors of the present invention have conducted intensive studies, and have found that the binder resin used for the toner contains both a polyester resin and a hybrid resin having a vinyl polymer unit and a polyester unit, so that the toner can be rotated. It has been found that the two problems of pressure member contamination and cold offset can be solved.

Since the binder resin contained in the toner contains both the polyester resin and the hybrid resin, the dispersibility of the wax in the toner and the ease of dissolution of the wax on the toner surface during heating are enhanced. Can be controlled. Therefore, the effect of releasing the wax can be exhibited without affecting the developability, and the contamination of the rotating pressure member can be prevented. Further, it is considered that the wax dissolved on the toner surface enhances the adhesive force between the toners and has an effect of preventing cold offset.

Preferably, the binder resin is a mixture of a polyester resin and a hybrid resin having a vinyl polymer unit and a polyethnit, and is a trivalent or higher polyvalent in a THF-soluble component having a toner molecular weight of less than 10,000. The content of carboxylic acids or their anhydrides is defined as W1 (mol
%), And the content of trivalent or higher polycarboxylic acids or their anhydrides in the THF-soluble component having a molecular weight of 10,000 or more is W2
(Mol%), 0 ≦ W1 ≦ 25, 0.1 ≦ W2 ≦ 30, more preferably 0.5 ≦ W1 ≦ 20, 1 ≦ W2 ≦ 25,
More preferably, 3 ≦ W1 ≦ 20 and 3 ≦ W2 ≦ 20. In particular, when the relationship between W1 and W2 satisfies W2> W1, it is possible to significantly improve the contamination of the rotating pressure member and the cold offset resistance. Do you get it.

Printing of about 5 sheets or less in a low-temperature environment
When printing is performed with an interval of 0 minutes or more, the surface temperature of the rotary pressing member rises only to about 120 ° C. at the maximum. However, it needs to be sufficiently melted, adhered to the recording material, and discharged. But at this time,
If the toner is completely melted and the viscosity becomes too low, on the contrary, the adhesion to the rotating pressure member becomes strong and it becomes difficult to discharge the toner. Therefore, it is also important to maintain appropriate elasticity.

In order to improve the cold offset resistance, it is necessary to provide a course in which the wax easily dissolves on the toner surface. However, if the viscosity of the toner becomes too low due to heating at the time of fixing, the wax dissolves the resin. Plasticization makes it difficult to dissolve on the toner surface.Conversely, if the elasticity of the toner is too high, even if the wax dissolves on the toner surface, the adhesive force between the toners cannot be increased, and the effect of preventing cold offset can be obtained. It becomes difficult.

In order for the toner to be melted at a low temperature, it is important that the THF-soluble component having a molecular weight of less than 10,000 is sufficiently melted. In addition, if the THF-soluble component having a molecular weight of less than 10,000 is crosslinked to some extent, the wax is less susceptible to the plasticizing effect and the wax easily dissolves on the toner surface, so that trivalent or higher polyvalent carboxylic acids or anhydrides thereof are used. It is preferable that the content W1 (mol%) of the satisfies the relationship of 0 ≦ W1 ≦ 25.

If the toner is completely melted at a low temperature and loses its elasticity, on the contrary, the adhesion to the rotary pressing member is increased, and the toner discharging property is deteriorated. Therefore, in order to maintain appropriate elasticity of the toner, the THF-soluble component having a molecular weight of 10,000 or more of the toner needs to be sufficiently cross-linked with a trivalent or higher polycarboxylic acid or an anhydride thereof.
For this purpose, it is preferable to satisfy 0.1 ≦ W2 ≦ 30.

Further, the relationship between W1 and W2 is expressed as W2> W1.
By doing so, the polymer side of the toner is more crosslinked than the low molecular side, so that the toner can sufficiently melt and have elasticity even at a low temperature at which the rotating pressure member stains, and the rotation It is difficult to accumulate on the pressing member, which is preferable in suppressing contamination of the rotating pressing member.

In addition, by controlling the degree of crosslinking between the high molecular side and the low molecular side in this manner, the wax does not excessively plasticize the resin and easily melts out on the toner surface. Is also effective.

When W1 exceeds 25, the crosslinking on the low molecular weight side proceeds too much, so that the toner cannot be sufficiently melted, the contamination of the rotating pressure member deteriorates, and the elasticity of the toner becomes too high, so that the cold offset resistance is reduced. Is easily deteriorated. On the other hand, when W2 exceeds 30, the crosslinking on the high molecular weight side proceeds too much, the elasticity of the toner becomes too large, the discharging property to the recording material is deteriorated, and the contamination of the rotating pressure member is deteriorated.

The difference between W1 and W2 is 0 <W2-W1
More preferably, it is <10. When the difference in the degree of crosslinking between the low molecular weight side and the high molecular weight side is within this range, the balance between the viscosity and the elasticity of the toner is optimally maintained, and the effect of suppressing the contamination of the rotating pressure member and the cold offset is most exerted.

In the present invention, fractionation of each molecular weight component of the toner can be obtained by the following method.

"Apparatus configuration" LC-908 (manufactured by Nippon Kagaku Kogyo Co., Ltd.) JRS-86 (company; repeat injector) JAR-2 (company; autosampler) FC-201 (Gilson; hula cushion collector) "Column configuration" JAIGEL-1H to 5H (20mm x 600m in diameter)
m: Preparative column) “Measurement conditions” Temperature: 40 ° C. Solvent: THF Flow rate: 5 ml / min Detector: RI In the sample, additives other than the polymer component are previously separated. As a fractionation method, a solvent time at which the molecular weight reaches 10,000 is measured in advance, and a sample is fractionated before and after that. The solvent is removed from the fractionated sample to obtain a sample for composition analysis of a component having a trivalent or higher polycarboxylic acid.

"Composition Analysis of Binder Resin" The sample obtained by the preparative column was hydrolyzed with 6 mol / l NaOH, extracted with ether, methylated for each sample, and multivalently analyzed by GC / MS. Carboxylic acid identified and GC
The content (mol%) was determined from the peak area value of.

The toner of the present invention preferably contains a wax so as to have at least one endothermic peak at 60 to 120 ° C. in differential thermal analysis.

The wax having a peak in this temperature range is sufficiently melted even at a low temperature at which the rotating pressure member stains and cold offset occur, and easily melts on the toner surface. The effect of deterring is high. When the endothermic peak is less than 60 ° C., the blocking resistance tends to deteriorate, and the endothermic peak is 1%.
If the temperature exceeds 20 ° C., the low-temperature fixability tends to deteriorate.

The wax used in the present invention has a weight average molecular weight (Mw) and a number average molecular weight (M
Those having a ratio (Mw / Mn) to n) of 1.0 to 2.0 and a sharp molecular weight distribution are preferred. A wax having a sharp molecular weight distribution exerts a sharp melt property when heated, and is thus effective for rotating press member contamination and cold offset. Further, the low-temperature fixability is improved, and the blocking resistance is not deteriorated.

The molecular weight of the wax is measured under the following conditions. Apparatus: GPC-150C (Waters) Column: GMH-HT 30 cm, 2 columns (manufactured by Tosoh Corporation) Temperature: 135 ° C Solvent: o-dichlorobenzene (0.1% by mass ionol added) Flow rate: 1.0 ml / min Sample: 0.45 ml of 0.15 mass% wax is injected. The measurement is performed under the above conditions, and the molecular weight of the wax is calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. In addition, Mark-Houwink
The molecular weight of the wax is calculated by converting to a polyethylene based on a conversion formula derived from the viscosity formula.

The wax has a number average molecular weight of 200 to 2
000 (more preferably 300 to 1500, still more preferably 350 to 1000), dispersibility in a binder resin, low-temperature offset resistance, high-temperature offset resistance,
It is more preferable in terms of blocking resistance and durability of many sheets.

Examples of the wax include a low molecular weight hydrocarbon wax composed of carbon and hydrogen, a long-chain alkyl alcohol wax having an OH group, a long-chain alkyl carboxylic acid wax having a COOH group, and an ester wax.

