JP2001337481A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a toner which is excellent in the balance of fixing property and offset resistance, which can form an image of high quality with little fog in any environment for a long time, which does not cause deposition or melt sticking of the toner in each member in a device or does not cause ejection of toner aggregates due to melting on a transfer material, and which is highly durable. SOLUTION: In the toner containing at least a binder resin and wax, the DSC curve measured by a differential scanning calorimeter indicates that the lowest on-set temperature of the endothermic peak is >=60 deg.C at the endothermic peak in temperature rise of the DSC curve and that the temperature region with >=1/10 heat flow of the maximum endothermic peak in the temperature range from 80 to 150 deg.C is 50 to 70 degrees. The wax is incorporated by 0.5 to 20 parts by mass to 100 parts by mass of the binder resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, a magnetic recording method, a toner jet method or the like, and relates to a fixing system for heating and fixing a formed visible image to a recording material. Related to the toner to be used.

[0002]

2. Description of the Related Art Conventionally, electrophotography has been disclosed in U.S. Pat. No. 2,297,691, Japanese Patent Publication No. 42-23910.
Many methods are known as described in Japanese Patent Application Laid-Open Publication No. Sho. 43-24748, and the like. Generally, a photoconductive substance is used to form an electric latent image on a photoreceptor by various means. After forming the latent image, the latent image is developed with a toner to form a visible image.If necessary, the toner image is transferred to a transfer material such as paper, and then the toner image is fixed on the transfer material by heat or pressure. To obtain a copy. Further, the toner particles remaining on the photoconductor without being transferred onto the transfer material are removed from the photoconductor by a cleaning process, and the above-described process is repeated.

In recent years, devices using electrophotography have begun to be used not only for conventional copiers but also for printers and facsimile machines for computer output. For example, as for printer devices, LBP printers or LED printers have become mainstream in the market these days, and the direction of technology is as follows.
Conventionally, 240, 300 dpi was replaced with 400, 60
0, 800, and even higher resolutions of 1200, 2400 dpi. Accordingly, a higher definition has also been required for the developing system. With the advancement of computers, the output images are required to have higher definition and higher image quality.Moreover, with the spread of personal computers, maintenance can be performed more easily and at the same time, higher As the reliability has been strictly pursued, the performance required of the printer has become higher, and a better machine cannot be realized unless the performance of the toner can be improved.

For example, the most important performance required of toner in digital printers and copying of high-resolution images is fixing performance. Regarding the fixing process,
Although various methods and devices have been developed, the most common method at present is a pressure heating method using a hot roller. The pressure heating method using a heating roller performs fixing by allowing the toner image surface of a sheet to be fixed to pass through the surface of a heat roller having a surface formed of a material having a releasable property with respect to the toner while contacting the surface under pressure. It is. In 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 heat efficiency at the time of fusing the toner image onto the sheet to be fixed is extremely good, and the fixing can be performed quickly. And is very effective in high speed electrophotographic copiers.

Conventionally, for the purpose of preventing toner from adhering to the surface of a fixing roller, for example, the roller surface is formed of a material having excellent releasability from the toner, such as silicone rubber or a fluorine-based resin, and an anti-offset agent is further formed on the surface. Further, in order to prevent the roller surface from being fatigued, the roller surface is coated with a thin film of a liquid having good releasability such as silicone oil. However, although this method is effective in preventing the offset of the toner, it has a problem that the fixing device becomes complicated because a device for supplying the liquid for preventing the offset is required.

Therefore, a release agent such as low-molecular-weight polyethylene or low-molecular-weight polypropylene is added to the toner from the viewpoint of supplying the anti-offset liquid during heating from the toner instead of using a silicone oil supply device. A method has been proposed. If a large amount of such an additive is added in order to obtain a sufficient effect, filming on the photoreceptor or contamination of the surface of the toner carrier such as a carrier or a sleeve will deteriorate the image and pose a practical problem. Therefore, a small amount of release agent is added to the toner to the extent that the image is not deteriorated, and a small amount of release oil is supplied or the toner that has been offset is cleaned by a roll-up type device using a member such as a web. It has been used together.

However, in view of recent demands for miniaturization, weight reduction, and high reliability, it is preferable to remove even these auxiliary devices.

It is known that a wax is contained in a toner as a release agent. For example, JP-A-52-330
No. 4, JP-A-52-3305, JP-A-57-3305.
A technique such as 52574 is disclosed.

These waxes are used to improve the offset resistance of the toner at low and high temperatures. However, while these properties are improved, blocking resistance is deteriorated and developability is deteriorated.

A toner containing two or more types of wax in order to exert the effect of adding wax from a low temperature region to a high temperature region is disclosed in, for example, Japanese Patent Publication No.
JP 3305, JP-A-58-215659, JP-A-62-100775, JP-A-4-12467
6, JP-A-4-299357, JP-A-4-299357
Techniques such as Japanese Patent No. 329553 and Japanese Patent Application Laid-Open No. 5-197192 are disclosed.

However, none of these toners satisfies all of the performances, causing some problems. For example, high-temperature offset resistance and developability are excellent, but low-temperature fixability is just one step away, or low-temperature offset resistance and low-temperature fixability are excellent, but blocking resistance is slightly inferior and developability decreases. And the offset resistance at low and high temperatures is not compatible.Blotch occurs due to uneven toner coating due to free wax components, causing image defects and fogging on the image. Was happening.

The waxes contained in these toners simply contained a wax component in a wide or uneven temperature range with respect to an endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter. Many of the components were insufficient to satisfy the above-mentioned performance, or deteriorated or had little effect.

Further, for the purpose of obtaining a wide range of low-temperature fixability and high-temperature offset resistance, Japanese Patent Application Laid-Open No. 5-346 is disclosed.
684 and JP-A-7-175257 propose the use of a wax having a half-value width of the maximum endothermic peak of 10 ° C. or more.

However, these documents do not describe the effect on dispersion of the wax component due to the interaction with other components of the toner or the effect due to the change in the crystal state.
No solution is disclosed for toner contamination / adhesion in apparatuses such as copiers and printers.

