JP3397541B2 - Electrostatic image developing toner, image forming method and process cartridge - Google Patents

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 electrophotography, electrostatic recording, etc., and in particular, an insulating magnetic toner, an image forming method using the magnetic toner, and a detachable type in an image forming apparatus main body. The present invention relates to a process cartridge having the toner.

[0002]

2. Description of the Related Art Conventionally, as an electrophotographic method, U.S. Pat. No. 2,297,691 and JP-B-42-23910 are known.
Publication (US Pat. No. 3,666,363) and Japanese Patent Publication No. 43-24748 (US Pat. No. 4,074)
No. 1,361), a number of methods are known, but generally, a photoconductive material is used to form an electric latent image on a photoconductor by various means. Then
Then, the latent image is developed with toner to form a visible image, and if necessary, the toner image is transferred to a transfer material such as paper and then fixed by heating, pressure, or both to obtain a copy. is there.

Various developing methods are known in which an electrostatic latent image is visualized using toner. For example, US Pat. No. 2,87
No. 4,063, a magnetic brush method, No. 2,618,552, a cascade developing method, and No. 2,221,776, a powder. Cloud method, fur brush development method,
Liquid developing methods and many developing methods are known.

Among these developing methods, a magnetic brush method, a cascade method, and a liquid developing method, which use a developer mainly composed of toner and carrier, have been widely put into practical use. All of these methods are excellent methods in which a good image can be obtained relatively stably, but on the other hand, they have the common drawbacks associated with a two-component developer, such as carrier deterioration and variation in the mixing ratio of toner and carrier.

In order to avoid such drawbacks, various developing methods using a one-component developer consisting only of toner have been proposed, but among them, many are excellent in the method using a developer consisting of magnetic toner particles. .

Various methods and devices have been developed for the step of fixing the toner image to a sheet such as paper, which is the final step of the above-mentioned electrophotography, but the most general method at present is a pressure heating method using a heat roller. Is.

The pressure-bonding heat method using a heating roller performs fixing by allowing the toner image surface of the sheet to be fixed to pass under pressure while contacting the surface of a heat roller having a surface having releasability for toner. is there.

In this method, since the surface of the heat roller and the toner image on the sheet to be fixed are brought into contact with each other under pressure, the thermal efficiency at the time of fusing the toner image on the sheet to be fixed is extremely good, and the fixing is carried out quickly. It can be performed and is very effective in high speed electrophotographic copiers.

Particularly, in the future, since copying machines are moving toward higher speeds, the toner must satisfy the requirements of improved fixability on recording materials such as paper, good image density in high-speed development, and high durability. Is not happening.

In such a heat roller fixing system,
In order to improve the offset resistance, a conventional technique is to add a polyolefin wax to the toner.

However, since the polyolefin wax has poor compatibility with the binder resin for the toner, the polyolefin wax is apt to cause poor dispersion of the wax during the production of the toner, which may cause free polyolefin during pulverization. .

Poor dispersion of the polyolefin wax in the toner not only leads to defective cleaning and deterioration of offset resistance during durability in a copying machine, but also causes variations in toner chargeability, and therefore, poor durability during copying. Image density is reduced.

JP-A-50-81342 and JP-A-5-
JP-A-6-144436, JP-A-58-11953 and JP-A-60-184260 disclose toners using a wax having a fatty acid ester and an ester component.

In these techniques, the process speed is 38 because it is not a fatty acid ester having a long chain alkyl group.
When applied to high-speed development of 0 mm / sec or more, the effect of improving fixability and anti-offset property is not sufficient, and especially when applied to toner having an average particle size of less than 10 μm May cause poor dispersion of the toner, which tends to cause variations in toner chargeability due to charge-up in a low-humidity environment, resulting in a decrease in image density during durability.

Particularly in the future, since the toner particle size tends to be further reduced, further improvement of the dispersibility of the wax component is demanded.

Since the toner particle size becomes small, toner charge-up becomes a problem especially in a low-humidity environment, and the problem of image density reduction accompanying it is an unavoidable problem.

Further, European Patent Publication EPA0606
873 describes a toner containing, as a binder resin, at least a part of a polyester resin modified with a compound having a long-chain alkyl group having 22 to 102 carbon atoms and a hydroxyl group or a carboxyl group at its end. Since this compound has been reacted with a resin having a large molecular weight such as polyester resin, it is an invention of a concept different from that of the present application.

[0018]

SUMMARY OF THE INVENTION An object of the present invention is to provide a toner that solves the above problems, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner which can obtain good fixing property and offset resistance even in a high speed copying machine, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner having a stable triboelectric charge amount between toner particles and between a toner and a toner carrier such as a sleeve, which can be controlled to a charge amount suitable for a developing system to be used. Another object of the present invention is to provide an image forming method and a process cartridge having the toner.

An object of the present invention is to make it possible to increase the density difference between dots which enables faithful development to a digital latent image, and to use a toner in which the edges of dots are reproduced sharply. Another object of the present invention is to provide an image forming method and a process cartridge having the toner.

An object of the present invention is to provide a toner which maintains the initial performance even when the toner is continuously used for a long period of time, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner with less fog and reversal fog even in an image forming process including post-charging, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner that reproduces a stable image that is not affected by changes in temperature and humidity, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner having excellent storage stability, which retains initial characteristics even after long-term storage, an image forming method using the toner, and a process cartridge having the toner.

An object of the present invention is to provide a toner that prevents charge-up of the toner, which is an adverse effect when the toner particle size is reduced, and imparts a good image density, an image forming method using the toner, and the toner. To provide a process cartridge.

[0027]

The present invention achieves the above object by the following constitutions.

The present invention includes at least (i) a binder resin,
(Ii) a colorant and (iii) (a) an ester compound obtained by reacting a monohydroxyl compound having a long chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group with a carboxylic acid having a molecular weight of 1,000 or less, and (b) )
A monocarboxylic compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a carboxyl group was reacted with an alcohol having a molecular weight of 1,000 or less.
Ester compound selected from the group consisting of ester compounds
A toner having toner particles containing things, diether
The stell compound has a number average molecular weight (Mn) of 1550 to
7,000 and a weight average molecular weight (Mw) of 1550
An optimum 7000, relates to a toner for negative charging electrostatic image development, wherein the volume average particle diameter of the toner particles is 3 to 8 [mu] m.

Furthermore, the present invention relates to an electrostatic charge image carrier on an electrostatic charge carrier.
An electrostatic latent image is carried by developing the electrostatic latent image by developing means in the developing section.
Form a toner image on the body and transfer the toner image to the recording material
Image formation in which the transferred toner image is fixed on the recording material
In the method, the developing means carries toner,
The toner is at least (i) a binder resin and (ii) a colorant.
And (iii) (a) an alkylene group having 40 or more carbon atoms
Monohidoroki having a long-chain alkyl Moto及 beauty hydroxyl with
Sillic compounds and carboxylic acids with a molecular weight of 1000 or less
Ester compound reacted with (b) having 40 or more carbon atoms
Long-chain alkyl groups having an alkylene group and carboxy
Group-containing monocarboxylic compound and molecular weight 10
Ester compound reacted with alcohols of 00 or less
A compound containing an ester compound selected from the group consisting of
A toner having toner particles, said ester compound
Has a number average molecular weight (Mn) of 1550 to 7000.
The weight average molecular weight (Mw) is 1550 to 7000.
And the volume average particle diameter of the toner particles is 3 to 8 μm.
A toner for developing a negatively charged electrostatic charge image, characterized in that
And an image forming method.

Further, the present invention is attached to the main body of the image forming apparatus.
A removable process cartridge, wherein the process cartridge
At least the electrostatic latent image carrier and the developing means.
And the developing means holds toner,
The toner is at least (i) a binder resin and (ii) a colorant.
And (iii) (a) an alkylene group having 40 or more carbon atoms
Having a long-chain alkyl group and a monohydroxy group having a hydroxyl group
Sillic compounds and carboxylic acids with a molecular weight of 1000 or less
Ester compound reacted with (b) having 40 or more carbon atoms
Long-chain alkyl groups having an alkylene group and carboxy
Group-containing monocarboxylic compound and molecular weight 10
Ester compound reacted with alcohols of 00 or less
A compound containing an ester compound selected from the group consisting of
A toner having toner particles, said ester compound
Has a number average molecular weight (Mn) of 1550 to 7000.
The weight average molecular weight (Mw) is 1550 to 7000.
And the volume average particle diameter of the toner particles is 3 to 8 μm.
The present invention relates to a process cartridge characterized by the following.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, a compound obtained by reacting a monohydroxyl compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group with a carboxylic acid having a molecular weight of 1,000 or less (hereinafter referred to as "ester Compound α)), or a compound obtained by reacting a monocarboxylic compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a carboxyl group with an alcohol having a molecular weight of 1,000 or less (hereinafter, “ester compound β”). (Hereinafter referred to as “)” is contained in the toner.
That is, the ester compounds α and β each have a long-chain alkyl group having an alkylene group having 40 or more carbon atoms in the structure and a residue of a hydroxyl group or a carboxyl group of an alcohol or carboxylic acid having a molecular weight of 1000 or less. Is.

