JP2002268281A - Toner for developing electrostatic images - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high-quality image in a wide range of electrostatic image developing devices from low speed to high speed, and to provide an image having very little reverse polarity and low charge components and little background dirt. The present invention provides a toner for developing an electrostatic charge image having excellent characteristics such that scattering of the toner in the developing device can be reduced and a stable image can be obtained from the initial use to the end of development. SOLUTION: In a toner for developing an electrostatic image containing a binder resin, a charge control agent and a release agent as essential components, the charge control agent is represented by the following general formula (I): (Wherein, R ^{1 to} R ⁸ each independently represent an alkyl group or hydrogen, and R ⁹ represents an alkylene group having 2 to 24 carbon atoms, etc.). A toner for developing an electrostatic image, comprising a polyolefin wax, a higher fatty acid ester and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wide range of electrostatic image developing devices from a low speed to a high speed, and provides a high quality image because of rapid rise of charge and excellent charge stability. The present invention relates to a toner for developing an electrostatic image, which has excellent properties such as finely dispersed in a binder resin and little scattering of background and toner.

[0002]

2. Description of the Related Art In copiers and printers utilizing the principle of electrophotography, a photosensitive material composed of an inorganic photoconductor such as selenium or an organic photoconductor such as polyvinyl carbazole is used. An electrostatic latent image is formed on a body, and a dry toner charged in advance is supplied to the electrostatic latent image to form a visible image. Generally, in the case of a one-component system in which a magnetic powder such as iron powder is internally added, the dry toner is formed by friction between toner particles. Are mixed and stirred to charge the surface of each toner particle.

In general, the quality of a printed image in electrostatic printing is greatly influenced by charging characteristics of toner particles, such as charge rising property, charging stability over time, and saturation charge amount. To use in a stable state,
In the production of toner particles, a charge control agent having a positive charge or a negative charge is often added internally.

In the case of a copying machine or a printer mainly having a selenium photosensitive drum, a positively chargeable toner is required. Nigrosine has been generally used as a charge control agent for imparting a positive charge to the toner. . However, nigrosine, although having a charge-imparting power, is intensely colored and is difficult to apply as a charge control agent for color toners, which has been increasing in demand in recent years.

Other commercially available positively chargeable charge control agents include quaternary ammonium salts disclosed in Japanese Patent Publication Nos. 2794797 and 16443496. Since these compounds are colorless or light-colored, they can also be used as charge control agents for color toners, but they do not have sufficient thermal stability and often undergo thermal decomposition and coloring during melt-kneading with toner resins. Is easy to occur. Also, as compared with nigrosine, the charge stability is relatively good, but there is a problem that the charge amount is considerably inferior. In recent years, safety requirements for chemical substances have become increasingly strict. Volatile organic compounds (VOCs) generated when a charge control agent is mixed with a toner resin or actually printed by a copying machine or a printer. Nigrosine is inevitable to leave harmful aniline, and quaternary ammonium salts are likely to decompose and generate amine compounds by heating during production or fixing. It is becoming a problem that cannot be ignored.

Japanese Patent Application Laid-Open Nos. 6-348061, 58-171060 and 51-9456 disclose polyamines as charge controlling agents. In JP-A-348061, the compounds described in the examples have a low melting point, are easily colored when kneaded with a toner resin, and are difficult to apply at least for color toners. On the other hand, the polyamines disclosed in JP-A-58-171060 and JP-A-51-9456 have almost no coloring, but the amine is linked by a methylene group or a substituted methylene group (usually, Linked by addition condensation of formaldehyde or other aldehydes), thermal decomposition during kneading is unavoidable, and since the compound itself is a hard resin, the dispersibility in the toner resin is poor. . For this reason, the reverse polarity and low charge components tend to be increased, and the background is easily stained. Further, scattering of toner in the developing device increases.

[0007] By the way, the binder resin is an essential component for imparting fixing performance, anti-offset performance and the like to the toner for developing an electrostatic image, and when kneading such a binder resin, particularly, the binder resin has a branched chain. If you have
In many cases, the molecular structure is easily broken, and the binder resin is softened during kneading, and as a result, the desired high-temperature offset property and fixing property cannot be obtained in many cases. Means for adding a release agent such as wax to solve this is known, but the release agent is easily released from the binder resin, and the required amount of the release agent is not uniformly mixed with the binder resin. It is difficult to improve offset properties. For this reason, stronger mixing is required to uniformly mix the binder resin and the release agent. As a result, the molecular chain of the binder resin is cut, so that the binder resin has a problem of further lowering the softening point.

Accordingly, the present invention can provide high-quality images in a wide range of electrostatic image developing devices ranging from low speed to high speed, and has very low reverse polarity and low charge components, which tend to be increased with positively charged polyester toner. Image with less background contamination, reduced scattering of toner in the developing device, a stable image from the beginning to the end of use of development, and a highly transparent polyester resin and black. It is an object of the present invention to provide a toner for developing an electrostatic image, which does not change the hue due to the charge control agent even when a colorant is used, and is excellent in offset resistance, fixability and the like.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have used a polyamine compound having a specific structure excellent in charge stability and the like as a charge control agent and a binder as a release agent. The present inventors have found that the above problems can be solved by using a polyolefin wax or the like which is finely dispersed uniformly in a resin, and completed the present invention.

