JP2003280275A - Positive charge green toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a positive charge green toner which gives an image of high quality with little contamination of the base, which prevents scattering or dropping of the toner in a developing device and which has a high and stable charge amount even for printing for a long time, and to provide a positive charge green toner having the above excellent developing characteristics in an electrostatic charge image developing device which develops as fast as 20 m or 30 m per minute. <P>SOLUTION: The positive charge green toner contains a binder resin, a yellow colorant and a blue colorant, and the yellow colorant is at least one kind of pigment selected from monoazo pigments, disazo pigments, isoindolinone pigments, isoindoline pigments and benzimidazolone pigments. The blue colorant is a phthalocyanine pigment, and neither the yellow colorant nor the blue colorant contains a halogen atom. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides a high-quality image in a wide range of electrostatic image developing devices from low speed to high speed because it has a fast charging rise and excellent charging stability. And a positively chargeable green toner having the same.

[0002]

2. Description of the Related Art As a toner composition for obtaining a visible image by electrophotography, a toner composition in which a black colorant such as carbon black is dispersed in a binder resin is often used. However, recently, cyan pigments,
Color toners containing magenta pigments, yellow pigments, or other chromatic pigments dispersed in a binder resin are also used, and full-color or mono-color copying machines and printers using these color toners have been developed. .

The characteristics required of such color toners are that the image after printing has a vivid color-forming property, and that it exhibits excellent transparency in color superposition when multicolor printing is performed, resulting in color turbidity. Has a clear color reproducibility that does not occur, or an overhead projector (hereinafter,
There is a demand for color reproduction characteristics such as displaying a clear color without turbidity when a color image obtained by transferring and fixing on a sheet (referred to as OHP) is projected on a screen.

By the way, in recent years, the speed of the machine has been increased, and in the field of color toner, development of a toner having an excellent charging performance suitable for high-speed development of 20 m / min or 30 m / min is desired. For a printer that performs such high-speed development, a photoconductor that is mainly composed of an inorganic photoconductor such as selenium is used, and a developing method is adopted in which a precharged dry toner is supplied to form a visible image. ing. The toner used in that case is a positively chargeable toner. In addition to the above-mentioned transparency and color reproducibility, charging characteristics suitable for various developing conditions are characteristics required of such a toner. In particular, under high-speed developing conditions, the toner has an excellent property of instantaneously reaching a desired charge amount in the developing device, that is, a so-called charge rising property, and has a high charge amount, It is important that the charge does not decay even when it is stirred for a long time.

Depending on the intended use of the color printer,
In order to print an image of a color other than the three primary colors of cyan, magenta, and yellow, for example, a green image, the toners of these three primary colors may not be superimposed and printed, but the green toner may be used alone for printing. As a colorant used for the green toner, for example, polychlorocopper phthalocyanine in which hydrogen of the benzene ring of copper phthalocyanine is replaced with chlorine and polybromocopper phthalocyanine in which bromine is replaced are known. However, although these colorants are green pigments, they have a strong negative chargeability and are not suitable as a colorant used for a positively chargeable green toner used in combination with a photoreceptor such as selenium. It was Even when a toner is manufactured by adding a positively chargeable charge control agent, the charge is drastically attenuated in the developing device, and the toner is scattered and spilled, making it difficult to actually use. there were.

Various techniques have been disclosed to solve this problem. For example, in Japanese Patent Application Laid-Open No. 62-54275, CIPigment Yellow 17 and CIPigment Blue 15 are used in combination, and in Japanese Patent Application Laid-Open No. 63-46472, CIPigment Yellow 14 and CIPigment.
A technique for producing a positively charged green toner by mixing and using Blue 15 has been proposed. However, C.
The structural formulas of the pigments of I. Pigment Yellow 17 and CI Pigment Yellow 14 include an electron-withdrawing chlorine atom,
The green toner containing these cannot stably maintain a high positive charging property, and the defect of the toner using the halogen-substituted phthalocyanine is not sufficiently improved.

[0007]

Therefore, according to the present invention, an image of high quality and less background stain can be obtained, and there is no toner scattering or toner spilling in the developing device, which is high and stable even in long-time printing. An object of the present invention is to provide a positively chargeable green toner having the above-mentioned charge amount. Another object of the present invention is to provide a positively chargeable green toner having the above-mentioned excellent developing characteristics in an electrostatic image developing device which develops at a high speed of 20 m / min or 30 m / min. .

[0008]

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.

That is, in order to solve the above problems, the present invention is a positively chargeable green toner containing a binder resin, a yellow colorant and a blue colorant, wherein the yellow colorant is
At least one pigment selected from monoazo pigments, disazo pigments, isoindolinone pigments, isoindoline pigments and benzimidazolone pigments,
It is intended to provide a positively chargeable green toner in which the blue colorant is a phthalocyanine pigment, and the yellow colorant and the blue colorant are pigments containing no halogen atom.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
As the binder resin of the toner used in the electrostatic image developer of the present invention, any binder resin may be used without particular limitation as long as the object of the present invention is not impaired. Specific examples include vinyl copolymer resins such as polystyrene resin, styrene acrylic resin, or styrene butadiene resin, and further polyester resin, epoxy resin, butyral resin, xylene resin, coumarone indene resin, and the like. However, among these, vinyl-based copolymer resins, polyester resins, and epoxy resins are preferable, and polyester resins can be particularly preferably used because they have a good balance of fixability, offset resistance, transparency, and the like. .