Further, Japanese Patent Application Laid-Open Nos. 8-278657, 8-334919, 8-334920
In order to obtain a toner having excellent low-temperature fixability and anti-offset properties, Japanese Patent Application Laid-Open Publication No. H11-216, and the like propose that the toner contains two types of wax components. Also, Japanese Patent Application Laid-Open No. 7-281
No. 478 discloses a polypropylene-based resin for lowering the minimum fixing temperature and increasing the hot offset temperature.
It has been proposed to use an acid-modified polyethylene resin as a release agent for toner. Also, JP-A-8-1
No. 66686 proposes a toner containing a polyester resin having a specific monomer constitution and two kinds of offset preventing agents having an acid value and different softening points.

However, although toners using these release agents have a wide range of low-temperature fixability and high-temperature offset resistance, it is difficult to uniformly disperse each wax component in the toner. In some cases, fog was increased and developability was deteriorated due to poor dispersion.

Further, there is no means for solving toner contamination / adhesion to fixing roller (heating roller, pressure roller, etc.), paper feeding roller, roller member, etc. in a copying machine, a printer or the like. Absent.

In particular, in intermittent copying / printing-out in a low-temperature environment, toner and paper dust tend to accumulate due to the cooling of the pressure roller of the fixing device, and the toner and paper powder are accumulated when the fixing device is heated. Discharge of the toner lump at a time causes a problem that the transfer member such as paper is stained.

[0019]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a toner having an excellent balance between fixing property and non-offset property, and to provide a high-quality image with less fog in any environment for a long period of time. To provide,
A highly durable toner that does not cause toner adhesion or fusing to each member in a device such as a copying machine or a printer, and does not discharge a fused toner mass onto a transfer material. It is to propose.

[0020]

According to the present invention, in a toner containing at least a binder resin and a wax, the lowest endothermic peak in the endothermic peak at the time of temperature rise of a DSC curve measured by a differential scanning calorimeter is provided. Set temperature is 6
The total of the temperature portions which are 0 ° C. or higher and become 1/10 peak intensity or more of the maximum endothermic peak in the temperature region of 80 to 150 ° C. is 50 to 70 deg, and the content of the wax is 100 mass of the binder resin. And 0.5 to 20 parts by mass of the toner.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The toner of the present invention has a minimum onset temperature of an endothermic peak measured by DSC of 60 ° C. or more, and has a peak intensity of 1/10 peak intensity or more in a temperature range of 80 to 150 ° C. The total temperature part is 50 to 70 deg, and the wax is 0.5 to 20 parts by mass based on 100 parts by mass of the polymer component. By having these characteristic endothermic peaks, it is possible to contribute to stable electrophotographic properties and low-temperature melting of toner, and to achieve high offset resistance at high temperatures, and in any environment. Also, the releasability of the fixing device from the heating roller and the pressure roller was remarkably improved, and further, the adhesion and fusion of the toner to the copying machine / printer member could be highly prevented.

That is, since the minimum onset temperature is 60 ° C. or higher, the blocking resistance of the toner can be secured irrespective of the use environment, and the heat absorption can be wide in a wide temperature range. , Because it simultaneously satisfies offset resistance and low-temperature fixability and has release properties over a wide temperature range, the internal temperature of the machine is high, such as during continuous double-sided printing in a high-temperature, high-humidity environment. In a state where the internal components are cooled, such as during cold start in a low-temperature, low-humidity environment, even when the
It has become possible to prevent toner adhesion and fusion to each member of a device such as a printer to a high degree.

The endothermic peak of the toner measured in the present invention will be described.

According to the present invention, the temperature range of the minimum onset temperature of the endothermic peak measured by DSC of the toner of 60 ° C. or more and the intensity of 1/10 or more of the maximum endothermic peak in the temperature range of 80 to 150 ° C. 50 in total
~ 70 deg.

Further, the total of the temperature portions where the endothermic peak measured by DSC of the toner becomes 以上 peak intensity of the maximum endothermic peak in the temperature range of 80 to 150 ° C. is 30 to 70 deg. And

Based on the characteristics of the endothermic peak of the toner as described above, the effect exhibited is considered as follows.

That is, when a machine such as a copying machine or a printer is cooled (for example, at the time of a cold start after being left in a low-temperature environment), a pressure roller of a fixing device in the machine, a paper feeding roller member, and the like are used. Is also a low temperature. Also,
Conversely, when the inside of the machine is heated, such as during continuous printout in a high-temperature environment, the temperature of each member is high, especially when the speed of the machine is increased or when both-side printing is performed.

Since the toner is used in such a wide temperature range, in order to maintain a state in which toner contamination does not occur at this time, toner performance having a high degree of releasability in a wide temperature range is required. That is, the lowest temperature at which the toner may be present in a molten state at the time of fixing.
It is important to have an endothermic characteristic in a range from 0 ° C. to 150 ° C., which is a temperature at which the temperature is increased by the heat given during fixing. It can be achieved by having endothermic heat derived from a wax as a release agent in a wide temperature range over a certain level or more.

In this state, it is important that heat is absorbed widely throughout the entire toner. When the heat absorption is 1/10 or more of the heat absorption peak, the toner has the ability to influence the releasability of the whole toner. In addition, if the heat absorption amount is 1/2 or more, the mold releasability can be sufficiently exhibited.

The endothermic peak of the toner in the temperature range of 80 to 150 ° C. is determined by the type of wax used and the state of dispersion in the toner. In other words, the type of wax
The temperature of the main peak is determined by the composition, and the size of the crystalline state due to the dispersion in the toner and the interaction with other toner composition components such as the resin component as shown in FIGS. The characteristic is the extent of the peak spread.

This endothermic peak may be achieved by one peak as shown in FIG. 1 or by a plurality of peaks as shown in FIG.

As a means for achieving such an endothermic peak, a wax having an endotherm in a wide temperature range may be used. At this time, the wax is widely dispersed in the toner,
It must be uniformly dispersed. However, it is not preferable that they are compatible with each other from the viewpoint of releasability, and it is preferable that the particles are uniformly dispersed with a certain domain diameter.

In order to control the dispersibility, it is preferable to modify the wax with a substance having an interaction with the resin (for example, a vinyl compound, a carboxylic acid compound, a hydroxyl group-containing compound, etc.).