By using the toner composition of the present invention, even in a high-speed copying machine having a process speed of 380 mm / sec or more (A4 copying speed 60 sheets / minute or more), good fixability in a low temperature environment can be obtained. And it is possible to provide a good image density in a low humidity environment.

In the present invention, the ester compounds α and β
The viscosity and plasticity can be controlled by the carboxylic acids or alcohols reacted with the above-mentioned monohydroxyl compound or monocarboxylic compound. In the present invention, the carbon number of the alkylene group of the monohydroxyl compound and the monocarboxylic compound is preferably 40 or more, preferably 40 to 200,
More preferably, 50 to 150 is good in terms of toner viscosity control and toner fixing property to paper.

When the carbon number of the alkylene group is less than 40, the viscosity control tends to be insufficient, and when the carbon number becomes too large, the dispersibility of the ester compounds α and β in the binder resin deteriorates. This may cause a problem in the developability as a toner.

In the present invention, the alkylene group of the monohydroxyl compound and the monocarboxylic compound may be, for example, a methylene chain or an ethylene chain. Particularly, the ethylene chain may be used as a control point for the viscosity and plasticity of the ester compounds α and β. Is preferred.

In the present invention, in the molecular weight distribution of the monohydroxyl compound by GPC, the number average molecular weight Mn is preferably 592 or more, more preferably 592.
In the molecular weight distribution by GPC of the monocarboxylic compound, the number average molecular weight Mn is preferably 620 or more, and more preferably 620 to 2860.

The Mn of the monohydroxyl compound is 59.
Mn of less than 2 or monocarboxylic compound is 620
In any of the cases below, the viscosity control tends to be insufficient, and when the Mn value is too large, the dispersibility of the ester compounds α and β in the binder resin may deteriorate. Problems may occur in the developability as a toner.

In the present invention, the Mn (number average molecular weight) of the ester compounds α and β by the GPC method is preferably 1550 to 7000, more preferably 1575 to 600.
0, and Mw (weight average molecular weight) is preferably 1550 to 7000, more preferably 1575 to 600.
It should be 0. This is because the Mn (number average molecular weight) of the ester compounds α and β in the present invention is 1550 or more and the Mw (weight average molecular weight) is 1550 or more, so that the binder resin and the ester compound α or β are melted by heat. The difference in viscosity with time can be reduced.

During thermal kneading, the difference in viscosity between the ester compound α or β and the binder resin during heat melting is reduced,
A more uniform shearing force acts on the binder resin and the ester compound α or β, and even when the compatibility between the binder resin and the ester compound α or β is not good, the ester compound in the binder resin It is possible to improve the dispersibility of α or β.

As a result, the poor dispersion of the ester compound α or β as a wax component in the binder resin can be prevented, and even a toner having a small particle size, particularly a toner having an average particle size of less than 10 μm can be incorporated into the binder resin. Ester compound α or β
1) It is possible to prevent occurrence of 1) image density reduction due to charge-up in a low humidity environment due to variations in toner chargeability and 2) cleaning failure.

Therefore, the Mn of the ester compound α or β
(Number average molecular weight) and Mw (weight average molecular weight) are 1550.
When the average particle size is less than 10 μm, when the image is formed by a high-speed copying machine with a process speed of 380 mm / sec or more, the image density is lowered due to charge-up in a low humidity environment. Easy,
Further, it is difficult to say that the fixing property and the offset resistance are sufficient.

In the present invention, the above action (even in a high speed copying machine having a process speed of 380 mm / sec or more,
The reason why good fixing properties in a low temperature environment and good image density in a low humidity environment are obtained) is not clear, but it is presumed that the following phenomenon occurs. When the toner on a recording material such as paper to which the ester compound α or β is added passes through the fixing roller and is heated by the fixing roller, the ester compound α or β oozes out on the toner surface even at a lower temperature.

At this time, 1) the slipperiness of the toner with respect to the fixing roller is improved,
The toner on the unfixed image preferentially adheres to the recording material, not to the fixing roller; 2) When the ester compound α or β oozes onto the toner surface due to the heating of the fixing roller, the ester compound Since α or β will cover the toner surface in a semi-molten or molten state, the heat transfer coefficient to the toner by the fixing roller will be improved as a result; I think it will improve.

Further, in the present invention, the reason why a good image density in a low humidity environment can be obtained by using the above ester compound α or β is not clear, but it is presumed that the reason is as follows.

Since the above-mentioned ester compound α or β can control the viscosity and plasticity, the dispersibility of the ester compound α or β in the binder resin can be improved, and as a result, the chargeability and environmental stability of the toner can be improved. Is considered to be good, charge-up of the toner in a low humidity environment is prevented, and a good image density can be obtained even in a low humidity environment.

In the present invention, the content of the ester compound α or β contained in the toner is preferably 1 to 20 parts by weight, more preferably 2 to 15 parts by weight with respect to 100 parts by weight of the binder resin. good.

The content of this ester compound α or β is
When the amount is less than 1 part by weight, it is difficult to achieve the effect of improving the fixing property as a toner, and when the amount is more than 20 parts by weight, the dispersibility in the binder resin may deteriorate.
Problems may occur in the developability as a toner.

In the present invention, the method of reacting the monohydroxyl compound and carboxylic acids or the method of reacting the monocarboxylic compound and alcohols is not particularly limited, and one example is monobutyltin oxide. , Dibutyltin oxide, antimony trioxide, tetrabutoxy titanate, zinc acetate,
A method of reacting in the presence of a catalyst such as magnesium acetate can be mentioned.

In the present invention, the saturated aliphatic monohydroxyl compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group is specifically,
Examples include those represented by the following formulas (I)-(IV).

[0050]

[Outside 5]

An example of the substance represented by the above formula (I) is wax alcohol produced by the production method described in US Pat. No. 2,892,858. The wax alcohol is produced in the steps of production, polymerization, oxidation and hydrolysis of triethylaluminum. The manufacturing process is shown below.

Production of triethylaluminum 2Al + 3H ₂ + 4Al (C ₂ H ₅ ) ₃ → 6Al (C ₂
H ₅ ) ₂ HAl (C ₂ H ₅ ) ₂ H + C ₂ H ₆ → Al (C
₂ H ₅ ) ₃ + H ₂

[Outside 6]

The wax alcohol obtained in this process can be used in the present invention.

Further, in the present invention, as an example of the saturated aliphatic monohydroxyl compound, Petrolite Corporation is used.
b Unilin (registered trademark of Unilin), which can be obtained from Mr. Amane Jun.

Further, in the present invention, the monohydroxyl compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group is a reaction product of a long-chain alkyl alcohol and a compound having one epoxy group in the molecule. Is included.

More specifically, the following formula (V), the formula (V), CH ₃ (CH ₂ ) _n OH (n ≧ 40), and the following formula (VI) having one epoxy group in the molecule.

[Outside 7]

(In the formula, R ″ is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₄ —CH ₂ — (R ₄
Represents an ether group or an ester group). ), A compound represented by the following formula (VI),

[Outside 8]

(In the formula, n represents a number of 40 or more, and p is 1
To R, R ″ represents hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₄ —CH ₂ — (R ₄
Represents an ether group or an ester group). ).

The reaction product represented by the above formula (VII) is excellent in improving the fixing property of the toner to the paper, but in the viscosity control point, the reaction product (I) is more preferable than the reaction product represented by the above (VII). The compound represented by-(IV) is preferred.

Specific examples of the compound of the above formula (VI) in which R ″ is hydrogen are shown below.

[0061]

[Outside 9]

In the above formula (VI), R ″ has 1 carbon atom.
Specific examples of the compound having 20 to 20 hydrocarbon groups are shown below.

[0063]

[Outside 10]

In the above formula (VI), R ″ is R ₁ -C.
Specific examples of the compound represented by H _2- (R ₄ represents an ether group or an ester group) are shown below.

[0065]

[Outside 11]

In the present invention, the saturated monocarboxylic compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a carboxyl group is specifically one represented by the following formulas (VIII)-(XI). Is mentioned.

[0067]

[Outside 12]

Examples of the substance represented by the above formula (VIII) include the substance represented by the above formula (I) (a wax alcohol produced by the production method described in US Pat. No. 2,892,858, Can be obtained by modifying (such as uniline available from Petrolite Corporation).

The method of modifying the substance represented by the above formula (I) to obtain the substance represented by the above formula (VIII) is not particularly limited, but one method is as follows. can give.

Specifically, the substance C represented by the above formula (I)
H ₃ (CH ₂ CH ₂ ) ₁ OH (l ≧ 20) was reacted with NaOH pellets under heating, and after cooling, toluene, H ₂ S
The substance represented by the above formula (I) is modified by a method of adding O ₄ , filtering, washing with water, and removing the solvent to obtain a substance represented by the above formula (VIII) CH ₃ (CH ₂ C
A method of obtaining H ₂ ) _q COOH (q ≧ 20) can be mentioned.

In the present invention, the carboxylic acids reacted with the monohydroxyl compound are not particularly limited, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid and lauryl. Acid, myristic acid, palmitic acid, stearic acid, acrylic acid, propionic acid, methacrylic acid, crotonic acid, oleic acid, and other monocarboxylic acids, and their acid anhydrides; fulic acid, nicotinic acid, isonicotinic acid, Heterocyclic carboxylic acids such as these, and their acid anhydrides; fumaric acid,
Unsaturated dicarboxylic acids such as maleic acid, citraconic acid, itaconic acid and their acid anhydrides; saturated dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid and their acid anhydrides; benzoic acid, toluic acid, Carbocyclic carboxylic acids such as naphthoic acid, cinnamic acid, phthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid, and their acid anhydrides; and one or more of them may be used in combination. Is possible.