That is, the present invention relates to a toner for developing an electrostatic image containing a binder resin, a charge controlling agent and a release agent as essential components, wherein the charge controlling agent is represented by the following general formula (I):

[0011]

Embedded image

(Wherein, R ^{1 to} R ⁸ each independently represent an alkyl group or hydrogen; R ⁹ represents an alkylene group having 2 to 24 carbon atoms which may be substituted with an alkyl group and / or a phenyl group; Or a polyamine compound represented by the following formula: wherein the main chain contains an alkylene group which may contain a phenylene group.) Wherein the release agent is a polyolefin wax, a modified polyolefin wax, a higher fatty acid ester, a higher aliphatic alcohol, or an amide. An object of the present invention is to provide a toner for developing an electrostatic image, comprising at least one selected from the group consisting of a system wax and a natural wax. By adopting such a configuration, a high-quality image can be obtained in a wide range of electrostatic image developing devices ranging from low speed to high speed, and the reverse polarity, which tends to increase with a positively charged polyester toner, has very little low charge components. An image with little background dirt can be obtained,
It can reduce the scattering of toner in the developing device, obtain a stable image from the beginning to the end of use of development, and use a highly transparent polyester resin or a hue due to the charge control agent even when using a colorant other than black. , And excellent offset resistance, fixability and the like can be obtained.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The binder resin used in the present invention includes, for example, polystyrene, styrene- (meth) acrylate copolymer, styrene-conjugated diene copolymer, polyester, epoxy resin, polybutyral resin, xylene resin. And a coumarone indene resin, or a hybrid resin obtained by combining a plurality of these resins. Of these, styrene- (meth)
It is preferable to use an acrylic ester copolymer, a styrene-conjugated diene copolymer, a polyester resin, or an epoxy resin.

The styrene- (meth) acrylate copolymer preferably used in the present invention can be obtained, for example, by copolymerizing the following monomers. (a) styrene and its derivatives; for example, styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, alkylstyrene such as hexylstyrene, heptylstyrene, octylstyrene, fluorostyrene And halogenated styrenes such as chlorostyrene, bromostyrene, dibromostyrene and iodostyrene, and nitrostyrene, acetylstyrene and methoxystyrene.

(B) (meth) acrylate monomers; for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl Alkyl (meth) acrylates such as (meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and cyclohexyl (meth) Alicyclic (meth) acrylates such as acrylates, aromatic (meth) acrylates such as benzyl (meth) acrylate, hydroxyl-containing (meth) acrylates such as hydroxyethyl (meth) acrylate, and (meth) acryloxy Phosphoric acid group-containing (meth) acrylates such as ciethyl phosphate, 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, and halogen atoms such as 2,3-dibromopropyl (meth) acrylate ( (Meth) acrylates, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, and ether group-containing (meth) acrylates such as 2-ethoxyethyl (meth) acrylate;
Examples thereof include a basic nitrogen atom or amide group-containing (meth) acrylate such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

(C) Unsaturated compounds copolymerizable therewith can be used if necessary. For example,
(Meth) acrylic acid, α-ethylacrylic acid, crotonic acid, α-methylcrotonic acid, α-ethylcrotonic acid, isocrotonic acid, addition-polymerizable unsaturated aliphatic monocarboxylic acid such as tiglic acid, ungeric acid, or maleic acid Addition-polymerizable unsaturated aliphatic dicarboxylic acids such as acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid and dihydromuconic acid.

(D) Still other copolymerizable unsaturated compounds include vinyl monomers containing a sulfo group such as sulfoethylacrylamide, vinyl monomers containing a nitrile group such as (meth) acrylonitrile, vinyl methyl ketone,
Ketone group-containing vinyl monomers such as vinyl isopropenyl ketone, N-vinylimidazole, 1-vinylpyrrole,
A vinyl monomer containing a basic nitrogen atom or an amide group, such as 2-vinylquinoline, 4-vinylpyridine, N-vinyl-2-pyrrolidone, and N-vinylpiperidone, can be used. (e) A crosslinking agent may be used together with the vinyl monomer. As a crosslinking agent, for example, divinylbenzene,
Divinyl naphthalene, divinyl ether, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth)
Acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, propylene glycol di (meth) acrylate,
Examples include dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and tetramethylolmethanetetra (meth) acrylate.

As a method for producing the styrene- (meth) acrylate copolymer, a usual polymerization method can be employed, and polymerization is carried out in the presence of a polymerization catalyst such as solution polymerization, suspension polymerization, or bulk polymerization. A method for carrying out the reaction may be mentioned. As the polymerization catalyst, for example, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobisisobutyronitrile,
1,1'-azobis (cyclohexane-1-carbonitrile),
Benzoyl peroxide, dibutyl peroxide,
Butyl peroxybenzoate and the like are used, and the amount of use is preferably 0.1 to 10.0% by weight of the vinyl monomer component.

The resin (ionomer) obtained by crosslinking a styrene- (meth) acrylate copolymer containing a carboxyl group-containing vinyl monomer as an essential component with a metal salt can also be used.

The polyester resin suitably used in the present invention can be obtained, for example, by dehydrating and condensing a dicarboxylic acid, an acid anhydride thereof and a lower alkyl ester thereof, and a diol by a usual method. Dicarboxylic acid, as the acid anhydride thereof, for example, phthalic anhydride, terephthalic acid,
Isophthalic acid, orthophthalic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid And dicarboxylic acids such as sebacic acid and derivatives thereof. Examples of the lower alkyl esters include those having an alkyl residue, preferably having 1 to 6 carbon atoms, and more preferably having 1 to 4 carbon atoms. Such a lower alkyl ester is obtained by subjecting the above-mentioned divalent polybasic acid or acid anhydride to a lower alcohol by an esterification reaction. Of these, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid and the like are particularly preferred. In the present invention, one or more of these can be used.

Examples of the diol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, bisphenol A, and polyoxyethylene.
(2.2) -2,2-bis (4-hydroxyphenyl)
Propane, polyoxyethylene- (2.0) -2,2-
Bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.
2) -polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (6) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene − (2.2) −
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.4) -2,2-bis (4-
(Hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and derivatives thereof. Among them, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, Oxypropylene- (2.0)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene- (2.2) -2,2-bis (4-
Hydroxyphenyl) propane, polyoxypropylene- (3.3) -2,2-bis (4-hydroxyphenyl) propane and the like are particularly preferred. In the present invention, one or more of these can be used.

Further, for example, polyethylene glycol,
Diols such as polypropylene glycol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-propylene oxide block copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and polycaprolactone diol can also be used.

