JP2003345067A - Electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrostatic charge image developing toner using a colorant containing no toxic substance and to provide an electrostatic charge image developing toner exhibiting stable charge behavior even for long-term use or printing in a large volume of copies, causing no scattering of the toner or fog, and producing a printed image with sufficient image density and no fluctuation in the image density. <P>SOLUTION: The electrostatic charge image developing toner contains a colorant dispersed in a binder resin. The binder resin is a polyester resin and/or epoxy resin. The colorant is a black pigment having a mixture composition of Fe<SB>2</SB>TiO<SB>5</SB>and a solid solution of Fe<SB>2</SB>O<SB>3</SB>-FeTiO<SB>3</SB>. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrostatic charge image developing device in a wide range from low speed to high speed, with less background stain.
The present invention relates to a toner for developing an electrostatic charge image, which is capable of providing a high-quality image and further uses a coloring agent containing no harmful substance.

[0002]

2. Description of the Related Art Conventionally, carbon black and black iron oxide (magnetite) have been mainly used as black pigments used in toners for developing electrostatic images. Carbon black is generally inexpensive, has a fine powder particle size, and is an excellent pigmentability. However, since carbon black is a bulky powder having a bulk density of 0.1 g / cm ^3, it is difficult to handle and the workability is poor. In addition, carbon black is classified into Group 2B by the International Cancer Research Institute, and other problems from the viewpoint of safety and health have been pointed out.

On the other hand, black iron oxide (magnetite) powder has a cohesive property due to the fact that Fe ₃ O ₄ has magnetism, and it is difficult to uniformly mix it with other toner raw materials. , Brown Fe ₂ O _{3 at} about 150 ° C
However, there is a drawback that the heat resistance is inferior.

The characteristics required for the black colorant used in the toner for developing an electrostatic image include coloring properties, safety, handleability during production, heat resistance, and electrical properties that affect the developing properties. There is. The electrical characteristics are one of the important characteristics required for the colorant. If the electrical characteristics are further subdivided and listed, the rising characteristics of charging,
The characteristics include long-term charge retention, charge uniformity (charge distribution), and charge environmental stability. Various factors may be mentioned as factors that affect the electrical characteristics, and examples thereof include dispersibility of the colorant, electric resistance value, and surface properties of the colorant. If the electrical properties of the colorant are poor, the charge amount of each toner particle becomes non-uniform and the charge amount distribution is widened. In addition, the ratio of reversely charged particles and weakly charged particles increases, and during development, toner is scattered inside the machine,
A fogging phenomenon occurs in which toner adheres to the non-image portion of the printed matter. Furthermore, the toner tends to be inferior in durability because the image density, resolution, and the like fluctuate in the printing for a long time or in a large number of copies.

By the way, the electrical characteristics peculiar to the colorant are greatly affected by the dispersion state of the colorant in the toner. No matter how excellent the colorant has electrical characteristics, if the colorant is not uniformly and finely dispersed in the binder resin of the toner, the charging property of the toner will not be excellent. Therefore, in order to make the charging property of the toner excellent, not only a colorant having excellent electric properties is used, but also a resin in which the colorant can be uniformly dispersed as fine particles is found. It is important to select and use the resin. So far, various materials have been studied as solutions to carbon black or black iron oxide (magnetite) and to replace them.
No satisfactory technique is disclosed for the combination of a specific colorant and a specific resin for improving the charging characteristics of the toner.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object thereof is to provide a toner for developing an electrostatic charge image using a colorant containing no harmful substance. It is in. Further, another object of the present invention is to
An object of the present invention is to provide an electrostatic charge image developing toner that exhibits stable charging behavior even after long-term use or printing of a large number of copies. It is another object of the present invention to provide a toner for developing an electrostatic charge image, which does not cause toner scattering or fog, has a sufficient image density, and can obtain a printed image with no fluctuation in image density.

[0007]

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using a specific colorant in combination with a specific resin. Heading out, the present invention has been completed.

That is, the present invention is a toner for developing an electrostatic image in which a colorant is dispersed in a binder resin, wherein the binder resin is a polyester resin and / or an epoxy resin, and the colorant is Fe ₂ TiO _{2. 5} and Fe ₂ O ₃ −
The present invention provides a toner for developing an electrostatic charge image, which is a black pigment having a mixed composition with a FeTiO ₃ solid solution.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The colorants used in the present invention are Fe ₂ TiO ₅ and Fe ₂ O.
A black pigment having a mixed composition with _3- FeTiO ₃ solid solution. Such a colorant is obtained, for example, by reducing a magnetite particle powder whose particle surface is coated with a titanium compound, a mixed powder of a magnetite particle powder and a titanium compound, or a hematite particle powder whose particle surface is coated with a titanium compound. Reduced powder, etc. 700 in a non-oxidizing atmosphere
It can be obtained by a method of heating and firing at a temperature of ℃ or more. When magnetite particle powder having a particle surface coated with a titanium compound is used as a raw material, particles having a small magnetization value are easily obtained, which is a preferable method for the purpose of making the colorant a nonmagnetic particle.