Further, it may be achieved by using a plurality of waxes in combination, but in this case, mutual dispersibility must be considered. Examples of preferred combinations include polypropylene, modified waxes thereof (acid-modified, alcohol-modified, styrene-modified, etc.), polyethylene, modified waxes thereof (acid-modified, alcohol-modified, styrene-modified, etc.), ethylene-propylene copolymer, A combination selected from the modified waxes (acid-modified, alcohol-modified, styrene-modified, etc.), paraffin wax, and Fischer-Tropsch wax is preferably used.

The minimum onset temperature of the endothermic peak measured by DSC of the toner must be 60 ° C. or higher. If the temperature is lower than 60 ° C., the blocking resistance is greatly affected, which is not preferable in terms of storage stability.

The endothermic peak temperature of the toner was measured using a differential thermal analyzer (DSC measuring apparatus): DSC-7 (manufactured by PerkinElmer) under the following conditions. Sample: 5 to 20 mg, preferably 10 mg Measurement method: A sample is placed in an aluminum pan, and an empty aluminum pan is used as a reference. Temperature curve: Temperature rise I (20 ° C. → 180 ° C., temperature rise rate 10 ° C./min.) Temperature fall I (180 ° C. → 10 ° C., temperature fall rate 10 ° C./min.) Temperature rise II (10 ° C. → 180 ° C., temperature rise (Temperature rate: 10 ° C./min.) An endothermic peak measured by heating II is used.

Next, the wax component suitably used in the present invention will be described.

The wax used in the present invention is obtained by thermally degrading a low molecular weight alkylene polymer or a high molecular weight alkylene polymer obtained by radical polymerization of alkylene under high pressure or polymerization under low pressure with a Ziegler catalyst, metallocene catalyst or the like. Waxes such as alkylene polymers and hydrocarbons obtained by hydrogenation of hydrocarbons obtained from the synthesis gas consisting of carbon monoxide and hydrogen by the Age method, or synthetic hydrocarbons obtained by hydrogenating these are used, and an antioxidant is added. May be. Further, those obtained by performing separation of hydrocarbon wax by use of a press sweating method, a solvent method, vacuum distillation, or a separation crystallization method are preferably used. The hydrocarbon as a base is synthesized by a reaction between carbon monoxide and hydrogen using a metal oxide-based catalyst (often a multi-component system of two or more types), for example, a zincol method, a hydrochol method (fluidized catalyst bed). Or an alkylene such as ethylene obtained by polymerizing with a Ziegler catalyst or a metallocene catalyst. The hydrocarbon is preferred because it is a straight-chain hydrocarbon having a small number of branches and a small saturation and a long saturation.

The wax used in the present invention preferably has an acid value in the range of 1 to 70 mgKOH / g. If the acid value is less than 1 mgKOH / g, the effect of the acid group cannot be obtained, the dispersion in the resin becomes insufficient, and fogging tends to occur. On the other hand, if the acid value exceeds 70 mgKOH / g, it is liable to be affected by environmental humidity, and it is difficult to obtain stable charging performance, which is not preferable. Furthermore, since the dispersion diameter in the resin becomes finer, it becomes difficult to obtain preferable releasability and offset resistance.

The acid value of the wax in the present invention was measured by the following measuring method.

<Dispensing of wax> Toner sample 0.5
Weighing about 1.0 g, and a cylindrical filter paper (for example, N
o. 86R) and 200 ml of toluene as a solvent
The mixture is subjected to Soxhlet extraction for 20 hours, and the soluble components extracted by the solvent are evaporated, followed by vacuum drying at 100 ° C. for several hours. Chloroform 20 is added to the obtained extract.
ml, and allowed to stand for 1 hour.
m and filtered to obtain a wax component.

<Measurement of acid value> ・ Instrument and apparatus Direct reading balance Erlenmeyer flask (200 ml) Measuring cylinder (100 ml) Microburet (10 ml) Electric heater ・ Reagent Xylene Dioxane 1 mol / l Potassium hydroxide standard methanol solution 1% phenol cover Rain solution (indicator)-Measurement method 1 to 1.5 g of a wax is precisely weighed in an Erlenmeyer flask, 20 ml of xylene is added thereto, and the mixture is heated and dissolved. After dissolution, 20 ml of dioxane is added, and titration is performed as soon as possible with a 1 mol / l standard potassium hydroxide methanol solution using a 1% phenolphthalein solution as an indicator while the solution does not become cloudy or hazy. Perform a blank test at the same time. Calculation formula Acid value = [5.61 × (AB) × f] / S where A: 1 mol / l of potassium hydroxide standard methanol solution required for this test B: 1 mol required for blank test / Ml Number of ml of potassium hydroxide standard methanol solution f: Factor of 1 mol / l potassium hydroxide standard methanol solution S: Sample (g)

A method for obtaining a wax having an acid value is as follows.
A method of adding an acid component to the wax component and a method of performing a graft reaction are preferably used. Acid monomers used for the modification include a carboxyl group, a carboxylic anhydride group,
Those containing at least one or more carboxylic acid groups are most preferred. For example, acrylic acid such as acrylic acid, methacrylic acid, α-ethylacrylic acid, crotonic acid and its α- or β-alkyl derivatives, fumaric acid, maleic acid, unsaturated dicarboxylic acids such as citraconic acid and its monoester derivatives or Maleic anhydride, etc.
A wax having a desired acid value is obtained by subjecting these monomers to a modification reaction alone or as a mixture.

Examples of the carboxylic acid compound to be added or grafted include acrylic acid, methacrylic acid, maleic acid, phthalic acid, itaconic acid, and mixtures thereof. Examples of the acid anhydride include maleic anhydride and itaconic anhydride. Acid, citraconic anhydride, allyl succinic anhydride,
Nadic anhydride and mixtures thereof.

The peroxide catalyst used for the addition or graft reaction includes benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide,
t-butylcumyl peroxide, dicumyl peroxide, t-butylperoxybenzoate, and 1,
1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane.

More preferably, an acid monomer selected from at least one of maleic acid, maleic acid half ester, and maleic anhydride in relation to constituent monomers preferably contained in a resin polymer component described later. Is modified by

The wax preferably used in the present invention has a melt viscosity at 160 ° C. of 50 to 20.
It is good to be in the range of 00 mPa · s.