Of these, carboxylic acids having a valence of 2 or more are particularly preferable in terms of improving the viscosity, plasticity and molecular weight control of the ester compound α.

Further, in the present invention, the molecular weight of the carboxylic acids to be reacted with the monohydroxyl compound is
The amount of 1000 or less, preferably 50 to 1000, and more preferably 100 to 1000 is good in terms of the viscosity, plasticity and molecular weight control as the ester compound α.

When the molecular weight of this carboxylic acid exceeds 1,000, it may be difficult to control the viscosity and plasticity of the ester compound α.

In the present invention, the alcohols to be reacted with the monocarboxylic compound are not particularly limited, and examples thereof include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol,
sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol,
1 such as cinnamyl alcohol and furfuryl alcohol
Polyhydric alcohol; ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol,
Dipropylene glycol, triethylene glycol,
1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, represented by the following formula Bisphenol derivative; formula

[Outside 13]

(Wherein R is an ethylene or propylene group, x and y are each an integer of 1 or more, and x +
The total value of y is 2 to 10. ) Are mentioned, and it is possible to use one kind or a combination of two or more of these.

Of these, dihydric or higher alcohols are particularly preferable in that the viscosity, plasticity and molecular weight of the ester compound β can be well controlled.

Further, in the present invention, the molecular weight of the alcohols reacted with the monocarboxylic compound is 1
000 or less, preferably 50 to 1000, more preferably 100 to 1000 is the viscosity as the ester compound β,
Good in terms of plasticity and molecular weight control. If the molecular weight of this alcohol exceeds 1,000, it may be difficult to control the viscosity and plasticity of the ester compound β.

In the present invention, monohydroxylic compounds, monocarboxylic compounds, ester compounds α
The values of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the ester compound β are those determined by gel permeation chromatography (GPC method). The GPC method is measured under the following conditions. Apparatus: GPC-150C (Waters Co.) Column: GMH-HT 30 cm 2 stations (manufactured by Tosoh Corp.) Temperature: 135 ° C. Solvent: o-dichlorobenzene (0.1% ionol added) Flow rate: 1.0 ml / min Sample: 0.15 % Of the sample is measured under the condition of 0.4 ml injection or more, and the molecular weight calibration curve prepared from the monodisperse polystyrene standard sample is used for calculating the molecular weight of the sample. Further, it is calculated by performing polyethylene conversion using a conversion formula derived from the Mark-Houwink viscosity formula.

In the present invention, the molecular weight values of the carboxylic acids reacted with the monohydroxyl compound and the alcohols reacted with the monocarboxylic compound are determined by subjecting the sample to be measured to derivatization such as silylation and methylation. It is preferable to use the values measured by GC-MS.

In the present invention, the binder resin of the toner is not particularly limited as long as it is a thermoplastic resin, but a polyester resin or a styrene-acrylic resin is preferable.

The polyester resin is not particularly limited and a general polyester resin can be used.
As the monomer constituting the polyester resin, the following substances can be used, but are not limited thereto. As the alcohol component, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A, and diols such as bisphenol derivatives represented by the above formula. To be

As the acid component, unsaturated dicarboxylic acids such as fumaric acid, maleic acid, citraconic acid and itaconic acid or acid anhydrides thereof; dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid or acid thereof Anhydrous; aromatic dicarboxylic acids such as phthalic acid and terephthalic acid.

Examples of trihydric or higher alcohols include glycerin, sorbit and sorbitan, and examples of trihydric or higher acids include trimellitic acid, pyromellitic acid and their acid anhydrides.

The method for producing the polyester resin used in the present invention is not particularly limited, and a conventionally known production method is applied.

The styrene-acrylic resin is not particularly limited, and a general styrene-acrylic resin can be used. The following substances can be used as the monomer constituting the styrene-acrylic resin, but are not limited thereto.

For example, styrene, o-methylstyrene,
m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, p- n-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o -Nitrostyrene, p-
Styrene derivatives such as nitrostyrene; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, Α-Methylene aliphatic monocarboxylic acid esters such as phenyl methacrylate; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid Acrylic esters such as 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate and phenyl acrylate; acrylic acid such as acrylonitrile, methacrylonitrile and acrylamide Methacrylic acid derivative; acrolein; carboxyl group-containing vinyl such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic anhydride, fumaric acid, maleic acid and their monoesters such as methyl, ethyl, butyl and 2-ethylhexyl An example is a system monomer.

In the present invention, a combination of a styrene-based monomer, methacrylic or an acrylic-based monomer and a carboxyl group-containing monomer is particularly preferable.

As the binder resin of the toner, in addition to polyester resin and styrene-acrylic resin, styrene-vinyl methyl ether copolymer, styrene-butadiene copolymer, styrene-vinyl methyl ketone copolymer, styrene-acrylonitrile. -Styrene-based copolymer of styrene of indene copolymer and other vinyl-based monomer; polymethylmethacrylate, polybutylmethacrylate, polyvinylacetate, polyamide, epoxy resin, polyvinylbutyral, polyacrylic acid, phenolic resin, aliphatic Alternatively, an alicyclic hydrocarbon resin, petroleum resin, chlorinated paraffin can be used.

In the present invention, a negative or positive charge control agent can be used if necessary.

As the charge control agent used in the present invention,
The following are listed.

The following substances control the toner to be negatively charged.

For example, an organometallic complex and a chelate compound are effective, and a monoazo metal complex, an acetylacetone metal complex, an aromatic hydroxycarboxylic acid, an aromatic dicarboxylic acid type metal complex can be mentioned. , Aromatic mono- and polycarboxylic acids, metal salts thereof, anhydrides thereof, esters thereof; and phenol derivatives such as bisphenol.

There are the following substances for controlling the toner to be positively charged.

For example, modified products of nigrosine and its fatty acid metal salt; tributylbenzylammonium-1-
Hydroxy-4-naphthosulfonates, quaternary ammonium salts such as tetrabutylammonium tetrafluoroborate, and their analogs such as onium salts such as phosphonium salts and lake pigments thereof; triphenylmethane dyes and lake pigments thereof ( As a lake agent,
Phosphotungstic acid, phosphomolybdic acid, phosphotungstic molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide, ferrocyanide are used); metal salts of higher fatty acids; dibutyltin oxide,
Diorganotin oxides such as dioctyltin oxide and dicyclohexyltin oxide; and diorganotin borates such as dibutyltin borate, dioctyltin borate, and dicyclohexyltin borate, may be used alone or in combination of two or more. Among these, nigrosine-based or quaternary ammonium salts are particularly preferably used.

In the toner of the present invention, as a colorant,
Metals such as iron, cobalt, nickel or aluminum of these metals, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth,
Cadmium, calcium, manganese, selenium, titanium,
It is possible to use magnetic materials such as alloys of metals such as tungsten, vanadium and mixtures thereof.

The ferromagnetic material, which is a magnetic material, has an average particle size of 0.1 to 2 μm, preferably 0.1 to 0.5 μm, and the amount of the component contained in the toner is 100 parts by weight of the resin component. Approximately 20 to 200 parts by weight, particularly preferably 40 to 150 parts by weight per 100 parts by weight of the resin component.

The magnetic properties of this magnetic material under the application of 10 K oersted are coercive force of 20 to 150 ested, saturation magnetization of 50 to 200 emu / g, and residual magnetization of 2 to 20 emu.
It is preferable to have / g.

The magnetic toner containing this magnetic material can be used as a magnetic one-component developer composed of only the toner.

Examples of the colorant that can be used in the toner of the present invention include any suitable pigment or dye in addition to the above magnetic material. Examples of pigments include carbon black, aniline black, acetylene black, naphthol yellow, hansa yellow, rhodamine lake, alizarin lake, red iron oxide, phthalocyanine blue, and indanthrene blue.

These are used in an amount necessary and sufficient for maintaining the optical density of the fixed image, and the amount added is 0.1 to 20 parts by weight, preferably 2 to 10 parts by weight, based on 100 parts by weight of the resin component. . Examples of the dye include azo dyes, anthraquinone dyes, and methine dyes. For the same purpose as in the case of the above pigment, 0.1 to 20 parts by weight, preferably 0 to 100 parts by weight of the resin component is used. The addition amount of 3 to 3 parts by weight is good.

The color toner containing the pigment or dye is used as a non-magnetic one-component developer composed of only the toner without being mixed with the carrier, or is composed of the toner and the carrier mixed with the carrier. It can also be used as a two-component developer.

As the above carrier, all known carriers can be used. For example, magnetic powder such as iron powder, ferrite and nickel powder, glass beads and the surface thereof are made of fluorine resin, vinyl resin or silicon. Examples include those treated with a resin such as a system resin.

The toner of the present invention contains a wax-like substance such as low molecular weight polyethylene or low molecular weight polypropylene in an amount of 0.5 to 100 parts by weight with respect to 100 parts by weight of a binder resin for the purpose of further improving offset resistance at the time of heat roll fixing. You may add about 10 weight part.