The magnetite particle powder and the hematite particle powder may be particles of any shape such as granular, spherical and acicular, and it is preferable to use particles having a size of about 0.03 to 1.5 μm. As the titanium compound used for producing the colorant used in the present invention, any of hydroxides, hydroxides and oxides of titanium can be used, but when mixed with magnetite particle powder, It is preferable to use a water-soluble titanium compound. The amount of titanium compound depends on the amount of Fe (II) and Fe (II
It is 15.0 to 50.0 atomic% in terms of Ti with respect to I). Within this range, the magnetization value of the black pigment obtained is appropriate and preferred.

The toner using the colorant obtained from the above exhibits a stable charging behavior even during long-term use or printing of a large number of copies, and further, has no toner scattering or fog and has a sufficient image density. Further, it becomes a toner for developing an electrostatic charge image that can obtain a printed image with no fluctuation in image density. Also, unlike carbon black, it does not contain harmful substances, so it is also excellent in terms of safety and hygiene.

The amount of the colorant used in the present invention is preferably in the range of 1 to 30 parts by mass, and particularly preferably in the range of 5 to 15 parts by mass, per 100 parts by mass of the toner. If it exceeds 30 parts by mass, the true specific gravity of the toner becomes large and the toner tends to scatter, which is not preferable.

Further, in the present invention, known colorants can be used for the purpose of adjusting the hue. For example, as the black colorant, carbon black such as furnace black, channel black, acetylene black, thermal black, lamp black and the like, which are classified by the manufacturing method, or C.I. I. Pigment Black 11 iron oxide pigments, aniline black, phthalocyanine cyanine black BX and the like. The colorant used in the present invention is characterized by containing no harmful substances,
Since the object of the present invention is to provide a toner for developing electrostatic images which does not contain harmful substances, when carbon black is used in combination, the content of harmful substances and the amount used in combination with the black colorant used in the present invention Should be fully considered.

As a blue colorant, a phthalocyanine type C.I. I. Pigment Blue 15-3, an indanthrone type C.I. I. Pigment Blue 60,
As a red colorant, quinacridone type C.I. I. Pig
ment Red 122, an azo-based C.I. I. Pigme
nt Red 22, C.I. I. Pigment Red4
8: 1, C.I. I. Pigment Red 48: 3,
C. I. PigmentRed 57: 1 and the like, as a yellow colorant, an azo C.I. I. PigmentYell
ow 12, C.I. I. Pigment Yellow 1
3, C.I. I. Pigment Yellow 14, C.I.
I. Pigment Yellow 17, C.I. I. Pi
gment Yellow 97, C.I. I. Pigmen
t Yellow 155, an isoindolinone-based C.I.
I. Pigment Yellow 110, a benzimidazolone-based C.I. I. Pigment Yellow 1
51, C.I. I. Pigment Yellow 154,
C. I. Pigment Yellow 180 and the like.

The polyester resin preferably used in the present invention comprises one or more polybasic acid compounds selected from the group consisting of dibasic or higher polybasic acids, acid anhydrides and lower alkyl esters thereof, and the compound represented by the formula 1,

[Chemical 6] (Formula 1) (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; Is a polyester resin obtained by reacting with a diol represented by the formula (1) as a main component.

Examples of the dibasic or higher polybasic acid and / or acid anhydride include phthalic anhydride, terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, adipic acid, maleic acid, maleic anhydride, fumaric acid, and the like. Itaconic acid, citraconic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, cyclohexanedicarboxylic acid, succinic acid, malonic acid, glutaric acid, azelaic acid,
Examples thereof include dicarboxylic acids such as sebacic acid, acid anhydrides thereof, and derivatives thereof. Examples of trivalent or higher polybasic acids and / or acid anhydrides include trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic anhydride. Further, as the lower alkyl ester thereof, an alkyl residue preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Such a lower alkyl ester can be obtained by subjecting the above-mentioned polybasic acid having a valence of 2 or more or an acid anhydride thereof to a lower alcohol in an esterification reaction. Among the above polybasic acids, terephthalic acid, isophthalic acid, orthophthalic acid,
Naphthalenedicarboxylic acid, maleic acid, maleic anhydride, fumaric acid and the like are particularly preferable.

Further, the diol represented by the formula 1 is an alkylene oxide adduct of bisphenol A, and examples thereof include polyoxyethylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane and polyoxy. Ethylene- (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.

The polyester resin used in the present invention includes
Polyhydric alcohols other than Formula 1 can also be used. For example, as the divalent aliphatic alcohol, ethylene glycol, polyethylene glycol, propylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol, neopentyl glycol, cyclohexanedimethanol, ethylene oxide-propylene oxide random copolymer Diol,
Examples thereof include ethylene oxide-tetrahydrofuran copolymer diol.

Further, as a trihydric or higher polyhydric alcohol,
Sorbitol, 1,2,3,6-hexanetetraol, 1,4-sorbitan, pentaerythritol, 1,
2,4-butanetriol, 1,2,5-pentanetriol, glycerin, 2-methylpropanetriol,
2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-
Trihydric or higher alcohol such as trimethylolbenzene, or ethylene glycol diglycidyl ether, hydroquinone diglycidyl ether, N, N-diglycidyl aniline, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether , Pentaerythritol tetraglycidyl ether, neopentyl glycol diglycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolac type epoxy resin, phenol novolac type epoxy resin, polymer of vinyl compound having epoxy group, or co- Polymer, epoxidized resorcinol-acetone condensate, partially epoxidized polybutadiene, semi-dry or dry fat There ester epoxy compounds.

