JP2001194830A - Toner - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide toner which has excellent balance between fixation and non offset character and by which image of less fogging and high quality can be obtained over a long period of time under any circumstance. SOLUTION: In the toner containing at least a binding resin having polymer components, wax and an organometallic compound, the organometallic compound is an azo-iron compound which can be generated from a monoazo compound having at least one alkyl group and two hydroxyl groups capable of combining with iron atom, and contains 0.2 to 20 pts. mass of the wax per 100 pts. mass of the binding resin and further the wax contains at least two kinds of wax having different melting points or different composition.

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 image forming method such as an electrophotographic method, an electrostatic recording method, a magnetic recording method and a toner jet method, and heats and fixes a formed visible image on a recording material. The present invention relates to a toner used for a fixing method.

[0002]

2. Description of the Related Art Toner must have a positive or negative charge, depending on the polarity of the electrostatic latent image to be developed. In order to retain the electric charge in the toner, it is possible to use the frictional charging property of the resin as a toner component. However, in this method, since the charging of the toner is not stable, the rise of the density is slow and fogging is easy. Therefore, a charge control agent is added to impart a desired triboelectric charge to the toner.

At present, as charge control agents known in the art, as triboelectric charge control agents, metal complex salts of monoazo dyes, metal complex salts of hydroxycarboxylic acid, dicarboxylic acid, aromatic diol, etc .; Resins containing components are known. Nigrosine dyes, azine dyes, triphenylmethane dyes and pigments, quaternary ammonium salts, and polymers having quaternary ammonium salts in the side chain are known as positive friction charge control agents.

However, these charge control agents are difficult to balance between image density and fog in a high humidity environment.
It has the drawbacks that it is difficult to obtain a sufficient image density, has poor dispersibility in resin, and has a bad influence on storage stability, fixability, and offset resistance, and many of them have insufficient performance.

Conventionally, metal complexes and metal salts of aromatic carboxylic acids have been disclosed in JP-A-53-127726 and JP-A-57-127726.
JP-A-1111541, JP-A-57-124357, JP-A-57-104940, JP-A-61-6
No. 9073, JP-A-61-73963, JP-A-61-267058, JP-A-62-10515
No. 6, JP-A-62-145255, JP-A-62-145255
JP-A-2-163601, JP-A-63-208865, JP-A-3-276166, JP-A-4-84
Some proposals have been made, such as JP-A-141, JP-A-8-160668, and JP-A-9-169919. However, these publications propose that although all of them are excellent from the viewpoint of imparting triboelectric charging, a simple developing device configuration enables stable development regardless of environmental changes, aging, and use conditions. Is rarely obtained. In addition, there are few examples in which replenishment is repeated and stable developability is obtained even during long-term durability. Further, there are many cases in which there is an influence of other raw materials and restrictions on other raw materials occur.

The amorphous metal complex disclosed in Japanese Patent Application Laid-Open No. 11-7164 is excellent in dispersibility and chargeability in toner, but is relatively soft, The toner may adhere to the photoreceptor or the deterioration of the toner may progress due to long-term use, and the developing property may gradually decrease.

At present, none of the above items are satisfactory.

The most important performance required of the toner is the 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 the toner from adhering to the surface of the fixing roller, for example, the roller surface is formed of a material having excellent release properties from the toner, such as silicone rubber or a fluororesin, and the surface of the roller is further provided with an offset preventing agent 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 a low molecular weight polyethylene or a low molecular weight polypropylene is added to the toner in view 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 to include wax as a release agent in a toner. For example, JP-A-52-330
No. 4, JP-A-52-3305, JP-A-57-3305.
A technique such as 52574 is disclosed.

[0013] 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
No. 6, JP-A-4-299357, JP-A-4-136295, JP-A-5-197192, and the like.

[0015] However, none of these toners can satisfy all the performances, and some problems have been caused. 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. And lived.

Also, JP-A-8-278657, JP-A-8-334919, and JP-A-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.

[0017] However, although the range of low-temperature fixing property and high-temperature offset property is certainly widened in the toner using these release agents, it is difficult to uniformly disperse each wax component in the toner. In some cases, an increase in fog and a deterioration in developability due to a defect were caused.

[0018]

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 capable of producing a high-quality image with little fog in any environment for a long period of time. It is to provide a toner that can be obtained.

[0019]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the use of an azo iron compound and a wax having specific properties makes it possible to obtain a good charge rise of toner, high chargeability, and fixing. While maintaining the resistance and offset resistance
It has been found that high chargeability can be imparted to the toner even when left in a high humidity environment, and that a toner that does not become excessively charged in a low humidity environment can be obtained.

That is, the present invention is as follows. (1) A toner containing at least a binder resin having a polymer component, a wax, and an organometallic compound, wherein the organometallic compound has one or more alkyl groups and two hydroxyl groups capable of bonding to an iron atom. Is an azo iron compound that can be produced from a monoazo compound having, containing 0.2 to 20 parts by mass of the wax based on 100 parts by mass of the binder resin,
In addition, the wax contains at least two types of waxes having different melting points. (2) The difference between the melting points of the two types of wax is 10 to 100.
° C. (3) A toner containing at least a binder resin having a polymer component, a wax, and an organometallic compound, wherein the organometallic compound has at least one alkyl group and two hydroxyl groups capable of binding to an iron atom. Is an azo iron compound that can be produced from a monoazo compound having, containing 0.2 to 20 parts by mass of the wax based on 100 parts by mass of the binder resin,
Further, the wax contains at least two kinds of waxes having different compositions. (4) The toner according to any one of (1) to (3), wherein the azo iron compound is crystalline. (5) The monoazo compound is represented by the following general formula (a):
(B) The toner according to (1) to (4), which can be represented by any of (c).

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(In the formula, R _{1 to} R ₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{1 to} R ₈ is an alkyl group.)