The polyester resin used in the present invention is produced by dehydration condensation of a polybasic acid compound selected from polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof and a polyhydric alcohol. Examples of polybasic acid compounds selected from polybasic acids and / or acid anhydrides and / or lower alkyl esters thereof include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, adipic acid and maleic acid. , Maleic anhydride, fumaric acid, itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid, sebacic acid and other dicarboxylic acids or derivatives thereof or Examples of the esterified product also include trifunctional or higher polyvalent carboxylic acids such as trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride, or derivatives or esterified products thereof.

As the polyhydric alcohol, there are the following aliphatic polyhydric alcohols. For example, 1,4-cyclohexanedimethanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, polyethylene glycol, polypropylene glycol, ethylene oxide-propylene oxide random. Diols such as copolymer diols, ethylene oxide-propylene oxide block copolymer diols, ethylene oxide-tetrahydrofuran copolymer diols, polycaprocactone diols, sorbitol, 1,2,3,6-hexane, etc. Tetraol,
1,4-sorbitan, pentaerythritol, 1,2,
4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol, 2-
Examples include trifunctional or higher polyhydric alcohols such as methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, and 1,3,5-trimethylolbenzene.

A compound having two or more glycidyl groups in one molecule also reacts with the above carboxylic acid compound.
It can also be used as a polyhydric or higher aliphatic alcohol.
Specific examples include neopentyl glycol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, and pentaerythritol tetraglycidyl ether.

As the aromatic polyhydric alcohol, for example, catechol, resorcinol, hydroquinone, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, Etc. Further, there are compounds having a bisphenol skeleton represented by the following formula 12 and the like.

[0015]

[Chemical 12] (Formula 12) (In the formula, R ¹ and R ² are the same or different and represent an ethylene group or a propylene group, m and n are the same or different and represent an integer of 0 to 7, and m + n is 0 to 7). Indicates the integer of.)

Specific examples of the compound represented by the formula 12 include 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)
Examples include propane and derivatives thereof.

When the polyester resin is used in the present invention, it is preferable to use an aliphatic alcohol having a valence of 2 or more as a main component as the polyhydric alcohol. In that case, the compound of formula 12 can be used as the aromatic polyhydric alcohol, but when the compound of formula 12 is used, the ratio of the compound of formula 12 in the total alcohol component is 40 mol% or less. It is preferably 20 mol% or less, and more preferably 20 mol% or less. Particularly, it is preferably 0 mol% (not used). By doing so, the molecular chain of the polyester resin becomes flexible, and when a toner using such a polyester resin is mixed with a carrier and used as a two-component developer, the effect of relieving the stress received by the carrier in the developing device is reduced. Therefore, the resin coating phase on the carrier surface can be prevented from peeling off, and as a result, the life of the developer can be extended. Further, even when it is used as a non-magnetic one-component developing toner, the share received when the toner passes between the developing sleeve and the charging member can be alleviated, and a highly durable developer can be obtained.

Further, by using the aliphatic polyhydric alcohol as the main component, the polyester main chain is softened and the fixing property at low temperature is improved. Further, adding a wax to the toner for the purpose of improving the fixing / offset performance is a generally used means, but a polyester resin using an aliphatic polyhydric alcohol has a particularly high compatibility with waxes. Good, the fixing performance at low temperature and offset resistance are further improved.

When an aliphatic polyhydric alcohol is used as a main component, naphthalene dicarboxylic acid and / or dimethyl naphthalate, diethyl naphthalate, dibutyl naphthalate, etc. are preferably used as the polybasic acid. These compounds are preferably used in an amount of 1 mol% or more, and more preferably 5 mol% or more of the total acid components.

The monomer containing a naphthalene ring structure is effective in increasing the Tg of the resin, and the heat-resistant cohesiveness of the resin is improved. In particular, in a system mainly containing a soft aliphatic alcohol as an alcohol component, it is possible to suppress a decrease in Tg of the resin, and it is possible to obtain both low temperature fixing property by using the aliphatic alcohol and heat cohesive property by the naphthalene dicarboxylic acid. It is possible to obtain a resin having both.

The polyester resin in the present invention can be obtained, for example, by carrying out a dehydration condensation reaction or a transesterification reaction using the above 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.

The polyester resin can be synthesized by adding a catalyst. Examples of the esterification catalyst used include organic metals such as dibutyltin dilaurate and dibutyltin oxide, and metal alkoxides such as tetrabutyl titanate. When the carboxylic acid component used is a lower alkyl ester, a transesterification catalyst can be used. Examples of the transesterification catalyst include metal acetates such as zinc acetate, lead acetate and magnesium acetate, metal oxides such as zinc oxide and antimony oxide, and metal alkoxides such as tetrabutyl titanate. The amount of the catalyst added is preferably in the range of 0.01 to 1 mass% with respect to the total amount of raw materials.

As the vinyl-based copolymer used in the present invention, a styrene- (meth) acrylic acid ester copolymer resin is preferable. Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene,
Examples include p-sulfone styrene and dimethylaminomethyl styrene.

Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl ( (Meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth)
Alkyl (meth) acrylates such as acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate; Alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate; Aromatic (meth) acrylates such as benzyl (meth) acrylate; Hydroxyl group-containing (meth) such as hydroxyethyl (meth) acrylate
Acrylate; Phosphoric acid group-containing (meth) acrylate such as (meth) acryloxyethyl phosphate; 2-chloroethyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 2,3-dibromopropyl (meth) acrylate Halogen atom-containing (meth) acrylate such as; Epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate; Ether group-containing (meth) such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate
Acrylate; basic nitrogen atom- or amide group-containing (meth) acrylate such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate; and the like.