When a polyhydric alcohol other than formula 1 is used as the alcohol component of the polyester resin used in the present invention, the amount of the polyhydric alcohol other than formula 1 used is 0 to 70 mol% based on the total alcohol component. It is preferably present, and more preferably 0 to 60 mol%. Especially, it is especially preferable that it is 0 to 50 mol%. The polyester resin containing a large amount of the compound of formula 1 is preferable because the colorant used in the present invention can be dispersed more uniformly and finely.

The polyester resin used 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 usually 2 to 24 at 150 to 300 ° C.
It's time. As the catalyst for carrying out the above reaction, for example, zinc oxide, stannous oxide, dibutyltin oxide, dibutyltin dilaurate or the like can be appropriately used. The mixing ratio (molar ratio) of the polybasic acid compound and the diol component is 8
/ 10 to 10/8, particularly preferably 9/10 to 10/9. A linear polyester resin can be obtained by reacting a divalent polybasic acid compound with a diol component. Further, when a divalent or trivalent or more polybasic acid compound is reacted with a polyhydric alcohol or the like, a branched or network polyester resin is obtained. The polyester resin thus obtained may be used alone, or a plurality of polyester resins may be blended and used so as to obtain desired performance.

In particular, it is preferable to use two or more kinds of polyester resins having different softening points in combination, because the fixing property and the offset resistance are improved in a wide temperature range. In this case, it is preferable to use a linear or branched resin as the low softening point resin and a branched or crosslinked resin as the high softening point resin. Among them, a polyester resin having a softening point of 80 to 110 ° C. is used as the low softening point resin, and a softening point of 1 is used as the high softening point resin.
It is particularly preferable to use a polyester resin of 15 to 200 ° C.

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

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 glass transition temperature of the binder resin used in the present invention is preferably 50 ° C. or higher, and particularly preferably 55 ° C. or higher. If the Tg is 50 ° C. or less, the blocking phenomenon (thermal aggregation) is likely to occur when the toner is stored, transported, or exposed to a high temperature in the developing device of the machine. The glass transition temperature referred to here is JISK7.
It is defined as the extrapolated glass transition start temperature obtained by the measurement according to 121. Shimadzu DSC-60 was used for the measurement.

The acid value of the binder resin is 1 to 30.
It is preferably mgKOH / g, 1 to 20 mgK
More preferably OH / g. Further, the hydroxyl value is preferably 10 to 100 mgKOH / g, and more preferably 10 to 60 mgKOH / g. When the acid value and the hydroxyl value are in the above ranges, the moisture resistance of the toner becomes good, which is preferable.

The toner for developing an electrostatic image of the present invention preferably has a softening point in the range of 90 to 180 ° C., and 95 to 1
More preferably, it is in the range of 60 ° C. If it is less than 90 ° C, offset at high temperature is likely to occur, and 180 ° C
If it is super, the fixability at low temperatures tends to deteriorate. In the present invention, the resin is selected so that the softening point of the toner falls within the above range. Especially when using two or more resins with different softening points,
The softening point and mixing ratio of these resins are appropriately set and used.

In the present invention, a known charge control agent can be used if necessary. For example, as the positive charge control agent, a nigrosine dye, a modified nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group, or the like can be used. As trimethylethane dyes, metal salts or complexes of salicylic acid, metal salts or complexes of benzylic acid, copper phthalocyanine, perylene, quinacridone, metal salts or complexes of azo compounds, calixarene type phenolic condensates, cyclic polysaccharides, A resin containing a carboxyl group and / or a sulfonyl group can be used.

Suitable positive charge control agents that can be used in the present invention include, for example, nigrosine dyes such as "NI
GROSINE BASE EX "," OIL BLA
CKBS ”,“ BONTRON N-01 ”,“ BON
TRON N-07 ”(above, Orient Chemical Co., Ltd.) and the like are modified“ BON ”as modified nigrosine dyes.
"TRON N-04", "BONTRON N-21"
(End of Orient Chemical Co., Ltd.), "CHUO-3"
(Chuo Gosei Kagaku Co., Ltd.) and the like. Further, as triphenylmethane, "OIL BLUE" (Orient Chemical Co., Ltd.), "COPY BLUE PR"
(Clariant Co., Ltd.) and the like.

Further, a quaternary ammonium salt compound can also be suitably used in the electrostatic image developing toner of the present invention. Examples of the quaternary ammonium salt compound include compounds represented by the following formulas 2 to 4.

[Chemical 7] (Equation 2) _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. ]

[0032]

[Chemical 8] (Equation 3) _[wherein, R _1, R 2, _{R 3} and _{R 4} each independently represent a hydrogen atom, the number 1 to 22 alkyl or alkenyl group having a carbon number of 1 to 20 unsubstituted or substituted carbon 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. ]

[0033]

[Chemical 9] (Formula 4) [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.