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[0022] (representing each of R ₉ to R ₁₈ is the formula independently represent a hydrogen atom, a halogen atom or an alkyl group, R ₉ to R
_At least one of the ₁₈ is an alkyl group. )

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[0023] (representing each of R ₁₉ to R ₃₀ is the formula independently represent a hydrogen atom, a halogen atom or an alkyl group, R ₁₉ to R
_At least one of the ₃₀ is an alkyl group. (6) wherein the monoazo compound has an alkyl group having 4 to 12 carbon atoms as a substituent.
The toner according to any of (4). (7) The toner according to (6), wherein the monoazo compound has an alkyl group having 6 to 10 carbon atoms as a substituent. (8) The toner according to (6), wherein the monoazo compound has a tertiary alkyl group having 4 to 12 carbon atoms as a substituent. (9) The toner according to (8), wherein the monoazo compound has a tertiary alkyl group having 6 to 10 carbon atoms as a substituent. (10) The azo iron compound is represented by the following general formulas (d) and (e)
Or (1) to (f),
The toner according to any one of (9).

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[0024]

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[0025]

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(In the formulas (d), (e) and (f), A and B each independently represent o-phenylene or 1,2-naphthylene, and at least one of A and B has at least one alkyl group. A and B may each further have a halogen atom as a substituent. M is a cation and represents a hydrogen ion, an alkali metal ion, an ammonium ion, or an organic ammonium ion.) (11) The toner according to any one of (1) to (10), wherein the azo iron compound is contained in an amount of 0.1 to 10 parts by mass based on 100 parts by mass of the binder resin. (12) The toner according to any one of (1) to (11), wherein the wax has a penetration at 25 ° C. of less than 10 mm. (13) The toner according to any one of (1) to (12), wherein the wax has a number average molecular weight measured by gel permeation chromatography (GPC) in the range of 100 to 3000 in terms of polyethylene. .

[0027]

BEST MODE FOR CARRYING OUT THE INVENTION The present inventors have found that the use of the above-mentioned azo iron compound and two kinds of waxes having different melting points or two kinds of waxes having different composition components make it possible to improve the charging property. A toner that can maintain high chargeability even when left in a high-humidity environment while maintaining good rise, high chargeability, fixability, and offset resistance, and that does not become overcharged even in a low-humidity environment. I found that I can get it.

The azo iron compound used in the present invention has good dispersibility in the toner, can make the charge amount distribution of the toner uniform, and gives the toner a stable rise of charge and good developability. can do. When the azo iron compound used in the present invention is used with two or more kinds of waxes having different melting points or two or more kinds of waxes having different compositions, excellent effects can be obtained. In other words, the two types of waxes described above allow the effect of plasticizing the toner and the effect of imparting the releasing action to be appropriately adjusted, and the azo iron compound is more preferably contained in the plasticized toner. The reason for this is that since the azo iron compound is dispersed, the effect on the chargeability of the azo iron compound is more clearly exhibited.

Further, when the azo iron compound of the present invention is well dispersed, the charging ability can be further improved. However, in general, when the azo compound is well dispersed, the releasability is lowered. This is because the wax component may be used to compensate for the release effect in order to maintain a high release property.

(1) Azo iron compound First, the azo iron compound used in the present invention will be described. The azo iron compound used in the present invention is an azo iron compound that can be produced from a monoazo compound having one or more alkyl groups and two hydroxyl groups capable of binding to an iron atom. The azo iron compound is a compound in which each hydroxyl group of the monoazo compound is coordinated to an iron atom, and is an iron complex, an iron complex salt, or a mixture thereof.

The monoazo compound used in the present invention is a compound represented by the above formulas (a), (b) and (c), which stabilizes developability such as rising charge, image density, fog and image quality. It is preferable to achieve.

Further, each monoazo compound, as long as it has at least one alkyl group in the molecule as a substituent, is not particularly limited position of the alkyl group, R ₁₃ ~ In the above formula (b) It is particularly preferred to have an alkyl group at the position of R ₁₈ , and further at the position of R ₁₅ , from the viewpoint of imparting stable chargeability to the toner.

Among the above-mentioned monoazo compounds, among them, a monoazo compound having an alkyl group having 4 to 12 carbon atoms as a substituent is preferable for obtaining a high charge amount, high image density and faithful latent image reproduction. The monoazo compound having an alkyl group having 4 to 12 carbon atoms as a substituent has improved compatibility with the binder resin in the toner due to the action of the alkyl group,
The toner chargeability is stabilized. More preferably, it has 4 to 4 carbon atoms.
A monoazo compound having, as a substituent, an alkyl group having 12 tertiary carbon atoms, and more preferably having 6 to 1 carbon atoms.
A monoazo compound having an alkyl group having 0 tertiary carbon as a substituent, most preferably

[Outside 14]

Is a monoazo compound having as a substituent, the charge retention ability is increased, the change with the passage of time is reduced, more uniform dispersion in the toner becomes possible, and the chargeability of the toner becomes more uniform. It will be. Also,
It is also preferable to have at least one halogen atom as a substituent together with the alkyl group in terms of stabilizing the charge distribution in the compound.

Such a monoazo compound can be obtained by a diazotization coupling reaction.

Further, the azo iron compound of the present invention is preferably crystalline in that a decrease in developability during long-term, durable use of the toner can be suppressed. Since the azo iron compound is crystalline, the azo iron compound is relatively hard, and deterioration due to long-term use is suppressed. In addition, due to the hardness, the triboelectric charging property of the toner surface is also improved, and higher developing property can be provided to the toner. Conventionally, when a crystalline azo iron compound is used in a toner, there has been a problem that the photoreceptor is easily damaged due to being hard or easily fall off from toner particles, but the azo iron compound of the present invention has an alkyl group. The toner has sufficient dispersibility in the toner, prevents the azo iron compound from falling off from the toner, and suppresses an increase in the degree of exposure of the azo iron compound on the toner surface during durable use. It does not hurt your body.

Further, the plasticity and the releasability of the toner are controlled by the above two kinds of wax, and
Since the dropout of the azo iron compound is suppressed, it is possible to prevent toner contamination caused by the CA agent on the toner surface contact member after the transfer material is fixed, particularly the discharge roller conveying roller member, and the like. It is possible to prevent adverse effects on images, such as traces of member toner on the transfer material.