Examples of the low molecular weight hydrocarbon wax include petroleum waxes such as paraffin wax, microcrystalline wax and petrolactam and derivatives thereof; low molecular weight polyolefin wax such as low molecular weight polyethylene; and polymethylene wax such as Fischer-Tropsch wax. . Since the low molecular weight polyolefin wax usually has a Mw / Mn value of more than 2.0, the Mw / Mn becomes 1.0 to 2.0 and the DS
It is preferable to purify so that the C endothermic main peak is 60 to 120 ° C.

Examples of the long-chain alkyl alcohol wax include a mixture of long-chain alkyl alcohols having 20 to 200 carbon atoms.

Examples of the ester wax include carnauba wax, purified candelilla wax, long-chain alkyl alcohol having 15 to 45 carbon atoms, and long-chain alkyl carboxylic acid having 15 to 45 carbon atoms. The toner of the present invention is preferably a low molecular weight hydrocarbon wax having a sharp molecular weight distribution in order to exhibit a more effective releasing effect.

The DSC endothermic peaks of the wax and the toner were measured with a differential thermal analyzer (DSC analyzer),
7 (PerkinElmer) using ASTM D3
It measures according to 418-82. Measurement sample is 2-10
Weigh accurately in mg range. This was put in an aluminum pan, and an empty aluminum pan was used as a reference. The temperature was raised at a rate of 10 ° C./min between 30 and 160 ° C.
Then, the measurement is performed under normal temperature and normal humidity.

When the toner has at least one endothermic peak in the differential thermal analysis at 60 ° C. or more and 120 ° C. or less, the wax acts from a low temperature region where the toner starts to be fixed, thereby further improving the fixing property. Low temperature fixability,
Both high-temperature offset resistance and blocking resistance can be achieved. When the endothermic peak is less than 60 ° C., the anti-blocking property tends to be poor, and
When the temperature exceeds ℃, low-temperature fixability tends to be inferior.

Further, the content of the THF-insoluble component in the toner is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and still more preferably 5 to 30% by mass. T
When the content of the HF-insoluble component is less than 1% by mass, long-term storage stability may be deteriorated or the high-temperature offset resistance may be affected.
In the fixing device used in the present invention, the cold offset resistance and the low-temperature fixing property of a halftone image tend to be inferior.

In the molecular weight distribution of the GPC of the THF-soluble component, the content (M1) of the component having a molecular weight of less than 10,000 is 40 to 7
0% by mass, content of components having a molecular weight of 10,000 to 50,000 (M2)
Is 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 (M3) is 2 to 25% by mass, and M1 ≧ M2> M
Satisfying 3 is preferable for balancing cold offset resistance, low-temperature fixing property, high-temperature offset resistance, storage stability, and developability.

In the GPC molecular weight distribution of the THF-soluble component of the toner, when the content M3 of the component having a molecular weight of more than 50,000 exceeds 25% by mass, the low-temperature fixability tends to deteriorate.
If the amount is less than 2% by mass, the high-temperature offset resistance tends to deteriorate.

When the content M1 of the component having a molecular weight of less than 10,000 is 70,
When the amount is more than 40% by mass, there are some problems in the storability of the toner and resistance to high-temperature offset, and when the amount is less than 40% by mass, contamination of the rotating pressure member and low-temperature fixability are likely to be deteriorated.

In order to obtain sufficient developability, a coloring agent,
It is necessary to disperse materials such as a charge control agent and a magnetic substance in the binder resin to make the chargeability uniform, and for this purpose, the content (M2) of the component having a molecular weight of 10,000 to 50,000 must be 25 to 50.
It is preferable to satisfy mass%.

Further, if M1 ≧ M2> M3 is not satisfied,
It is difficult to achieve both excellent low-temperature fixability and high-temperature offset resistance while achieving excellent developability and storage stability.

The molecular weight of the THF-soluble component of the toner is measured by gel permeation chromatography (GPC). As a specific GPC measurement method, a sample obtained by previously extracting the toner with a THF (tetrohydrofuran) solvent for 10 hours using a Soxhlet extractor was used, and the column configuration was A-801, 802, 80 manufactured by Showa Denko.
3, 804, 805, 806 and 807 are connected, and the molecular weight distribution is measured using a standard polystyrene resin calibration curve.
The content of the component having a molecular weight of less than 10,000 (M1), the content of the component having a molecular weight of 10,000 to 50,000 (M2), and the content of the component having a molecular weight exceeding 50,000 (M3) are represented by the mass ratio based on the area ratio of the GPC chromatogram. %. The lower limit of the molecular weight region of the content (M1) of the component having a molecular weight of less than 10,000 is set to 800 in consideration of noise at the time of measuring the molecular weight.

The THF-soluble component of the toner particles can be separated by subjecting the toner to a Soxhlet extractor of THF to extract the THF-soluble component, and solidifying the extract.

The content of the THF-insoluble component in the toner particles was determined by weighing about 1 g of the toner (W3 g), placing it in a cylindrical filter paper (for example, No. 86R manufactured by Toyo Filter Paper), passing through a Soxhlet extractor and using 200 ml of THF as a solvent. After extracting for a time and evaporating the soluble component extracted with the THF solvent, the resultant is vacuum-dried at 100 ° C. for several hours, and the weight of the THF-soluble resin component (W4 g) is weighed. The mass of components other than the binder resin component such as the colorant and the wax in the toner is measured in advance, and is set to W5 g. The THF insolubles are
It is obtained from the following equation.

[0066]

(Equation 1)

To stabilize the chargeability of the toner, a charge control agent is added (internally added) in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the binder resin, or mixed with toner particles. (External addition) is preferred.

The charge control agent makes it possible to control the amount of charge optimally according to the development system. In addition, by using a metal compound as a charge control agent and satisfying W2> W1, crosslinking progresses between a polyvalent carboxylic acid and a metal compound which are present on the high molecular weight side in the molecular weight distribution of the toner, and a non-offset region is formed. Spreads. On the low molecular weight side, the crosslinking is moderately performed, though not so much as on the high molecular weight side. As a result, the releasability from the rotary pressing member is improved.

The following substances control the toner to be negatively charged. For example, an organic metal complex and a chelate compound are effective, and examples thereof include a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid, and an aromatic dicarboxylic acid-based metal complex. Other examples include aromatic hydroxycarboxylic acids, aromatic monocarboxylic acids, aromatic polycarboxylic acids, metal salts thereof, anhydrides thereof, esters thereof, and phenol derivatives such as bisphenol.

The following substances are controlled to be positively charged. Modified product with nigrosine and an aliphatic metal salt; tributylbenzylammonium-1-hydroxy-4-
Quaternary ammonium salts such as naphthosulfonate and tetrabutylammonium tetrafluoroborate, and onium salts such as phosphonium salts which are analogs thereof, lake pigments thereof, triphenylmethane dyes and lake pigments thereof As phosphorous tungsten,
Phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid, pheiliocyanide, ferrocyanide, etc.), metal salts of higher fatty acids; diorganotin oxides such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; Diorganotin borates such as dibutyl tin borate, dioctyl tin borate and dicyclohexyl tin borate; these can be used alone or in combination of two or more.

The above-mentioned charge control agent is preferably used in the form of fine particles.

In the present invention, it is preferable to use an aromatic hydroxycarboxylic acid compound having a good rise in chargeability in the early stage of durability. Further, it is preferable to use an aromatic hydroxycarboxylic acid compound of aluminum because a good crosslinking effect can be obtained.

In the present invention, it is also preferable to use an iron complex of a monoazo compound, which has stable chargeability in long-term durability.

Further, in the present invention, a good crosslinking effect and
In order to maintain the chargeability over a long period of time, it is preferable to use an aluminum aromatic hydroxycarboxylic acid compound and an iron complex of a monoazo compound in combination.

Examples of hydroxycarboxylic acids and azo compounds preferably used in the present invention are shown below.