[0035]

[Chemical 10] Compound (2-1)

[0036]

[Chemical 11] Compound (3-1)

[0037]

[Chemical 12] Compound (3-2)

[0038]

[Chemical 13] Compound (3-3)

[0039]

[Chemical 14] Compound (3-4)

[0040]

[Chemical 15] Compound (3-5)

[0041]

[Chemical 16] Compound (3-6)

[0042]

[Chemical 17] Compound (3-7)

[0043]

[Chemical 18] Compound (3-8)

[0044]

[Chemical 19] Compound (3-9)

[0045]

[Chemical 20] Compound (3-10)

[0046]

[Chemical 21] Compound (3-11)

[0047]

[Chemical formula 22] Compound (4-1)

[0048]

[Chemical formula 23] Compound (4-2)

Suitable negatively chargeable charge control agents that can be used in the present invention are metal salts or complexes of azo compounds, metal salts or complexes of salicylic acid, metal salts or complexes of benzylic acid, or those represented by the following formula 5. There is a compound.

[0050]

[Chemical formula 24] (Formula 5) (In the formula, R ₁ is quaternary carbon, methine, or methylene;
N, S, O, P may contain a hetero atom, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond, and R
₂ , R ₃ are each independently an alkyl group, an alkenyl group,
Alkoxy group, optionally substituted aryl group or aryloxy group, aralkyl group or aralkyloxy group, halogen group, hydrogen, hydroxyl group, optionally substituted amino group, carboxyl group, carbonyl group, nitro Base,
Represents a nitroso group, a sulfonyl group, a cyano group, R ₄ represents hydrogen or an alkyl group, t is an integer of 0 to 1 to 12, m is an integer of 1 to 20, n is an integer of 0 to 1 to 20, k Is an integer of 0 to 1 to 4, p is an integer of 0 to 1 to 4, q is an integer of 0 to 1 to 3, r is an integer of 1 to 20, and s is 0 or an integer of 1 to 20. )

Specific examples of the compound represented by the formula 5 include the following compounds (5-1) to (5-3).

[0052]

[Chemical 25] Compound (5-1)

[0053]

[Chemical formula 26] Compound (5-2)

[0054]

[Chemical 27] Compound (5-3)

The metal salt or complex of benzylic acid which can be preferably used in the present invention is a compound represented by the following formula 6.

[0056]

[Chemical 28] (Formula 6) (In the formula, R ₁ and R ₄ represent a hydrogen atom, an alkyl group, a substituted or unsubstituted aromatic ring (including a condensed ring), and R ₂ and R ₃ represent a substituted or unsubstituted aromatic ring ( (Including a condensed ring), M represents one trivalent metal selected from B, Al, Fe, Ti, Co and Cr, and X ⁺ represents a cation).

Specific examples of the compound of formula 6 include the following compound (6-1) and compound (6-2).

[0058]

[Chemical 29] Compound (6-1)

[0059]

[Chemical 30] Compound (6-2)

Further, as the metal salt or complex of the azo compound which can be preferably used in the present invention, for example, the following compound (7
-1) to compound (7-5).

[0061]

[Chemical 31] Compound (7-1)

[0062]

[Chemical 32] Compound (7-2)

[0063]

[Chemical 33] Compound (7-3) The cation is NH ₄ ⁺ and H ⁺ , Na ⁺ , K ^+, or a mixed ion thereof.

[0064]

[Chemical 34] Compound (7-4) The cation is NH ₄ ⁺ and H ⁺ , Na ⁺ , K ^+, or a mixed ion thereof.

[0065]

[Chemical 35] The compound (7-5) cation is NH ₄ ⁺ and H ⁺ , Na ⁺ , K ^+, or a mixed ion thereof.

In the present invention, it is preferable to use one or more selected from the above charge control agents. Further, it is particularly preferable to use a black charge control agent among the above charge control agents. Examples of the black positively chargeable charge control agent include the above-mentioned nigrosine dye, modified nigrosine dye, and triphenylmethane dye. Among them, in order to improve the dispersibility in the resin, when a modified nigrosine dye modified with rosin or maleic acid is used, the amount of toner particles that are reversely charged or weakly charged is reduced, and scumming and toner scattering are reduced, and the image quality is reduced. It is particularly preferable because it becomes good. As the black negatively chargeable charge control agent, there are metal salts or complexes of the above azo compounds. By using these black charge control agents together with the black colorant used in the present invention, the electrostatic charge image developing toner of the present invention can be made a toner having a higher degree of blackness. By using the black charge control agent, the amount of the black colorant used in the present invention can be reduced. As a result, the true specific gravity of the toner can be lowered, and the toner scattering can be prevented. When a black charge control agent is used, the amount of the black colorant used in the present invention is preferably 3 to 12 parts by mass, and particularly preferably 5 to 9 parts by mass, per 100 parts by mass of the toner. . The true specific gravity of the electrostatic image developing toner of the present invention is preferably 1.50 or less,
It is more preferably 70 to 1.45.

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

In the electrostatic image developing toner of the present invention, various known release agents, for example, polyolefin wax such as polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax and / or modified polyolefin are used. wax,
Alternatively, a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound can be appropriately used as a release agent. Among them, in the present invention, it is preferable to use a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound.