The crystallinity of the azo iron compound can be confirmed by analyzing the X-ray diffraction spectrum of the azo iron compound. To indicate that an X-ray diffraction spectrum is crystalline is defined as an X-ray diffraction pattern showing a prominent diffraction peak as shown in FIG. This is 2θ =
The azo iron compound has a plurality of peaks in the X-ray diffraction spectrum in the range of 5 ° to 30 ° (θ is the Bragg angle). Preferably, 2θ = 10 ° to 25
X of azo iron compound in the range of ° (θ is Bragg angle)
The line diffraction spectrum has one or more peaks in the range of every 5 °. When a plurality of diffraction peaks are obtained, it is preferable that the degree of crystallinity can be calculated, and the ratio (crystallinity) of the total intensity of the crystal part to the total intensity calculated by the multiple peak separation method exceeds 50%. .
The effect of the crystallinity is higher as the degree of crystallinity is higher. To obtain better durability, the degree of crystallinity is 55%.
More preferably, it is at least 60%.

Whether the azo iron compound is crystalline or not can be determined, for example, under the following conditions.

For example, X manufactured by Mac Science Co., Ltd.
X-ray diffraction spectrum by CuKα ray is measured by a line diffraction apparatus MXP ³ system. The X-ray diffraction spectrum is in the range of 2θ = 5 ° to 30 ° (θ is Bragg angle)
Is further separated into a whole spectrum and a spectrum of a crystal part. 2θ = 5 ° to 30 ° for each spectrum of the separated chart
(Θ is the Bragg angle), the total of the total strength and the total of the strength of the crystal part are determined by the crystallinity measurement method, and the crystallinity is calculated by the following equation.

Crystallinity (%) = (total strength of crystal parts / total strength) × 100 Specific examples of the monoazo compound preferably used in the present invention are described below.

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[0042]

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[0044]

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[0045]

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[0065]

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[0074]

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[0077]

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The azo iron compound used in the present invention is a reaction product of iron and a monoazo compound, and is an azo iron compound in which the above monoazo compound is coordinated to an iron atom. The azo iron compound is an iron complex, an iron complex salt, or a mixture thereof, and is an azo iron compound selected from the azo iron compounds represented by the general formulas (d), (e), (f), and the like, or a mixture thereof. .

In the present invention, since the iron reacts with the monoazo compound having an alkyl group, the compound becomes more stable thermally and with time as compared with the case where another metal is used. Performance can be imparted.

The azo iron compound used in the present invention can be obtained by reacting a monoazo compound capable of binding to an iron atom with an ironing agent in water and / or an organic solvent (preferably in an organic solvent). .

In general, the reaction product obtained in an organic solvent can be taken out by filtration and washing with water, or by dispersing in an appropriate amount of water, collecting the precipitate by filtration, washing with water, and drying. Examples of the organic solvent used in such an ironation reaction include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Alcohols such as propylene glycol monomethyl ether, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglyme), ethylene glycol diethyl ether, triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme), ethylene glycol and propylene glycol; Ether-based and glycol-based organic solvents; N, N-
Water-soluble organic solvents such as aprotic polar solvents such as dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone and dimethylsulfoxide can be mentioned. Preferred as the organic solvent are isopropanol, ethylene glycol monomethyl ether (methyl cellosolve), ethylene glycol monoethyl ether (ethyl cellosolve), and ethylene glycol, which are preferable in that a crystalline azo iron compound is synthesized. It is also preferable to recrystallize the azo iron compound obtained in another solvent in the above-mentioned organic solvent.

The amount of the organic solvent to be used is not particularly limited, but is 2 to 5 times by mass the monoazo compound used as a ligand.

Preferred examples of the ironing agent include ferric chloride, ferric sulfate, and ferric nitrate. The ironing agent is generally a monoazo compound 1 serving as a ligand.
1/3 to 2 equivalents, preferably 1/2 to 2/3 equivalents, of iron atom equivalents are used per mol.

The method of incorporating the azo iron compound in the toner in the present invention includes a method of adding (internally adding) the toner to the inside of the toner and a method of externally adding the toner. When the azo iron compound is internally added, the amount is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 10 parts by mass, based on 100 parts by mass of the binder resin.
It is 5 to 5 parts by mass. In addition, when externally added, the amount of the azo iron compound to be added is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 3 parts by mass. When the azo iron compound is externally added to the toner, it is particularly preferable that the azo iron compound is mechanochemically fixed to the toner surface.

The compounds of the present invention may be used in combination with known charge control agents generally used in toners, including those described in the description of the prior art. For example, there are other organic metal complexes, metal salts, chelate compounds, and the like, and specific examples include acetylacetone metal complexes, hydroxycarboxylic acid metal complexes, polycarboxylic acid metal complexes, and polyol metal complexes. Other examples include carboxylic acid derivatives such as metal salts of carboxylic acids, carboxylic anhydrides and esters, and condensates of aromatic compounds. Further, phenol derivatives such as bisphenols and calixarenes are also used.

(2) Wax Next, the wax component used in the present invention will be described.

When the azo iron compound used in the present invention is used with two or more kinds of waxes having different melting points or two or more kinds of waxes having different compositions, excellent effects can be obtained. That is, by the two types of wax as described above,
The effect of plasticizing the toner and the effect of imparting the releasing action can be appropriately adjusted, and the azo iron compound is more well dispersed in the plasticized toner. This is because the effect on the chargeability is more clearly exhibited.

The azo iron compound of the present invention is crystalline, so that excessive plasticization can be suppressed.
This is preferable because deterioration of blocking resistance can be prevented.

When the azo iron compound of the present invention is well dispersed, the charging ability can be further improved. However, in general, when the azo compound is well dispersed, the releasability is lowered. In some cases, a wax component is used to supplement the releasing effect in order to maintain a high releasing property.

The content of the wax component in the toner according to the present invention is 0.2 to 100 parts by mass of the binder resin component.
-20 parts by mass. The content of the wax is preferably 0.1 to 100 parts by mass of the binder resin component.
5 to 15 parts by mass, more preferably 1.0 to 15 parts by mass.
Parts by weight. If the content of the wax is less than the above range, the effect of releasing the wax at a high temperature cannot be obtained because the release effect of the wax cannot be sufficiently exerted. May also deteriorate. On the other hand, if the content is more than the above range, it becomes difficult to uniformly disperse the wax component in the toner, which affects the chargeability of the toner, so that a preferable image density cannot be obtained. Or fog due to poor charging may increase.