Further, if necessary, a trifunctional or higher functional aromatic carboxylic acid such as trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride or a derivative thereof, or sorbitol, 1,2,3 , 6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,2,4-butanetriol,
Trifunctional or higher alcohols such as 5-pentanetriol, glycerin, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trimethylolbenzene Or bisphenol A type epoxy resin, bisphenol F type epoxy resin, ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidylaniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane Glycidyl ether, pentaerythritol tetraglycidyl ether, neopentyl glycol diglycidyl ether, cresol novolak type epoxy resin, phenol novolak Epoxy resins, polymers or copolymers of vinyl compounds having epoxy groups, epoxidized resorcinol-acetone condensate, partially epoxidized polybutadiene, semi-dry or dry fatty acid ester They can be used together. When using a polyvalent epoxy compound,
When a monoepoxy compound is used in combination, the low-temperature fixability is further improved. Examples of the monoepoxy compound include phenyl glycidyl ether, alkyl phenyl glycidyl ether, alkyl glycidyl ether, alkyl glycidyl ester, glycidyl ether of an alkylphenol alkylene oxide adduct, α-olefin oxide, and monoepoxy fatty acid alkyl ester.

The polyester resin in the present invention can be obtained, for example, by conducting a dehydration condensation reaction or a transesterification reaction using the above-mentioned raw material components in the presence of a catalyst. The reaction temperature and reaction time at this time are not particularly limited, but are usually 150 to 300 ° C. and 2 to 24 hours. As a catalyst for performing the above reaction, for example, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate, and the like can be used as appropriate. The mixing ratio (molar ratio) of the polybasic acid compound and the diol component is 8 /
It is preferably from 10 to 10/8, particularly preferably from 9/10 to 10/9.
When a divalent polybasic acid compound is reacted with a diol component, a linear polyester resin is obtained. Also,
When a dibasic or trivalent or higher polybasic acid compound is reacted with a polyhydric alcohol or the like, a branched or network-like polyester resin is obtained. The polyester resin thus obtained may be used alone, so that the desired performance is obtained.
A plurality of polyester resins may be blended and used.

Further, in the present invention, a styrene-conjugated diene copolymer can be suitably used. The styrene-conjugated diene copolymer can be obtained by a known and commonly used method, but can be easily obtained by an in-situ method in which monomers are charged at once or in a multi-stage, for example, emulsion polymerization.

The monomer used in the styrene-conjugated diene copolymer is styrene or its derivative exemplified in the above (a), and the conjugated diene is, for example, butadiene, isoprene and the like. Butadiene is preferred among the conjugated dienes.

The styrene-conjugated diene copolymer may be a multi-component copolymer with other copolymerizable monomers as long as the properties of the copolymer of styrene and conjugated diene are not impaired. . Such copolymerizable monomers include, for example, vinyl chloride and vinyl acetate, as well as the above (b) to (e)
And the monomers exemplified above.

The weight average molecular weight (Mw) of the copolymer of styrene and conjugated diene is preferably from 40,000 to 200,000. If it is less than 40,000, it is difficult to obtain a sufficient strength of the toner layer in the image area, and the anti-offset performance (the effect of preventing the toner from being adhered to the heat rolls) becomes extremely low. On the other hand, when it exceeds 200,000, the fixing temperature is increased due to an increase in the softening point, and the fixing performance is liable to be greatly reduced under general fixing conditions.

The ratio of the monomer components constituting the styrene-butadiene copolymer is preferably from 5 to 20% by weight as the butadiene monomer ratio. 5% by weight
If less, the effect of imparting rubber elasticity is not always sufficient. If the content is 20% by weight or more, the heat resistance tends to be deteriorated, and a trouble is likely to occur in a general toner use environment and storage environment.

When an epoxy resin is used as the binder resin, for example, bisphenol A
Epoxy resins such as epoxy resin, hydrogenated bisphenol A type, bisphenol F type, bisphenol S type, phenol novolak type, and cresol novolak type. Among them, aromatic epoxy resins such as epoxy resin obtained from bisphenol A and epihalohydrin can be used. It is preferable that the main body is constituted. Examples of commercially available epoxy resins that can be used in the present invention include “Epiclon 3050” (softening point 94 to 102 ° C.) manufactured by Dainippon Ink and Chemicals, Inc.
"Epiclon 4050" (softening point 96-104 ° C),
“Epiclon 7050” (softening point 122-131 ° C.),
"Epicoat 1002" manufactured by Yuka Shell Epoxy Co., Ltd.
(Softening point 83 ° C.), “Epicoat 1003” (softening point 8
9 ° C.), “Epicoat 1004” (softening point 98 ° C.),
“Epicoat 1007” (softening point 128 ° C.), “Epicoat 1009” (softening point 148 ° C.), “Araldide 7072” manufactured by Ciba-Geigy Corporation (softening point 75 to 8)
5 ° C), “Araldide 7072” (softening point 75 to 85)
° C), "araldide 6084" (softening point 96-104)
° C), "Araldide 7097" (softening point of 115 to 12)
5 ° C.). These binder resins may be used as a mixture of a plurality of them, or may be used as a mixture with a small amount of another epoxy resin.

In the present invention, a small amount of polyethylene, a styrene-acrylic copolymer resin and a polyester resin may be used in combination with the epoxy resin in order to improve image properties and fixability. The use ratio of the epoxy resin in the binder resin used in the present invention is preferably in the range of 50 to 100% by weight.

The styrene-acrylate copolymer, styrene-conjugated diene copolymer, polyester resin, and epoxy resin used in the present invention may have a glass transition point and a softening point appropriate for a toner. The softening point (ring and ball method; JIS K2531, K2548) is preferably from 100 to 180 ° C, more preferably from 110 to 170 ° C. If the temperature is lower than 100 ° C., offset at a high temperature tends to occur, and if it exceeds 180 ° C., the fixability at a low temperature tends to deteriorate. Further, the Tg is preferably in the range of 45 to 75 ° C. The acid value is desirably 30 or less, and is preferably 15 or less.
It is particularly desirable that: When the acid value is more than 30, the charge amount is reduced, and it becomes difficult to obtain a desired charge amount.