Among waxes containing higher fatty acid ester compounds and / or aliphatic alcohol compounds, carnauba wax, rice wax, scale wax, montan ester wax and the like derived from natural products and synthetic ester wax are As the tetrabehenate ester of pentaerythritol and the alcohol wax, a higher alcohol wax obtained by oxidizing Fischer-Tropsch wax or the like is particularly preferable.

The melting point (dropping point, softening temperature) of the release agent is 60.
The temperature is preferably 180 ° C to 180 ° C, more preferably 65 to 170 ° C. If the melting point is too low, the particles tend to aggregate during storage and the toner fluidity tends to decrease. If the melting point is too high, it is difficult to melt in the image fixing step, and it is difficult to exert a sufficient releasing effect.

Further, since the releasing agent may adhere to a charging member such as a blade or a carrier, which may cause instability of charging performance and deterioration of image quality, its hardness is controlled from the viewpoint of suppressing the adhesion. The higher the better, the penetrability at 25 ° C is preferably 5 or less, more preferably 2 or less.

Natural wax, synthetic ester wax, and alcohol wax have an acid value of about 2 to 40 in catalog value due to the structure or free acid, but these values are different for the same reason as in the case of resin. The lower the better.

The release agents may be used alone or in combination, and by containing 0.1 to 15 parts by mass, preferably 1 to 5 parts by mass with respect to the binder resin, good fixing offset performance can be obtained. can get. If the amount is less than 0.1 parts by mass, the offset resistance is liable to be impaired, and if it is more than 15 parts by mass, the fluidity of the toner is liable to deteriorate, and the sticking to the charging member is liable to adversely affect the charging characteristics of the toner. .

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

The electrostatic image developing toner of the present invention can be obtained by a very general manufacturing method, not by a specific manufacturing method. For example, the resin, the colorant, and the charge control agent can be obtained by melt-kneading at a melting point (softening point) or higher of the resin, 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 with a Henschel mixer or the like before melt-kneading. The conditions for this mixing are not particularly limited, but they may be mixed in several stages. The colorant and the charge control agent used here may be pre-flushed so as to be uniformly dispersed in the resin, or a masterbatch melt-kneaded with the resin at a high concentration may be used.

The above mixture is mixed by a kneading means such as a two-roll, three-roll, pressure kneader, or twin-screw extruder. At this time, the colorant and the like may be uniformly dispersed in the resin, and the conditions of the melt-kneading are not particularly limited, but usually 80 to 180 ° C. and 30 seconds to 2 hours are preferable.

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.

Then, 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, a counter jet mill, a collision plate jet mill, and classifying with a wind classifier or the like is used. Can be mentioned. Equipment for fine pulverization and classification, conditions are desired particle size,
The particle size distribution and particle shape may be selected and set.

Other methods for producing the electrostatic image developing toner of the present invention are disclosed by emulsion polymerization method, suspension polymerization method, JP-A-5-66600 and JP-A-8-62891. There is a phase inversion emulsification method. The phase inversion emulsification method is to generate a discontinuous phase of Water in Oil by adding an aqueous medium (water or a liquid medium containing water as a main component) to a mixture of a binder resin, a colorant and the like and an organic solvent, Oil in Water by adding more water
By inversion into a discontinuous phase of, and further adding an aqueous medium to form a suspension in which the mixture floats as particles (droplets) in the aqueous medium, and then removing the organic solvent. It is a method for producing toner particles.

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

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 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. .

Among them, as the external additive suitably used for the positively charged toner, hydrophobic silica obtained by surface-treating silicon dioxide with various polyorganosiloxanes, silane coupling agents and the like can be mentioned. Specifically, there are products marketed under the following trade names. AEROSIL; RA200HS, RA200H [Japan Aerosil Co., Ltd.] WACKER; 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 a hydrophobic grade whose surface is treated with octylsilane or the like. For example, there are commercially available products with the following trade names. Titanium oxide T
805 [Degussa Co., Ltd.], titanium oxide P25 [Japan Aerosil Co., Ltd.], titanium oxide JMT-150ANO
[Taika Co., Ltd.] and the like. Examples of alumina include aluminum oxide C [Degussa Co., Ltd.] 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 /.
It is 10 or less. Further, these external additives may be used in combination of two or more kinds having different average particle diameters. The silica content is usually 0.05 to 5% by mass, preferably 0.1 to 3% by mass, 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 agent of the carrier, iron powder, magnetite, ferrite, etc., which are used in the usual two-component development 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 a spherical shape so that it has fluidity. Ferrite or magnetite, which has a good value, 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 size is generally 10 to 500 μm, but 30 to 100 for printing high resolution images.
μm is preferred.

Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl carbazole, polyvinyl ether polyvinyl ketone, vinyl chloride. / Vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin consisting of organosiloxane bond or modified product thereof, fluororesin, (meth) acrylic resin,
Polyester, polyurethane, polycarbonate, 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.

In the non-magnetic one-component developing method, a contact type non-magnetic one-component developing method in which a developing sleeve carrying toner is brought into contact with a photosensitive drum having an electrostatic latent image for development, and a non-magnetic one-component developing method is used. There is a non-contact type developing method in which the toner of (3) is made to fly onto the photosensitive member to be developed, and the electrostatic image developing toner of the present invention can be suitably used for either of them.