The following are examples of the wax used in the present invention. For example, aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin wax, Fischer-Tropsch wax; oxides of aliphatic hydrocarbon waxes such as oxidized polyethylene wax Or a block copolymer thereof; a plant wax such as candelilla wax, carnauba wax, wood wax, jojoba wax; an animal wax such as beeswax, lanolin, and whale wax; a mineral wax such as ozokerite, ceresin, and petrolactam. Waxes; waxes mainly containing fatty acid esters such as montanic acid ester wax and caster wax; and those obtained by partially or entirely deoxidizing fatty acid esters such as deoxidized carnauba wax. It is. Further, saturated straight-chain fatty acids such as palmitic acid, stearic acid, montanic acid, or long-chain alkyl carboxylic acids having a longer-chain alkyl group; unsaturated fatty acids such as brassic acid, eleostearic acid, and barinaric acid; stearyl alcohol , Eicosyl alcohol, behenyl alcohol,
Saturated alcohols such as carnaubavir alcohol, seryl alcohol, melisyl alcohol, or long-chain alkyl alcohol having a longer-chain alkyl group; polyhydric alcohols such as sorbitol; linoleamide, oleic amide, lauric amide Fatty acid amides; saturated fatty acid bisamides such as methylene bisstearic acid amide, ethylenebiscapric acid amide, ethylenebislauric acid amide, hexamethylenebisstearic acid amide; ethylenebisoleic acid amide, hexamethylenebisoleic acid amide, N, N ' Unsaturated fatty acid amides such as dioleyl adipamide and N, N'-dioleyl sebacamide; aromatic bisamides such as m-xylene bisstearic acid amide and N, N'-distearyl isophthalic acid amide ; Fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate, and magnesium stearate (commonly referred to as metal soaps); grafted onto aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid Waxes; partially esterified products of fatty acids such as behenic acid monoglyceride and polyhydric alcohols; and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

Preferable waxes include polyolefins obtained by radical polymerization of olefins under high pressure;
A polyolefin obtained by purifying a low-molecular-weight by-product obtained during polymerization of a high-molecular-weight polyolefin; a polyolefin polymerized under a low pressure using a catalyst such as a Ziegler catalyst or a metallocene catalyst; a polyolefin polymerized using radiation, electromagnetic waves or light; Low molecular weight polyolefin obtained by pyrolysis of polyolefin; paraffin wax, microcrystalline wax, Fischer-Tropsch wax; synthetic hydrocarbon wax synthesized by the Zintall method, hydrocoll method, Age method, etc .; Synthetic wax, a hydrocarbon wax having a functional group such as a hydroxyl group or a carboxyl group; a mixture of a hydrocarbon wax and a hydrocarbon wax having a functional group; styrene, maleic Esters, acrylates, methacrylates, and a graft-modified wax with such vinyl monomers of maleic acid.

These waxes may be obtained by sharpening the molecular weight distribution using a press sweating method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method or a liquid crystal deposition method, or a low molecular weight solid fatty acid. , Low molecular weight solid alcohol,
Low molecular weight solid compounds and those from which other impurities have been removed are also preferably used.

In the first embodiment of the present invention, two different melting points are used.
It is characterized by using more than one kind of wax. In the case of a wax having a similar structure, a wax having a relatively low melting point exerts a plasticizing action, and a wax having a high melting point exerts an effect on a mold release action. That is, the wax having a low melting point contributes to the low-temperature fixability of the toner, and the wax having a high melting point contributes to the high-temperature offset resistance.

The difference between the melting points of these two or more waxes is 1
In the case of 0 ° C to 100 ° C, the above-mentioned functional separation can be effectively exhibited. The difference between the melting points is more preferably 20 to 80 ° C. If the difference in melting point is smaller than the above range, the effect of separating functions is difficult to appear, and if the difference in melting point is larger than the above range, it is difficult to emphasize functions by interaction.

[0096] Of the two or more kinds of waxes having different melting points, the wax having a relatively low melting point has a melting point of 60 to 60.
It is preferred to use a wax at 120 ° C. Further, as the wax having a relatively high melting point, the melting point is 100 to 160.
It is preferred to use a wax at a temperature of ° C.

As the two or more kinds of waxes having different melting points, for example, any of the above-mentioned waxes that can be used in the present invention and having different melting points can be used in any combination.

The second aspect of the present invention is characterized in that two or more kinds of waxes having different compositions are used.
In the present invention, “different in composition” means that the constituent elements of wax and their compounding ratio or molecular structure are different. As a combination of two or more kinds of waxes having different compositions, for example, those having a linear structure and those having a branched structure; those having a polar group and those having no polarity; Examples include those modified with different components and those unmodified.

The wax having a relatively branched structure, a wax having a polar group such as a functional group, or a wax modified with a component different from the main component exerts a plasticizing action and contributes to the low-temperature fixability of the toner. I do. Further, those having a more straight-chain structure, non-polar ones having no functional group, and unmodified straight ones exhibit a releasing effect and contribute to the offset resistance of the toner.

As the two kinds of waxes having different compositions, for example, any of the above-mentioned waxes that can be used in the present invention and having different compositions can be used in any combination.
Although not particularly limited, preferable combinations include the following. For example, a combination of a polyethylene homopolymer or copolymer based on ethylene and a polyolefin homopolymer or copolymer based on an olefin other than ethylene; a combination of a polyolefin and a graft-modified polyolefin; an alcohol wax, a fatty acid wax or an ester wax, and a hydrocarbon Combination of Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystalline wax; Combination of Fischer-Tropsch wax and polyolefin wax; Combination of paraffin wax and microcrystalline wax; Carnauba wax, candelilla wax, rice wax or Montan A combination of a wax and a hydrocarbon wax is exemplified.

As described above, by using two or more kinds of waxes having different melting points or two or more kinds of waxes having different compositions, excellent developing properties and fixing properties can be exhibited to a high degree.

In the present invention, the melting point of the wax component is measured by a differential thermal analyzer (DSC analyzer), DSC-7.
(Perkin Elmer) 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, heating rate 10 ° C / min.) The endothermic peak temperature measured by heating II is defined as the melting point.

The penetration of the above wax at 25 ° C. is 1
Preferably it is less than 0 mm. More preferably,
8 mm or less. If the penetration is larger than the above range, the offset resistance at high temperatures is deteriorated, and further, the powder fluidity and the cohesion of the toner are adversely affected, and the fading phenomenon and fogging are deteriorated. .

Various techniques are conceivable for controlling the degree of penetration of the wax into the above-mentioned range, and examples thereof include a method of adjusting the molecular weight, molecular weight distribution, density, and composition of the wax. By measuring the penetration of the wax when each of the above parameters is changed, a wax having a penetration in the above range can be obtained.