The charge controlling agent used in the present invention is a polyamine compound having the general formula (I) as a repeating unit.
Among them, R ^{1 to} R ⁸ are the same or different and are preferably a hydrogen atom or a methyl group or an ethyl group. When all are hydrogen atoms (piperazine residue), one is a methyl group and the other is a hydrogen atom. In some cases (2-methylpiperazine residue) is particularly preferred. R ⁹ is an alkyl group and / or a phenyl group which may be substituted alkylene group having a carbon number of 2 to 24, or the main chain alkylene group having from 2 to 24 carbon atoms which may contain a phenylene group . this house,
An ethylene group, a polymethylene group having 3 to 15 carbon atoms, and an ethylene group having a phenylene group between two methylene groups are preferable. Preferred examples include an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group,
Examples include a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, a tridecamethylene group, a tetradecamethylene group, a pentadecamethylene group, a p-xylylene group, an m-xylylene group, and an o-xylylene group. Further, an ethylene group and a polymethylene group having 3 to 15 carbon atoms are more preferable.

The number average molecular weight of the polyamine compound represented by the general formula (I) is preferably in the range of 500 to 100,000, particularly preferably in the range of 5,000 to 30,000. If the molecular weight is less than 500, the melting point of the polyamine is too low, so that the polyamine is easily scattered during kneading, and if it exceeds 100,000, the dispersibility during kneading is inferior.

Such a charge controlling agent is generally prepared by dissolving a piperazine compound which is a basic compound of the general formula (I) in an organic solvent, and forming a dihalide (eg, Dihalogenated alkane, etc.) or alkane disulfonate compound (eg hexane-
After reacting 1,6-di-p-toluenesulfonate), the product can be easily produced by neutralizing the product with an alkali. The piperazine-based compound used in the synthesis of the above compound is not particularly limited as long as two secondary amino groups present in the compound structure are retained, but piperazine and 2-methylpiperazine are particularly useful. It is. At the time of the reaction, two or more piperazine compounds can be mixed and reacted.

The dihalide used as a raw material for forming the alkylene group includes, for example, 1,2-
Dichloroethane, 1,3-dichloropropane, 1,4-
Dichlorobutane, 1,5-dichloropentane, 1,6-
Dichlorohexane, 1,7-dichloroheptane, 1,8
-Dichlorooctane, 1,9-dichlorononane, 1,1
0-dichlorodecane, 1,11-dichloroundecane,
1,12-dichlorododecane, 1,13-dichlorotridecane, 1,14, -dichlorotetradecane, 1,15
-Dichloropentadecane, 1,6-dibromohexane,
1,8-dibromooctane, 1,6-diiodohexane, 2,2-dimethyl-1,3-dichloropropane, p
-Xylylene dichloride, m-xylylene dichloride, o-xylylene dichloride, etc., of which 1,6-dichlorohexane, 1,8-dichlorooctane and 1,10-dichlorodecane are particularly preferred. Such dihalides are not necessarily limited to one kind, and two or more kinds can be used in combination. Mixing ratio (molar ratio) of the piperazine compound and dihalide at the time of synthesis of the polyamine disclosed in the present invention
Is preferably 0.5 to 2.0, particularly preferably 0.8 to 1.5.

The addition amount of the charge control agent to the toner for developing an electrostatic image is preferably in the range of 0.1 to 15 parts by weight, more preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the binder resin.
A range of 10 parts by weight is particularly preferred. When the ratio of the charge control agent in the toner is less than 0.1 part by weight, the rising property at the time of charging tends to be deteriorated, and the toner tends to be scattered. On the other hand, when the proportion of the charge control agent in the toner is more than 15 parts by weight, the charge stability of the toner tends to be poor.

The toner for developing an electrostatic image of the present invention may contain other charge control agents as long as the performance of the charge control agent and the intended use of the toner are not impaired. The combination can charge controlling agent, triphenylmethane dyes, nigrosine dyes, quaternary ammonium salts,
Resins containing a quaternary ammonium group and / or an amino group and / or an amine group are exemplified. Examples of the positive charge control agent that can be used in combination include the following products, but are not limited to the examples.

Examples of triphenylmethane dyes include “OIL BLUE” (Orient Chemical Co., Ltd.),
"Copy Blue PR" (Clariant Co., Ltd.)
And the like. Nigrosine dyes include “NIG
ROSINE BASE EX ”,“ OIL BRAC ”
KBS "," BONTORON N-01 "," BO
Notoron N-04 "," Bontoron N-
07 "," BONTORON N-21 "(all Orient Chemical Co., Ltd.) and the like. As a quaternary ammonium salt compound, "BONTORON P-51"
(Orient Chemical Co., Ltd.), "TP-302", "TP
-610 "," TP-415 "(above, Hodogaya Chemical Co., Ltd.)," COPY CHARGE PSY "(Clariant, Inc.) and the like. Examples of the resin containing a quaternary ammonium group and / or an amino group include “FCA
-201-PS "(Fujikura Kasei Co., Ltd.) and the like.

The release agent used in the present invention is at least one selected from the group consisting of polyolefin wax, modified polyolefin wax, higher fatty acid ester, higher aliphatic alcohol, amide wax and natural wax. As long as the release agent used here has the same structure and shape, the same effect can be obtained even if the production method is different.

The release agent is desirably selected according to the binder resin used in combination. When a release agent having poor dispersibility in the binder resin is selected, exposure of the release agent to the surface of the toner particles tends to increase, and the fluidity of the toner tends to decrease. Further, in the pulverizing step in the toner production process, the release agent is easily detached, the amount of the release agent contained in the toner is reduced, and the fixing / offset performance is easily reduced. Further, in the process of developing the toner, the released release agent is liable to cause background fouling and scattering,
Image quality is likely to be reduced. When the dispersion in the binder resin is excessively advanced or when the release agent is compatible with the resin, the fixing / offset performance is liable to decrease. For these reasons, it is preferable to select a release agent that is appropriately dispersed in the binder resin, and the particle size of the release agent dispersed in the binder resin is preferably in the range of 0.01 to 5 μm.
More preferably, it is in the range of 1 to 3 μm.