To prepare the toner according to the present invention, a binder resin, the ester compound α or β, a pigment as a colorant, a dye or a magnetic substance, and if necessary, a charge control agent, a metal salt or a metal complex, etc. Henschel mixer,
After sufficiently mixing with a mixer such as a ball mill, using a heat kneader such as a heating roll, a kneader, an extruder, kneading, and kneading, the metal compounds, pigments, and the like in the resin are mutually compatible. Toner particles can be obtained by dispersing or dissolving a dye and a magnetic material, cooling and solidifying, and then pulverizing and classifying.

Further, if necessary, desired additives may be sufficiently mixed with the toner particles by a mixer such as a Henschel mixer to obtain the toner according to the present invention.

In the toner of the present invention, the charging stability,
To improve developability, fluidity and durability, it is preferable to add fine silica powder.

The silica fine powder used in the present invention is BE.
Specific surface area due to nitrogen adsorption measured by T method is 30 m ² / g
Those in the above range (particularly 50 to 400 m ² / g) give good results. The fine silica powder is used in an amount of 0.01 to 8 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the toner.

The fine silica powder used in the present invention contains, if necessary, a silicone varnish, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, functional groups for the purpose of hydrophobizing and controlling the charging property. It is also preferred that the silane coupling agent having a silane coupling agent or other treating agent such as an organic silicon compound is appropriately used alone or in combination.

Other additives include, for example, Teflon,
Lubricants such as zinc stearate and polyvinylidene fluoride;
Abrasives such as cerium oxide, silicon carbide and strontium titanate (among them, strontium titanate is preferred); for example, fluidity-imparting agents such as titanium oxide and aluminum oxide (among which hydrophobic is particularly preferred);
An anti-caking agent; a conductivity-imparting agent such as carbon black, zinc oxide, antimony oxide or tin oxide; a developability improving agent such as reverse polarity white fine particles or reverse polarity black fine particles can also be used.

In the present invention, the toner preferably has a volume average particle diameter of 3 to 8 μm from the viewpoint of improving image quality. In the present invention, the volume average particle diameter of the toner is preferably measured by the Coulter counter method.

As an example of the procedure of the measuring method, a surfactant is added as a dispersant to an electrolytic aqueous solution (for example, NaCl aqueous solution), and then a measurement sample is added. An electrolytic solution in which the sample is suspended is subjected to a dispersion treatment with an ultrasonic disperser, and a method of measuring by a Coulter counter method can be mentioned.

Further, an image forming apparatus and a process cartridge using the toner of the present invention will be described with reference to FIG.

The surface of the photoconductor (electrostatic latent image carrier) 1 is positively charged by the primary charger (charging means) 2, and light image exposure (latent image forming means) 5 (slit exposure or laser beam scanning exposure). To form a latent image (analog or digital) by image scanning with the magnetic blade 11 and the magnet 1.
The latent image is developed with a negatively chargeable one-component magnetic developer 10 held in a developing device (developing means) 9 having a developing sleeve 4 containing 4 therein. Between the conductive substrate of the photosensitive drum (photoconductor) 1 and the developing sleeve 4 in the developing section,
Alternating bias, pulse bias and / or DC bias are applied by the bias applying means 12. When the transfer material P is conveyed and reaches the transfer portion, the secondary charging device (transfer means) 3 charges the back surface of the transfer material P (the surface opposite to the photosensitive drum side) to develop a developed image on the surface of the photosensitive drum. The (toner image) is electrostatically transferred onto the transfer material P. Photosensitive drum 1
The transfer material P separated from is subjected to a fixing process by the heating and pressure roller fixing device (fixing means) 7 in order to fix the toner image on the transfer material P.

The one-component developer remaining on the photosensitive drum after the transfer step is removed by a cleaning device (cleaning means) 8 having a cleaning blade. The photosensitive drum 1 after cleaning is erased by erase exposure 6 and the process starting from the charging process by the primary charger 2 is repeated again.

The electrostatic latent image carrier (photosensitive drum) 1 has a photosensitive layer and a conductive substrate, and moves in the arrow direction. The non-magnetic cylindrical developing sleeve 4, which is a toner carrier, rotates so as to move in the same direction as the surface of the electrostatic latent image carrier in the developing section. Inside the non-magnetic cylindrical sleeve 4, a multi-pole permanent magnet (magnet roll) which is a magnetic field generating means is arranged so as not to rotate. The one-component insulating magnetic developer 10 in the developing device (developing means) 9 is supplied by the developer supply roller 13 and applied on the non-magnetic cylindrical surface, and due to the friction between the surface of the sleeve 4 and the toner particles, Toner particles are given a negative triboelectric charge, for example. Further, by arranging an iron magnetic doctor blade (developer layer thickness regulating member) 11 close to the cylindrical surface (interval 50 μm to 500 μm) and facing one magnetic pole position of the multipolar permanent magnet, the developer layer Is regulated to be thin (30 μm to 300 μm) and uniformly so that the developer layer thinner than the gap between the electrostatic latent image carrier 1 and the toner carrier (developing sleeve) 4 in the developing section is not in contact. To form. By adjusting the rotation speed of the toner carrier 4, the sleeve surface speed is made substantially equal to or close to the speed of the electrostatic latent image carrier surface. Permanent magnets may be used as the magnetic doctor blade 11 instead of iron to form the opposing magnetic poles. An AC bias or a pulse bias may be applied by the bias means 12 between the toner carrier 4 and the electrostatic latent image carrier surface in the developing section.

Upon transfer of the toner particles in the developing portion, the toner particles are transferred to the electrostatic latent image side by the action of the electrostatic force of the electrostatic latent image bearing surface and the AC bias or the pulse bias.

Instead of the magnetic doctor blade 11, an elastic blade made of an elastic material such as silicone rubber is used to regulate the layer thickness of the developer layer by pressing, and the developer is coated on the developer carrier. Is also good.

An electrophotographic apparatus is constructed by integrally combining a plurality of constituent elements such as the above-mentioned electrostatic latent image carrier, developing means and cleaning means as a process cartridge, and the process cartridge is used as an image. Main body of forming apparatus (for example, copier, laser beam printer,
It may be configured to be attachable to and detachable from a facsimile). For example, the developing unit and the electrostatic latent image carrier are integrally supported to form a cartridge, which is a process cartridge that can be attached to and detached from the main body of the image forming apparatus, and is attachable and detachable using a guide unit such as a rail of the main body of the image forming apparatus. You can At this time, the process cartridge may be provided with a charging unit and / or a cleaning unit.

When the image forming apparatus is used as a copying machine or a printer, the optical image exposure 5 is reflected light or transmitted light from an original, or an original is read and converted into a signal, and scanning of a laser beam or an LED is performed by this signal. It is performed by driving the array or the liquid crystal shutter array.

When the image forming apparatus of the present invention is used as a printer for a facsimile, the optical image exposure 5 is exposure for printing received data. FIG. 2 is a block diagram showing an example of this case.

The controller 21 controls the image reading section 20 and the printer 29. The entire controller 21 is CP
It is controlled by U27. The read data from the image reading unit is transmitted to the partner station through the transmission circuit 23. The data received from the partner station is sent to the printer 29 through the receiving circuit 22. Predetermined image data is stored in the image memory. The printer controller 28 is the printer 2
9 is controlled. 24 is a telephone.

The image received from the line 25 (image information from the remote terminal connected through the line) is demodulated by the receiving circuit 22, and then the CPU 27 decodes the image information and sequentially processes the image memory 26. Stored in. Then, when at least one page of image is stored in the sac Q6,
The image of that page is recorded. CPU 27 is a memory 2
The image information of one page is read from 6 and the combined image information of one page is sent to the printer controller 28. The printer controller 28 is the one from the CPU 27.
When the image information of the page is received, the printer 29 is controlled to record the image information of the page.

The CPU 27 is receiving the next page while the printer 29 is recording.

The image is received and recorded as described above.

[0126]

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

A production example of a compound (ester compound β) obtained by reacting a compound (ester compound α) obtained by reacting a monohydroxyl compound with alcohols and a carboxylic acid of a monocarboxylic compound is shown below.

(Production Example 1)

[Outside 14]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound A.

Mn of ester compound A by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 2361 and Mw = 2516, respectively.

(Production Example 2)

[Outside 15]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound B.

Mn of ester compound B by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 2020 and Mw = 2190, respectively.

(Production Example 3)

[Outside 16]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound C.

Mn of ester compound C by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 3118 and Mw = 3336, respectively.

(Production Example 4)

[Outside 17]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound D.

Mn of ester compound D by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 1605 and Mw = 1702, respectively.

(Production Example 5)

[Outside 18]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 150 minutes. This was designated as ester compound E.

Mn of ester compound E by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 839 and Mw = 890, respectively.

(Production Example 6)

[Outside 19]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound F.

Mn of ester compound F by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 1635 and Mw = 1740, respectively.

(Production Example 7)

[Outside 20]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound G.

Mn of ester compound G by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 1690 and Mw = 1812, respectively.

(Production Example 8)

[Outside 21]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound H.

Mn of ester compound H by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 801 and Mw = 931, respectively.

(Production Example 9)

[Outside 22]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound I.

Mn of ester compound I by GPC method
The (number average molecular weight) and Mw (weight average molecular weight) were Mn = 920 and Mw = 1005, respectively.