The melt viscosity at 160 ° C. is 50 mPa ·
If the viscosity is less than s, the viscosity is too low to deteriorate the dispersion in the toner, and the offset resistance and the releasability are adversely affected. When it exceeds 2000 mPa · s, it is not preferable because it adversely affects the fixing property.

The viscosity in the present invention was measured by the following method.

Using a Brookfield-type rotational viscometer, the beaker containing the sample was immersed in a thermostat maintained at 160 ° C., and the viscosity was measured.

In the present invention, the wax component is used in an amount of 0.5 to 20 parts by mass based on 100 parts by mass of the binder resin. Preferably it is 1 to 15 parts by mass, more preferably 2 to 10 parts by mass.

If the amount is less than 0.5 part by mass, it is difficult to obtain the effect of adding the wax. If the amount is more than 20 parts by mass, the amount of free wax components increases, so that fog increases and it becomes difficult to control charging. It is difficult to obtain an appropriate image density.

The kind of the binder resin used in the present invention is, for example, a homopolymer of styrene such as polystyrene, poly-p-chlorostyrenestyrene, polyvinyltoluene and a substituted product thereof; styrene-p-chlorostyrene copolymer. Polymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-
Styrene such as vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer Copolymers: polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resin, epoxy resin , Xylene resin, polyvinyl butyral, terpene resin, coumarone indene resin, petroleum resin and the like can be used. Further, a crosslinked styrene resin is also a preferable binder resin.

Examples of comonomers for the styrene monomer of the styrene copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Such as dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. A monocarboxylic acid having a heavy bond or a substituted product thereof;
For example, dicarboxylic acids having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate and the like, and substituted products thereof; for example, vinyl esters such as vinyl chloride, vinyl acetate, vinyl benzoate and the like For example, ethylene-based olefins such as ethylene, propylene, butylene and the like; vinyl ketones such as vinyl methyl ketone and vinylhexyl ketone;
For example, vinyl monomers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; and the like, or a vinyl monomer such as vinyl monomers, may be used alone or in combination.

As the crosslinking agent, a compound having two or more polymerizable double bonds is mainly used, for example, an aromatic divinyl compound such as divinylbenzene, divinylnaphthalene or the like; for example, ethylene glycol diacrylate , Ethylene glycol dimethacrylate,
Carboxylic acid esters having two double bonds such as 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide and divinyl sulfone; and compounds having three or more vinyl groups; Can be used alone or as a mixture.

The polymer component used in the present invention does not substantially contain a THF-insoluble component, and has a molecular weight of at least 3 × 10 ^{3 to} 3 × 10 ^{4 in} a GPC (gel permeation chromatogram) of a THF-soluble component. It is preferable to have a main peak in the region and a subpeak or shoulder in the region having a molecular weight of 1 × 10 ^{5 to} 3 × 10 ⁶ .

The phrase "substantially free from THF insolubles" means specifically 5% by mass or less, preferably 3% by mass or less based on the resin composition.

The term “THF-insoluble component” in the present invention indicates the mass ratio of the polymer component (substantially crosslinked polymer) insoluble in the THF solvent in the resin composition in the toner. It can be used as a parameter indicating the degree of crosslinking of the contained resin composition. The THF insolubles are defined with the values measured as follows.

0.5 to 1.0 g of a toner sample is weighed.
(W₁g), cylindrical filter paper (for example, No. 86 made by Toyo Filter Paper)
R) and run through a Soxhlet extractor, where T
Extract with 200 ml of HF for 6 hours and extract with solvent
After evaporating the discharged soluble components, the
After vacuum drying for a time, the amount of the THF-soluble resin component is weighed (W
_Twog). Resin component such as magnetic substance or pigment in toner
Of the composition other than (W_Threeg). THF insolubles
Is obtained from the following equation.

THF insoluble matter (%) = [((W ₁ − (W ₂ +
W ₃ )) / (W ₁ −W ₃ )] × 100

When the content of the THF-insoluble component exceeds 5% by mass, not only the fixing property is deteriorated, but also the wax component used in the present invention is poorly dispersed in the toner, and the fog suppression is deteriorated. There is a risk that various toner contact members may be damaged, or adverse effects such as easy adhesion and fusion of the toner may occur.

The T of the polymer component in the toner composition of the present invention
The chromatogram of GPC measured by HF-soluble matter has a main peak at least in a region of a molecular weight of 3 × 10 ^{3 to} 3 × 10 ⁴ and a sub-peak or a sub-peak in a region of a molecular weight of 1 × 10 ^{5 to} 3 × 10 ^6. It is preferable to have a shoulder.

If the main peak of GPC of the polymer component is less than 3 × 10 ³ , the melt viscosity of the resin is too low to disperse the wax component of the present invention effectively, thereby obtaining preferable releasability. And a molecular weight of 3
When the ratio is more than × 10 ⁴ , not only adversely affects the fixability, but also increases the load in kneading during the production of the toner, and lowers the productivity. At the same time, the dispersion of each component of the toner raw material becomes non-uniform, and the stable charging performance is obtained. Is difficult to obtain.

Further, by having a sub-peak or a shoulder in the molecular weight region of 1 × 10 ^{5 to} 3 × 10 ⁶ , it is possible to appropriately adjust the high-temperature offset resistance and further adjust the melt viscosity and viscoelasticity of the whole toner. This makes it possible to appropriately adjust the dispersion of other raw materials in the toner.

In the present invention, the molecular weight distribution (GPC) of the toner composition is measured under the following conditions. Apparatus: GPC-150C (manufactured by Waters) Column: KF801 to 7 (manufactured by Shodex) Temperature: 40 ° C Solvent: THF (tetrahydrofuran) Flow rate: 1.0 ml / min. Sample: 0.1 ml of a sample having a concentration of 0.05 to 0.6% by mass
Injection

Under the above conditions, the molecular weight of the sample was calculated using a monodisperse polystyrene standard sample (A-
500, A-1000, A-2500, A-5000,
F-1, F-2, F-4, F-10, F-20, F-4
0, F-80, F-128, F-288, F-450,
Use 10 or more points in combination, such as F-850).

The binder resin used in the present invention preferably has an acid value of 0.5 to 50 mgKOH / g.
This is because the wax component used in the present invention can be effectively dispersed, the charging performance can be stabilized, the releasability of the toner can be improved, and adhesion and fusion can be prevented.