Further, an unsaturated compound copolymerizable therewith can be used if necessary. For example, carboxyl group-containing vinyl monomers such as (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid; sulfo group-containing vinyl monomers such as sulfoethylacrylamide; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Ketone group-containing vinyl monomers such as vinyl methyl ketone and vinyl isopropenyl ketone; N-vinyl imidazole, 1-vinyl pyrrole, 2
-Vinylquinoline, 4-vinylpyridine, N-vinyl 2
-Vinyl monomers containing a basic nitrogen atom or an amide group such as -pyrrolidone and N-vinylpiperidone can be used.

The cross-linking agent may be used in the range of 0.1 to 2% by mass based on the vinyl monomer. Examples of the cross-linking agent include divinylbenzene, divinylnaphthalene, 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, dipropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tetra (meth) Acrylate etc. are mentioned.

As a method for producing a styrene- (meth) acrylic acid ester copolymer, an ordinary polymerization method can be adopted. The polymerization reaction is carried out in the presence of a polymerization catalyst such as solution polymerization, suspension polymerization or bulk polymerization. The method of doing is mentioned.

Examples of the polymerization catalyst include 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2 '.
-Azobisisobutyronitrile, 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, dibutyl peroxide, butyl peroxybenzoate, and the like are used, and the amount thereof is 0. 1 to 10.0 mass% is preferable.

As the epoxy resin used in the present invention, an epoxy resin having a conventionally known structure can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin,
Examples thereof include dicyclopentadiene type epoxy resin and biphenyl type epoxy resin. Above all, it is preferable to use a bisphenol A type epoxy resin or a cresol novolac type epoxy resin, and it is particularly preferable to use a bisphenol A type epoxy resin. Specifically, as the bisphenol A type epoxy resin, for example, "Epiclon 2055" manufactured by Dainippon Ink and Chemicals, Inc.
(Softening point 80 to 90 ° C.), “Epiclone 3050” (Softening point 94 to 102 ° C.), “Epiclone 4050” (Softening point 96 to 104 ° C.), “Epiclone 7050” (Softening point 122 to 131 ° C.), oilification "Epicoat 1002" (softening point 83 ° C), "Epicoat 1003" (softening point 89 ° C) manufactured by Shell Epoxy Co., Ltd., "Epicoat 100"
4 "(softening point 98 ° C)," Epicoat 1007 "(softening point 128 ° C)," Epicoat 1009 "(softening point 148
℃) and the like. Examples of the cresol novolac type epoxy resin include "Epiclon N-690" (softening point 85 to 9 manufactured by Dainippon Ink and Chemicals, Inc.).
5 ° C.), “Epiclone N-695” (softening point 90 to 10)
0 ° C.) and the like.

The toner using an epoxy resin as a binder resin can be used not only in the heat roll fixing method but also in the flash fixing method. Epoxy resin has excellent fixability in the flash fixing method and also has excellent void resistance, and a printed matter of excellent image quality without image defects can be obtained.

The binder resin used in the present invention preferably has a glass transition temperature (Tg) of 50 ° C. or higher.
Above all, those having a Tg of 55 ° C. or higher are particularly preferable.
If the Tg is 50 ° C. or less, a blocking phenomenon (thermal aggregation) is likely to occur when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine.

The softening point of the binder resin used in the present invention is 90 ° C. or higher, especially 90 ° C. to 18 ° C.
It is preferably in the range of 0 ° C, more preferably 95 ° C.
Is in the range of to 160 ° C. When the softening point is lower than 90 ° C., the toner is apt to cause an agglomeration phenomenon and tends to cause troubles during storage and printing, and when the softening point is higher than 180 ° C., fixability is often deteriorated.

Further, when the color reproducibility and the transparency when fixed on the OHP sheet are required as the green toner, the softening point of the resin is 90 ° C. to 140 ° C.
Is preferable, more preferably 95 ° C to 1
It is in the range of 30 ° C.

The softening point of the resin in the present invention is defined as the T1 / 2 temperature measured using a constant load extrusion type capillary rheometer, Flow Tester CFT-500 manufactured by Shimadzu Corporation. The measurement conditions with the flow tester are: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 m.
m, die hole diameter 1 mm, measurement starting temperature 50 ° C., temperature rising rate 6 ° C./min, and sample weight 1.5 g.

The acid value is preferably 20 or less, more preferably 10 or less. If the acid value is too high, the charge amount is lowered and the desired charge amount cannot be obtained.

In the present invention, a yellow colorant and a blue colorant are mixed and used as the colorant. The yellow colorant used in the present invention is at least one pigment selected from monoazo pigments, disazo pigments, isoindolinone pigments, isoindolin pigments and benzimidazolone pigments, and has a chemical structure of It is a pigment containing no halogen atom such as fluorine, chlorine, bromine and iodine. The blue colorant used in the present invention is a phthalocyanine-based pigment, which is a pigment having no halogen atom in its chemical structure, like the above-mentioned yellow pigment. In the conventional technology, copper phthalocyanine (CIPigment Gr) having bromine or chlorine in the molecule is used.
een 7, 36) and toners using chlorine-containing yellow pigments (CIPigment Yellow 12, 13, 14, 14, 17, etc.) and copper phthalocyanine pigment have been proposed. Since it has an electrically attractable halogen atom therein, it was difficult to obtain the charging characteristics required for the positively charging green toner. However, since the toner of the present invention uses a combination of a yellow colorant and a blue colorant having no halogen atom as described above, it exhibits high and stable charging characteristics even during long-term printing, and , No scattering or spilling of toner.

The monoazo pigments, disazo pigments, isoindolinone pigments, isoindoline pigments and benzimidazolone pigments used in the present invention are compounds having a structure having no halogen atom in the molecule. Although not particularly limited, it is preferable to use a pigment having the following structure.