(Production Example 10)

[Outside 23]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound J.

Mn of ester compound J by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 1890 and Mw = 2005, respectively.

(Production Example 11)

[Outside 24]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound K.

Mn of ester compound K by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 2041 and Mw = 2181, respectively.

(Production Example 12)

[Outside 25]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound L.

Mn of ester compound L by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 4843 and Mw = 5181, respectively.

(Production Example 13)

[Outside 26]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound M.

Mn of ester compound M by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 1636 and Mw = 1751, respectively.

(Production Example 14)

[Outside 27]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound N.

Mn of ester compound N by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 847 and Mw = 907, respectively.

(Production Example 15)

[Outside 28]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound O.

Mn of ester compound O by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 1602 and Mw = 1701, respectively.

(Production Example 16)

[Outside 29]

Was reacted in the presence of monobutyltin oxide, and after a reaction time of 150 minutes, the reaction product was taken out. This was designated as ester compound P.

Mn of ester compound P by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 2631 and Mw = 2816, respectively.

(Production Example 17)

[Outside 30]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound Q.

Mn of ester compound Q by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 821 and Mw = 961, respectively.

(Production Example 18)

[Outside 31]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 120 minutes. This was designated as ester compound R.

Mn of ester compound R by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 590 and Mw = 688, respectively.

The ester compounds A to R produced in the above Production Examples 1 to 18, the number average molecular weight and the weight average molecular weight of the monohydroxyl compound, the monocarboxylic compound used in the reaction, and the molecular weight and the monocarboxylic acid of the carboxylic acid and alcohols. The carbon numbers of the alkylene groups of the hydroxylic compound and the monocarboxylic compound are shown in Tables 1 and 2.

[0183]

[Table 1]

[0184]

[Table 2]

Example 1 Polyester resin 100 parts by weight (bisphenol A-trimellitic acid-terephthalic acid-neopentyl glycol polyester; Mw 45,000) -Magnetic iron oxide 90 parts by weight-Negatively charge control agent 2 Parts by weight / ester compound A 3 parts by weight The above materials were well mixed in a blender and then kneaded by a twin-screw kneading extruder set at 110 ° C. The obtained kneaded product is cooled, coarsely pulverized by a cutter mill, and then finely pulverized by a fine pulverizer using a jet stream, and the finely pulverized powder obtained is classified to have a volume average particle diameter of 6.52 μm. Magnetic black fine powder (toner) of To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively chargeable hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a magnetic toner. A magnetic one-component developer was used.

The one-component type developer was applied to a commercially available copying machine Canon NP-9800 (process speed 503 mm / sec) which is an image forming apparatus shown in FIG. 1, and was used at room temperature and low humidity (23.5 ° C., 5% Rh). ) The image was printed under the environmental conditions. Table 3 shows the image output test results. As is clear from Table 3, both the initial image and the 30,000-sheet endurance image had a high image density and were good images. The amount of charge on the developing sleeve was stable at the initial stage and after the endurance of 30,000 sheets, and neither cleaning failure nor drum fusion occurred during the image output endurance. The fixability was at a good level such that the image density reduction rate was 8.3% at 15 ° C. and 10% Rh and 8.7% at 7.5 ° C. and 10% Rh, and the offset resistance was also good. .

The resolving power, which is an evaluation criterion for the image quality of the copied image, is 8.0 lines / mm even after the initial durability of 30,000 sheets.
It was good and stable.

In the above examples, evaluations of the charge amount of the toner layer on the developing sleeve, the resolving power of the copied image, which is an evaluation standard of the image quality of the copied image, the fixing property and the offset resistance were carried out by the following methods. . The charge amount of the toner layer on the developing sleeve The charge amount of the toner layer on the developing sleeve per unit area was determined by using a so-called suction type Faraday cage method.
That is, by pressing the outer cylinder against the developing sleeve to suck all the toner on a certain area on the developing sleeve, and at the same time measuring the amount of charge accumulated in the inner cylinder electrostatically shielded from the outside. The amount of electric charge per unit area on the developing sleeve was determined.

In the present invention, the resolution of a copied image was measured by the following method. That is, in a pattern composed of five thin lines having the same line width and spacing, 2.8, 3.2, 3.6, 4.0, 4.5, 5.0,
5.6, 6.3, 7.1, 8.0, 9.0, 10.0 Create an original image that is drawn as if there were 10. An image obtained by copying an original document having these 12 types of line images under proper copying conditions is observed with a magnifying glass, and the number of images (lines / mm) in which fine lines are clearly separated is taken as the value of resolution. To do.

The larger this number is, the higher the resolution is.・ Fixing property The fixing property is that the evaluation machine and the fixing device inside the evaluation machine are completely cold when the evaluation machine is left overnight in a low temperature and low humidity environment (15 ° C, 10% Rh and 7.5 ° C, 10% Rh). 200 copies of the copied image were taken continuously from the state of acclimatization to a low humidity environment, and the 200th copy of the copied image was used for evaluation of fixing property. To evaluate the fixing property, the image was rubbed with a sillbon paper 10 times in a reciprocating manner under a load of about 100 g, and the peeling of the image was evaluated by the reduction rate (%) of reflection density. Therefore, as the value of the reduction rate of the reflection density after rubbing (image density reduction rate) is larger, the rate of peeling of the image due to rubbing is higher, and the toner fixability is worse. -Offset resistance The offset resistance was evaluated based on whether or not the toner once taken in the cleaning wave was transferred to the upper fixing roller to contaminate the copied material when the copying was continuously performed. As an evaluation method, in a low-temperature low-humidity environment (15 ° C., 10%), after continuously taking 200 copy images, one copy image is taken at intervals of 30 seconds for up to 3 minutes, resulting in image contamination. I checked. Furthermore, low temperature and low humidity environment (7.5 ° C, 10
%), After taking 500 consecutive copy images,
Copy images were taken at intervals of one second for up to 3 minutes, and it was examined whether image contamination occurred. The offset resistance of the toner was evaluated according to the following evaluation criteria. ○: No image contamination occurred ×: Image contamination occurred

Example 2 The same material as in Example 1 was used except that the ester compound B was used in place of the ester compound A, and the magnetic black fine powder (volume average particle size 6.24 μm) was prepared by the same method. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As is clear from Table 3, the results show that the image density is high in both the initial image and the 30,000-sheet endurance image,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. Also,
Regarding the fixability, the image density reduction rate was a good level of 9.5% at 15 ° C. and 10% Rh, but was 7.5% at 10%.
It was 14.6% under Rh. The offset resistance was good.

Example 3 The same material as in Example 1 was used except that the ester compound C was used in place of the ester compound A, and the magnetic black fine powder (volume average particle size 6.48 μm) was obtained by the same method. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As is clear from Table 3, the results show that the initial image and the 30,000-sheet durability image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 5.1 at 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, a good level of 5.3% was obtained, and the offset resistance was also good.

Example 4 The same material as in Example 1 was used except that the ester compound A was used in place of the ester compound D, and the magnetic black fine powder (volume average particle diameter 6.55 μm) was obtained by the same method. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As is clear from Table 3, the results show that the image density is high in both the initial image and the 30,000-sheet endurance image,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 8.6 at 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, a good level of 10.5%, and good offset resistance.

Reference Example 1 A magnetic black fine powder (volume average particle diameter: 6.57 μm) was prepared in the same manner as in Example 1 except that the ester compound E was used in place of the ester compound A and the same method was used. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As is clear from Table 3, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is 10. When the image density reduction rate is 15 ° C. and 10% Rh.
It was a good level of 5%, but 7.5 ° C, 10% Rh
Below it was 17.2%. The offset resistance was good.

Example 5 A magnetic black fine powder having a volume average particle diameter of 5.04 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material in Example 1. To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a magnetic toner. Got

Using this magnetic toner as a magnetic one-component type developer, the same evaluation as in Example 1 was performed.

As is clear from Table 3, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 8.4 at 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, and a good level of 9.4%, and offset resistance was also good.

The resolution, which is a criterion for evaluating the image quality of a copied image, was 9.0 lines / mm at the initial stage, even after running 30,000 sheets, and was good and stable.

Reference Example 2 A magnetic black fine powder having a volume average particle size of 10.5 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material in Example 1. To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a magnetic toner. Got

Using this magnetic toner as a magnetic one-component type developer, the same evaluation as in Example 1 was carried out.

As is clear from Table 3, the results show that the image density is high in both the initial image and the 30,000-sheet endurance image.
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 8.6 at 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, a good level of 9.8%, and good offset resistance.

The resolution, which is a criterion for evaluating the image quality of a copied image, is 5.6 lines / mm at the initial stage and is 5. 5 after running 30,000 sheets.
The number was 0 lines / mm, which was a slightly lower level than in Example 1.

Comparative Example 1 A magnetic black fine powder having a volume average particle diameter of 6.51 μm was prepared by the same method as in Example 1 except that the ester compound F was used in place of the ester compound A. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As is clear from Table 3, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. However, the fixability is that the image density reduction rate is 15% at 10%.
It was 11.4% under Rh, but was 7.5% at 10% R
Under h, it was 22.6%, and the offset resistance was good after 200 sheets under 15 ° C. and 10% Rh, but after 500 sheets under 7.5 ° C. and 10% Rh. , Image pollution occurred.