The melting point (drop point, softening temperature) of the release agent is 60
To 180 ° C, more preferably 65 to 170 ° C. If the melting point is too low, the toner tends to aggregate during storage and the fluidity of the toner tends to decrease. If the melting point is too high, it is difficult to fuse in the image fixing step, and it is difficult to exert a sufficient releasing effect. When the hardness of the release agent is low, it causes adhesion in the developing machine or carrier spent, so that the penetration (25 ° C.) which is an index of the hardness is 1%.
It is preferably 0 or less, more preferably 5 or less.

When a polyester resin or an epoxy resin is used as the binder resin, polyolefin wax, modified polyolefin wax, higher fatty acid ester, higher fatty alcohol, amide wax and natural wax can be used. A release agent containing an aliphatic alcohol compound as a main component has a similar structure to that of the binder resin, and thus has good dispersibility, and has good fixing / offset performance and image quality. Examples of the release agent containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a main component include natural waxes, higher fatty acid esters, and higher aliphatic alcohols.

Natural waxes are release agents derived from animals and plants, and include, for example, carnauba wax, candelilla wax, rice wax, scale insect wax, lanolin and the like. When these release agents are purified and pulverized, the dispersibility in the binder resin is further improved. Although good performance can be obtained by using these release agents as they are, those having been chemically deodorized or deoxidized can obtain better performance. Natural wax has an acid value of about 2 to 40 in catalog value due to its structure or free acid. However, it is desirable that these values be lower for the same reason as in the case of resin.

The higher fatty acid ester can be obtained by purifying a natural product or a synthetic product of carboxylic acids and alcohols. The release agent may have a plurality of ester groups in the structure, or may be a mixture of compounds having different numbers of ester groups. Higher fatty acid esters obtained by synthesis include, for example, behenyl behenate, monoester compounds such as stearyl behenate, montanic acid esters,
1,4-butanedibehenyl, diester compounds such as 1,4-butanedistearyl, triester compounds, tetraester compounds such as pentaerythritol and the like, from which high purity and low acid value can be obtained, It is suitable as a release agent for polyester or epoxy resin. Commercially available synthetic higher fatty acid esters include WEP-5, WEP-6 (Nippon Yushi Co., Ltd.), Ho
e-Wax E, F, OP (Clariant Co., Ltd.) and the like.

The higher aliphatic alcohols can be obtained by refining natural products or reducing oils and fats under pressure.
By oxidizing a polyolefin wax such as Fischer-Tropsch wax or polyethylene wax, a wax mainly composed of higher aliphatic alcohol can be obtained. Commercially available higher aliphatic alcohols include behenyl alcohol derived from natural products, Unilin 425, Unilin 550 (Petrolite Co., Ltd.), N
PS-9210, OX-1949, Paracor 5070
(Nippon Seiro Co., Ltd.) and the like.

When a styrene- (meth) acrylate copolymer or a styrene-conjugated diene copolymer is used as the binder resin, a polyolefin wax, a modified polyolefin wax, a higher fatty acid ester, a higher aliphatic alcohol, an amide wax, Natural wax can be used, and among them, polyolefin wax and modified polyolefin wax are preferable because of good dispersibility in the binder resin, good fixing / offset performance, and good image quality of printed images.

As the polyolefin wax, polyethylene wax, polypropylene wax, Fischer-Tropsch wax, paraffin wax, ethylene-
α-olefin copolymers and the like. For example, commercially available polyethylene waxes include High Wax 800P, 400P, 200P, 100P, and NL1.
00, NL200, NL500 (Mitsui Chemicals, Inc.), H
oe-WAX PE130, PE190, PE520
(Clariant Co., Ltd.), Sunwax LEL-
250 (Sanyo Kasei Co., Ltd.) and the like, and as polypropylene wax, viscol 330P, 550P, 660
P (Sanyo Chemical Co., Ltd.), High Wax NP055, N
P105, NP505, NP805 (Mitsui Chemicals), Hoe-Wax PP230 (Clariant) and the like. H-1, A-1 (Sasol Co., Ltd.), FT
100 (Nippon Seiro Co., Ltd.) and the like, HNP-9 and SP-160 (Nippon Seiro Co., Ltd.) as the paraffin wax, and High Wax 720P and 410P as the ethylene-α-olefin copolymer. And 420P (Mitsui Chemicals, Inc.).

As the modified polyolefin wax, high wax 405MP, 4051E (Mitsui Chemicals, Inc.) obtained by oxidatively modifying a polyolefin wax to introduce a polar group into its structure, OX-0414, OX-0416 (Nihon Seiro Co., Ltd.) )) Or a high wax obtained by graft polymerization modification of a styrene monomer 1140H, 1160H
(Mitsui Chemicals, Inc.) and the like.

The release agent may be used alone or in combination, and good fixing offset performance can be obtained by adding 0.1 to 15 parts by weight, preferably 1 to 5 parts by weight, to the binder resin. can get. If the amount is less than 0.1 part by weight, the offset resistance tends to be impaired, and if the amount is more than 15 parts by weight, the fluidity of the toner tends to deteriorate, and the spent carrier is generated by adhering to the carrier surface,
This tends to adversely affect the charging characteristics of the toner.

In the present invention, a coloring agent can be used. Well-known coloring agents can be used.
Examples of the black colorant include carbon black such as furnace black, channel black, acetylene black, thermal black, and lamp black classified according to the production method; I. Pigment Black 1
1 iron oxide pigments, C.I. I. Pigment Bla
ck12, a phthalocyanine-based cyanine black BX, and the like. It is also possible to use a plurality of pigments other than black to achieve black toning. As a blue colorant, a phthalocyanine C.I. I.
Pigment Blue 15-3 and indanthrone C.I. I. Pigment Blue 60 and the like are quinacridone-based C.I. I. Pigment
Red 122, an azo C.I. I. Pigment R
ed 22, C.I. I. Pigment Red 48: 1,
C. I. Pigment Red 48: 3, C.I. I. P
azo-based C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 13, C.I.
I. Pigment Yellow 14, C.I. I. Pi
gment Yellow 17, C.I. I. Pigmen
t Yellow 97, C.I. I. Pigment Ye
low 155, isoindolinone-based C.I. I. Pi
gment Yellow110, a benzimidazolone C.I. I. Pigment Yellow 151,
C. I. Pigment Yellow 154, C.I.
I. Pigment Yellow 180 and the like. The content of the colorant is in the range of 1 part by weight to 20 parts by weight based on 100 parts by weight of the toner for developing an electrostatic image.
These colorants can be used alone or in combination of two or more.