[0038]

[Chemical 13] (Formula 1) Monoazo pigment (CIPigment Yellow 74)

[0039]

[Chemical 14] (Formula 2) Isoindolinone pigment (CIPigment Yellow 139)

[0040]

[Chemical 15] (Formula 3) Disazo pigment (CIPigment Yellow 155)

[0041]

[Chemical 16] (Formula 4) Benzimidazolone pigment (CIPigment Yellow 151)

[0042]

[Chemical 17] (Formula 5) Benzimidazolone pigment (CIPigment Yellow 180)

[0043]

[Chemical 18] (Formula 6) Isoindoline pigment (CIPigment Yellow 185)

The phthalocyanine-based pigment used in the present invention is not particularly limited as long as it is a compound having a structure having no halogen atom in the molecule, but it is preferable to use a pigment having the following structure.

[0045]

[Chemical 19] (In the formula, M represents Cu or TiO) (Formula 7)

[0046]

[Chemical 20] (Equation 8)

Among the pigments of the formula 7, as shown in the following formula 7-1,
When M is Cu, the pigment is CI Pigment Blue 1
5, CIPigment Blue 15: 1, CIPigment Blue 15: 2,
CIPigment Blue 15: 3, CIPigment Blue 15: 4, CI
Pigment Blue 15: 6 etc.

[0048]

[Chemical 21] (Formula 7-1)

Further, among the pigments of the formula 7, the pigment in which M is TiO, as in the following formula 7-2, is a pigment called titanyl phthalocyanine.

[0050]

[Chemical formula 22] (Formula 7-2)

Further, the pigment represented by the formula 8 is CI
There is Pigment Blue 16. In the present invention, it is preferable to use the organic pigment represented by Formula 1 or Formula 5 as the yellow colorant among the above. Above all, it is more preferable to use the yellow pigment represented by the formula 5. Further, as a blue colorant, a pigment of the formula 7-1, especially CI Pigment
It is more preferable to use Blue 15: 3.

The amount of the colorant used in the present invention is preferably in the range of 1 to 50 parts by mass per 100 parts by mass of the toner,
The range of 2 to 30 parts by mass is more preferable, and the range of 2 to 20 parts by mass is particularly preferable. The mass ratio (Y / C) of the yellow colorant (Y) and the blue colorant (C) is 95/5 to 5 /.
95 is preferable and 90 / 10-40 / 60 is more preferable. Among them, 80/20 to 50/50 is particularly preferable.

In the toner of the present invention, various known waxes such as polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax and the like can be appropriately used as a releasing agent. A wax containing an ester compound and / or an aliphatic alcohol compound is preferably used as a release agent.

Among the waxes containing a higher fatty acid ester compound and / or an aliphatic alcohol compound, natural waxes such as carnauba wax, montan ester wax, rice wax, scale wax, and / or synthetic ester wax are particularly preferable. . As the synthetic ester wax, tetrabehenic acid ester of pentaerythritol is particularly preferable.

These waxes show particularly good dispersibility in the polyester resin, and are markedly improved in fixing property and offset resistance. Furthermore, even when printing a large number of sheets of these waxes for a long time, for example, when used as a non-magnetic one-component developing toner, the wax does not adhere to the charging member pressed against the developing sleeve and the toner is stably charged. It is possible to print high-quality and high-definition images without image defects and background stains. Furthermore, when a color toner is used together with the colorant used in the present invention, a color toner having excellent transparency is obtained as compared with a hydrocarbon wax such as polypropylene wax. A color toner having such characteristics has transparency and is suitable for printing on an OHP sheet for which a vivid projection image is required, and for printing an intermediate color with good color reproducibility by printing two or more colors in an overlapping manner. Are suitable.

As carnauba wax, it is preferable to use free fatty acid type carnauba wax from which free fatty acids have been removed by purification. The acid value of the free fatty acid type carnauba wax is preferably 3 or less, more preferably 2 or less. The free fatty acid type carnauba wax becomes finer crystals than the conventional carnauba wax, and the dispersibility in the polyester resin is improved. The montan ester wax is refined from minerals, and by refining, it becomes microcrystalline like carnauba wax, and dispersibility in the polyester resin is improved. The acid value of the montan ester wax is preferably 30 or less. The rice wax is a refined rice bran wax, and preferably has an acid value of 13 or less. Scale insect wax is scale insect (also known as rotifer)
Waxy ingredients secreted by the larvae of, for example, dissolved in boiling water,
It can be obtained by separating the upper layer after cooling and solidifying, or by repeating it. The scale insect wax purified by such means is white in a solid state, has an extremely sharp melting point, and is suitable as a wax for toner in the present invention. Acid value of 10 after purification
Below, 5 or less is preferable for toner.

The above waxes may be used alone or in combination, and are used in an amount of 0.3 to 40 relative to the binder resin.
Good fixing offset performance can be obtained by incorporating the compound in an amount of 1 part by mass, preferably 1 to 30 parts by mass. It is more preferably 1 to 20 parts by mass. If it is less than 0.3 parts by mass, the offset resistance is impaired, and if it is more than 40 parts by mass, the fluidity of the toner is deteriorated, and in the two-component development method, spent carriers are generated by adhering to the carrier surface, This may adversely affect the charging characteristics of the toner, or in the non-magnetic one-component developing system, the toner may adhere to the layer thickness regulating member pressed against the developing roll.

In the present invention, a positively chargeable charge control agent can be used if necessary. Examples of the positive charge control agent include nigrosine dyes, triphenylmethane dyes, quaternary ammonium salts, and resins containing quaternary ammonium groups and / or amino groups.

Particularly in the present invention, it is desirable to use a colorless charge control agent, and examples thereof include compounds represented by the following formulas 9 to 11.