[0076]

Embedded image

As the colorant used in the present invention, a black colorant that uses carbon black, a magnetic substance, or a yellow / magenta / cyan colorant shown below and is toned to black is used.

Examples of the yellow colorant include condensed azo compounds, isoindolinone compounds, anthraquinone compounds,
A compound represented by an azo metal complex, a methine compound or an allylamide compound is used. Specifically, C.I. I. Pigment Yellow 12, 13, 14, 15, 17, 6
2, 74, 83, 93, 94, 95, 97, 109, 1
10, 111, 120, 127, 128, 129, 14
7, 168, 174, 176, 180, 181, 191
Etc. are preferably used.

Examples of the magenta colorant include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacdrine compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds and perylene compounds. Specifically, C.I.
I. Pigment Red 2, 3, 5, 6, 7, 23, 4
8: 2, 48: 3, 48: 4, 57: 1, 81: 1, 1
44, 146, 166, 169, 177, 184, 18
5, 202, 206, 220, 221, 254 are particularly preferred.

As the cyan coloring agent, copper phthalocyanine compounds and derivatives thereof, 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, 62, 66 can be used particularly preferably.

When a magnetic material is used as a black colorant, unlike other colorants, 30 parts per 100 parts by mass of resin is used.
Used in an amount of up to 200 parts by mass.

As the magnetic material, there is a metal oxide containing an element of iron, cobalt, nickel, copper, magnesium, manganese, aluminum or silicon. Among them, those containing iron oxide as a main component, such as triiron tetroxide and γ-iron oxide, are preferable. From the viewpoint of controlling the chargeability of the toner, another metal element such as a silicon element or an aluminum element may be contained. These magnetic particles are obtained by BE adsorption using a nitrogen adsorption method.
The T specific surface area is preferably from ² to 30 m ² / g, particularly preferably from ³ to 28 m ² / g, and more preferably the Mohs hardness is from 5 to 7.

The specific surface area was determined by adsorbing nitrogen gas on the sample surface according to the BET method, and calculating the specific surface area using the BET multipoint method.

The shape of the magnetic material may be an octahedron, a hexahedron,
There are spherical, needle-like, scale-like, but octahedral, hexahedral, spherical,
An amorphous type having a small anisotropy is preferable for increasing the image density, and a spherical shape is particularly preferable. In order to further increase the image density, a magnetic material containing silica is particularly preferable.

The average particle size of the magnetic material is 0.05 to
1.0 μm is preferred, and more preferably 0.1 to 0.1 μm.
6 μm, more preferably 0.1 to 0.4 μm.

The average particle size of the magnetic material was measured by taking a transmission electron micrograph of the magnetic powder and arbitrarily selecting 250 particles having a particle size of 0.01 μm or more per 40,000-fold magnification. The Martin diameter (the length of a line segment that bisects the projected area in a fixed direction) in the projected diameter is measured, and is represented by the number average diameter.

Examples of the polyester-based monomer constituting the polyester unit contained in the polyester resin and the hybrid resin used in the present invention include the following.

The alcohol component monomers include ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, , 6-hexanediol, neopentyl glycol, 2-ethyl-1,3-
There are hexanediol, hydrogenated bisphenol A, bisphenol derivatives represented by the following formula (A), and diols represented by the following formula (A).

[0089]

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Examples of the acid component monomer include benzenedicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and phthalic anhydride or anhydrides thereof and lower alkyl esters thereof; succinic acid, adipic acid, sebacic acid, azelaic acid and the like. Alkyl dicarboxylic acids or their anhydrides or lower alkyl esters thereof, and further having 6 to 18 carbon atoms
And unsaturated anhydrides thereof such as fumaric acid, maleic acid, citraconic acid, itaconic acid, and mesaconic acid, and anhydrides thereof. Examples of the acid component monomer include trivalent or higher polycarboxylic acids such as trimellitic acid and pyromellitic acid.

Examples of the acid component monomer include methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, and methyl itaconate half Half esters of unsaturated dicarboxylic acids such as esters, methyl alkenyl succinate half ester, methyl half fumarate and methyl half mesaconic acid; and unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate.

In the toner of the present invention, the binder resin is cross-linked by a trivalent or higher polycarboxylic acid. Preferred examples of the crosslinking component include trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and its anhydride, benzophenonetetracarboxylic acid, pentaerythritol, and oxyalkylene ether of novolak type phenol resin.

In the toner of the present invention, the binder resin may be crosslinked with a polyhydric alcohol in addition to the trivalent or higher polycarboxylic acid. Glycerin, pentaerythritol, sorbit, sorbitan,
Further, for example, polyhydric alcohols such as oxyalkylene ether of novolak type phenol resin and the like can be mentioned.

The vinyl monomers constituting the vinyl polymer unit contained in the hybrid resin used in the present invention include the following.

Styrene; o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene,
p-butylstyrene, p-tert-tributylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxy Styrene, p-chlorostyrene, 3,4-dichlorostyrene,
Styrene and its derivatives such as m-nitrostyrene, o-nitrostyrene and p-nitrostyrene; unsaturated monoolefins such as ethylene, propylene, butylene and isobutylene; unsaturated polyenes such as butadiene and isoprene; vinyl chloride, odor Vinyl halides such as vinyl chloride and vinyl fluoride; vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate and isobutyl methacrylate Α-methylene fats such as n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate Monocarboxylic acid esters: methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, acrylic acid Acrylic esters such as 2-chloroethyl and phenyl acrylate; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; N-vinyl Pyrrole, N-vinylcarbazole, N
N- such as vinylindole and N-vinylpyrrolidone
Vinyl compounds; vinyl naphthalenes; and acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide.

Furthermore, α, β-unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid and cinnamic acid; α, β-unsaturated acid anhydrides such as crotonic anhydride and cinnamic anhydride; An anhydride of a β-unsaturated acid and a lower fatty acid; monomers having a carboxyl group such as alkenyl malonic acid, alkenyl glutaric acid, alkenyl adipic acid and monoesters thereof.

Further, acrylic acid or methacrylic acid esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate; 4- (1-hydroxy-1-methylbutyl) styrene, 4- (1- Monomers having a hydroxy group such as (hydroxy-1-methylhexyl) styrene are exemplified.

Further, methyl maleate half ester, maleic acid ethyl half ester, maleic acid butyl half ester, citraconic acid methyl half ester, citraconic acid ethyl half ester, citraconic acid butyl half ester, itaconic acid methyl half ester, alkenyl succinate Unsaturated dicarboxylic acid half esters such as methyl acid half ester, methyl fumarate half ester and methyl mesaconate half ester; unsaturated dicarboxylic acid diesters such as dimethyl maleate and dimethyl fumarate; maleic acid, citraconic acid, itaconic acid Unsaturated dicarboxylic acids such as alkenyl succinic acid, fumaric acid and mesaconic acid; unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride and alkenyl succinic anhydride Can be used carboxylic acid anhydrides as vinyl monomers, when calculating the ratio of the polyester monomer component on the total monomer components used to prepare the binder resin in the present invention as a reference,
Only these are calculated as polyester monomer components.

Further, if necessary, the polymer may be cross-linked with a cross-linkable monomer as exemplified below.

Examples of aromatic divinyl compounds include divinylbenzene and divinylnaphthalene; examples of diacrylate compounds linked by an alkyl chain include:
Ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate and the above compounds In which acrylate is replaced with methacrylate;
Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and diethylene glycol diacrylate. Propylene glycol diacrylate and those obtained by replacing the acrylates of the above compounds with methacrylates; diacrylate compounds linked by a chain containing an aromatic group and an ether bond include, for example, polyoxyethylene (2)-
2,2-bis (4-hydroxydiphenyl) propane diacrylate, polyoxyethylene (4) -2,2-bis (4-hydrodiphenyl) propane diacrylate and those obtained by replacing the acrylate of the above compound with methacrylate are listed. The polyester type diacrylates include, for example, MANDA (Nippon Kayaku).

Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, tetramethylolmethanetetraacrylate, oligoester acrylate and those obtained by replacing acrylate of the above compounds with methacrylate; Triallyl cyanurate and triallyl trimellitate;

These crosslinking agents can be used in an amount of 0.01 to 10.0 parts by mass (more preferably 0.03 to 5 parts by mass) based on 100 parts by mass of the other vinyl monomer component.

In the present invention, the vinyl copolymer component and / or the polyester resin component preferably contain a monomer component capable of reacting with both resin components. Among the monomers constituting the polyester resin component, those that can react with the vinyl copolymer include, for example, fumaric acid, maleic acid,
Unsaturated dicarboxylic acids such as citraconic acid and itaconic acid or anhydrides thereof are exemplified. Among the monomers constituting the vinyl copolymer component, those which can react with the polyester resin component include those having a carboxyl group or a hydroxy group, acrylic acid or methacrylic acid esters, and the like.

As a method for obtaining a reaction product of a vinyl resin and a polyester resin, one of the above-described methods is used in the presence of a polymer containing a monomer component capable of reacting with each of the above-mentioned vinyl resins and polyester resins. Alternatively, a method obtained by polymerizing both resins is preferable.

Examples of the polymerization initiator used for producing the vinyl copolymer of the present invention include, for example, 2,2′-
Azobisisobutyronitrile, 2,2′-azobis (4
-Methoxy-2,4-dimethylvaleronitrile), 2,
2′-azobis (-2,4-dimethylvaleronitrile), 2,2′-azobis (-2methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate,
1,1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2,4 -Dimethyl-4-methoxyvaleronitrile, 2,2′-azobis (2-methyl-propane), methyl ethyl ketone peroxide,
Ketone peroxides such as acetylacetone peroxide and cyclohexanone peroxide; 2,2-
Bis (t-butylperoxy) butane, t-butyl hydroperoxide, cumene hydroperoxide,
1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, di-cumyl peroxide, α,
α'-bis (t-butylperoxydiisopropyl) benzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, di- Isopropyl peroxydicarbonate, di-2-ethylhexylperoxycarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethylperoxydicarbonate, di-methoxyisopropylperoxydicarbonate, di (3- Methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexylsulfonyl peroxide, t-butylperoxyacetate, t-butylperoxyisobutyrate, t-butylperoxyneo Canoate, t-butyl peroxy 2-ethylhexanoate, t-butyl peroxy laurate, t-butyl peroxy benzoate, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxy isophthalate, t- Butyl peroxyallyl carbonate, t-amyl peroxy 2-ethylhexanoate, di-t-butyl peroxy hexahydroterephthalate, di-t-butyl peroxyazelate are exemplified.

As the initiator used for producing the vinyl polymer unit used in the present invention, the following polyfunctional polymerization initiators may be used alone or in combination with a monofunctional polymerization initiator. May be.

Specific examples of the polyfunctional polymerization initiator having a polyfunctional structure include 1,1-di-t-butylperoxy-
3,3,3-trimethylcyclohexane, 1,3-bis- (t-butylperoxyisopropyl) benzene,
2,5-dimethyl-2,5- (t-butylperoxy)
Hexane, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, tris- (t-butylperoxy) triazine, 1,1-di-t-butylperoxycyclohexane, 2,2 -Di-t-butylperoxybutane, 4,4-di-t-butylperoxyvaleric acid-n-butyl ester, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate , Di-t-butylperoxytrimethyl adipate, 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane and 2,2-t
A polyfunctional polymerization initiator having a functional group having a polymerization initiation function such as two or more peroxide groups in one molecule such as butyl peroxyoctane; and diallyl peroxy dicarbonate, tributyl peroxy maleic acid, t
Polyfunctional polymerization initiators having both a functional group having a polymerization initiation function such as a peroxide group and a polymerizable unsaturated group in one molecule such as -butylperoxyallyl carbonate and t-butylperoxyisopropyl fumarate; No.

Among these, more preferred are 1,
1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-t-butylperoxycyclohexane, di-t-butylperoxyhexahydroterephthalate, di-t-butylperoxyazelate And 2,2-bis- (4,4-di-t-butylperoxycyclohexyl) propane, and t-butylperoxyallyl carbonate.

In the present invention, the binder resin contains a hybrid resin component. The hybrid resin means a resin in which at least a part of the polyester resin component and at least a part of the vinyl polymer component are chemically bonded. The chemically bonded polyester resin component side is a polyester unit, and the chemically bonded vinyl polymer component is a vinyl polymer unit.

Specifically, polymerization is carried out by including a vinyl monomer having a polyester unit and a carboxylic acid such as (meth) acrylic acid, or a vinyl monomer having a carboxylic ester group such as (meth) acrylic ester. And a vinyl polymer unit formed by an esterification reaction or a transesterification reaction. As a form of the copolymerization, it is preferable to form a graft copolymer or a block copolymer in which a vinyl polymer unit is used as a trunk polymer and a polyester unit is used as a branch polymer.

Therefore, in the present invention, the hybrid resin component means that at least a part of the polyester unit and the vinyl polymer unit are at least partly formed.

[0112]

Embedded image Are connected via

In the present invention, examples of the method for producing a hybrid resin include the following methods (1) to (7).

(1) After separately producing a vinyl polymer and a polyester resin, the resin is dissolved / swelled in an organic solvent, an esterification catalyst and, if necessary, an alcohol are added, and the esterification reaction is carried out by heating. And / or after transesterification, the organic solvent is distilled off to produce. In this step, waxes may be added.

(2) This is a method in which a polyester-based monomer is added in the presence of a vinyl-based polymer, followed by polymerization and an esterification reaction and / or a transesterification reaction with the vinyl-based polymer. At this time, if necessary, a vinyl-based monomer may be further added for polymerization. Also in this case, an organic solvent can be appropriately used. In this step, waxes may be added.

(3) This is a method in which a vinyl monomer is added in the presence of a polyester resin, followed by polymerization and an esterification reaction and / or a transesterification reaction. At this time, if necessary, a polyester-based monomer may be added for polymerization. Also in this case, an organic solvent can be appropriately used. In this step, wax may be added.

(4) In the presence of a vinyl polymer and a polyester resin, a vinyl monomer and / or a polyester monomer are added, and a polymerization and esterification reaction or / and
And a transesterification reaction. Also in this case, an organic solvent can be appropriately used. Also,
In this step, wax may be added.

(5) A method in which a vinyl-based monomer and a polyester-based monomer are mixed and subjected to an addition polymerization and a polycondensation reaction and an esterification reaction and / or a transesterification reaction. Also in this case, an organic solvent can be appropriately used. In this step, wax may be added.

(6) The resin containing the hybrid resin component produced in the above (1) to (5) is further dissolved / swelled with a vinyl polymer and / or polyester resin in, for example, an organic solvent. And the organic solvent is distilled off.

(7) In the presence of the resin containing the hybrid resin component produced in the above (1) to (5), a vinyl monomer and / or a polyester monomer is further added, and the polymerization and esterification reaction or And / or a transesterification reaction. Further, an organic solvent can be appropriately used. In this step, wax may be added.

In the production methods (1) to (4) and (6), a plurality of polymers having different molecular weights and different degrees of crosslinking can be used as the vinyl polymer and / or polyester resin.

Among the production methods (1) to (7),
In particular, the production method (3) is preferable in that the molecular weight can be easily controlled, the generation of the hybrid resin component can be controlled, and when a wax is added, the dispersion state can be controlled.

In the present invention, charge stability, developability,
In order to improve the storage stability, it is preferable to externally add an inorganic fine powder such as silica, alumina and titania, or a double oxide thereof. Further, it is preferably silica. For example, as the silica, both dry silica produced by vapor phase oxidation of a silicon halide and an alkoxide, dry silica called fumed silica, and wet silica produced from alkoxide and water glass can be used. although, as having less silanol groups on the inner surface and the silica fine powder, also Na ^₂ O, SO ₃ ^2-
Dry silica with little production residue such as is preferred. In the case of fumed silica, for example, in the production process, by using other metal halides such as aluminum chloride and titanium chloride together with silicon halide, it is also possible to obtain a composite fine powder of silica and other metal oxides, Is also included.