When the acid value is less than 0.5 mgKOH / g, it is difficult to obtain this effect. When the acid value exceeds 50 mgKOH / g, it is liable to be affected by environmental humidity.

As the binder resin used for obtaining the above acid value, a polymer containing at least one of a carboxyl group, a carboxylic acid anhydride group and a carboxylic acid group is most preferred. For example, acrylic acid, methacrylic acid,
There are acrylic acid such as α-ethylacrylic acid and crotonic acid and α- or β-alkyl derivatives thereof; fumaric acid, maleic acid, unsaturated dicarboxylic acids such as citraconic acid and monoester derivatives thereof, and maleic anhydride. The desired polymer is obtained by copolymerizing these monomers alone or in combination with other monomers.

Among these, particularly preferred monomer components include maleic acid, maleic acid half ester and maleic anhydride. This is because maleic acid has a carboxyl group adjacent to it, which more efficiently derives the effect of the acid group, increases affinity with transfer materials such as paper, and improves compatibility with acid-modified wax. This is because it is excellent.

The measurement of the acid value of the binder resin is as follows.

Measurement of Acid Value 1) A crushed sample of 0.1 to 0.2 g is precisely weighed, and its weight is defined as W (g). 2) The sample is placed in a 20 cc Erlenmeyer flask, and 10 cc of a mixed solution of toluene / ethanol (2: 1) is added and dissolved. 3) Add a few drops of phenolphthalein alcohol solution as indicator. 4) Using an alcohol solution of 1 mol / l KOH, titrate the solution in the flask with a burette. The amount of the KOH solution at this time is defined as S (ml). At the same time, a blank test is performed, and the amount of the KOH solution at this time is defined as B (ml). 5) Calculate the acid value by the following equation.

Acid value = (S−B) × f × 5.61 / W
(F: KOH factor)

The toner of the present invention preferably uses an organometallic compound as a charge control agent. In particular, a toner containing an organic compound rich in vaporization and sublimation as a ligand or counter ion is useful. As such a metal complex, a metal complex type monoazo compound is preferably used from the viewpoint of chargeability. Examples of metal complex type monoazo compounds include JP-B Nos. 41-20153, 42-27596 and 44.
And metal complexes of monoazo dyes described in JP-A-6397 and JP-A-45-26478. Especially dispersibility
From the viewpoint of chargeability and the like, a metal complex-type monoazo compound represented by the following general formula (I) is preferable, and among them, a metal complex-type monoazo iron compound having a central metal of iron is preferable. More preferably, a monoazo iron complex represented by the following general formula (II) is used.

[0075]

Embedded image

[0076]

Embedded image

The content of the metal complex type monoazo compound is preferably from 0.5 to 5 parts by mass, more preferably from 0.2 to 3 parts by mass, per 100 parts by mass of the toner binder resin. If the content of the metal complex type monoazo compound is too large, the fluidity of the toner deteriorates and fogging easily occurs, while if it is too small, it is difficult to obtain a sufficient charge amount.

The toner of the present invention has a magnetic material containing a magnetic material.
It is preferably used as a neutral toner. Can be used
Magnetic materials include iron, cobalt, nickel, copper, mag
Elements such as nesium, manganese, aluminum and silicon
And the like. These magnetic particles are nitrogen
BET specific surface area by adsorption method is preferably 1 to 20 m ^Two
/ G, especially 2.5 to 12 m^Two/ G, and Mohs hardness of 5
To 7 magnetic powders are preferred. The shape of the magnetic material is eight
Body, hexahedron, sphere, needle, scale, etc., but 8
Those having low anisotropy such as a body, a hexahedron, and a sphere are preferable.
Those having an isotropic shape, as in the present invention, a binder resin
・ Also achieves good dispersion for wax.
Because it can. 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, and more preferably 0.1 to 0.4 μm.

The magnetic material is preferably added in an amount of 60 to 200 parts by mass based on 100 parts by mass of the toner binder resin.
Particularly preferably, it is 70 to 150 parts by mass. If the amount is less than 60 parts by mass, the toner transportability is insufficient, and the toner layer on the toner carrier becomes uneven, which tends to cause image unevenness. It was easy to occur. On the other hand, when the amount exceeds 200 parts by mass, the toner cannot be sufficiently charged, so that the image density tends to decrease.

The toner of the present invention has environmental stability,
In order to improve charge stability, developability, fluidity and storage stability, it is preferable that inorganic fine powder or hydrophobic inorganic fine powder is mixed. For example, fine silica powder, fine titanium oxide powder, or a hydrophobized product thereof may be used. They are preferably used alone or in combination.

As the silica fine powder, there can be used both a so-called dry method produced by vapor phase oxidation of a silicon halide or a so-called fumed silica, and a so-called wet silica produced from water glass or the like. There are few silanol groups on the surface and inside,
a ₂ O, towards less dry silica with production residue SO ₃ ^2-like. In the case of fumed silica, it is also possible to obtain a composite fine powder of silica and another metal oxide by using another metal halide such as aluminum chloride and titanium chloride together with a silicon halide in the production process. They are also included.

Further, the silica fine powder is preferably subjected to a hydrophobic treatment. The hydrophobization treatment is applied by chemically treating with an organic silicon compound or the like which reacts or physically adsorbs with the fine silica powder. As a preferred method, after treating the dry silica fine powder generated by the vapor phase oxidation of the silicon halide compound with the silane compound,
Alternatively, a method of treating with a silane compound and at the same time with an organosilicon compound such as silicone oil may be used.

Examples of the silane compound used in the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyldichloro. Silane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane , Dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-di Vinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and containing from 2 to 12 siloxane units per molecule, with the terminal units containing up to one silicon-bonded hydroxyl group each Dimethylpolysiloxane and the like.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils have a viscosity of 30 to 1000 mm ² / s at 25 ° C., for example, dimethyl silicone oil, methylphenyl silicone oil, α-methylstyrene-modified silicone oil, chlorophenyl silicone oil, fluorine-modified silicone oil And the like are particularly preferred.