[Chemical formula 23] (Equation 9) _[wherein, R 1 to R ₃ represents _C n _{H 2n + 1} group. However,
n shows the integer of 1-10. R _{1 to} R ₃ may be the same or different. ]

[0060]

[Chemical formula 24] (Formula 10) [In formula, R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > respectively independently represent a hydrogen atom, a C1-C22 alkyl group or an alkenyl group, a C1-C20 unsubstituted or substituted. An aromatic group and an aralkyl group having 7 to 20 carbon atoms are represented, and A ⁻ represents a molybdate anion or a tungstate anion, or a molybdenum or a heteropolyacid anion containing a tungsten atom. ]

[0061]

[Chemical 25] (Formula 11) [In formula, m shows 1, 2 or 3, and n is 0, 1
Or 2 and M is a hydrogen atom or a monovalent metal ion. X and Z represent 1 or 2, and Y represents 0 or 1. Further, when X = 1, Y = 1 and Z = 1, and when X = 2, Y = 0 and Z = 2. R _{5 to} R ₁₂ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, an alkoxylene group having 1 to 4 carbon atoms, and a general formula (—C 2-5 alkylene-O). ) N-
Represents a polyalkyloxylene group represented by R (wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms or an acyl group, and n is an integer of 1 to 10), R ₁ , R ₂ ,
R ₃ and R ₄ are hydrogen or a straight chain having 1 to 30 carbon atoms,
Or a branched saturated or unsaturated alkyl group,
Or the general formula _{(-CH 2 -CH 2 -O) n} -R ( where,
R is hydrogen or an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10), and a mononuclear or polynuclear alicyclic group having 5 to 12 carbon atoms. Represents a residue, a mononuclear- or polynuclear aromatic residue or an araliphatic residue. ]

More specifically, there are the following compounds.

[0063]

[Chemical formula 26] Compound (9-1)

[0064]

[Chemical 27] Compound (10-1)

[0065]

[Chemical 28] Compound (10-2)

[0066]

[Chemical 29] Compound (10-3)

[0067]

[Chemical 30] Compound (10-4)

[0068]

[Chemical 31] Compound (10-5)

[0069]

[Chemical 32] Compound (10-6)

[0070]

[Chemical 33] Compound (10-7)

[0071]

[Chemical 34] Compound (10-8)

[0072]

[Chemical 35] Compound (10-9)

[0073]

[Chemical 36] Compound (10-10)

[0074]

[Chemical 37] Compound (10-11)

[0075]

[Chemical 38] Compound (11-1)

[0076]

[Chemical Formula 39] Compound (11-2)

The above charge control agents may be used alone or in combination, and are added in an amount of 0.3 to 100 parts by mass of the toner.
By containing 15 parts by mass, preferably 0.5 to 5 parts by mass, good charging performance can be obtained.

The manufacturing method for obtaining the toner of the present invention is as follows:
It can be obtained by any known means. For example, a resin, a colorant, and optionally a wax, various additives are melt-kneaded at a melting point (softening point) or higher of the resin, and then pulverized,
It can be obtained by classifying. In order to further exert the effect of the present invention, it is preferable to disperse the colorant in a part of the binder resin at a high concentration and then dilute and disperse this dispersion in the binder resin to be used.

As described above, as the step of previously dispersing the coloring agent in a high concentration in the binder resin, a conventionally known method,
That is, a masterbatch method, a flushing method or the like can be used. The masterbatch method is a method in which a good dispersion is obtained by using a kneader or a roll mill and kneading a coloring agent at a high concentration with a resin so as to have a high share. The flushing method is a method in which a water-containing paste of a pigment and a binder resin are heated and kneaded with a pressure kneader to replace water with the binder resin and remove water to obtain a dispersion having a high pigment concentration.

The proportion of the binder resin and the colorant in this high pigment concentration dispersion is preferably such that the amount of the colorant is 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the binder resin.

Specifically, for example, the above resin and colorant are mixed as essential components by a kneading means such as a two-roll, three-roll, pressure kneader, or twin-screw extruder. At this time, the colorant may be uniformly dispersed in the resin,
The conditions of the melt-kneading are not particularly limited,
It is usually at 80 to 180 ° C. for 10 minutes to 2 hours.

Further, if necessary, coarse pulverization is carried out for the purpose of reducing the load in the fine pulverization process and improving the pulverization efficiency. The apparatus and conditions used for coarse pulverization are not particularly limited, but it is common to coarsely pulverize to a particle size of 3 mm mesh pass or less by a rotoplex, palpelizer or the like.

Next, a method of finely pulverizing with an air pulverizer such as a mechanical pulverizer such as a turbo mill and a kryptron, a spiral jet mill counter jet mill, a collision plate jet mill and the like and classifying with a wind classifier and the like can be mentioned. To be The apparatus and conditions for fine pulverization and classification may be selected and set so as to obtain a desired particle size, particle size distribution and particle shape.

In the present invention, various additives (referred to as external additives) can be used for surface modification of the toner such as improvement of fluidity of toner and improvement of charging characteristics. Examples of the external additive that can be used in the present invention include silicon dioxide, titanium oxide, aluminum oxide, cerium oxide, zinc oxide, tin oxide,
Inorganic fine powder such as zirconium oxide and those surface-treated with a hydrophobic treatment agent such as silicone oil and silane coupling agent, polystyrene, acryl, styrene acryl, polyester, polyolefin, cellulose, polyurethane, benzoguanamine, melamine, nylon, Resin fine powders such as silicone, phenol, and vinylidene fluoride are used.

Among these, silicon dioxide (silica) whose surface is hydrophobized with various polyorganosiloxanes, hexamethylenedisilazane, silane coupling agents and the like can be particularly preferably used. As such,
For example, there are products marketed under the following trade names.