[0088]

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.

(Synthesis Example of Resin) A synthesis example of the binder resin used for preparing the toner is shown below.

(Synthesis of linear polyester A-1) -Terephthalic acid: 664 parts by mass-Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 850 parts by mass-Ethylene Glycol: 124 parts by mass

The above materials were placed in a 2-liter four-necked flask equipped with a stirrer, a condenser and a thermometer, 4 parts by mass of tetrabutyl titanate was added under a nitrogen gas stream, and water produced by dehydration condensation was removed. While 240
The reaction was carried out at 0 ° C for 15 hours under normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction is ASTM E28
Followed by the softening point according to -517, the reaction was terminated when the softening point reached 90 ° C. Polyester resin A-1 with softening point: 97 ° C, acid value: 9.8, Tg: 61 ° C
Got

(Synthesis of cross-linked polyester B-1) -Terephthalic acid: 498 parts by mass-Isophthalic acid: 166 parts by mass-Polyoxypropylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane: 850 parts by mass, ethylene glycol: 93 parts by mass, trimethylolpropane: 55 parts by mass

Polyester resin B-having a softening point of 162 ° C., an acid value of 4.9, and a Tg of 64 ° C. measured by DSC was obtained by using the above materials and synthesizing the same as polyester A-1. Got 1.

(Synthesis of Crosslinked Polyester B-2) ・ Terephthalic acid: 664 parts by mass ・ Ethylene glycol: 150 parts by mass ・ Neopentyl glycol: 166 parts by mass Trimethylolpropane: 80 parts by mass

Polyester resin B-having a softening point of 161 ° C., an acid value of 2.3 and a Tg of 61 ° C. according to the DSC measurement method was obtained by using the above materials and synthesizing the same as polyester A-1. Got 2.

(Synthesis of Styrene Acrylic Resin C-1) Styrene: 380 parts by mass Butylmethacrylate: 120 parts by mass Divinylbenzene: 10 parts by mass Benzoyl peroxide: 5 parts by mass Thermometer, glass air flow introducing tube To a 2-volume four-necked round-bottomed flask equipped with a stirring rod equipped with a vacuum-proof sealing device and a water-cooled Dimroth condenser, 500 parts of xylene, the above-mentioned monomers and all of the initiator were charged. Nitrogen gas was introduced from a glass air flow introduction tube to replace the inside of the reactor with an inert atmosphere, and then the contents were gradually heated by a mantle heater with a slider box to raise the temperature to 75 ° C. The reaction is 65
The temperature was raised to 130 ° C to complete the polymerization after 10 to 12 hours, while the temperature was kept at 80 ° C to 80 ° C. 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 vacuum adapter was connected to the vacuum adapter via a manometer and a trap with a rubber tube for pressure reduction, and preparation for vacuum distillation was completed. When the mantle heater is heated and the contents are sufficiently stirred and the vacuum pump is operated to reduce the pressure to 20 mmHg, the liquid temperature is 75 ° C and the distilling temperature is 38.
At x ° C, xylene or possibly unreacted monomer began to distill. Finally, the solvent was completely removed by reducing the pressure to 0.5 mmHg at a liquid temperature of 180 ° C. The obtained polymer C-1 was opened in a stainless pan while being in a high temperature molten state, cooled to room temperature and then crushed. The resulting polymer C-1 had a softening point of 145.
C, Tg: 61C.

(Production of Black Colorant 1) Average Diameter 0.2 μm
And 100 g of granular magnetite particles having a magnetization value of 85.0 emu / g were mixed with 0.26 mol of TiOSO _4.
Was dispersed and mixed in an aqueous solution containing, and then NaOH was added to the mixed solution for neutralization to deposit Ti hydroxide on the surface of the particles at pH 8, followed by filtration and drying. Further, after heating and firing at 750 ° C. for 120 minutes under N ₂ gas flow, it was pulverized to obtain a powder of “black colorant 1”. The particle size of this "black colorant 1" was 0.25 μm. In addition, the particles were found to have Fe ₂ TiO ₅ and Fe ₂ O by X-ray diffraction.
It was confirmed to be a mixed composition with a _3- FeTiO ₃ solid solution.

(Example 1) <Manufacture of toner> -Polyester resin A-1 84 parts by mass-Black colorant 1 12 parts by mass-Compound (2-1) 1 part by mass-Purified carnauba wax No. 1 powder (Kato Hiroyuki) (Manufacture) 3 parts by mass A Henschel mixer was used to prepare a mixture of the above raw materials, and the mixture was temporarily stored in a hopper. Then, the mixture was kneaded with a biaxial melt kneader. The kneaded material thus obtained was pulverized by a mechanical pulverizer and then classified to obtain a toner base material 1 having a volume average particle diameter of 9.8 μm. Toner base material 1 100 parts by mass HVK2150 0.5 part by mass Obtained toner base material 1 and the above-mentioned hydrophobic silica are mixed by a Henschel mixer and then sieved to give Example 1.
Toner was obtained.