The toner for developing an electrostatic image of the present invention may contain additives other than a binder resin, a release agent, a charge control agent, and a colorant. For example, cerium oxide, silicon carbide and the like can be used as lubricants and abrasives such as metal soap and zinc stearate, and magnetite and ferrite can be used as magnetic powder.

The toner for developing an electrostatic image of the present invention can be obtained by an extremely general manufacturing method irrespective of a specific manufacturing method. For example, it can be obtained by melt-kneading the resin, the colorant, and the charge control agent at a temperature equal to or higher than the melting point (softening point) of the resin, and then pulverizing and classifying. Specifically, for example, the components such as the resin, the colorant, the release agent, and the charge control agent are uniformly mixed in advance by a Henschel mixer or the like before melt-kneading. The conditions for the mixing are not particularly limited, but the mixing may be performed in several stages so as to obtain a desired uniformity. The coloring agent and the charge controlling agent used here may be subjected to a flushing treatment in advance so as to be uniformly dispersed in the resin, or a master batch melt-kneaded with the resin at a high concentration may be used.

The above mixture is mixed by kneading means such as a two-roll, three-roll, pressure kneader or a twin-screw extruder. At this time, the colorant or the like may be uniformly dispersed in the resin, and the conditions for the melt-kneading are not particularly limited. However, it is usually preferable that the temperature is 80 to 180 ° C. for 30 seconds to 2 hours. The kneaded material is usually cooled by a cooling belt, a roller, or the like, but since the dispersion state of the release agent changes depending on the cooling conditions, the cooling conditions can be set so as to obtain a desired dispersion state.

If necessary, coarse pulverization is performed for the purpose of reducing the load in the fine pulverization step and improving the pulverization efficiency. The apparatus and conditions used for the coarse pulverization are not particularly limited, but the coarse pulverization is generally performed to a particle size of 3 mm or less by a rotoplex or a pulperizer.

Then, fine pulverization is performed by a mechanical pulverizer such as a turbo mill or a kryptron, or an air pulverizer such as a spiral jet mill, a counter jet mill, or an impingement plate jet mill, and then classified by an air classifier or the like. No. Fine grinding and classification equipment, conditions are the desired particle size,
What is necessary is just to select and set it so that it may become a particle size distribution and a particle shape.

The volume average particle diameter of the particles constituting the toner is as follows:
Although not particularly limited, it is preferably adjusted to be usually 5 to 15 μm.

In the present invention, various additives (referred to as external additives) can be used for modifying the surface of the toner such as improving the fluidity of the toner and improving the charging characteristics. As the external additive that can be used in the present invention, for example, inorganic fine powders such as silicon dioxide, titanium oxide, and alumina and those obtained by surface-treating them with a hydrophobizing agent such as silicone oil, resin fine powders, and the like are used. .

Among these, hydrophobic silica obtained by surface-treating silicon dioxide with various polyorganosiloxanes, silane coupling agents and the like is preferably used as an external additive of the positively charged toner. Specifically, there is one that is commercially available under the following trade names. AEROSIL; RA200HS, RA200H [Nippon Aerosil Co., Ltd.] PACKER; H2050, HVK2150, HDK
H30TA, H13TA, H05TA (Wacker Chemicals Co., Ltd.), CABOSIL; TG820F (Cabot Specialty Chemicals, Inc.) and the like.

The titanium oxide may be a hydrophilic grade, or may be a hydrophobic grade surface-treated with octylsilane or the like. For example, there is one that is commercially available under the following trade names. Titanium oxide T
805 [Degussa Co., Ltd.], titanium oxide P25 [Nippon Aerosil Co., Ltd.], titanium oxide JMT-150ANO
[Taika Co., Ltd.]. Examples of the alumina include aluminum oxide C (Degussa Corporation) and the like.

The particle diameter of these external additives is preferably 1/3 or less of the diameter of the toner, and particularly preferably 1/3.
10 or less. Further, these external additives may be used in combination of two or more kinds having different average particle diameters. The use ratio of silica is usually 0.05 to 5% by weight, and preferably 0.1 to 3% by weight, based on the toner.

When the electrostatic image developing toner of the present invention is used in a two-component developing system, the following carriers can be used. As the core material of the carrier, iron powder, magnetite, ferrite, etc. used in the ordinary two-component developing method can be used, but among them, the true specific gravity is low, the resistance is high, the environmental stability is excellent, and it is easy to form into a spherical shape. Ferrite or magnetite having a good value is preferably used. The shape of the core agent can be used without any particular problem, such as spherical or amorphous. The average particle size is generally 10 to 500 μm, but 30 to 100 to print a high-resolution image.
μm is preferred.

Examples of coating resins for covering these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, and vinyl chloride. / Vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin comprising organosiloxane bond or its modified product, fluororesin, (meth) acrylic resin, polyester, polyurethane, polycarbonate, phenolic resin, amino resin, melamine resin , Benzoguanamine resin, urea resin, amide resin, epoxy resin, acrylic polyol resin and the like can be used. Among these,
In particular, silicone resins, fluororesins, and (meth) acrylic resins are excellent in charge stability, coating strength, and the like, and can be more preferably used. That is, the resin-coated carrier used in the present invention is:
It is preferable that the magnetic carrier is a resin-coated magnetic carrier that uses ferrite or magnetite as a core agent and is coated with at least one resin selected from silicone resins, fluororesins, and (meth) acrylic resins.