Comparative Example 2 A magnetic black fine powder having a volume average particle size of 6.47 μm was prepared by the same method as in Example 1 except that the ester compound G was used in place of the ester compound A. Toner). To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed by a Henschel mixer. The same evaluation as was done.

As a result, as is clear from Table 3, both the initial image and the 30,000-sheet durability image were high in image density and were good images. Initial charge on the developing sleeve is 30
It was stable even after 000 sheets were durable, and neither cleaning failure nor drum fusion occurred during image formation durability. However, the fixing property is that the image density reduction rate is 15 ° C, 10% R.
It was 12.6% under h, but was 7.5 ° C, 10% Rh.
Below, it was 24.1%, and further, the offset resistance showed image contamination after 500 sheets at 15 ° C. and 10% Rh.

Comparative Example 3 A magnetic black fine powder having a volume average particle size of 6.28 μm was prepared in the same manner as in Example 1 except that the ester compound H was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to parts by weight and mixing with a Henschel mixer.

As is clear from Table 3, the initial image was good, but the image density decreased as the image output durability was increased, and the image density became 1.11 at 6,500 sheets. The durability was stopped at 6,500 sheets. Further, the toner charge amount on the developing sleeve after the endurance of 6,500 sheets was −20.3 μC / g.

During the image output durability test, cleaning failure occurred near 6400 sheets and drum fusion occurred around 6350 sheets.

The fixability is such that the image density reduction rate is 15 ° C. and 10
It was a poor level of 20.7% under% Rh, and the offset resistance caused image contamination due to wave stains.

Comparative Example 4 A magnetic black fine powder having a volume average particle size of 6.17 μm was prepared in the same manner as in Example 1 except that the ester compound I was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to parts by weight and mixing with a Henschel mixer.

As is clear from Table 3, the initial image was good, but the image density decreased as the image output durability was increased, and the image density was 1.07 at 4,100 sheets. Durability was stopped at 4,100 sheets. The toner charge amount on the developing sleeve after 4,100 sheets after running was −21.1 μC / g.

During image output durability, defective cleaning occurred around 4000 sheets, and drum fusion occurred around 4050 sheets.

The fixability is such that the image density reduction rate is 15 ° C., 10
It was a low level of 21.5% under% Rh, and the anti-offset property caused image contamination due to wave stain.

Comparative Example 5 Magnetic black fine powder having a volume average particle size of 6.31 μm was prepared in the same manner as in Example 1 except that low molecular weight polyethylene was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 1
In the same manner as in Example 1, negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ^{2 /} g) of 0.6 parts by weight was used.
Parts by weight were added and mixed with a Henschel mixer, and the same evaluation as in Example 1 was performed.

As a result, as is apparent from Table 3, the initial image was good, but the image density decreased as the image output durability was increased, and the image density became 1.12 after 3000 sheets. Durability was stopped at 3000 sheets. The amount of electrified toner on the developing sleeve after 3,000 sheets after running was −23.1 μC / g.

During the image output endurance, cleaning failure occurred around 2850 sheets, and drum fusion occurred around 2900 sheets.

The fixing property is that the image density reduction rate is 15 ° C., 10%.
It was a poor level of 23.4% under% Rh, and the anti-offset property caused image contamination due to wave stain.

The results of Examples 1 to 7 and Comparative Examples 1 to 5 are shown in Table 3.

[0224]

[Table 3]

Example 6 A magnetic black fine powder having a volume average particle size of 6.24 μm was prepared in the same manner as in Example 1 except that the ester compound J was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is 8. when the image density reduction rate is 15 ° C. and 10% Rh.
It was a good level of 9.1% under 4%, 7.5 ° C. and 10% Rh, and the offset resistance was also good.

The resolving power, which is a criterion for evaluating the image quality of the copied image, was 30,000 initially and 8.0 lines / mm after the durability test, which was good and stable.

Example 7 A magnetic black fine powder having a volume average particle size of 6.51 μm was prepared in the same manner as in Example 1 except that the ester compound K was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 9.9 at 15 ° C. and 10% Rh.
%, It was 14.4% under 7.5 ° C. and 10% Rh, and the offset resistance was good.

Example 8 A magnetic black fine powder having a volume average particle diameter of 6.37 μm was prepared in the same manner as in Example 1, except that the ester compound L was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is apparent from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 4.7 at 15 ° C. and 10% Rh.
%, A good level of 5.1% under 7.5 ° C. and 10% Rh, and good offset resistance.

Example 9 A magnetic black fine powder having a volume average particle diameter of 6.31 μm was prepared in the same manner as in Example 1, except that the ester compound M was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 8.8 at 15 ° C. and 10% Rh.
%, 7.5 ° C., and 10% Rh, the level was as good as 10.6%, and the offset resistance was also good.

Reference Example 3 A magnetic black fine powder having a volume average particle size of 6.45 μm was prepared in the same manner as in Example 1 except that the ester compound N was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is apparent from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is 10.4 at an image density reduction rate of 15 ° C. and 10% Rh.
%, But was 17.7% at 7.5 ° C. and 10% Rh, and the offset resistance was good.

Example 10 The magnetic black fine powder having a volume average particle diameter of 5.01 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material in Example 6 . To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of negatively chargeable hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a magnetic toner. Obtained.

Using this magnetic toner as a magnetic one-component developer, the same evaluation as in Example 1 was carried out.

As is clear from Table 4, the results were good images with high image density in both the 30,000 initial images and the durable images. Initial charge on the developing sleeve is 30
It was stable even after 000 sheets were durable, and neither cleaning failure nor drum fusion occurred during image formation durability. The fixability is 8.6 when the image density reduction rate is 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, and a good level of 9.4%, and offset resistance was also good.

The resolving power, which is an evaluation criterion for the image quality of the copied image, was 9.0 lines / mm at the initial stage, even after running 30,000 sheets, and was good and stable.

Reference Example 4 The magnetic black fine powder having a volume average particle diameter of 10.7 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material in Example 6 . To 100 parts by weight of the obtained magnetic black fine powder, 0.6 part by weight of negatively chargeable hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a magnetic toner. Obtained.

Using this magnetic toner as a magnetic one-component developer, the same evaluation as in Example 1 was carried out.

As is clear from Table 4, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is 8.8 when the image density reduction rate is 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, a good level of 9.6%, and good offset resistance.

The resolution, which is a criterion for the image quality of the copied image, is 5.6 lines / mm at the initial stage and is 5. 5 after running 30,000 sheets.
The number was 0 lines / mm, which was a slightly lower level than in Example 6 .

Comparative Example 6 A magnetic black fine powder having a volume average particle size of 6.47 μm was prepared in the same manner as in Example 1, except that the ester compound O was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the results show that the image density is high in both the initial image and the 30,000-sheet endurance image,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. However, the fixability is that the image density reduction rate is 15% at 10%.
Under Rh, it was 11.6%, but at 7.5 ° C, 10%
Under Rh, it was 22.9%, and the offset resistance was good after 200 sheets under 15 ° C. and 10% Rh, but after 500 sheets under 7.5 ° C., 10% Rh, the image was Contamination has occurred.

Comparative Example 7 A magnetic black fine powder having a volume average particle size of 6.38 μm was prepared in the same manner as in Example 1, except that the ester compound P was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the results show that the image density is high in both the initial image and the 30,000-sheet endurance image.
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. However, the fixability is such that the image density reduction rate is 15 ° C and 10% R.
It was 12.7% under h, but was 7.5 ° C. and 10% Rh.
Below, it is 24.5%, and the offset resistance is
After 200 sheets at 15 ° C and 10% Rh, it was good,
Image contamination occurred after 500 sheets at 7.5 ° C. and 10% Rh.

Comparative Example 8 A magnetic black fine powder having a volume average particle diameter of 6.41 μm was prepared in the same manner as in Example 1 except that the ester compound Q was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the initial image was good, but the image density decreased as the image output durability was increased, and the image density became 1.10 at 6450 sheets. The durability was stopped at 6,450 sheets. The charge amount of the toner on the developing sleeve at the time of 6450 sheets after running was −20.5 μC / g.

During the image output durability, defective cleaning occurred around 6380 sheets and drum fusion occurred around 6400 sheets.

The fixing property is that the image density reduction rate is 15 ° C., 10%.
It was a low level of 20.1% under% Rh, and the anti-offset property caused image contamination due to wave stain.

Comparative Example 9 A magnetic black fine powder having a volume average particle size of 6.37 μm was prepared in the same manner as in Example 1 except that the ester compound R was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As is clear from Table 4, the initial image was good, but the image density decreased as the image development durability increased, and the image density became 1.09 after 4000 sheets. Durability was stopped at 4000 sheets. The amount of electrified toner on the developing sleeve at 4000 sheets after running was −21.8 μC / g.

During the image output durability test, cleaning failure occurred around 3900 sheets and drum fusion occurred around 3930 sheets.

The fixing property is that the image density reduction rate is 15 ° C., 10%.
It was a low level of 21.7% under% Rh, and the anti-offset property caused image contamination due to wave stain.

[0256] The above Example 6-10, the results of Reference Examples 1 to 2 and Comparative Examples 6-9 are shown in Table 4 together with the results of Comparative Example 5.