The penetration of the wax in the present invention can be measured according to JIS K-2207. Specifically, it is a numerical value representing a penetration depth per unit time when a needle having a conical tip having a diameter of about 1 mm and a vertex angle of 9 ° is penetrated with a constant load in a unit of 0.1 mm. The measurement conditions of the penetration in the present invention are as follows: sample temperature 25 ° C., load 1
00g, penetration time 5 seconds.

The wax has a number average molecular weight (Mn) of preferably from 100 to 3000, more preferably from 300 to 2,000 in terms of polyethylene, as measured by gel permeation chromatography (GPC).

When Mn is smaller than the above range, it is difficult to impart a sufficient releasing effect to the toner, and it is also difficult to satisfactorily disperse the wax in the toner. On the other hand, if Mn is larger than the above range, the fixability of the toner is adversely affected, which is not preferable.

The measurement of the molecular weight in the present invention can be performed by the following method.

<Method of Measuring Number Average Molecular Weight of Wax by GPC> Apparatus: GPC-150C (manufactured by Waters) Column: GMH-HT (manufactured by Tosoh Corporation) Duplex temperature: 135 ° C. Solvent: o-dichlorobenzene (0 .1% ionol) Flow rate: 1.0 ml / min. Sample: 0.4 ml of a 0.15% by weight sample was injected. The measurement was performed under the above conditions, and the molecular weight of the sample was calculated using a molecular weight calibration curve prepared from a monodisperse polystyrene standard sample. TSK StandardPOLYSTYRENE A-500, A
-1000, A-2500, A-5000, F-1, F-2, F-4, F-10, F-20,
Use F-40, F-80, F-128, F-288, F-450, F-850. Further, the molecular weight of the wax is calculated by conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

(3) Toner Hereinafter, the toner of the present invention containing the above-described azo iron compound and wax will be described.

The toner of the present invention further contains a binder resin having a polymer component. Examples of the type of binder resin used in the present invention include, for example, polystyrene, poly-p-chlorostyrene styrene, a homopolymer of styrene such as polyvinyl toluene and a substituted product thereof; a styrene-p-chlorostyrene copolymer, Styrene-vinyltoluene copolymer,
Styrene-vinyl naphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether Styrene-based copolymers such as copolymers, styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers Coalescence: 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, cumarone indene resin, petroleum Resin or the like can be used. Further, a crosslinked styrene resin is also a preferable binder resin.

Examples of the comonomer 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, a dicarboxylic acid having a double bond such as maleic acid, butyl maleate, methyl maleate, dimethyl maleate, and the like; and vinyl chloride;
Vinyl esters such as vinyl acetate, vinyl benzoate and the like, for example, ethylene olefins such as ethylene, propylene, butylene and the like; vinyl ketones such as vinyl methyl ketone and vinyl hexyl 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. Here, as the cross-linking 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 toner of the present invention is preferably used as a magnetic toner containing a magnetic material. Examples of magnetic materials that can be used include metal oxides containing elements such as iron, cobalt, nickel, copper, magnesium, manganese, aluminum, and silicon. These magnetic materials preferably have a BET specific surface area of 1 to ²⁰ m ² /
g, more preferably 2.5 to 12 m ² / g. The Mohs hardness of the magnetic material is 5
To 7 is preferable. Examples of the shape of the magnetic material include an octahedron, a hexahedron, a sphere, a needle, and a scaly shape, and an octahedron, a hexahedron, and a sphere having little anisotropy are preferable. This is because a material having an isotropic shape can achieve good dispersion even in a binder resin / wax.

The average particle size of the magnetic material is 0.05-1.
It is preferably 0 μm, more preferably 0.1 to 0.6 μm, and even more preferably 0.1 to 0.4 μm.

The magnetic material is preferably added in an amount of 60 to 200 parts by mass, more preferably 60 to 150 parts by mass, per 100 parts by mass of the toner binder resin. When the addition amount of the magnetic material is too small, the transportability of the toner to the developing site becomes insufficient and the thickness of the developer layer on the developer carrier becomes uneven, which tends to cause image unevenness. is there. Further, there is a tendency that the image density is easily reduced due to an excessive increase in the charge of the developer. On the other hand, if the amount of the magnetic material is too large, the developer may not be sufficiently charged, and the image density may be easily reduced.

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 fine silica powder, both a so-called dry method produced by the 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 can be used. But,
Surface and having less silanol groups inside, also Na ₂
Dry silica with less production residues such as O and SO ₃ ^2- is more preferable. 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 preferable method, a method of treating a dry silica fine powder produced by vapor phase oxidation of a silicon halide with a silane coupling agent, or treating with a silane coupling agent and simultaneously with an organosilicon compound such as silicone oil. Is mentioned.

Examples of the silane coupling agent used in the hydrophobizing treatment include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, and allylphenyl. Dichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane,
Chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethyldiethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyl Disiloxane, 1,3-diphenyltetramethyldisiloxane and dimethylpolysiloxane having from 2 to 12 siloxane units per molecule and containing at most one hydroxyl group bonded to one silicon atom at each terminal unit Is mentioned.

Examples of the organosilicon compound include silicone oil. Preferred silicone oils are those having 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 oils and the like are particularly preferred.

As a method of treating the silicone oil, for example, silica fine powder treated with a silane coupling agent 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 mixed. 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 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 amount of the resin fine particles, inorganic fine powder, or hydrophobic inorganic fine powder mixed with the toner is 0.1 to 5 parts by mass (preferably 0.1 to 5 parts by mass) based on 100 parts by mass of the toner.
3 parts by mass).