[0064]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

The first step was used in preparing the toner.
The synthesis example of the binder resin is shown below. Each synthesis example
The polyester resin obtained in the above is treated with tetrahydrofuran (T
HF), which was obtained by filtering the solution left for 12 hours.
The molecular weight of the THF soluble component was measured. Analyze the gel
・ Permeation chromatography (GPC) method
Using the calibration curve created with standard polystyrene,
The amount was calculated. GPC device: HLC-8120 GPC manufactured by Tosoh Corporation Column: TSK Guardcol manufactured by Tosoh Corporation
Um SuperH-H TSK-GEL Supe
rHM-M 3 connection Concentration: 0.5% by weight Flow rate: 1.0 ml / min
After refluxing for 8 hours using THF as a solvent in a Kessler extractor
Was calculated from the residue on the filter paper. Acid value is JIS K690
Tg was measured according to JIS K7121. Ma
The melt viscosity characteristics are constant load extrusion type capillary rheometer.
(CFT-500C manufactured by Shimadzu Corporation)
Stone cross section 1cm^Two , Cylinder pressure 0.98MPa,
Die length 1mm, die hole diameter 1mm, measurement start temperature 50 °
C, heating rate 6 ° C / min, sample weight 1.5g
I went in. T10^FiveIs a constant load extrusion type capillary rheometer
The viscosity of the viscosity-temperature curve is 10 ^Fiveat the time of poise
Represents temperature.

(Resin (1); Synthesis of linear polyester) Terephthalic acid: 664 parts by weight Polyoxyethylene- (2.2) -2,2-bis (4
-Hydroxyphenyl) propane: 640 parts by weight-Ethylene glycol: 150 parts by weight The above-mentioned materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser, and a thermometer.
A part by weight of tetrabutyl titanate was added, and the mixture was reacted at 240 ° C. for 15 hours under normal pressure while removing water generated by dehydration condensation. Thereafter, the pressure was sequentially reduced, and the reaction was continued at 5 mmHg. The reaction was followed by a softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 105 ° C. The molecular weight of the obtained polyester, assuming that the weight average molecular weight is Mw and the number average molecular weight is Mn,
Mn: 3550 and Mw: 7430. T10 ⁵ :
115 ° C, acid value: 7.8, T in DSC measurement
g: 64 ° C.

(Resin (2); Synthesis of Crosslinked Polyester Resin) Terephthalic acid: 664 parts by weight Ethylene glycol: 120 parts by weight Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) ) Propane: 688 parts by weight Trimethylolpropane: 80 parts by weight The above-mentioned materials were placed in a two-liter four-necked flask equipped with a stirrer, a condenser, and a thermometer.
A part by weight of tetrabutyl titanate was added, and the mixture was reacted at 240 ° C. for 10 hours under normal pressure while removing water generated by dehydration condensation. Thereafter, the pressure was sequentially reduced, and the reaction was continued at 5 mmHg. The reaction was followed by a softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 160 ° C. The obtained cross-linked polyester resin has M
n: 5450, Mw: 152200, T10 ⁵ : 170
゜ C, acid value was 5.8, and Tg by DSC measurement was 62 ° C.

(Resin (3): Synthesis of styrene- (meth) acrylate copolymer) Styrene: 380 parts by weight butyl methacrylate: 120 parts by weight Divinylbenzene: 10 parts by weight Benzoyl peroxide: 5 parts Parts by weight 500 parts of xylene and the total amount of the above monomer and initiator are placed in a two-capacity, four-necked round bottom flask equipped with a thermometer, a glass air flow inlet tube, a stir bar equipped with a vacuum-resistant sealing device, and a water-cooled Dimroth condenser. did. After the inside of the reactor was replaced with an inert atmosphere by introducing nitrogen gas from a glass air flow inlet tube, the content was gradually heated to 75 ° C. by a mantle heater with a slider box. Reaction is 65 ° C ~ 80
C., and the temperature was raised to 130.degree. C. to complete the reaction after 10 to 12 hours to complete the polymerization.
Next, the water-cooled condenser and the glass air flow introducing tube were removed from the flask, and a capillary for vacuum distillation and a Claisen fractionating tube were attached instead. A thermometer and a water-cooled Liebig condenser were connected to the Claisen distillation tube, and the outlet of the condenser was connected to an eggplant type flask via a suction adapter. The suction adapter and the vacuum pump were connected with a rubber tube for depressurization via a manometer and a trap, and preparation for vacuum distillation was completed. When the mantle heater was heated and the content was sufficiently stirred and the vacuum pump was operated to reduce the pressure to 20 mmHg, xylene or unreacted monomer in some cases started to distill at a liquid temperature of 75 ° C and a distilling temperature of 38 ° C. Finally, the liquid temperature is 180 ℃
Then, the pressure was reduced to 0.5 mmHg to completely remove the solvent. The obtained polymer (hereinafter referred to as polymer (a)) was poured into a stainless steel pan in a high-temperature molten state, cooled to room temperature, and crushed.
The obtained polymer had a T10 ^{5 of} 145 ° C. and a Tg of 55 ° C.

(Resin (4): Styrene-butadiene copolymer) A commercially available styrene-butadiene copolymer was used. Styrene: butadiene = 89:11 Mn: 12,400 Mw: 88,500 T10 ⁵ : 138 ° C Tg: 56 ° C

(Resin (5): Epoxy resin) A commercially available epoxy resin (Epiclon 4050, Dainippon Ink and Chemicals, Inc.) was used.

(Resin (6): Epoxy resin) A commercially available epoxy resin (Epiclon 7050, Dainippon Ink and Chemicals, Inc.) was used.