The inorganic fine powder used in the present invention is BET.
The specific surface area by measuring nitrogen adsorption 30 m ² / g or more by law, in particular 50 to 400 m ² / g give good results in the range of fine silica powder with respect to 100 parts by weight of the toner particles 0.1-8 It is preferable to use it by mass, preferably 0.5 to 5 mass parts, more preferably more than 1.0 to 3.0 mass parts.

The inorganic fine powder used in the present invention may be a silicone varnish, if necessary, for the purpose of hydrophobicity and charge control.
Treatment with silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents with functional groups, and other treating agents such as organosilicon compounds and organotitanium compounds, alone or in combination. Is preferred.

According to the BET method, a specific surface area was measured by adsorbing nitrogen gas on the sample surface using a specific surface area measuring apparatus, Auto Soap 1 (manufactured by Yuasa Ionics), and calculating the specific surface area using the BET multipoint method.

In order to maintain stable toner storability, it is preferable that the inorganic fine powder be treated with at least silicone oil.

An external additive other than the silica fine powder may be added to the toner of the present invention, if necessary. For example, resin fine particles that function as a charge auxiliary agent, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent during hot roll fixing, a lubricant, an abrasive, and the like.

As a method for producing the toner of the present invention,
After sufficiently mixing the above-mentioned toner constituent materials with a ball mill or other mixer, the mixture is kneaded well using a heat kneader such as a hot roll kneader or an extruder, and after cooling and solidifying, mechanically pulverized to obtain a pulverized powder. A method of obtaining a toner by classification is preferable. Another method is a polymerization method in which a monomer to form a binder resin is mixed with a predetermined material to form an emulsified suspension and then polymerized to obtain a toner. In the microcapsule toner, a method in which a predetermined material is contained in a core material or a shell material, or both of them; a method in which a constituent material is dispersed in a binder resin solution and then spray-dried to obtain a toner. Further, if necessary, the desired additive and the toner particles are sufficiently mixed by a mixer such as a Henschel mixer to produce the toner of the present invention.

For example, as a mixer, Henschel mixer (manufactured by Mitsui Mining); super mixer (manufactured by Kawata); ribocorn (manufactured by Okawara Seisakusho); Nauta mixer, turbulizer, cyclomix (manufactured by Hosokawa Micron); Spiral pin mixers (manufactured by Taiheiyo Kiko Co., Ltd.); Reedige mixers (manufactured by Matsubo Co., Ltd.); kneading machines include KRC kneader (manufactured by Kurimoto Tekkosho); bus co-kneader (manufactured by Buss); TEM Mold extruder (manufactured by Toshiba Machine Co., Ltd.); TEX twin-screw kneader (manufactured by Nippon Steel Works); PCM kneader (manufactured by Ikegai Iron Works); three roll mill, mixing roll mill, kneader (manufactured by Inoue Seisakusho); knee Tex (Mitsui Mining Co., Ltd.); MS type pressure kneader, Nidder router (Moriyama Seisakusho); Bunbury mixer (Kobe) And a pulverizer such as a counter jet mill, a micron jet, an inomaizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic) and a cross jet mill (Kurimoto Iron Works) Ullmax (Nisso Engineering); SK Jet
O-Mill (manufactured by Seishin Enterprise Co., Ltd.); Kryptron (manufactured by Kawasaki Heavy Industries, Ltd.); and Turbo Mill (manufactured by Turbo Kogyo Co., Ltd.). Classifiers include Crasheal, Micron Classifier, and Spedd Classifier (Seishin Enterprise). Turbo Classifier (manufactured by Nissin Engineering); Micron separator, Turboflex (ATP), TSP separator (manufactured by Hosokawa Micron); Elbow jet (manufactured by Nippon Steel Mining), dispersion separator (manufactured by Nippon Pneumatic) YM Micro Cut (manufactured by Yasukawa Shoji Co., Ltd.). Examples of the sieving apparatus used for sieving coarse particles and the like include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona Sheep, Gyro Shifter (Tokuju Kogyo Co., Ltd.) ); Vibrasonic System (Dalton Ltd.); Soni clean (Sintokogio Co., Ltd.), manufactured by Turbo Screener (Turbo Kogyo Co., Ltd.), manufactured by micro-shifter (Makino Mfg. Co., Ltd.); circular vibration sieve, and the like.

On the other hand, as a fixing device, a device that achieves both energy saving (low power consumption) and improvement in user operability (quick print) is disclosed in Japanese Patent Application Laid-Open No. 59-337.
As shown in JP-A-87-87, an induction heating type fixing device using high frequency induction as a heating source has been proposed.

In this induction heating fixing device, a coil is arranged concentrically inside a hollow fixing roller made of a metal conductor, and a high-frequency magnetic field generated by applying a high-frequency current to this coil causes an induced eddy current to flow through the fixing roller. Is generated, and the fixing roller itself generates Joule heat by the skin resistance of the fixing roller itself.

According to the fixing device of the induction heating system, since the electric-heat conversion efficiency is greatly improved, it is possible to shorten the wait time.

By combining a coil with a core (magnetic field blocking member) made of a magnetic material, a high-frequency magnetic field can be generated efficiently.

In particular, when a T-shaped core is used,
Due to the effective concentration of the high-frequency magnetic flux and the effect of shielding the magnetic field from a portion other than the heat generating portion, the amount of heat required for the fixing device can be generated with low power.

Referring to the drawings, preferred embodiments of a fixing device used in the present invention will be illustratively described in detail. However, the dimensions, materials, shapes, relative arrangements, and the like of the components described in this embodiment are not intended to limit the scope of the present invention thereto unless otherwise specified. Absent.

The heating device according to the embodiment of the present invention is applied to an image forming apparatus such as a copying machine or a printer. However, since the image forming apparatus is a known technique, a detailed description thereof will be omitted. .

In the following embodiment, a case where a heating device is applied as a so-called fixing device provided in an electrophotographic image forming apparatus will be described.

The configuration in this case will be briefly described. In order to form an unfixed toner image on a sheet by a known electrophotographic process and then apply heat and pressure to the sheet to fix the toner image, A fixing device is provided.

FIGS. 1 to 3 are schematic sectional views of a fixing device according to an embodiment of the present invention.

The fixing roller 1, which is a rotary heating member, is provided on an iron core metal cylinder 11 (heating layer) having an outer diameter of 40 mm and a thickness of 0.7 mm, for example, with PTFE having a thickness of 10 to 50 μm in order to enhance the surface releasability. Alternatively, it is configured by providing a release layer 12 having a PFA of 10 to 50 μm.

The pressure roller 2, which is a rotary pressure member, comprises a hollow cored metal 14 and an elastic layer 15, which is a surface-releasable heat-resistant rubber layer formed on the outer peripheral surface thereof.

Bearings are formed at both ends of the pressure roller 2, and are rotatably attached to a fixing unit frame (not shown).

The fixing roller 1 and the pressure roller 2 are rotatably supported, so that only the fixing roller 1 is driven.

The pressure roller 2 is in pressure contact with the surface of the fixing roller 1 and is arranged so as to be driven to rotate by frictional force at a pressure contact portion (nip portion).

The pressure roller 2 is pressed in the rotation axis direction of the fixing roller 1 by a mechanism (not shown) using, for example, a spring.

The pressure roller 2 is, for example, 294 N (30 k
g weight), and the width (nip portion; N in FIG. 3) of the press contact portion in that case is configured to be about 6 mm.

Of course, the nip width (N) may be changed by changing the load in consideration of the use conditions and the like.

The temperature sensor 6 is arranged so as to be in contact with the surface of the fixing roller 1, and the power supply to the exciting coil 3 as the exciting means is increased or decreased based on the detection signal of the temperature sensor 6, so that the temperature of the fixing roller 1 is increased. Is automatically controlled so that the surface temperature becomes a predetermined constant temperature.