AEROSIL R972, R974, R
202, R805, R812, RX200, RY20
0, R809, RX50, RA200HS, RA20
OH [Japan Aerosil Co., Ltd.] WACKER HDK H2000, H1018,
H2050EP, HDKH3050EP, HVK215
0 [Wacker Chemicals East Asia Co., Ltd.] Nipsil SS-10, SS-15, SS-2
0, SS-50, SS-60, SS-100, SS-5
0B, SS-50F, SS-10F, SS-40, SS
-70, SS-72F, [Nippon Silica Industry Co., Ltd.] CABOSIL TG820F, TS-530, TS
-720 [Cabot Specialty Chemicals, Inc.]

The particle diameter of the external additive is 1/3 of the diameter of the toner.
It is preferably not more than, and particularly preferably not more than 1/10. Further, these external additives may be used in combination of two or more kinds having different average particle diameters.

Particularly in the case of non-magnetic one-component developing toner, the toner fluidity and the developing durability are improved by using the one having a large particle diameter and the one having a small particle diameter in combination, and the toner is fixed to the blade of the developing machine. In addition, it is preferable because the prevention of fogging and the long-term stability of charging during running can be obtained.

The proportion of the external additive used is 0.05 to 5% by mass, preferably 0.1 to 100% by mass of the base toner.
It is 3% by mass.

The silica may be externally added to the toner particles by using, for example, a Henschel mixer which is an ordinary powder mixing machine, or a so-called surface modifier such as a hybridizer. In this external addition treatment, silica may be attached to the surface of the toner particle, or a part of silica may be embedded in the toner particle.

The positively chargeable green toner of the present invention can be used as a one-component developer, a non-magnetic one-component developer or a two-component developer mixed with a carrier for developing an electrostatic latent image by electrophotography. The type of carrier is not particularly limited, and known and commonly used iron powder, ferrite, magnetite, or the like, or a carrier coated with a resin thereof can be used.

As the core agent of the carrier, iron powder, magnetite, ferrite and the like used in the usual two-component developing method can be used. Among them, the true specific gravity is low, the resistance is high, the environmental stability is excellent, and the spherical shape is easy. Ferrite or magnetite having good fluidity is preferably used. The shape of the core agent may be spherical, amorphous or the like, and may be used without any particular problem.
The average particle diameter is generally 10 to 500 μm, but 30 to 120 μm is preferable for printing a high resolution image.

Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether, polyvinyl ketone, and chloride. Vinyl / vinyl acetate copolymers, styrene / acrylic copolymers, straight silicone resins composed of organosiloxane bonds or modified products thereof, fluororesins, (meth) acrylic resins, polyesters, polyurethanes, polycarbonates,
Phenol resin, amino resin, melamine resin, benzoguanamine resin, urea resin, amide resin, epoxy resin, acrylic polyol resin and the like can be used. Among these, silicone resins, fluororesins, and (meth) acrylic resins are particularly excellent in charging stability and coating strength and can be used more preferably. That is, the resin-coated carrier used in the present invention is a resin-coated magnetic carrier that uses ferrite or magnetite as a core agent and is coated with one or more resins selected from silicone resin, fluororesin, and (meth) acrylic resin. It is preferable.

When the positively chargeable green toner of the present invention is used as a non-magnetic one-component developing toner, it is preferably used as a contact type non-magnetic one-component developing toner. The contact-type non-magnetic one-component developing method is a method in which toner is triboelectrically charged by passing between a developing sleeve and a layer thickness regulating member pressed against the developing sleeve, and then an electrostatic latent image formed on the surface of the photoconductor. Is a method of developing.

In this case, the material for the charging member of the developing device is not particularly limited as long as it is used under normal conditions. For example, aluminum, stainless steel, urethane rubber,
A development sleeve made of silicone rubber, aluminum, stainless steel, duralumin, copper, or a layer thickness regulating member obtained by laminating urethane rubber or silicone rubber to these can be preferably used.

Further, when the toner is used as the non-magnetic one-component developing toner, the developing device suitable for the positively charging green toner of the present invention to exert its effect is composed of the developing sleeve and the layer thickness regulating member. When either one is a metal such as aluminum or stainless steel, the most effective combination (developing sleeve / layer thickness regulating member) is a combination of a developing sleeve made of urethane rubber or silicone rubber and a stainless layer thickness regulating member. Or a combination of a stainless developing sleeve and a urethane rubber or silicone rubber layer thickness regulating member.

[0097]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In the following Examples and Comparative Examples, "parts" means "parts by mass" unless otherwise specified.

<Synthesis Example of Resin> (Synthesis Example of Resin R1) Isophthalic acid 116 parts Terephthalic acid 166 parts Trimellitic anhydride 38 parts Diethylene glycol 26 parts Neopentyl glycol 104 parts Ethylene glycol 50 parts Tetrabutyl titanate 2.5 parts or more Put the raw material in a glass 2-liter four-necked flask, attach a thermometer, a stir bar and a nitrogen introduction tube, and react in an electric heating mantle heater at 240 ° C. for 10 hours under a normal pressure nitrogen stream, and then successively reduce the pressure to 10 mmHg. And the reaction continued. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 148 ° C. The obtained polymer (hereinafter referred to as resin E) was a colorless solid, had an acid value of 4, and a glass transition temperature of 72 according to the DSC measurement method.
The softening point was 151 ° C.

The softening point of the resin is a constant load extrusion type thin tube rheometer, a flow tester CFT-500 manufactured by Shimadzu Corporation.
Is defined as the T1 / 2 temperature measured using. Measurement conditions with a flow tester are: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1 mm, die hole diameter 1
mm, measurement start temperature 50 ° C, temperature rising rate 6 ° C / mi
n, and the sample mass was 1.5 g.