The toner of the present invention is prepared 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, a kneader or an 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); a super mixer (manufactured by Kawata); a ribocorn (manufactured by Okawara Seisakusho); a Nauta mixer, a turbulizer, a cyclomix (manufactured by Hosokawa Micron); Spiral pin mixer (manufactured by Taiheiyo Kiko Co., Ltd.); Ledige mixer (manufactured by Matsubo), and kneading machines include KRC kneader (manufactured by Kurimoto Iron Works); 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 pressurized kneader, nider ruder (manufactured by Moriyama Seisakusho); Include Ltd.) as the grinder, a counter jet mill, micron jet,
Inomaizer (manufactured by Hosokawa Micron); IDS type mill,
PJM Jet Pulverizer (Nippon Pneumatic Industries); Cross Jet Mill (Kurimoto Iron Works); Ulmax (Nisso Engineering); SK Jet
O-Mill (manufactured by Seishin Enterprise); Kryptron (manufactured by Kawasaki Heavy Industries); Turbo Mill (manufactured by Turbo Kogyo). Classifiers include Crasheal, Micron Classifier, and Spedd Classifier (Seisin 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) Made);
YM Microcut (manufactured by Yasukawa Shoji Co., Ltd.) is mentioned. As a sieving device used for sifting coarse particles, Ultrasonic (manufactured by Koei Sangyo Co., Ltd.); Resona sieve, gyro shifter (Tokuju Kosakusho); Sonic System (Dalton); Sonic Clean (Shinto Kogyo); Turbo Screener (Turbo Kogyo);
Micro shifter (manufactured by Makino Sangyo Co., Ltd.); circular vibrating sieve and the like.

[0130]

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

<Production example 1 of azo iron compound> 4-Chloro-2-
A monoazo compound synthesized by a general diazotization coupling reaction of aminophenol and 6-t-octyl-2-naphthol was added to N, N-dimethylformamide (DMF) and stirred. Sodium carbonate was added to this solution, the temperature was raised to 70 ° C., iron (II) sulfate heptahydrate was added, and the mixture was reacted for 5 hours. Then, after allowing to cool to room temperature, the precipitated product was collected by filtration, added to isopropanol, heated and dissolved at 70 ° C., and then allowed to cool to room temperature to crystallize the azo iron compound. This reaction solution is dispersed in water, filtered, washed with water, dried,
An azo iron compound (I) represented by the following formula (I) was obtained. The crystallinity of the azo iron compound (I) was 68.0%. FIG. 1 shows the X-ray diffraction spectrum of the azo iron compound (I).

[Outside 52]

<Production Example 2 of Azo Iron Compound> A production method similar to that of Production Example 1 of an azo iron compound was used except that 4-t-pentyl-2-aminophenol was used as a raw material in Production Example 1 of an azo iron compound. An azo iron compound represented by the following formula (II) (I
I got. The crystallinity of the azo iron compound (II) was 61.2%.

[Outside 53]

<Production example 3 of azo iron compound> In the production example 1 of the azo iron compound, except that 2-aminophenol was used as a raw material, a method similar to that of Production Example 1 of an azo iron compound was used, and the following formula (III) was used. The azo iron compound (III) represented was obtained. The crystallinity of the azo iron compound (III) was 63.1%.

[Outside 54]

<Production example 4 of azo iron compound> The same procedure as in Production Example 1 of azo iron compound was carried out except that 6-t-butyl-2-naphthol was used as a raw material in Production Example 1 of azo iron compound. An azo iron compound (IV) represented by the formula (IV) was obtained. The crystallinity of the azo iron compound (IV) was 64.8%.

[Outside 55]

<Azo-iron compound production example 5> The following formula (I) was prepared using the same method as in the azo-iron compound production example 1 except that 6-methyl-2-naphthol was used as a raw material in the azo-iron compound production example 1. An azo iron compound (V) represented by V) was obtained.
The crystallinity of the azo iron compound (V) was 66.1%.

[Outside 56]

<Azo-iron compound production example 6> The following formula was prepared using the same method as in the azo-iron compound production example 1 except that 3-n-butyl 2-naphthol was used as a raw material in the azo iron compound production example 1. An azo iron compound (VI) represented by (VI) was obtained. The crystallinity of the azo iron compound (VI) was 65.8%.

[Outside 57]

<Production example 7 of azo iron compound> In Production example 1 of azo iron compound, 2-naphthol and 4-methyl-
An azo iron compound (VII) represented by the following formula (VII) was obtained in the same manner as in Example 1 for producing an azo iron compound except that 2-aminophenol was used. The crystallinity of the azo iron compound (VII) was 67.2%.

[Outside 58]

<Azochrome compound production example 8> An azo iron compound production example was the same as the azo iron compound production example 1 except that 2 naphthol, 4-t-pentyl-2-aminophenol and chromium (III) formate were used. An azochrome compound (VIII) represented by the following formula (VIII) was obtained using the same method as in 1. The crystallinity of the azochrome compound (VIII) was 63.7%.

[Outside 59]

<Preparation Example 9 of Azo Iron Compound> A compound represented by the following formula (IX) was prepared in the same manner as in Preparation Example 1 of azo iron compound except that 2-naphthol was used as a raw material in Preparation Example 1 of azo iron compound. Azo iron compound (IX) to be obtained was obtained. The crystallinity of the azo iron compound (IX) was 69.6%.

[Outside 60]

<Production example 10 of azo iron compound> In Production example 7 of azo iron compound, N, N-dimethylformamide (DMF) was used without performing the crystallization process in isopropanol.
The reaction solution was dispersed in water, filtered, washed with water, and dried to obtain an amorphous azo iron compound (X). The crystallinity of the azo iron compound (X) was 13.8%.

Example 1 (1) Production of Toner As a binder resin, a styrene-butyl acrylate-monobutyl maleate copolymer synthesized by a known method (peak molecular weight 30,000, glass transition point temperature 61 ° C.)
100 parts by mass, azo iron compound (I) 2 parts by mass, spherical magnetic iron oxide 100 parts by mass, polypropylene wax (W
1) (melting point 143 ° C, penetration (25 ° C) 0.5 mm, G
3 parts by mass of number average molecular weight (Mn) measured by PC (converted to polyethylene) 1010) and paraffin wax (W2) (melting point 75 ° C., penetration (25 ° C.) 6.5 mm,
3 parts by mass of Mn 520) were uniformly mixed in advance.
The mixture was melt-kneaded with a twin-screw extruder heated to 0 ° C. After cooling the kneaded product, it was roughly pulverized with a hammer mill and further finely pulverized with a jet mill, and the obtained pulverized product was subjected to air classification to obtain a classified powder having a weight average diameter D _{4 of} 6.5 μm.

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. Table 1 shows the composition and physical properties of the toner T1.