The transport guide 7 is arranged at a position where the transfer material 16 transported while carrying the unfixed toner image 8 is guided to a pressure contact portion (nip portion) between the fixing roller 1 and the pressure roller 2. .

The separation claw 10 is disposed in contact with or close to the surface of the fixing roller 1 to prevent the transfer material 16 on which the fixed image 13 is formed from being wound around the fixing roller 1.

The exciting coil 3 has a structure in which a conductive wire is wound around a central protruding portion of a magnetic core 4 (hereinafter, referred to as a core) having a T-shaped cross section so as to extend along the inner peripheral surface of the fixing roller.
It is provided outside the holder 5 made of a heat-resistant resin such as PS, PEEK, and phenol resin.

This excitation coil 3 has a frequency of 10 to 100 kHz.
Is applied.

The magnetic field induced by the alternating current is guided to the core 4 as a magnetic field interrupting means having a high magnetic permeability to generate a magnetic flux and an eddy current on the inner surface of the fixing roller 1 as the heat generating means. Joule heat is generated by the specific resistance of 1.

In order to increase the heat generation, the number of turns of the exciting coil 3 should be increased, the core 4 should be made of ferrite or permalloy having a high magnetic permeability and a low residual magnetic flux density, or the frequency of the alternating current should be increased. .

The core 4 has a T-shaped cross section extending in the direction of the rotation axis of the fixing roller 1.
The magnetic field generated by the excitation is cut off, and the magnetic field is concentrated toward the heating unit.

When the surface temperature of the fixing roller 1 is adjusted to a predetermined value, for example, 190 ° C. which is optimal for fixing with the above-described configuration, about 200 W of electric power needs to be supplied to the exciting coil. At that time, the temperature of the exciting coil becomes about 210 ° C., and the temperature of the magnetic core becomes about 200 ° C.

When a large number of images are continuously fixed at a speed of about 30 sheets per minute, an electric power of about 450 W is required to be supplied to the exciting coil.
℃, the temperature of the magnetic core becomes about 220 ℃.

In the above description, the case where the fixing roller is used as the heating member has been described. However, it is of course possible to adopt a configuration made of a thin metal film instead of the fixing roller.

[0160]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the present invention is limited thereto.

(Preparation Example 1 of Binder Resin) A polyester resin having a monomer composition shown in Table 1 was synthesized by dehydration-condensation polymerization. Let the obtained polyester resin be binder resin a.

(Preparation Example 2 of Binder Resin) A styrene-acryl resin having a monomer composition shown in Table 1 was synthesized by addition polymerization. The obtained styrene-acrylic resin is referred to as a binder resin b.

(Binder Resin Production Example 3) BPA-PO (bisphenol A PO adduct (2 mol addition)) 35 mol% BPA-EO (bisphenol A EO adduct (2 mol addition)) 15 mol% TPA (terephthalic acid) 11 mol% TMA (trimellitic acid) 22 mol% FA (fumaric acid) 17 mol% Dibutyltin oxide was used as the above polyester monomer.
Charge the autoclave together with 0 mmol and equip it with a decompression device, a water separation device, a nitrogen gas introduction device, a temperature measurement device and a stirrer, and carry out the polycondensation reaction while heating to 210 ° C. under a reduced pressure under a nitrogen atmosphere in a conventional manner. As a result, a polyester resin A was obtained.

Next, 85 parts by mass of the obtained polyester resin and styrene / 2-ethylhexyl acrylate (mass% of each monomer: 84 parts by mass) were added to 50 parts by mass of xylene.
/ 16) 15 parts by mass of a vinyl monomer mixture and 0.3 parts by mass of dibutyltin oxide as an esterification catalyst were charged into an autoclave, and equipped with a pressure reducing device, a water separator, a nitrogen gas introducing device, a temperature measuring device, and a stirring device. Under a nitrogen atmosphere under reduced pressure according to a conventional method.
Heated to ℃ to dissolve and swell. Under a nitrogen atmosphere, a radical initiator solution in which 1 part by mass of t-butyl hydroperoxide was dissolved in 10 parts by mass of xylene was added dropwise over about 30 minutes. The temperature was further maintained for 10 hours to complete the radical polymerization reaction. By further reducing the pressure while heating and removing the solvent, a binder resin c containing a hybrid resin component was obtained. Table 1 shows the physical properties of the binder resin c.

(Binder Resin Production Example 4) BPA-PO 35 mol% BPA-EO 15 mol% TPA 30 mol% TMA 5 mol% SA 15 mol% The composition of the polyester-based monomer was the same as that of Binder Resin Production Example 3 as described above. To obtain a polyester resin ro. A binder resin d containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 3, except that the polyester resin was 75 parts by mass and the vinyl monomer mixture was 25 parts by mass. Table 1 shows the physical properties of the binder resin d.

(Binder Resin Production Example 5) BPA-PO 15 mol% BPA-EO 35 mol% TMA 31 mol% FA 19 mol% The composition of the polyester monomer was as described above, and the polyester was produced in the same manner as in the binder resin production example 3. Resin C was obtained. A binder resin e containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 3, except that the polyester resin C was 90 parts by mass and the vinyl monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin e.

(Binder Resin Production Example 6) BPA-PO 15 mol% BPA-EO 35 mol% TMA 41 mol% FA 9 mol% The composition of the polyester monomer was as described above, and the polyester was produced in the same manner as in the binder resin production example 3. Resin was obtained. A binder resin f containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 3, except that the polyester resin was 90 parts by mass and the vinyl monomer mixture was 10 parts by mass. Table 1 shows the physical properties of the binder resin f.

(Binder Resin Production Example 7) BPA-PO 35 mol% BPA-EO 15 mol% TPA (terephthalic acid) 15 mol% FA 35 mol% The composition of the polyester-based monomer was as described above, and the binder resin production example 1 Similarly, a polyester resin was obtained.
The obtained resin was designated as binder resin g, and the physical properties of binder resin g are shown in Table 1.

(Binder Resin Production Example 8) BPA-PO 35 mol% BPA-EO 15 mol% TPA 30 mol% FA 20 mol% The composition of the polyester monomer was as described above, and the polyester was produced in the same manner as in the binder resin production example 3. Resin E was obtained. A binder resin h containing a hybrid resin component was obtained in the same manner as in Binder Resin Production Example 3, except that the polyester resin was 80 parts by mass and the vinyl monomer mixture was 20 parts by mass. Table 1 shows the physical properties of the binder resin h.

<Example 1>-Binder resin a 40 parts by mass-Binder resin c 60 parts by mass-Magnetic material (shape: spherical, average particle size: 0.20 µm) 100 parts by mass-Aluminum aromatic hydroxycarboxylic acid Acid compound 1 part by mass (di-t-butylsalicylic acid compound)-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) ) After pre-mixing the above materials with a Henschel mixer, 13
The mixture was melt-kneaded by a twin-screw kneading extruder (PCM-30, manufactured by Ikegai Iron Works) set at 0 ° C. The obtained kneaded material was cooled, coarsely pulverized by a cutter mill, then pulverized by a fine pulverizer using a jet stream, and the obtained finely pulverized powder was classified using a multi-part classifier utilizing the Coanda effect. Thus, a magnetic toner having a weight average particle size of 7.0 μm was obtained.

To the obtained magnetic toner, 1.0% by mass of dry silica treated with silicone oil and hexamethyldisilazane was added and mixed with a mixer to obtain Toner 1. Table 3 shows the physical properties of Toner 1 thus obtained.

Example 2 30 parts by mass of binder resin a 70 parts by mass of binder resin f 100 parts by mass of magnetic material (shape: spherical, average particle diameter: 0.20 μm) 100 parts by mass of aromatic hydroxycarboxylic acid of aluminum Acid compound 1 part by mass (di-t-butylsalicylic acid compound)-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) The toner 2 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 2 thus obtained.