As a method of treating the silicone oil, for example, silica fine powder treated with a silane compound and silicone oil may be directly mixed using a mixer such as a Henschel mixer, or silica fine powder serving as a base may be used. A method of spraying silicone oil on the body may be used. Alternatively, a method of dissolving or dispersing a silicone oil in an appropriate solvent, adding a silica fine powder, mixing and removing the solvent may be used.

An external additive other than silica fine powder or titanium oxide fine powder may be added to the toner of the present invention, if necessary.

For example, a charging auxiliary, a conductivity-imparting agent, a fluidity-imparting agent, an anti-caking agent, a release agent for fixing with a hot roll,
Examples thereof include resin fine particles and inorganic fine particles that function as a lubricant, an abrasive, and the like.

For example, lubricants such as Teflon (registered trademark), zinc stearate, and polyvinylidene fluoride are preferable, and polyvinylidene fluoride is particularly preferable. Or cerium oxide, silicon carbide, abrasives such as strontium titanate,
Among them, strontium titanate is preferable. Or, for example, a fluidity imparting agent such as titanium oxide and aluminum oxide,
Among them, a hydrophobic substance is particularly preferable. An anti-caking agent or a conductivity-imparting agent such as, for example, carbon black, zinc oxide, antimony oxide, or tin oxide, or white and black fine particles of opposite polarity can be used in a small amount as a developability improver.

The fine resin particles, inorganic fine particles or hydrophobic inorganic fine particles mixed with the toner are used in an amount of 0.1 to 5 parts by mass (preferably 0.1 to 3 parts by mass) per 100 parts by mass of the toner.
Parts by mass).

The toner of the present invention is obtained by sufficiently mixing the toner constituting materials with a mixer such as a ball mill, and then melting, kneading and kneading using a hot kneader such as a heating roll, kneader or extruder, and cooling and solidifying. It can be produced by post-milling and strict classification.

For example, as a mixer, a Henschel mixer (manufactured by Mitsui Mining Co., Ltd.); a super mixer (manufactured by Kawata Corporation); a ribocorn (manufactured by Okawara Seisakusho); 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 Decks (manufactured by Mitsui Mining Co., Ltd.); MS type kneader, kneader router (manufactured by Moriyama Seisakusho); Banbury mixer (manufactured by Kobe) And a pulverizer such as a counter jet mill, a micron jet, an inomizer (manufactured by Hosokawa Micron); an IDS-type mill, a PJM jet pulverizer (manufactured by Nippon Pneumatic) and a cross jet mill (Kurimoto Tekko) 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, Turboplex (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 device used for sifting coarse particles and the like include Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resonasive, Gyro Shifter (Tokuju Kogyo Co., Ltd.) ), Vibrasonic System (Dal Made emissions Co., 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.

[0092]

EXAMPLES The present invention will be described below with reference to specific examples, but the present invention is not limited to these examples.

Example 1 300 parts by mass of xylene was charged into a four-necked flask, and the inside of the vessel was sufficiently purged with nitrogen while stirring, and then heated to reflux.

Under reflux, a mixture of 68 parts by mass of styrene, 23 parts by mass of n-butyl acrylate, 9 parts by mass of monobutyl maleate and 1.5 parts by mass of di-tert-butyl peroxide was added for 4 hours. After the addition, the mixture was kept for 2 hours to complete the polymerization, thereby obtaining a low molecular weight polymer (L-1) solution. A part of the polymer solution was sampled, dried under reduced pressure, and the obtained low molecular weight polymer (L-1) was analyzed. As a result, Mw = 14000 and PMw = 1500.
0, Mw / Mn = 2.7, Tg = 61 ° C.

After 180 parts by weight of degassed water and 20 parts by weight of a 2% by weight aqueous solution of polyvinyl alcohol were charged into a four-necked flask, 70 parts by weight of styrene, 25 parts by weight of n-butyl acrylate, and 5 parts by weight of monobutyl maleate were used. Parts, 0.003 parts by mass of divinylbenzene, and 2,2-bis (4,
4-di-tert-butylperoxycyclohexyl)
A mixed solution of 0.1 parts by mass of a solution of propane (having a half-life of 10 hours and a temperature of 92 ° C.) was added and stirred to form a suspension.

After sufficiently replacing the inside of the flask with nitrogen, 8
The temperature was raised to 5 ° C. to initiate polymerization. After maintaining at the same temperature for 24 hours, 0.1 parts by mass of benzoyl peroxide (half-life 10 hours, temperature 92 ° C.) was added. Further, the polymerization was completed by holding for 12 hours. This was separated by filtration, washed with water and dried to obtain a high molecular weight polymer (H-1). When this was analyzed, Mw = 900,000, PMw = 830,000, Mw / Mn =
2.3, Tg = 61 ° C.

70 parts by mass of the low molecular weight polymer (L-1) and 30 parts by mass of the high molecular weight polymer (H-1) were mixed with refluxing xylene 1
After dissolving in 00 parts by mass, the organic solvent was distilled off, and the obtained resin was solidified by cooling and then pulverized to obtain a resin raw material for toner (R-1). The analytical values of (R-1) are shown in Table 1.

On the other hand, 40 parts by mass of low molecular weight polypropylene obtained by thermally degrading high molecular weight polypropylene and 60 parts by mass of low molecular weight polyethylene obtained by thermally degrading high molecular weight polyethylene were mixed with a xylene solvent. In a molten state. 400 g of this mixture
Then, 3.2 g of maleic anhydride was added thereto, and a 2% by mass xylene solution of di-t-butyl peroxide was added to 1
Of the wax (W
1) (acid value 3.5 mgKOH / g, melt viscosity at 160 ° C. 110 mPa · s) was prepared.

100 parts by mass of the resin raw material for the toner, 7 parts by mass of the wax (W1), 100 parts by mass of the spherical magnetic iron oxide, and 2 parts by mass of the metal monoazo compound represented by the following formula are uniformly mixed in advance. The mixture was melt-kneaded with a twin-screw extruder heated to 100 ° C. After cooling the kneaded product, it was coarsely pulverized by a hammer mill and further finely pulverized by a jet mill.
₄ obtained a classified powder of 6.9 μm.

[0100]

Embedded image

To 100 parts by mass of the classified powder, 1.2 parts by mass of hydrophobized silica fine powder was dry mixed and externally added to obtain a toner (T1).