The measurement of the melting point of each wax was carried out by using the method using the DSC measuring apparatus described in the embodiment of the present invention. The sample used for the melting point measurement was 1 mg. Similarly, the melting point and penetration of the wax were measured using the method described in the embodiment of the invention.

(2) Evaluation Printout was performed using the toner T1 obtained as described above, and the image density, fog, toner fixability and offset resistance were evaluated.

High temperature and high humidity (32.5 ° C., relative humidity 80%)
And a low-temperature, low-humidity (15 ° C., 10% relative humidity) environment, a commercially available laser beam printer LBP-93.
0EX (manufactured by Canon) was modified to 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 at a primary charge of -670 V, a gap (290 μm) is set without contact between the photosensitive drum and the developer layer on the developer carrier (magnet inclusion), and an AC bias (f = 2000 Hz; Vpp) = 1600V)
And a DC bias (Vdc = -500 V) was applied to the developing drum. The printout speed is 45 sheets (A
(4 horizontal) / 1 minute. The obtained images were evaluated for the following items.

(A) Image Density Evaluation was made by maintaining the image density at the end of printing out 25,000 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 Co., Ltd.) with respect to a printout image of a white background portion having a document density of 0.00.

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

(C) Toner Contamination of Roller Member in Paper Discharge Unit 100,000 printouts were made on ordinary paper for copying machines (75 g / m ² ) in a high temperature and high humidity environment (32.5 ° C., relative humidity 80%). After that, the degree of toner contamination on the roller member in the sheet discharge conveyance section after the fixed sheet discharge was evaluated. ：: No contamination ：: Almost no contamination 若干: Slightly contaminated X: Severely contaminated (d) Fixability The printability was fixed in a low-temperature and low-humidity (15 ° C., 10% relative humidity) environment. A fixed image was rubbed with a soft thin paper by applying a load of 50 g / cm ^{2 to} the image, and the image density was reduced and evaluated before and after rubbing (%). ◎ (excellent): less than 5% ○ (good): 5 to 10% △ (acceptable): 10 to 20% × (poor): 20% or more (e) Offset resistance The offset resistance is a half-solid black sample The image was printed out and evaluated based on the degree of stain on the unprinted solid white portion on the image. As a test paper, plain paper for a copying machine (64 g / m ² ) was used. ◎: not generated ：: hardly generated △: slightly generated ×: severely offset generated The evaluation results are shown in Table 2.

Example 2 A toner T2 was obtained in the same manner as in Example 1 except that the azo iron compound (II) was used in place of 2 parts by mass instead of the azo iron compound (I). Obtained toner T
2 was evaluated in the same manner as in Example 1. Table 1 shows the composition and physical properties of Toner T2, and Table 2 shows the evaluation results.

Example 3 A toner T3 was obtained in the same manner as in Example 1, except that the azo iron compound (III) was used in place of 2 parts by mass instead of the azo iron compound (I). The same evaluation as in Example 1 was performed for the obtained toner T3. Toner T
Table 1 shows the composition and physical properties of No. 3, and Table 2 shows the evaluation results.

Example 4 As a wax component, polyethylene wax (W3) (melting point: 102 ° C., penetration (25
C) 4.5 mm, 3 parts by mass of number average molecular weight (Mn) measured by GPC (converted to polyethylene) 1500), and polyethylene wax (W4) (melting point 122 ° C., penetration (25 ° C.) 0.5 mm, Number average molecular weight (Mn) measured by GPC (polyethylene equivalent: 2800) 3
In the same manner as in Example 1 except that the toner T4
I got The same evaluation as in Example 1 was performed for the obtained toner T4. Table 1 shows the composition and physical properties of Toner T4.
Table 2 shows the evaluation results.

Example 5 A toner T5 was obtained in the same manner as in Example 1, except that the azo iron compound (IV) was changed to 2 parts by mass instead of the azo iron compound (I). Obtained toner T
5 was evaluated in the same manner as in Example 1. Toner T5
Is shown in Table 1 and the evaluation results are shown in Table 2.

Example 6 A toner T6 was obtained in the same manner as in Example 1, except that the azo iron compound (V) was changed to 2 parts by mass instead of the azo iron compound (I). Obtained toner T
6 was evaluated in the same manner as in Example 1. Toner T6
Is shown in Table 1 and the evaluation results are shown in Table 2.

Example 7 A toner T7 was obtained in the same manner as in Example 1, except that the monoazo iron compound (VI) was changed to 2 parts by mass instead of the azo iron compound (I). The same evaluation as in Example 1 was performed for the obtained toner T7. Table 1 shows the composition and physical properties of Toner T7, and Table 2 shows the evaluation results.

Example 8 A toner T8 was obtained in the same manner as in Example 1 except that the azo iron compound (VII) was used in place of 2 parts by mass instead of the azo iron compound (I). The same evaluation as in Example 1 was performed for the obtained toner T8. Toner T
Table 1 shows the composition and physical properties of 8 and Table 2 shows the evaluation results.

Example 9 As a wax component, 3 parts by mass of polyethylene wax (W1), paraffin wax W5 (melting point 69 ° C., penetration (25 ° C.) 15 mm, GP
Toner T9 was obtained in the same manner as in Example 1 except that 3 parts by mass of the number average molecular weight (Mn) (460 in terms of polyethylene) measured by C was used. The same evaluation as in Example 1 was performed for the obtained toner T9. Table 1 shows the composition and physical properties of Toner T9, and Table 2 shows the evaluation results.

(Example 10) As a wax component, polyethylene wax (W6) (melting point 128 ° C, penetration (2
5 ° C.) 0.1 mm, except that the number average molecular weight (Mn) measured by GPC (Mn) (in terms of polyethylene, 3300) was 3 parts by mass and paraffin wax W5 was 3 parts by mass.
In the same manner as in the above, a toner T10 was obtained. Obtained toner T
10 were evaluated in the same manner as in Example 1. Toner T
Table 1 shows the composition and physical properties of No. 10, and Table 2 shows the evaluation results.

Example 11 As a wax component, polyethylene wax (W7) (melting point: 116 ° C., penetration (2
5 mm) 0.2 mm, 3 parts by mass of number average molecular weight (Mn) measured by GPC (900 in terms of polyethylene), 3 parts by mass, styrene graft-modified polyethylene wax (W8) (melting point: 104 ° C., penetration: 25 ℃) 1.0m
m, and a toner T11 was obtained in the same manner as in Example 1 except that 3 parts by mass of the number average molecular weight (Mn) measured by GPC (1800 in terms of polyethylene) was used. The same evaluation as in Example 1 was performed for the obtained toner T11. Table 1 shows the composition and physical properties of Toner T11, and Table 2 shows the evaluation results.