Then, the toners of Examples 2 to 7 and Comparative Examples 1 and 2 were produced in the same manner as in Example 1 with the formulations shown in Table 1.

[0100]

[Table 1] ・ Mogal L; carbon black (manufactured by Cabot) ・ Carnava; carnauba wax No. 1 powder (manufactured by Yoko Kato) ・ 550P; Viscor 550P (manufactured by Sanyo Kasei Co., Ltd.) ・ PETB; pentaerythritol tetrabehenate ester N-04; Bontron N-04 (Orient Chemical,
Nigrosine dye) ・ Epoxy resin; Epicron 7050 (Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., softening point 126 ° C)

<Toner Test of Examples and Comparative Examples> Using the silicone-coated ferrite carrier (particle size 100 μm) and the toners of Examples and Comparative Examples, a developer was prepared so that the toner concentration would be 5% by mass. The following tests were performed using each developer.

(Measurement of Transfer Efficiency) A commercially available copying machine was used to develop a solid image (length 100 mm × width 20 mm),
It was stopped when the solid image on the photoreceptor passed 50% through the transfer portion. After that, the untransferred image (solid) on the photoreceptor
Each unfixed image after transfer is taped (30 mm × 20
mm), the toner amount of the untransferred image and the toner amount after the transfer are measured, and the transfer efficiency (%) is calculated from the following formula.
Was calculated. The results are shown in Table 2. Transfer efficiency (%) = {1- (toner amount after transfer / toner amount of untransferred image)} × 100

(Comparison of rising of charge) The developer 50
115 RP for 100 cc polyethylene container containing g
After stirring for 3 minutes with a ball mill of m, the developer was sampled and the charge amount was measured with a blow-off charge amount measuring device. After further stirring for 7 minutes (total 10 minutes), the charge amount was measured in the same manner. The test results are shown in Table 2.

(Fixing Performance Test) Regarding the fixing temperature range, the fixing temperature was obtained by the following test, and the range between the upper limit value and the lower limit value was defined as the fixing temperature range. A test sample in which a belt-shaped unfixed image was formed on a paper was prepared with a printer using a commercially available organic optical semiconductor as a photoconductor, using the toners of Examples and Comparative Examples. Using a heat roll (oilless type) of RICOH IMAGIO DA-250, fixing was performed while changing the surface temperature at a fixing speed of 90 mm / sec. Mending tape (3
The temperature range of the heat roll, in which the image density (ID) after peeling and peeling was applied to 90% or more of the original ID and no offset was observed, was defined as the fixing temperature range. The results are shown in Table 2.

[0105]

[Table 2]

(Printing durability test) 100,000 sheets were continuously printed using a commercially available high-speed printer (220 sheets of A4 paper / minute), the density of the image area and the background stain density were measured, and the charge amount of the developer was measured. Was measured. The image density and background stain were measured with a Macbeth densitometer RD-918. The background stain was obtained by subtracting the white paper density before printing from the white background density of the print density. ○, 0.0 when the difference is less than 0.01
When it was 1 to less than 0.03, it was evaluated as Δ, and when it was 0.03 or more, it was evaluated as x. The test was conducted in an environment of 25 ° C. and 60%.

Further, the state of toner scattering inside the developing machine was visually observed. No scattering is observed ◎, almost no scattering is visible, but toner stain is observed when wiping the inside of the device with a waste cloth ○, In-machine scattering is visually confirmed △, severe scattering inside the machine is confirmed The state that can be done was set as x.

The charge amount was measured by using a blow-off charge amount measuring device (manufactured by Toshiba Chemical Co.) after collecting the toner from the developing device. The above results are shown in Table 3.

[0109]

[Table 3]

Example 8 <Production of Toner> Polyester Resin A-1 43 parts by mass Polyester Resin B-1 43 parts by mass Black Coloring Agent 19 parts by mass Compound (6-3) 2 parts by mass Purified carnauba wax No. 1 powder (manufactured by Yoko Kato) 3 parts by mass of the above raw materials are mixed using a Henschel mixer, melt-kneaded with a twin-screw kneader, cooled, and then finely pulverized with a jet mill,
A toner having an average particle diameter of 8.0 μm was prepared by classification.

Next, with respect to 100 parts by mass of this toner, 1 part by mass of silica "NAX50" manufactured by Nippon Aerosil Co., Ltd. and "RY
Example 11 was obtained by externally adding 1 part by mass of "-200".
Toner was obtained.

In the same manner, toners having the compositions shown in Table 4 were manufactured, and the external addition process was performed in the same manner as in Example 8 to obtain toners in Examples 9 to 12 and Comparative examples 3 to 4.

[0113]

[Table 4] * E-84; Bontron E-84 (metal complex compound of salicylic acid "Orient chemistry"

(Printing Durability Test) The toner of the commercially available non-magnetic one-component developing type printer (“Ipcio Color 2000” manufactured by Ricoh Co., Ltd.) was used to remove the special toner, and the washed cartridge was used in the examples shown in Table 4. Also, the toner of the comparative example was filled, and 10000 sheets were continuously printed at an image density of 5%. The test was performed in an environment of 25 ° C. and 60%.