The results of DSC analysis of this toner (T1) are shown in Table 2.

Example 2 Instead of the wax (W1), a wax (W2P) obtained by modifying a low molecular weight polypropylene obtained by thermally degrading a high molecular weight polypropylene with maleic anhydride (acid value of 4.0 mg KOH /
g, melt viscosity (160 ° C.) 120 mPa · s, softening point 1
39 ° C.) wax (W2E) obtained by modifying a low molecular weight polyethylene obtained by thermally degrading a high molecular weight polyethylene with maleic anhydride (acid value 3.5 m).
gKOH / g, melt viscosity (160 ° C) 220 mPa
s, softening point 115 ° C.) A toner (T2) was obtained in the same manner as in Example 1 except that the amount was changed to 4 parts by mass.

The results of DSC analysis of this toner (T2) are summarized in Table 2.

Example 3 Instead of wax (W1), 20 parts by mass of wax (W2P) and low molecular weight polyethylene 80 obtained by thermally degrading high molecular weight polyethylene
A wax (W3) obtained by mixing parts by mass in a xylene solvent in a heated and molten state (acid value 3.8 mgKOH / g, melt viscosity (160 ° C) 75 mPa · s, softening point 148 ° C)
Was changed to 7 parts by mass in the same manner as in Example 1 to obtain a toner (T3).

The results of DSC analysis of this toner (T3) are summarized in Table 2.

Example 4 As a low molecular weight polymer, 72 parts by mass of styrene, 19 parts by mass of n-butyl acrylate,
Styrene-butyl acrylate-acrylic acid copolymer (L-2) obtained by polymerizing 9 parts by mass of acrylic acid as a monomer and using 2 parts by mass of di-tert-butyl peroxide as an initiator (Mw = 9800, PMw = 105
(Mw / Mn = 2.9, Tg = 61 ° C.) is 75 parts by mass and the high molecular weight polymer (H-1) is 30 parts by mass.
(See Table 1 for analytical values), and wax (W1)
A toner (T4) was obtained in the same manner as in Example 1 except that the addition amount was changed to 11 parts by mass.

The results of DSC analysis of this toner (T4) are summarized in Table 2.

Example 5 Toner (T5) was prepared in the same manner as in Example 4 except that the wax component was changed to 0.6 parts by mass.
I got

Table 2 summarizes the results of DSC analysis of this toner (T5).

Example 6 A low molecular weight polymer (L-3) (Mw) obtained from 87 parts by mass of styrene, 13 parts by mass of n-butyl acrylate, and 2 parts by mass of di-tert-butyl peroxide = 9700, PMw = 9900, M
w / Mn = 2.6, Tg = 63 ° C.), 75 parts by mass, 70 parts by mass of styrene, 30 parts by mass of n-butyl acrylate, 0.003 parts by mass of divinylbenzene, and 2.2 parts by mass.
-Bis (4,4-di-tert-butylperoxycyclohexyl) propane (half-life 10 hours, temperature 97 ° C)
A resin raw material for toner (R-3) obtained by solution-blending 25 parts by mass of the high molecular weight polymer (H-2) obtained from 0.1 parts by mass (see Table 1 for analysis values) was used. A toner (T6) was obtained in the same manner as in Example 1 except for the above.

The results of DSC analysis of this toner (T6) are summarized in Table 2.

Example 7 Instead of the wax (W1), a wax obtained by blending 10 parts by weight of the wax (W2P) and 90 parts by weight of a wax obtained by modifying high-density polyethylene with maleic anhydride in a molten state. (W
4) (acid value 3.5 mg KOH / g, melt viscosity (160
C.) 2300 mPa · s, softening point 130 ° C.) was changed to 5 parts by mass in the same manner as in Example 1 to obtain a toner (T7).

Table 2 summarizes the results of the DSC analysis of this toner (T7).

Example 8 Instead of the wax (W1), 30 parts by mass of a low molecular weight polypropylene obtained by thermally degrading a high molecular weight polypropylene and a low molecular weight polypropylene obtained by thermally degrading a high molecular weight polyethylene. A wax (W5) obtained by mixing 70 parts by mass of a polyethylene having a molecular weight in a xylene solvent in a heated and melted state and modified with maleic anhydride (acid value 55 mgKOH / g, melt viscosity (16
A toner (T8) was obtained in the same manner as in Example 1 except that the wax component was set to 7 parts by mass (0 ° C.) 300 mPa · s and the softening point 105 ° C.).

Table 2 summarizes the results of the DSC analysis of this toner (T8).

Example 9 Instead of the wax (W1), 30 parts by mass of a low molecular weight polypropylene obtained by thermally degrading a high molecular weight polypropylene and a low molecular weight polypropylene obtained by thermally degrading a high molecular weight polyethylene. Wax (W6) obtained by mixing 70 parts by mass of high molecular weight polyethylene in a xylene solvent in a heated and molten state (acid value 0 mg KO)
H / g, melt viscosity (160 ° C.) 350 mPa · s, softening point 126 ° C.) A toner (T9) was obtained in the same manner as in Example 1 except that the wax component was changed to 7 parts by mass.

The results of DSC analysis of this toner (T9) are summarized in Table 2.

[Comparative Example 1] As a resin composition for a toner,
A styrene-butyl acrylate-divinylbenzene copolymer (R-4; peak molecular weight 30,000, acid value 0 mgKOH / g) containing 20% THF-insoluble matter, and a polypropylene-based wax having no acid value as a wax component ( Acid value 0mgKOH / g, melt viscosity (160 ° C) 200
mPa · s, softening point 150 ° C.) in the same manner as in Example 1 except that 4 parts by mass of the toner (T10) was obtained.

The results of DSC analysis of this toner (T10) are summarized in Table 2.

Comparative Example 2 Comparative Example 1 was repeated except that only 7 parts by mass of paraffin wax (acid value 0 mg KOH / g, melt viscosity (100 ° C.) 6 mPa · s, softening point 80 ° C.) was used as the wax component. In the same manner as in Example 1, the toner (T1
1) was obtained.

The results of analyzing the toner (T11) by DSC are shown in Table 2.