(Synthesis of Charge Control Agent (A): Polyamine Compound) In a 1-liter four-necked flask equipped with a reflux condenser, a thermometer, a Dean Stark trap and a stirrer, 100 g of anhydrous piperazine and ethanol 15 were added.
After charging 0 g, the content is heated to 80 ° C. while stirring, and 175 g of 1,6-dichlorohexane is added dropwise while maintaining the temperature. After completion of the dropwise addition, stirring was continued for another 4 hours to complete the reaction. Next, after 90 g of ethanol was distilled off, 92 g of 98% caustic soda was further added to 200 g of deionized water.
, And a neutralization reaction was performed at 90 ° C. for 1 hour. Then, the contents are filtered, washed with water, and finally
After drying at 10 ° C. for 3 hours, 169 g of compound-1 was obtained.
(Melting point 148-150 ° C)

Example 1 <Preparation of Toner> Resin (1): 36 parts by weight Resin (2): 54 parts by weight Black Pearls 460 (made by Cabot Specialty Chemicals, Inc.): 5 parts by weight Carnauba wax No. 1 powder (Yoko Kato): 3 parts by weight-Charge control agent (A): 2 parts by weight The above materials were mixed with a Henschel mixer and kneaded with a twin-screw kneader. The kneaded material thus obtained was pulverized and classified to obtain a toner base having a volume average particle diameter of 10.1 μm. 100 parts by weight of the obtained toner base material and silica RA200HS
After mixing 0.3 parts by weight (Aerosil Co., Ltd.) with a Henschel mixer, the mixture was sieved to obtain a toner (1).
Similarly, toners 2 (Example 2) to 2
7 (Example 27) and 28 and 29 (Comparative Examples 1 and 2) were obtained.

[0074]

[Table 1]

<Adjustment of Developer> 5 parts of “Toner 1” and 95 parts of carrier (silicone resin-coated ferrite carrier) were mixed and stirred to prepare Developer 1. With a similar formulation,
Developers 1 (Example 1) to 22 (Example 22) and 23,
24 (Comparative Examples 1 and 2) were obtained.

<Fixing Offset Test and Printing Test>
For the developers obtained in the above Examples and Comparative Examples, fixing start temperature, hot offset start temperature, fixing strength test,
A print test was performed as follows. (Offset generation temperature) A 2 cm wide and 20 cm long band-shaped unfixed image sample was prepared on A4 paper using a commercial copier remodeling machine, and a heat roll fixing unit having the following specifications was used.
Fixing was performed by changing the roll temperature, and the presence or absence of the hot offset phenomenon was confirmed.

<Fixing conditions> Upper roll load 15 kg Nip width 8 mm Paper feed speed 90 mm / s The offset start temperature was a temperature at which an offset phenomenon was visually observed by observing a fixed image sample.

(Fixing Strength) An image fixed by changing the roll temperature obtained in the offset resistance test was used. After applying a mending tape (Sumitomo 3M, 810) to this fixed image at a constant pressure, it was peeled off at a constant speed from a certain direction. The fixing strength was determined by an image density remaining ratio calculated by the following equation. Image density is Macbeth image densitometer RD-
918. Fixing strength test residual ratio = image density after peeling test / image density before peeling test The fixing strength was a level at which the residual ratio was 80% or more and had no practical problem, and the lowest temperature was defined as the fixing start temperature. (Printing test) Using a commercially available laser beam printer (equipped with a selenium photoreceptor), print quality, charge amount, and toner scattering amount in the apparatus after continuous printing of 10,000 sheets were evaluated. The charge amount was measured by a blow-off charge amount measuring machine, the image density was measured by a Macbeth densitometer RD-918, and the background stain was obtained by subtracting the density before printing from the density of the white background. The amount of toner scattered was determined by visually observing stains on the photoreceptor, peripheral portions of the developing device, and the like after printing. Table 2 shows the results.

[0079]

[Table 2]

The electrostatic image developing toners of Examples 1 to 22 have a larger initial charge amount and are free from background stains, especially initial background soil, as compared with the electrostatic image developing toners of Comparative Examples 1 and 2.
Also, the amount of toner scattering was small.

[0081]

The toner for developing an electrostatic image of the present invention can provide high-quality images in a wide range of electrostatic image developing devices from low speed to high speed, and the reverse is likely to occur with positively charged polyester toner. An image with very little polarity and low charge components can be obtained with little background contamination, toner scattering in the developing device can be reduced, a stable image can be obtained from the beginning to the end of use of development, and transparency can be obtained. Even when a high polyester resin or a coloring agent other than black is used, there is no change in hue due to the charge control agent, and the toner is excellent in offset resistance, fixability, and the like. Further, by selecting a specific release agent having a good dispersibility with respect to the binder resin, the exposure of the release agent to the surface of the toner particles is reduced, and the fluidity of the toner is improved. In the pulverizing step in the toner manufacturing process,
The release agent is hardly released, the amount of the release agent contained in the toner does not decrease, and the fixing / offset performance is improved. Further, in the process of developing the toner, background dirt and scattering are reduced, and the image quality is improved.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G03G 9/08 333

Claims (6)

[Claims] 1. An electrostatic image developing toner comprising a binder resin, a charge control agent, and a release agent as essential components, wherein the charge control agent is represented by the following general formula (I): (Wherein, R ^{1 to} R ⁸ each independently represent an alkyl group or hydrogen, and R ⁹ represents an alkylene group having 2 to 24 carbon atoms which may be substituted with an alkyl group and / or a phenyl group;
Or an alkylene group which may contain a phenylene group in the main chain. Wherein the release agent comprises at least one selected from the group consisting of polyolefin waxes, modified polyolefin waxes, higher fatty acid esters, higher aliphatic alcohols, amide waxes and natural waxes. Characteristic toner for developing electrostatic images. 2. The electrostatic image developing toner according to claim 1, wherein R ⁹ is an ethylene group or a polymethylene group of 3 to 15. 3. The method according to claim 1, wherein the binder resin contains a polyester resin, and the release agent contains one or more release agents selected from the group consisting of higher fatty acid esters, higher aliphatic alcohols and natural waxes. The toner for developing an electrostatic image according to claim 1 or 2, wherein 4. The binder resin contains a styrene- (meth) acrylate copolymer, and the release agent contains at least one release agent selected from a polyolefin wax and a modified polyolefin wax. The toner for developing an electrostatic image according to claim 1, wherein: 5. The method according to claim 1, wherein the binder resin contains a styrene-conjugated diene copolymer, and the release agent contains at least one release agent selected from a polyolefin wax and a modified polyolefin wax. The toner for developing an electrostatic image according to claim 1. 6. The binder resin contains an epoxy resin, and the release agent is selected from the group consisting of higher fatty acid esters, higher fatty alcohols and natural waxes.
3. The toner for developing an electrostatic image according to claim 1, further comprising at least one release agent.