[0257]

[Table 4]

Example 11 Polyester resin (polyester consisting of bisphenol A-trimellitic acid-terephthalic acid-neopentyl glycol; Mw 430,000) 100 parts by weight Carbon Black Mogul L (manufactured by Cabot) 3 parts by weight Negatively charged Control agent 1 part by weight Ester compound A 3 parts by weight The above materials were well mixed by a blender and then kneaded by a twin-screw kneading extruder set at 110 ° C. The obtained kneaded product was cooled and coarsely pulverized with a cutter mill, and then finely pulverized using a fine pulverizer using a jet stream, and the obtained fine pulverization was classified to have a volume average particle diameter of 6.39 μm. A non-magnetic black fine powder (toner) was obtained. To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of a negatively-charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added and mixed with a Henschel mixer to obtain a toner. The toner thus obtained and a post-fluorine resin-coated carrier (300/350 mesh) were mixed at a toner concentration of 5% to obtain a two-component developer.

A commercial copying machine Canon NP-5060 (process speed 324 mm / s)
ec), and image formation was performed under ambient temperature and low humidity (23.5 ° C., 5%) environmental conditions. Table 5 shows the results of the image output test conducted in the same manner as in Example 1. As is clear from Table 5, both the initial image and the 30,000-sheet durability image were high in image density and were good images. The amount of charge on the developing sleeve was stable at the initial stage and after the endurance of 30,000 sheets, and neither cleaning failure nor drum fusion occurred during the image output endurance.

The fixability is such that the image density reduction rate is 15 ° C. and 10
% Rh 8.5%, 7.5 ° C., 10% Rh 8.7
%, And the offset resistance was also good.

The resolving power, which is an evaluation criterion for the image quality of the copied image, is 8.0 lines / mm even after the initial durability of 30,000 sheets.
It was good and stable.

Example 12 The same materials as in Example 11 were used, except that the ester compound J was used in place of the ester compound A, and the same method was used to produce a non-magnetic black powder having a volume average particle size of 6.47 μm. A fine powder (toner) was obtained. Obtained black fine powder 10
0 parts by weight, as in Example 11 , negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ^{2 /} g) 0.6
After adding parts by weight and mixing with a Henschel mixer, the same evaluation as in Example 11 was carried out by mixing with a fluororesin carrier.

As is clear from Table 5, the results show that the image density is high for both the initial image and the 30,000-sheet endurance image.
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability.

The fixability is such that the image density reduction rate is 15 ° C. and 10
8.6% under% Rh, 7.5 ° C, under 10% Rh, 8.
It was a good level of 9%, and the offset resistance was also good.

Example 13 In Example 11 , non-magnetic black fine powder having a volume average particle diameter of 5.03 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material. To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a toner. .

[0266] were mixed with the toner Similarly fluorine resin-coated carrier as in Example 11, as a two-component developer was subjected to the same evaluation as in Example 11.

As is clear from Table 5, the results show that the image density is high for both the initial image and the 30,000-sheet endurance image.
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 8.7 at 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, a good level of 9.5%, and good offset resistance.

The resolving power, which is an evaluation criterion for the image quality of the copied image, was 9.0 lines / mm after the initial durability of 30,000 sheets, which was good and stable.

Reference Example 5 In Example 11 , non-magnetic black fine powder having a volume average particle diameter of 10.3 μm was obtained by changing the pulverization and classification conditions of the kneaded material of the toner material. To 100 parts by weight of the obtained black fine powder, 0.6 part by weight of negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) was added in the same manner as in Example 1 and mixed with a Henschel mixer to obtain a toner. .

[0270] The toner was mixed in the same manner as in the fluorine resin-coated carrier as in Example 11, as a two-component developer was subjected to the same evaluation as in Example 11.

As is clear from Table 5, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is 8.6 when the image density reduction rate is 15 ° C. and 10% Rh.
%, 7.5 ° C., 10% Rh, and a good level of 9.7%, and the offset resistance was also good.

The resolution, which is a criterion for the image quality of the copied image, is 5.6 lines / mm at the initial stage and is 5. 5 after running 30,000 sheets.
The number was 0 lines / mm, which was a slightly lower level than in Example 11 .

Comparative Example 10 A nonmagnetic black material having a volume average particle size of 6.35 μm was prepared in the same manner as in Example 11 except that the ester compound F was used in place of the ester compound A. A fine powder (toner) was obtained. Obtained black fine powder 10
0 parts by weight, as in Example 11 , negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ^{2 /} g) 0.6
After adding parts by weight and mixing with a Henschel mixer, the same evaluation as in Example 11 was carried out by mixing with a fluororesin carrier.

As is clear from Table 5, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on the developing sleeve is 3
It was stable even after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. The fixability is such that the image density reduction rate is 11.6 at 15 ° C. and 10% Rh.
%, But was 22.8% at 7.5 ° C. and 10% Rh, and the offset resistance was good after 200 sheets at 15 ° C. and 10% Rh, but was 7.5 ° C. , 10% Rh
Image staining occurred after the lower 500 sheets.

Comparative Example 11 A nonmagnetic black material having a volume average particle size of 6.31 μm was prepared in the same manner as in Example 11 , except that the ester compound O was used in place of the ester compound A. A fine powder (toner) was obtained. Obtained black fine powder 10
0 parts by weight, as in Example 11 , negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ^{2 /} g) 0.6
After adding parts by weight and mixing with a Henschel mixer, a fluororesin carrier was mixed and the same evaluation as in Example 11 was performed.

As is clear from Table 5, the results show that the initial image and the 30,000-sheet endurance image have high image densities,
It was a good image. Initial charge on active sleeve is 3
It was stable after running 0000 sheets, and neither cleaning failure nor drum fusion occurred during image running durability. Fixability is 11.5% at 15 ° C, 10% Rh, image density reduction rate.
However, the offset resistance was 23.0% at 7.5 ° C. and 10% Rh, and the offset resistance was good after 200 sheets at 15 ° C. and 10% Rh. Image staining occurred after 500 sheets under 10% Rh.

Comparative Example 12 The same materials as in Example 11 were used except that low molecular weight polyethylene was used in place of the ester compound A,
By the same method, a non-magnetic black fine powder (toner) having a volume average particle diameter of 6.41 μm was obtained. 100 parts by weight of the obtained black fine powder was mixed with negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) as in Example 11.
After 0.6 part by weight was added and mixed with a Henschel mixer, the mixture was mixed with a fluororesin-coated carrier and the same evaluation as in Example 11 was performed.

As is clear from Table 5, the result was that the initial image was good, but the image density decreased as the image output durability was increased, and the image density became 1.10 after 3000 sheets. Durability was stopped at 3000 sheets. The toner charge on the developing sleeve after 3,000 sheets after running was −23.5 μC / g.

During the image output durability, cleaning failure occurred near 2650 sheets and drum fusion occurred around 2700 sheets.

The fixing property is that the image density reduction rate is 15 ° C. and 10%.
It was a low level of 23.7% under Rh, and the anti-offset property caused image contamination due to wave stain.

[0281]

[Table 5]

(Production Example 19) CH ₃ (CH ₂ CH ₂ ) ₂₇ OH 788 parts by weight Propylene oxide 290 parts by weight The above-mentioned materials were used in the presence of sodium ethoxide at a pressure of 1.
The reaction was carried out under the conditions of 72 × 10 ⁵ Pa and a temperature of 140 ° C. After a reaction time of 20 minutes, the reaction product was taken out. This was designated as Compound A. Compound A had the following structure.

[0283]

[Outside 32]

Was reacted in the presence of monobutyltin oxide, and the reaction product was taken out after a reaction time of 150 minutes. This was designated as ester compound S.

Mn of ester compound S by GPC method
(Number average molecular weight) and Mw (weight average molecular weight) were Mn = 3189 and Mw = 3381, respectively.

In the compound A, which is a monohydroxyl compound used in this reaction, the number of carbon atoms of the alkylene group in the long-chain alkyl group is 54, and the number average molecular weight (Mn) is
, 1083 weight average molecular weight (Mw) was 1148, and the carboxylic acid had a molecular weight of 210.

Example 14 A magnetic black fine powder having a volume average particle size of 6.54 μm was prepared by the same method as in Example 1 except that the ester compound S was used in place of the ester compound A. (Toner) was obtained. The obtained magnetic black fine powder 100
The same evaluation as in Example 1 was performed by adding 0.6 part by weight of a negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ² / g) to the parts by weight and mixing with a Henschel mixer.

As a result, both the initial image and the 30,000-sheet durability image were images with stable image density. The amount of charge on the developing sleeve was stable at the initial stage and after the endurance of 30,000 sheets, and neither cleaning failure nor drum fusion occurred during the image output endurance. The fixability is such that the image density reduction rate is 15
It was 3.5% at 10 ° C. and 10% Rh and 3.8% at 7.5 ° C. and 10% Rh, which were good levels, and the offset resistance was also good.

The evaluation results are shown in Table 3 showing the evaluation results of Example 1.
It was also written inside.

Example 15 A nonmagnetic black material having a volume average particle diameter of 6.37 μm was prepared in the same manner as in Example 11 except that the ester compound S was used in place of the ester compound A. A fine powder (toner) was obtained. Obtained black fine powder 10
0 parts by weight, as in Example 11 , negatively charged hydrophobic dry colloidal silica (BET specific surface area 300 m ^{2 /} g) 0.6
After adding parts by weight and mixing with a Henschel mixer, the same evaluation as in Example 11 was carried out by mixing with a fluororesin carrier.