(Synthesis example of resin R2) terephthalic acid 332 parts isophthalic acid ...... 332 parts polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane ...... 700 parts trimethylolpropane ...... 80 parts ethylene glycol ...... 75 parts tetrabutyl titanate ...... 3 parts The above composition was placed in a four-necked flask equipped with a stirrer, condenser, and thermometer, and water generated by dehydration condensation was removed under a nitrogen gas stream. While reacting at 240 ° C. for 10 hours under normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 10 mmHg. The reaction is tracked by the softening point, and the softening point is 1
The reaction was terminated when the temperature reached 51 ° C. The obtained polymer had a softening point of 153 ° C., an acid value of 4, and a Tg of 65 ° C. according to the DSC measurement method.

(Synthesis Example of Resin R3) Styrene 380 parts Butyl methacrylate 120 parts Divinylbenzene 5 parts Benzoyl peroxide 5 parts Thermometer, glass air flow introducing tube, stirring rod with vacuum-proof sealing device and water-cooled Dimroth condenser Into a 2-volume four-necked round-bottomed flask described above, 500 parts of xylene, the above monomers, and the total amount of the initiator were charged. Nitrogen gas was introduced from a glass air flow introducing pipe to replace the inside of the reactor with an inert atmosphere, and then the contents were gradually heated by a mantle heater equipped with a slider and heated to 75 ° C. Reaction is from 75 ℃ to 80 ℃
The temperature was raised to 130 ° 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 instead, a capillary for vacuum distillation and a Claisen fractionating tube were attached. A thermometer and a water-cooled Leibitz condenser were connected to the Claisen distillation tube, and the outlet of the condenser was connected to an eggplant-shaped flask via a suction adapter. The suction adapter and the vacuum pump were connected with a rubber tube for pressure reduction through a manometer and a trap, and preparation for vacuum distillation was completed. When the mantle heater was heated and the contents were sufficiently stirred and the vacuum pump was operated to reduce the pressure to 20 mmHg, xylene or possibly unreacted monomer started to distill at a liquid temperature of 75 ° C and a distilling temperature of 38 ° C. Finally, the solvent was completely removed by reducing the pressure to 0.5 mmHg at a liquid temperature of 180 ° C. The obtained polymer was opened in a stainless pan while being in a high-temperature molten state, cooled to room temperature, and then crushed. The resulting polymer has a softening point of 1
The temperature was 43 ° C and the Tg was 55 ° C.

(Example 1) <Production of toner> 90 parts of R1 resin 2 parts of pigment of formula 5 2 parts of pigment of formula 7-1 2 parts of charge control agent 11-1 wax Wax carnauba wax 2 Parts (refined carnauba wax No. 1, acid value 5, manufactured by Celarica NODA Co., Ltd.) are mixed with a Henschel mixer and kneaded with a biaxial kneader. The kneaded material thus obtained was pulverized and classified to obtain "Toner A before external addition" having a volume average particle diameter of 7.8 microns.

[0103] 100 parts of "Toner A before external addition" and 0.5 part of silica (TG820F; made by Cabot Specialty Chemicals, Inc.) are mixed with a Henschel mixer, and then sieved.
“Toner A” was obtained.

[0104] <Adjustment of developer> ・ 3 parts of "Toner A" above ・ Carrier 97 copies   (Ferrite carrier coated with silicone resin) Was mixed and stirred to prepare a developer A.

In the same manner, toners were manufactured in the same manner as shown in Table 1, and a developer A (Example 1) to a developer H (Example 7), and a developer I (Comparative Example 1) to a developer J (Comparative Example). 2) was produced.

[0106]

[Table 1]

[0107] Epoxy resin: Epiclone 3050 / Epiclone 7050 = 1/9                         Softening point 127 ° C (manufactured by Dainippon Ink and Chemicals, Inc.) PETB: tetrabehenate of pentaerythritol C.I.Pigment Green 7: Green copper phthalocyanine with chlorine atom in the molecule C.I.Pigment Yellow 17 ： Yellow disazo pigment having chlorine atom in the molecule

The fixing start temperature, the hot offset start temperature, and the printing test were conducted on the developers obtained in the above Examples and Comparative Examples as follows.

(Evaluation of heat roll fixing / offset performance) An unfixed image sample of A-4 paper size was prepared with a remodeling machine of a commercial copying machine, and the fixing start temperature and offset were measured using a heat roll fixing unit having the following specifications. The presence or absence of the phenomenon was confirmed. Roll material Top: Ethylene tetrafluoride Bottom: HTV silicone roll shape Diameter: 50mm Length: 370mm Top roll load: 15kg Top / bottom roll nip width: 8mm Paper feed speed: 300mm / sec

Under the above fixing conditions, various temperatures were changed, and fixing experiments of unfixed images were conducted. The fixing start temperature was determined by measuring the rubbing and fixing strength of the obtained image sample after fixing. The rubbing and fixing strength was judged by the remaining ratio of the rubbing and fixing strength test calculated by the following formula. Image density is Macbeth image densitometer R
It was measured by D-918. Scratch fixing strength test residual ratio =
Image density after rubbing test / image density before rubbing test As the rubbing and fixing strength, a residual ratio of 80% or more was set to a level at which there was no practical problem, and the lowest temperature was taken as the rubbing and fixing start temperature. Here, the image density after the rubbing test means the Gakshin type friction fastness tester (rubber: Whatman filter paper No. 42, load: 500).
g, rubbing operation: 20 strokes), and the image density after rubbing the fixed image with a Macbeth image densitometer. The offset start temperature was a temperature at which the offset phenomenon was visually observed by observing the fixed image sample.