Example 3 50 parts by mass of binder resin a 50 parts by mass of binder resin d 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass of aromatic hydroxycarboxylic acid of aluminum Acid compound 1 part by mass-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) Thus, Toner 3 was obtained. Table 3 shows the physical properties of Toner 3 thus obtained.

Example 4 60 parts by mass of binder resin a 40 parts by mass of binder resin e 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) Aromatic hydroxycarboxylic acid of aluminum Acid compound 1 part by mass (di-t-butylsalicylic acid compound)-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) The toner 4 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 4 thus obtained.

<Example 5>-Binder resin a 40 parts by mass-Binder resin c 60 parts by mass-Magnetic material (shape: spherical, average particle size: 0.20 µm) 100 parts by mass-Aluminum aromatic hydroxycarboxylic acid Acid compound 1 part by mass (di-t-butylsalicylic acid compound)-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Paraffin wax 3 parts by mass (DSC endothermic peak 64.1 ° C, Mw / Mn = 1.1) The toner 5 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 5 thus obtained.

Example 6 • Binder resin a 40 parts by mass • Binder resin c 60 parts by mass • Magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass • Aluminum aromatic hydroxycarboxylic acid Acid compound 1 part by mass (di-t-butylsalicylic acid compound) ・ Iron complex of monoazo compound (chemical formula I) 2 parts by mass ・ Low molecular weight polypropylene 4 parts by mass (DSC endothermic peak 135.2 ° C., Mw / Mn = 7.6) The toner 6 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 6 thus obtained.

<Example 7>-Binder resin a 40 parts by mass-Binder resin c 60 parts by mass-Magnetic substance (shape: spherical, average particle size: 0.20 µm) 100 parts by mass-Aluminum aromatic hydroxycarboxylic acid Acid compound 2 parts by mass (di-t-butylsalicylic acid compound) Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C., Mw / Mn = 1.3) Toner 7 in the same manner as in Example 1 using the above materials. I got Table 3 shows the physical properties of Toner 7 thus obtained.

Example 8 Binder resin a 40 parts by mass Binder resin c 60 parts by mass Magnetic body (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Iron complex of monoazo compound ( Chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) Toner 8 was obtained in the same manner as in Example 1 using the above materials. Table 3 shows the physical properties of Toner 8 thus obtained.

<Example 9>-Binder resin a 40 parts by mass-Binder resin c 60 parts by mass-Magnetic material (shape: spherical, average particle size: 0.20 µm) 100 parts by mass-Chromium complex of monoazo compound ( Chemical formula II) 1 part by mass ・ Low molecular weight polypropylene 4 parts by mass (DSC endothermic peak: 135.2 ° C., Mw / Mn = 7.6) A toner 9 was obtained in the same manner as in Example 1 using the above materials. Table 3 shows the physical properties of Toner 9 thus obtained.

Example 10 Binder Resin g 20 parts by mass Binder Resin h 80 parts by mass Magnetic material (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Aromatic hydroxycarboxylic acid of aluminum Acid compound 5 parts by mass (di-t-butylsalicylic acid compound)-Iron complex of monoazo compound (chemical formula I) 2 parts by mass-Low molecular weight polyethylene 4 parts by mass (DSC endothermic peak 104.7 ° C, Mw / Mn = 1.3) The toner 10 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 10 thus obtained.

Comparative Example 1 50 parts by mass of binder resin b 50 parts by mass of binder resin 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) aromatic aromatic carboxyl of aluminum Acid compound 1 part by mass (di-t-butylsalicylic acid compound) ・ Iron complex of monoazo compound (chemical formula I) 2 parts by mass ・ Low molecular weight polypropylene 4 parts by mass (DSC endothermic peak 135.2 ° C., Mw / Mn = 7.6) The toner 11 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 11 thus obtained.

Comparative Example 2 Binder Resin b 20 parts by mass Binder Resin f 80 parts by mass Magnetic body (shape: spherical, average particle size: 0.20 μm) 100 parts by mass Aluminum aromatic hydroxycarboxylic acid Acid compound 3 parts by mass (di-t-butylsalicylic acid compound) ・ Iron complex of monoazo compound (chemical formula I) 2 parts by mass ・ Low molecular weight polypropylene 4 parts by mass (DSC endothermic peak 135.2 ° C., Mw / Mn = 7.6) The toner 12 was obtained by using the above materials in the same manner as in Example 1. Table 3 shows the physical properties of Toner 12 thus obtained.

Comparative Example 3 50 parts by mass of binder resin b 50 parts by mass of binder resin d 100 parts by mass of magnetic material (shape: spherical, average particle size: 0.20 μm) 100% by mass of chromium complex of monoazo compound ( Chemical formula II) 2 parts by mass-Low molecular weight polypropylene 4 parts by mass (DSC endothermic peak 135.2 ° C, Mw / Mn = 7.6) Toner 13 was obtained in the same manner as in Example 1 using the above materials. Table 3 shows the physical properties of Toner 13 thus obtained.

Table 2 shows the formulations of the toners used in Examples and Comparative Examples.

The evaluation method is described below.

[Fixing Property and Offset Test] The fixing temperature of the fixing device of the electromagnetic induction type shown in FIG. 1 can be set arbitrarily, and the process speed is set to 75 mm / sec.
c, an external fixing device having a pressure of 78 N and a nip of 3 mm was used. 5 in the temperature range of 110-220 ° C
The temperature was adjusted every ° C., an unfixed solid black image was fixed using 75 g / m ² paper at each temperature, and the obtained image was rubbed back and forth five times with silbon paper under a load of 4.9 kPa. The point at which the rate of decrease in image density before and after rubbing was 5% or less was defined as the fixing temperature. The lower the temperature, the better the low-temperature fixability of the toner.

With respect to the high-temperature offset resistance, the temperature at which the image was stained by the offset phenomenon in the fixing test was visually checked. The higher the temperature is, the more excellent the high-temperature offset resistance is.

Regarding the cold offset resistance, a halftone image was fixed in the same manner as in the above fixing test, and the temperature at which the image was stained by the offset phenomenon was visually observed. The lower this temperature is, the more excellent the cold offset resistance is.

[Development Test] A commercially available laser beam printer LBP-450 (A4, 12 sheets / min: manufactured by Canon Inc.) was modified to incorporate a fixing device of an electromagnetic induction type, and an A4 size image area ratio of 5% was obtained. A4 size A4 size transfer paper of 75 g / m ² at room temperature and normal humidity (23.5 ° C, 60
% RH), an image output test of 5000 sheets was performed, and the image density of the solid black image at the beginning and after the endurance was measured. The image density was measured by using a Macbeth densitometer (manufactured by Macbeth) to measure the reflection density using an SPI filter and calculating the average of five points.

[Preservation property] 10 g of the toner was placed in a 50 ml polycup, placed in a thermostat at 50 ° C. for 5 days, and the degree of blocking of the toner at that time was evaluated. ◎: Fluidity of toner does not change ○: Fluidity is reduced but recovers immediately △: Aggregate is present ×: Blocking

[Rotating Pressure Member Stain] Using a remodeling machine used in the endurance development test, three continuous prints of an original with an image area ratio of 5% on A4 size transfer paper of 75 g / m ² in a low temperature and low humidity environment. In the print mode of stopping for 10 minutes after,
An image output test was performed on 000 sheets. After the test, the degree of dirt on the rotary pressing member of the fixing device and whether or not dirt such as black spots appeared on the transfer paper were visually evaluated. ：: There is no dirt on the rotary pressing member. ○: Slight dirt is on the rotary pressing member, but no dirt is shown on the transfer paper. Δ: Slight dirt is shown on the transfer paper. X: Transfer paper. Terrible dirt on the whole

Table 4 summarizes the evaluation results.

[0193]

[Table 1]

[0194]

[Table 2]

[0195]

[Table 3]

[0196]

[Table 4]

[0197]

According to the present invention, the image forming method having the above-described structure is combined with a toner to provide a developing property,
It is possible to provide a toner and an image forming method which are excellent in storability, low-temperature fixing property, high-temperature offset resistance, and cold offset resistance, and exhibit particularly excellent performance in preventing contamination of a rotating pressure member.