As a result, both the initial image and the 30,000-sheet durability image were images with stable image density. The amount of charge on the developing sleeve was stable at the initial stage and after the endurance of 30,000 sheets, and neither cleaning failure nor drum fusion occurred during the image output endurance. The fixability is that the image density reduction rate is 15 ° C,
At 10% Rh, 3.6%, 7.5%, and at 10% Rh, 3.7%, which were favorable levels, and the offset resistance was also good.

The evaluation results are also shown in Table 5 showing the evaluation results of Example 11.

[0293]

According to the present invention, the toner contains 4 carbon atoms.
Monohydric compound having long-chain alkyl group having 0 or more alkylene groups and hydroxyl group and molecular weight 100
Reaction product with a carboxylic acid of 0 or less (ester compound α), or reaction product of a monocarboxylic compound having a long-chain alkyl group having a C 40 or more alkylene group and a carboxyl group with an alcohol having a molecular weight of 1000 or less ( Since it contains an ester compound β), it has excellent fixability and anti-offset properties, and a process speed of 380
Even in a high-speed image forming apparatus of mm / sec or more, a fixed image having a good image density can be stably obtained in a low humidity environment.

[Brief description of drawings]

FIG. 1 is a schematic view of an image forming apparatus for explaining an image forming method of the present invention.

FIG. 2 shows a block diagram of a facsimile using the image forming apparatus as a printer.

[Explanation of symbols]

1 Electrostatic latent image carrier (electrophotographic photoreceptor) 2 charging means 3 Transfer means 4 Development sleeve 5 Latent image forming means 6 erase exposure 7 fixing means 8 Cleaning means 9 Developing means 10 developer 11 Developer layer thickness control member 12 Bias applying means 13 Developer supply roller P recording material

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Yuji Mitsuri, 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (56) Reference JP-A-5-72802 (JP, A) JP-A-60 −247250 (JP, A) (58) Fields surveyed (Int.Cl. ⁷ , DB name) G03G 9/08

Claims (21)

(57) [Claims] 1. A monohydroxyl compound having at least (i) a binder resin, (ii) a colorant, and (iii) (a) a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group, and a molecular weight of 1,000 or less. Ester compounds obtained by reacting with carboxylic acids of (4) and (b) having 40 carbon atoms
Containing mono carboxylic compound with a molecular weight of 1,000 or less alcohol and an ester compound selected from the group consisting of esterification <br/> compound obtained by reacting with a long chain alkyl group and a carboxyl group having an alkylene group having at least You
A toner having toner particles having a number average molecular weight (Mn) of 1550.
To 7,000 and a weight average molecular weight (Mw) of 155
0 to a 7000, negatively chargeable toner for developing electrostatic images, wherein the volume average particle diameter of the toner particles is 3 to 8 [mu] m. 2. The negatively chargeable electrostatic image developing device according to claim 1, wherein the ester compound is contained in the toner in an amount of 1 to 20 parts by weight based on 100 parts by weight of the binder resin. toner. 3. The monohydroxylic compound has the following formulas (I)-(IV): 3. The toner for developing a negatively chargeable electrostatic image according to claim 1 or 2 , which is a compound represented by 4. The monohydroxylic compound is a reaction product of a long-chain alkyl alcohol and a compound having one epoxy group in the molecule.
4. The toner for developing a negatively chargeable electrostatic image according to any one of 3 above. 5. A reaction product of a long-chain alkyl alcohol and a compound having one epoxy group in the molecule is represented by the following formula (VI):
I) [External 2] (In the formula, n represents a number of 40 or more, P represents a number of 1 to 10, R ″ represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group represented by R ₄ —CH ₂ — ( R ₄ represents an ether group or an ester group)), and the negatively chargeable electrostatic image developing toner according to claim 4, wherein R ₄ is a compound. Wherein said alcohol is 2 or more valences negatively chargeable toner according to claim 1 or 2, characterized in that an alcohol. 7. The alcohols are negatively chargeable toner according to any one of claims 1 to 6, characterized in that it has a molecular weight of 50 to 1,000. 8. The monocarboxylic compound has the following formula (VIII)-(XI): The toner for developing a negatively chargeable electrostatic image according to any one of claims 1 to 7 , which is a compound represented by 9. The carboxylic acids, 2 or more valences negatively chargeable toner according to any one of claims 1 and 2 characterized in that it is a carboxylic acid. 10. The carboxylic acids, according to claim 1, 2 and negatively chargeable toner according to any one of 9 characterized by having a molecular weight of 50 to 1,000. 11. The toner is negatively chargeable toner according to any one of claims 1 to 10, characterized in that a heat fixing toner. 12. The toner is a magnetic toner containing a magnetic material as a colorant, and the magnetic toner is used as a magnetic one-component developer.
12. The toner for developing a negatively charged electrostatic image according to any one of items 1 to 11 . 13. The toner is a color toner containing a pigment or a dye as a colorant, and the color toner is
Negatively chargeable toner according to any one of claims 1 to 11, characterized by being used as a nonmagnetic one-component developer. 14. The toner is a color toner containing a pigment or a dye as a colorant, and the color toner is
The toner for developing a negatively chargeable electrostatic image according to any one of claims 1 to 11 , which is used as a two-component developer by being mixed with a carrier. 15. The carboxylic acids are formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, pivalic acid, lauric acid, myristic acid, palmitic acid, stearic acid, acrylic acid, propionic acid, methacrylic acid, croton. acid,
Oleic acid, phthalic acid, nicotinic acid, isonicotinic acid,
Fumaric acid, maleic acid, citraconic acid, itaconic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, benzoic acid, toluic acid, naphthoic acid, cinnamic acid, phthalic acid,
It is selected from the group consisting of terephthalic acid, trimellitic acid, pyromellitic acid and their acid anhydrides, and the alcohols are methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, n-amyl alcohol, isoamyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, capryl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, Cinnamyl alcohol, furfuryl alcohol, ethylene glycol, propylene glycol, 1,3-butanediol,
1,4-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6
-Hexanediol, neopentyl glycol, pentaerythritol diallyl ether, trimethylene glycol, 2-ethyl-1,3-hexanediol, hydrogenated bisphenol A and the following formula (In the formula, R is an ethylene or propylene group, and x, y
Are each an integer of 1 or more, and the total value of x + y is 2 to 10. 2. The toner for developing a negatively chargeable electrostatic image according to claim 1, which is selected from the group consisting of bisphenol derivatives represented by 16. An electrostatic latent image on the electrostatic image bearing member is developed by a developing unit in a developing unit to form a toner image on the electrostatic latent image bearing member, and the toner image is transferred to a recording material, In the image forming method of fixing the transferred toner image on the recording material, the developing unit has a toner, and the toner includes at least (i) a binder resin, (ii) a colorant, and (iii) ( a) an ester compound obtained by reacting a monohydroxyl compound having a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a hydroxyl group with a carboxylic acid having a molecular weight of 1,000 or less, and (b) having an alkylene group having 40 or more carbon atoms Monocarboxylic compound having long-chain alkyl group and carboxyl group and molecular weight 1
And 000 following alcohols containing S. ether compound selected from the group consisting of esters <br/> product obtained by reacting
A toner having toner particles, wherein the ester compound has a number average molecular weight (Mn) of 1550.
To 7,000 and a weight average molecular weight (Mw) of 155
0 to a 7000, an image forming method, wherein the volume average particle diameter of the toner particles is a toner for negative charging electrostatic image development, which is a 3 to 8 [mu] m. 17. A process speed of 380 mm / sec
The image forming method according to claim 16 , wherein the image is formed as described above. 18. The toner according to claim characterized in that it is a toner according to any one of claims 2 to 15 16
Or the image forming method according to item 17 . 19. A process cartridge attachable to and detachable from a main body of an image forming apparatus, wherein the process cartridge has at least an electrostatic latent image carrier and developing means, and the developing means holds toner. The toner contains at least (i) a binder resin, (ii) a colorant, and (iii) (a) a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a monohydroxyl compound having a hydroxyl group, and a molecular weight of 1,000 or less. With an ester compound obtained by reacting with carboxylic acids of (1) and (b) a long-chain alkyl group having an alkylene group having 40 or more carbon atoms and a monocarboxylic compound having a carboxyl group, and a molecular weight of 1
Containing an ester compound selected from the group consisting of ester compounds reacted with not more than 000 alcohols
A toner having toner particles, wherein the ester compound has a number average molecular weight (Mn) of 1550.
To 7,000 and a weight average molecular weight (Mw) of 155
0 to a 7000, the process cartridge, wherein the volume average particle diameter of the toner particles is 3 to 8 [mu] m. 20. The process cartridge has at least one of a charging unit and a cleaning unit in addition to the developing unit and the electrophotographic photosensitive member as the electrostatic latent image carrier, and the developing unit, 20. The process cartridge according to claim 19, wherein the electrostatic latent image carrier and at least one of the charging unit and the cleaning unit are integrally formed as a cartridge and can be attached to and detached from the main body of the image forming apparatus. 21. The toner according to claim characterized in that it is a toner according to any one of claims 2 to 15 19
Alternatively, the process cartridge according to 20 .