(Printing Test) Commercially available laser beam printer (with selenium photosensitive member: developing speed of 50 m / min, 1
(Equivalent to a printing speed of 80 sheets / minute) was used to evaluate the print quality by continuous printing, and the charge amount of the developer was measured. Replenishment of toner during continuous printing was automatically performed during continuous printing by filling the toner hopper of the machine with toner after silica addition.
The charge amount was measured with a blow-off charge amount measuring device. The image density was measured with a Macbeth densitometer RD-918, and the background stain was obtained by subtracting the white paper density before printing from the white background density.

(Toner scattering amount) 50 KP (50,000 sheets) After observing the inside of the machine after printing, the case where there is almost no stain due to the scattered toner on the photoconductor, the peripheral portion of the developing device, etc. is marked, and the case where the stain is slightly generated is marked. When there was severe dirt, it was marked as x.

Table 2 shows the above evaluation results.

[0114]

[Table 2]

The indications in the table are as follows.

* “Charge amount”; μC / g * “Evaluation of background stain” ◯: less than 0.01, Δ: 0.01 to
Less than 0.03, ×: 0.03 or more * "Toner scattering"; 50KP (50,000 sheets) Visual observation after printing ○: Almost no scattering △: Slightly scattered stains ×: Severe scattering

(Measurement of Rise of Charge Amount) The developers A to J are placed in a cylindrical polyethylene container having a diameter of 5 cm and a height of 6 cm, and the polyethylene container is rotated at 115 rpm for 3 times.
After stirring for a minute, the charge amount was measured with a blow-off charge amount measuring device (manufactured by Toshiba Chemical). Stir for another 7 minutes (total 10
Then, the charge amount was measured in the same manner. The results are summarized in Table 3.

[0118]

[Table 3]

[0119]

EFFECT OF THE INVENTION According to the positively chargeable green toner of the present invention, there is no scattering of toner in the developing device, stable charging characteristics are exhibited from the beginning of use of the developer to the end thereof, and there is no background stain. A high quality printed image can be obtained. Further, the positively chargeable green toner of the present invention can be developed in a device that develops at a high speed of 20 m / min or 30 m / min.
It exhibits the above-mentioned excellent developing characteristics.

Claims (6)

[Claims] 1. A positively chargeable green toner containing a binder resin, a yellow colorant and a blue colorant, wherein the yellow colorant is a monoazo pigment, a disazo pigment, an isoindolinone pigment, or an isoindoline. At least one pigment selected from the group consisting of pigments and benzimidazolone pigments, wherein the blue colorant is a phthalocyanine pigment, and the yellow colorant and the blue colorant both do not contain a halogen atom. A positively chargeable green toner. 2. The yellow pigment has formulas 1 to 6; (Equation 1) (Equation 2) (Formula 3) (Formula 4) (Equation 5) The positively chargeable green toner according to claim 1, wherein the positively chargeable green toner is one or more selected from the compounds represented by (formula 6). 3. The blue pigment is represented by Formula 7 and Formula 8: (In the formula, M represents Cu or TiO) (Formula 7) The positively chargeable green toner according to claim 1, wherein the positively chargeable green toner is at least one selected from compounds represented by formula (8). 4. The binder resin comprises (A) a dibasic or higher polybasic acid, one or more polybasic acid compounds selected from the group consisting of acid anhydrides and lower alkyl esters thereof, and (B) a divalent polybasic acid compound. The positively chargeable green toner according to claim 1, further comprising a polyester resin obtained by reacting the above aliphatic alcohol as a main component. 5. Further, as a positive charge control agent, a compound represented by the formula 9, (Equation 9) _[wherein, R 1 to R ₃ represents _C n _{H 2n + 1} group. However,
n shows the integer of 1-10. R _{1 to} R ₃ may be the same or different. ] Equation 10, (Formula 10) [In formula, R < ₁ >, R < ₂ >, R < ₃ > and R < ₄ > are respectively independently a hydrogen atom, a C1-C22 alkyl group or an alkenyl group, a C1-C20 unsubstituted or substituted. An aromatic group and an aralkyl group having 7 to 20 carbon atoms are represented, and A ⁻ represents a molybdate anion or a tungstate anion, or a molybdenum or a heteropolyacid anion containing a tungsten atom. ] And equation 11, (Equation 11) {wherein m represents 1, 2 or 3, and n is 0, 1
Or 2 and M is a hydrogen atom or a monovalent metal ion. X and Z represent 1 or 2, and Y represents 0 or 1. Further, when X = 1, Y = 1 and Z = 1, and when X = 2, Y = 0 and Z = 2. R ₁ , R ₂ ,
R ₃ and R ₄ are hydrogen or a straight chain having 1 to 30 carbon atoms,
Or a branched saturated or unsaturated alkyl group,
Or the general formula _{[(-CH 2 CH 2 O)} n -R ( Here, R
Is hydrogen or an alkyl group or an acyl group having 1 to 4 carbon atoms, and n is an integer of 1 to 10], and a mononuclear or polynuclear alicyclic residue having 5 to 12 carbon atoms. Represents a group, a mononuclear or polynuclear aromatic residue, or an araliphatic residue. R _{5 to} R ₁₂ are hydrogen, a linear or branched saturated or unsaturated alkyl group having 1 to 30 carbon atoms, an alkoxylene group having 1 to 4 carbon atoms, a general formula [(-
C2-5 alkylene-O) _n -R (wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms or an acyl group,
n is an integer of 1 to 10]]. The positively chargeable green toner according to claim 1, which contains one or more compounds selected from the following. 6. The positively chargeable green toner according to claim 1, further comprising a higher fatty acid ester compound and / or an aliphatic alcohol compound as a release agent.