(Image density / background stain / charge amount) The image density and background stain of the printed matter were measured with a Macbeth densitometer RD-918. The background stain was obtained by subtracting the white paper density before printing from the white background density after printing. When the difference is less than 0.01, it is ○, when it is 0.01 to less than 0.03, it is Δ, 0.03.
The above time was marked as x. In addition, the charge amount of the print toner was measured using a suction type small charge amount measuring device Mode210HS (manufactured by Trek). The results are shown in Table 5.

(Toner dropping / toner scattering) After printing 10,000 sheets, toner is not spilled from the developing sleeve mounted on the cartridge (toner dropping) or scattered around the developing device (toner scattering) to contaminate the inside of the machine. Was evaluated as ◯, a state where a small amount of toner was dropped or toner scattering was recognized as Δ, and a state where a large amount of toner was dropped or toner scattering was recognized as x. The results are shown in Table 5.

[0117]

[Table 5]

[0118]

EFFECT OF THE INVENTION Fe ₂ TiO ₅ and Fe ₂ O ₃ -FeTi
The toner for developing an electrostatic image of the present invention, which uses a black pigment having a mixed composition with an O ₃ solid solution, exhibits stable charging behavior even during long-term use or printing of a large number of copies, and is free from background stain and image density. It is possible to perform printing without fluctuation of

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03G 9/087 G03G 9/08 331 9/097 333 351 346 F term (reference) 2H005 AA01 AA06 CA07 CA08 CA14 CA21 CA22 CA25 CA28 CA30 CB03 CB07 DA03 EA03 EA07 EA10 4J002 CD051 CD061 CF031 CF051 CF081 DE186 EA047 EC069 EG019 EJ068 EN137 EQ018 FD096 FD107 FD108 FD169 GT00

Claims (9)

[Claims] 1. A toner for developing an electrostatic charge image, wherein a colorant is dispersed in a binder resin, wherein the binder resin is a polyester resin and / or an epoxy resin, and the colorant is Fe ₂ TiO ₅ and Fe ₂ O ₃ toner for developing electrostatic images, wherein the mixture is a black pigment having a composition of the -FeTiO ₃ solid solution. 2. The coloring agent is Fe (II) or Fe (II).
The toner for developing an electrostatic charge image according to claim 1, which is a black pigment containing 15.0 to 50.0 atomic% of titanium in terms of Ti based on I). 3. The polyester resin comprises one or more polybasic acid compounds selected from the group consisting of dibasic or higher polybasic acids, acid anhydrides and lower alkyl esters thereof, and a compound of the formula 1, (Formula 1) (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; The toner for developing an electrostatic charge image according to claim 1, which is a polyester resin obtained by reacting with a diol represented by the formula (1) as a main component. 4. The polyester resin is a mixture of two or more polyester resins having different softening points.
Or the toner for developing an electrostatic charge image according to any one of 3). 5. The polyester resin has a softening point of 80 to
110 ° C polyester resin and softening point 115-200 ° C
The toner for developing an electrostatic charge image according to claim 1, which is a mixture of the polyester resin according to claim 1. 6. A nigrosine dye as a charge control agent,
The electrostatic image developing toner according to claim 1, further comprising at least one selected from a modified nigrosine dye, a triphenylmethane dye, and a compound having a quaternary ammonium salt structure. 7. The compound having a quaternary ammonium salt structure is represented by the formula 2, (Equation 2) _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 3, (Equation 3) _[wherein, R _1, R 2, _{R 3} and _{R 4} each independently represent a hydrogen atom, the number 1 to 22 alkyl or alkenyl group having a carbon number of 1 to 20 unsubstituted or substituted carbon 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. ] Or Formula 4, (Formula 4) [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. ] The toner for developing an electrostatic charge image according to claim 6, which is a compound represented by the formula: 8. As a charge control agent, a metal salt or complex of an azo compound, a metal salt or metal complex of salicylic acid, a metal salt or metal complex of benzylic acid, or a compound represented by the formula 5, (Formula 5) (In the formula, R ₁ is quaternary carbon, methine, or methylene;
N, S, O, P may contain a hetero atom, Y represents a cyclic structure connected by a saturated bond or an unsaturated bond, and R
₂ , R ₃ are each independently an alkyl group, an alkenyl group, an alkoxy group, an aryl group which may have a substituent, an aryloxy group, an aralkyl group or an aralkyloxy group, a halogen group, hydrogen, a hydroxyl group, a substituent May have an amino group, a carboxyl group, a carbonyl group, a nitro group,
Represents a nitroso group, a sulfonyl group, a cyano group, R ₄ represents hydrogen or an alkyl group, t is an integer of 0 to 1 to 12, m is an integer of 1 to 20, n is an integer of 0 to 1 to 20, k Is an integer of 0 to 1 to 4, p is an integer of 0 to 1 to 4, q is an integer of 0 to 1 to 3, r is an integer of 1 to 20, and s is 0 or an integer of 1 to 20. )
The electrostatic image developing toner according to claim 1, containing at least one selected from the compounds represented by: 9. The static accelerating composition according to claim 1, further comprising a higher fatty acid ester compound and / or an aliphatic alcohol compound as a releasing agent. Toner for charge image development.