Comparative Example 3 A toner (T1) was prepared in the same manner as in Comparative Example 1, except that only 3 parts by mass of a wax component (rice value: 8 mg KOH / g) was used.
2) was obtained.

The results of analyzing the toner (T12) by DSC are shown in Table 2.

(Evaluation) Evaluation was performed using the toner thus obtained. The printout test, fixability and offset resistance test were performed as follows.

<Print-out test> High temperature and high humidity (32.
5 ℃ ・ 80% RH), low temperature and low humidity (15 ℃ ・ 10% RH)
Under each environment, commercially available laser beam printer L
BP-950 (manufactured by Canon) was modified into the following configuration, and a printout test was performed under the following conditions. When the toner was exhausted, a cutout was made in the toner container at the top of the cartridge, and the toner was replenished therefrom to continue the printout test. An electrostatic latent image is formed by setting the primary charge to -670 V, a gap (290 μm) is set without contact between the photosensitive drum and the toner layer on the toner carrier (magnet inclusion), and an AC bias (f = 2000 Hz; Vpp = 160).
0 V) and a DC bias (Vdc = -500 V). Printout speed is 50
It was remodeled so that the number of sheets (A4 horizontal) per minute. The obtained images were evaluated for the following items.

Image Density Evaluation was made by maintaining the image density at the end of printing out 20,000 sheets on ordinary plain paper for copying machines (75 g / m ² ).
The image density was measured by using a "Macbeth reflection densitometer" (manufactured by Macbeth) with respect to the printout image of a white background portion having a document density of 0.00.

The whiteness of the transfer paper measured by a fog reflectometer (manufactured by Tokyo Denshoku Co., Ltd.) and low temperature and low humidity (15 ° C., 10% RH)
Under the environment, fog was calculated from a comparison of the solid white color after 10,000 sheets of durability printing and the whiteness of the transfer paper after printing.

Fixability The fixability was evaluated by applying a load of 4.9 kPa, rubbing the fixed image with soft thin paper, and evaluating the reduction rate (%) of the image density before and after rubbing. ◎: less than 5% ○: 5% or more and less than 10% △: 10% or more and less than 20% ×: 20% or more

Offset Resistance The offset resistance was evaluated by printing out a sample image having an image area ratio of about 5% and evaluating the degree of stain on the image. Plain paper for copying machines (64 g / m ² ) was used as test paper. ◎: not generated ○: hardly generated △: slightly generated ×: remarkable dirt generated

Degree of toner adhesion to fixing device pressure roller / paper transport roller member Under a low temperature and low humidity (15 ° C., 10% RH) environment, plain paper for copier (80 g) containing 15% by mass of calcium carbonate as a filler.
/ M ² ) is intermittently imaged at a rate of 5,000 sheets per sheet per minute, and then the surface of the fixing device pressure roller and the paper transport roller member is visually observed to determine the degree of toner adhesion to the roller. Was evaluated. ◎: not generated ：: hardly generated △: toner adhered only to the end ×: toner adhered to entire surface

Further, after confirming that the fixing unit of the printer was sufficiently cooled, the paper was passed through and the stain caused by the toner mass discharged onto the paper was evaluated. ◎: Not generated ○: Dirt of 1 mm or less is 5 points or less Δ: Dirt of 1 mm or less is 10 points or less ×: Dirt of 1 mm or more is present

The toners of Examples 1 to 9 and Comparative Examples 1 to 3 were evaluated by the above evaluation methods. Table 3 shows the results
It is described collectively.

[0134]

[Table 1]

[0135]

[Table 2]

[0136]

[Table 3]

[0137]

As described above, the present invention is a toner which is excellent in balance between fixing property and non-offset property, and is capable of producing a high quality image with less fog for a long time under any environment. And provide
A highly durable toner that does not cause toner adhesion or fusing to each member in a device such as a copying machine or a printer, and does not discharge a fused toner mass onto a transfer material. Can be suggested.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram showing an endothermic peak derived from wax of a toner of the present invention.

FIG. 2 is an explanatory diagram showing an endothermic peak derived from wax of the toner of the present invention.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tsuneo Nakanishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Within Canon Inc. (72) Inventor Katsuhisa Yamazaki 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Kaori Hiratsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo F-term (reference) 2H005 AA01 AA06 CA02 CA13 CA14 CA16 DA06 EA03 EA06 EA07 EA10

Claims (8)

[Claims] 1. A toner containing at least a binder resin and a wax, wherein a minimum onset temperature of an endothermic peak in a DSC curve measured by a differential scanning calorimeter at a temperature rise is 60 ° C. or more. In a temperature range of 80 to 150 ° C., the sum of the temperature portions having a peak intensity of 1/10 or more of the maximum endothermic peak is 50 to 70 deg, and the content of the wax is 0 to 100 parts by mass of the binder resin. 0.5 to 20 parts by mass of the toner. 2. DS measured by a differential scanning calorimeter
In the endothermic peak at the time of temperature rise in the C curve, 80 to 150 ° C.
The toner according to claim 1, wherein the total of the temperature portions having a peak intensity equal to or more than 最大 of the maximum endothermic peak in the temperature range of 30 to 70 deg. 3. The wax has an acid value of 1 to 70 mg KOH.
/ G. 3. The toner according to claim 1, wherein 4. The wax having an acid value is maleic acid,
4. A wax modified with an acid monomer selected from at least one of maleic acid half ester and maleic anhydride.
The toner according to any one of the above. 5. The toner according to claim 1, wherein the melt viscosity of the wax at 160 ° C. is in the range of 50 to 2000 mPa · s. 6. The GPC (gel permeation chromatogram) of the binder resin containing substantially no THF insoluble matter and having a THF soluble content of at least 3 × 10 3
^6. The method according to claim 1, wherein the compound has a main peak in a region of ^{3 to} 3 × 10 ⁴ and a subpeak or shoulder in a region of a molecular weight of 1 × 10 ^{5 to} 3 × 10 ⁶ . toner. 7. The method according to claim 1, wherein the binder resin is 0.5 to 50 mg KO.
7. An acid value of H / g.
The toner according to any one of the above. 8. The binder resin according to claim 1, wherein the binder resin is a vinyl polymer having an acid monomer selected from at least one selected from the group consisting of maleic acid, maleic acid half ester and maleic anhydride. The toner according to claim 1.