Example 12 Toner T12 was produced in the same manner as in Example 2 except that 3 parts by mass of polyethylene wax (W3) and 3 parts by mass of polyethylene wax modified with styrene (W8) were used as wax components. I got The same evaluation as in Example 1 was performed for the obtained toner T12. Table 1 shows the composition and physical properties of Toner T12, and Table 2 shows the evaluation results.

(Comparative Example 1) A toner T13 was obtained in the same manner as in Example 10, except that 2 parts by mass of the azochrome compound (VIII) was used instead of the azo iron compound (I). The same evaluation as in Example 1 was performed for the obtained toner T13. Table 1 shows the composition and physical properties of Toner T13, and Table 2 shows the evaluation results.

Comparative Example 2 A toner T14 was obtained in the same manner as in Example 10 except that 2 parts by mass of the azo iron compound (IX) was used instead of the azo iron compound (I). The same evaluation as in Example 1 was performed for the obtained toner T14. Table 1 shows the composition and physical properties of Toner T14, and Table 2 shows the evaluation results.
Shown in

(Comparative Example 3) As a wax component, only 6 parts by mass of the polypropylene wax W1 was used.
In the same manner as in Example 8, a toner T15 was obtained. The same evaluation as in Example 1 was performed for the obtained toner T15.
Table 1 shows the composition and physical properties of Toner T15. Table 2 shows the evaluation results.

Comparative Example 4 Toner T17 was obtained in the same manner as in Comparative Example 3, except that 2 parts by mass of the azo iron compound (X) was used instead of the azo iron compound (VII). The same evaluation as in Example 1 was performed for the obtained toner T17. Table 1 shows the composition and physical properties of Toner T17, and Table 2 shows the evaluation results.
Shown in

[0164]

[Table 1]

[0165]

[Table 2]

[0166]

As described above, the toner of the present invention is a toner having an excellent balance between the fixing property and the non-offset property, and can produce a high-quality image with little fog under any environment for a long time. To provide a toner that can be obtained over a wide range.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction spectrum of an azo iron compound (1).

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ogawa ▲ Yoshi ▼ Kan 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Yama ▲ Saki ▼ Katsuhisa 3-chome Shimomaruko, Ota-ku, Tokyo 30-2 Canon Inc. (72) Inventor Tsuneo Nakanishi 3-30-2 Shimomaruko, Ota-ku, Tokyo Tokyo Inside (72) Inventor Kaori Hiratsuka 3-30-2 Shimomaruko, Ota-ku, Tokyo Inside Canon Inc. (72) Inventor Hirohide Tanigawa Inside Canon Inc. 3- 30-2 Shimomaruko, Ota-ku, Tokyo

Claims (14)

[Claims] 1. A toner containing at least a binder resin having a polymer component, a wax, and an organometallic compound, wherein the organometallic compound has one or more alkyl groups and two or more groups capable of bonding to an iron atom. An azo iron compound that can be produced from a monoazo compound having a hydroxyl group, containing the wax in an amount of 0.2 to 20 parts by mass based on 100 parts by mass of the binder resin, and the waxes are two types of waxes having different melting points. A toner containing at least 2. The difference between the melting points of the two kinds of waxes is 10
2. The toner according to claim 1, wherein the temperature is from 100 to 100C. 3. A toner containing at least a binder resin having a polymer component, a wax, and an organometallic compound, wherein the organometallic compound has one or more alkyl groups and two or more groups capable of bonding to an iron atom. Is an azo iron compound that can be produced from a monoazo compound having a hydroxyl group, wherein the wax contains 0.2 to 20 parts by mass with respect to 100 parts by mass of the binder resin, and the wax has two different compositions. A toner comprising at least a wax. 4. The toner according to claim 1, wherein the azo iron compound is crystalline. 5. The toner according to claim 1, wherein the monoazo compound can be represented by any of the following general formulas (a), (b), and (c). [Outside 1] (In the formula, R _{1 to} R ₈ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and at least one of R _{1 to} R ₈ is an alkyl group.) (In the formula, R _{9 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{9 to} R ₁₈ is an alkyl group.) (In the formula, R _{19 to} R ₃₀ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{19 to} R ₃₀ is an alkyl group.) 6. The monoazo compound according to the following general formula (b)
5. The toner according to claim 1, wherein the toner is represented by the following formula. [Outside 4] (In the formula, R _{9 to} R ₁₈ each independently represent a hydrogen atom, a halogen atom or an alkyl group, and at least one of R _{13 to} R ₁₈ is an alkyl group.) 7. The toner according to claim 1, wherein the monoazo compound has an alkyl group having 4 to 12 carbon atoms as a substituent. 8. The toner according to claim 7, wherein the monoazo compound has an alkyl group having 6 to 10 carbon atoms as a substituent. 9. The toner according to claim 7, wherein the monoazo compound has a tertiary alkyl group having 4 to 12 carbon atoms as a substituent. 10. The monoazo compound having 6 to 10 carbon atoms.
10. The toner according to claim 9, having a tertiary alkyl group as a substituent. 11. The toner according to claim 1, wherein the azo iron compound is represented by the following general formula (d), (e) or (f). [Outside 5] [Outside 6] [Outside 7] (In the formulas (d), (e) and (f), A and B each independently represent o-phenylene or 1,2-naphthylene, and at least one of A and B has at least one alkyl group. A and B may each further have a halogen atom as a substituent, M is a cation,
Represents hydrogen ion, alkali metal ion, ammonium ion and organic ammonium ion. ) 12. The binder resin according to claim 1, wherein the azo iron compound is
The toner according to any one of claims 1 to 11, wherein the toner is contained in an amount of 0.1 to 10 parts by mass with respect to 0 parts by mass. 13. The wax according to claim 1, wherein the penetration of the wax at 25 ° C. is less than 10 mm.
3. The toner according to any one of 2. 14. The wax according to claim 1, wherein a number average molecular weight of the wax measured by gel permeation chromatography (GPC) is in the range of 100 to 3000 in terms of polyethylene. Toner.