[Brief description of the drawings]

FIG. 1 is a schematic configuration sectional view of a fixing device according to an embodiment of the present invention.

FIG. 2 is a schematic cross-sectional view of a fixing device according to an embodiment of the present invention.

FIG. 3 is a schematic sectional view of a fixing device according to an embodiment of the present invention.

[Description of Signs] 1 Rotary heating member (fixing roller) 2 Rotating pressing member (pressure roller) 3 Exciting coil (magnetic field generating means) 4 Core 5 Holder 6 Temperature sensor 7 Transport guide 8 Toner image 10 Separating claw 11 Heat generating layer 12 release layer 13 fixed image 14 hollow core metal 15 elastic layer 16 transfer material (recording material) N nip

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) G03G 9/08 331 346 (72) Inventor Hiroshi Yusa 3- 30-2 Shimomaruko, Ota-ku, Tokyo Canon Stocks In-house (72) Inventor Yuki Karaki 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H005 AA01 AA02 AA06 CA04 CA08 CA13 CA14 CA17 CA18 CA22 CA25 DA02 DA06 DA10 EA03 EA06 EA07 FA06 FB01 2H033 AA02 AA09 BA25 BA58 BB18 BE06

Claims (28)

[Claims] 1. A rotating heating member having at least (i) a magnetic field generating means, (ii) a heating layer which generates heat by electromagnetic induction and a release layer, and (iii) a rotating member forming a nip with the rotating heating member. A toner applied to an image forming method of forming a fixed image on a recording material by heating and fixing a toner image on the recording material while pressing the rotation heating member through the recording material with a pressing member; The toner comprises at least a binder resin, a colorant and a wax, and the binder resin comprises a mixture of a polyester resin and a hybrid resin having a vinyl polymer unit and a polyester unit. 2. The content of trivalent or higher polycarboxylic acids or their anhydrides in a THF-soluble component having a molecular weight of less than 10,000 of the toner is W1 (mol%), and T is a molecular weight of 10,000 or more.
When the content of the trivalent or higher polycarboxylic acid or its anhydride in the HF-soluble component is W2 (mol%), 0 ≦ W1 ≦ 25 and 0.1 ≦ W2 ≦ 30. The toner according to claim 1. 3. The content of trivalent or more polyvalent carboxylic acids or anhydrides thereof in a THF-soluble component having a molecular weight of less than 10,000 of the toner is W1 (mol%), and T is a molecular weight of 10,000 or more.
When the content of the trivalent or higher polyvalent carboxylic acid or its anhydride in the HF-soluble component is W2 (mol%), 0.5 ≦ W1 ≦ 20 and 1 ≦ W2 ≦ 25. The toner according to claim 1. 4. The toner according to claim 2, wherein W1 and W2 satisfy W2> W1. 5. The toner according to claim 1, wherein the toner has one main DSC endothermic peak at 60 to 120 ° C. 6. The GPC molecular weight distribution of the wax contained in the toner, wherein the ratio Mw / Mn of the number average molecular weight (Mn) to the weight average molecular weight (Mw) is 1.0 to 2.0. The toner according to claim 1. 7. The toner has a THF-insoluble content of 1%.
In the GPC molecular weight distribution of the THF-soluble component, the content (M1) of the component having a molecular weight of less than 10,000 is 40 to 70% by mass, and the content of the component having a molecular weight of 10,000 to 50,000 (M2). ) Is 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 (M3) is 2 to 25% by mass, and M1 ≧
7. A method according to claim 1, wherein M2> M3 is satisfied.
The toner according to any one of the above. 8. The toner according to claim 1, wherein the toner contains 0.1 to 10 parts by mass of a metal compound based on 100 parts by mass of the binder resin. 9. The toner according to claim 8, wherein the metal compound is an organometallic compound. 10. The toner according to claim 8, wherein the metal compound is an aromatic hydroxycarboxylic acid compound. 11. The toner according to claim 8, wherein the metal compound is an aromatic hydroxycarboxylic acid compound of aluminum. 12. The toner according to claim 8, wherein the metal compound is an iron complex of a monoazo compound. 13. The toner according to claim 8, wherein the metal compound is a mixture of an aromatic hydroxycarboxylic acid compound of aluminum and an iron complex of a monoazo compound. 14. The toner according to claim 1, wherein the toner contains 30 to 200 parts by mass of a magnetic material as the colorant based on 100 parts by mass of the binder resin. 15. An image forming method for forming a fixed image on a recording material by heating and fixing a toner image on a recording material by heating and pressing means, wherein the toner forming the toner image includes at least a binder resin, A colorant and a wax; wherein the binder resin comprises a polyester resin and a mixture of a hybrid resin having a vinyl polymer unit and a polyester unit; and the heating and pressurizing unit includes: (i) a magnetic field generating unit; (Ii) a rotary heating member having at least a heat generating layer and a release layer that generate heat by electromagnetic induction; and (iii) a rotary pressing member forming a nip with the rotary heating member via a recording material. An image forming method in which a toner image on the recording material is heated and fixed while pressing a member to form a fixed image on the recording material. 16. The THF-soluble component having a molecular weight of less than 10,000 in the toner has a content of trivalent or higher polyvalent carboxylic acid or an anhydride thereof of W1 (mol%) in a THF-soluble component having a molecular weight of 10,000 or more. The content of the trivalent or higher polyvalent carboxylic acid or its anhydride is represented by W2 (mol%), where 0 ≦ W1 ≦ 25 and 0.1 ≦ W2 ≦ 30. Image forming method. 17. The THF-soluble component having a molecular weight of less than 10,000 in the THF-soluble component has a content of trivalent or more polyvalent carboxylic acid or anhydride thereof of W1 (mol%) in the THF-soluble component having a molecular weight of 10,000 or more. The content of trivalent or higher polycarboxylic acids or their anhydrides is represented by W2 (mol%), wherein 0.5 ≦ W1 ≦ 20 and 1 ≦ W2 ≦ 25. Image forming method. 18. The image forming method according to claim 16, wherein W1 and W2 satisfy W2> W1. 19. The image forming method according to claim 15, wherein said toner has one DSC endothermic main peak at least at 60 to 120 ° C. 20. GPC of wax contained in the toner
20. The image forming apparatus according to claim 15, wherein in a molecular weight distribution, a ratio Mw / Mn of a number average molecular weight (Mn) to a weight average molecular weight (Mw) is 1.0 to 2.0. Method. 21. The toner has a THF-insoluble content of 1 to 50% by mass and a content (M1) of a component having a molecular weight of less than 10,000 in a molecular weight distribution of GPC of a THF-soluble component.
Is 40 to 70% by mass, the content (M2) of the component having a molecular weight of 10,000 to 50,000 is 25 to 50% by mass, the content of the component having a molecular weight exceeding 50,000 (M3) is 2 to 25% by mass, and Ml
21. The image forming method according to claim 15, wherein the following condition is satisfied: M2> M3. 22. The image forming method according to claim 15, wherein the toner contains 0.1 to 10 parts by mass of a metal compound based on 100 parts by mass of the binder resin. 23. The image forming method according to claim 22, wherein the metal compound is an organometallic compound. 24. The image forming method according to claim 22, wherein the metal compound is an aromatic hydroxycarboxylic acid compound. 25. The method according to claim 22, wherein the metal compound is an aromatic hydroxycarboxylic acid compound of aluminum. 26. The image forming method according to claim 22, wherein the metal compound is an iron complex of a monoazo compound. 27. The image forming method according to claim 22, wherein the metal compound is a mixture of an aromatic hydroxycarboxylic acid compound of aluminum and an iron complex of a monoazo compound. 28. The image forming apparatus according to claim 15, wherein the toner contains 30 to 200 parts by mass of a magnetic material as the colorant based on 100 parts by mass of the binder resin. Method.