JP2003345066A - Electrostatic charge image developing toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide electrostatic charge image developing toner by which the occurrences of toner scattering, fogging and the fluctuation of image density are eliminated by showing stable electrification behavior in the use of a long term or the printing of many sheets and also whose safety for an environment is excellent by using colorant not incorporating a harmful material. <P>SOLUTION: The electrostatic charge image developing toner is constituted by dispersing the colorant in binder resin and the colorant incorporates C.I. Pigment Black 12. <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.

By the way, the characteristics required for the black colorant used in the toner for developing an electrostatic image are colorability and
In addition to safety, handleability during manufacturing, and heat resistance, there are electrical characteristics that affect development characteristics. The electrical characteristics are one of the important characteristics required for the colorant. When the electrical characteristics are further subdivided and listed, the charging rising characteristics, the characteristics of holding the charging for a long time, the charging uniformity (charging amount distribution), the charging environmental stability, and the like can be mentioned. 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 proportion of the oppositely charged particles or the weakly charged particles increases, which causes the scattering of the toner inside the machine during development and the fog phenomenon in which the 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.

Various materials have been studied to solve the drawbacks of carbon black or black iron oxide (magnetite) and replace them. Among them, in Japanese Patent Laid-Open No. 3276/1993, particles having magnetite particles whose surfaces are coated with a titanium compound, or mixed powder of magnetite particles and a titanium compound are 70
Black particle powder and the like obtained by heating and baking at a temperature of 0 ° C. or higher have been proposed, and a technology relating to a toner using the same has been disclosed. However, the purpose of the publication is to provide a black colorant which is safe, harmless, and has excellent workability and heat resistance, and the improvement of the electrical characteristics is not considered. In addition, JP-A-2000-
No. 319021 also proposes a black particle powder in which a certain amount of titanium component is contained in magnetite particles, and a toner using the black particle powder.
As in the above publication, no consideration is given to the improvement of electrical characteristics.

As described above, in the prior art, the technology relating to the toner using the novel black colorant which can solve the drawbacks of carbon black or black iron oxide (magnetite) and further satisfy the electrical characteristics of the toner is known. Not disclosed.

[0007]

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.

[0008]

The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, C.I. I. Pig
The inventors have found that the above problems can be solved by using a toner containing ment Black 12, and have completed the present invention.

That is, the present invention provides a toner for developing an electrostatic charge image in which a colorant is dispersed in a binder resin, wherein the colorant is C.I. I. The present invention provides a toner for developing an electrostatic charge image, which is a colorant containing Pigment Black 12.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The colorant used in the present invention is C.I. I. Pigment
It is a coloring agent classified into Black 12. The colorant is a composite oxide of titanium and iron, and has a spinel structure represented by FeTiO _2.
own spinel). The colorant having such a structure is a colorant having a high degree of blackness. Also,
The toner using the colorant exhibits stable charging behavior even during long-term use or printing of a large number of copies.
The toner for electrostatic charge image development is free from toner scattering and fog, has a sufficient image density, and can obtain a printed image without fluctuations in the image density. Also, unlike carbon black, it does not contain harmful substances, so it is also excellent in terms of safety and hygiene.

C. I. Pigment Black 1
Examples of commercially available colorants classified into 2 include Ba
tleship Gray No. 6, Chestn
utBrown No. 180, Chocolate
Brown No. 20, Russet Brown
No. 8 (above, Shepherd ColorCom
pany), Irgacolor 10358 (made by Ciba Geigy), and the like. The above are black or dark colorants. When the toner of the present invention is used as a black toner, it is particularly preferable to use the Battleship Gray No. 6,
Alternatively, Chocolate Brown No. 20
Is preferably used. In addition, brown or light brown C.I. I. Pigment Black 12 is a colorant classified as Autumn Brown N.
o. 156, Golden Brown No. 19
(Above, Shepherd Color Compan
y made) etc. When the toner of the present invention is a brown toner, these colorants may be used.

The amount of the colorant used in the present invention is preferably in the range of 3 to 30 parts by weight, more preferably 5 to 15 parts by weight, per 100 parts by weight of the toner. If it exceeds 30 parts by weight, the true specific gravity of the toner becomes large and the toner tends to scatter, which is not preferable.

Although the above-mentioned colorant is used in the present invention, a known colorant can be used for the purpose of adjusting the hue. For example, as black colorants, furnace black, channel black, which is classified according to the manufacturing method,
Carbon black such as acetylene black, thermal black, lamp black, or C.I. I. Pigme
nt Black 11 iron oxide pigments, aniline black, phthalocyanine cyanine black BX and the like. The colorant used in the present invention is characterized in that it does not contain harmful substances, and the object of the present invention is to provide a toner for developing electrostatic images which does not contain harmful substances. It is necessary to pay sufficient attention to the content of harmful substances and the amount used in combination with the black colorant used in the present invention.

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.

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 which 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 preferably 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 1 to 3.

[Chemical 5] (Equation 1) _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. ]

[0018]

[Chemical 6] (Equation 2) _[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. ]

[0019]

[Chemical 7] (Formula 3) [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.

[0021]

[Chemical 8] Compound (1-1)

[0022]

[Chemical 9] Compound (2-1)

[0023]

[Chemical 10] Compound (2-2)

[0024]

[Chemical 11] Compound (2-3)

[0025]

[Chemical 12] Compound (2-4)

[0026]

[Chemical 13] Compound (2-5)

[0027]

[Chemical 14] Compound (2-6)

[0028]

[Chemical 15] Compound (2-7)

[0029]

[Chemical 16] Compound (2-8)

[0030]

[Chemical 17] Compound (2-9)

[0031]

[Chemical 18] Compound (2-10)

[0032]

[Chemical 19] Compound (2-11)

[0033]

[Chemical 20] Compound (3-1)

[0034]

[Chemical 21] Compound (3-2)

Suitable negatively chargeable charge control agents that can be used in the present invention include metal salts or complexes of azo compounds, metal salts or complexes of salicylic acid, metal salts or complexes of benzylic acid, or the following formula 4. There is a compound.

[0036]

[Chemical formula 22] (Formula 4) (In formula, R < ₁ > is quaternary carbon, methine, and 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 4 include the following compounds (4-1) to (4-3).

[0038]

[Chemical formula 23] Compound (4-1)

[0039]

[Chemical formula 24] Compound (4-2)

[0040]

[Chemical 25] Compound (4-3)

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 5.

[0042]

[Chemical formula 26] (Formula 5) (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 5 include the following compound (5-1) and compound (5-2).

[0044]

[Chemical 27] Compound (5-1)

[0045]

[Chemical 28] Compound (5-2)

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 (6
-1) to compound (6-5).

[0047]

[Chemical 29] Compound (6-1)

[0048]

[Chemical 30] Compound (6-2)

[0049]

[Chemical 31] Compound (6-3) The cation is NH ₄ ⁺ and H ⁺ , Na ⁺ , K ^+, or a mixed ion thereof.

[0050]

[Chemical 32] Compound (6-4) The cation is NH ₄ ⁺ and H ⁺ , Na ⁺ , K ^+, or a mixed ion thereof.

[0051]

[Chemical 33] The compound (6-5) 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 of 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,
It is possible to prevent toner scattering and the like. 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 weight, and particularly preferably 5 to 9 parts by weight, per 100 parts by weight of the toner. .
The true specific gravity of the toner for developing an electrostatic image of the present invention is preferably 1.50 or less, and more preferably 0.70 to 1.45.

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

As the binder resin used in the toner for developing an electrostatic image of the present invention, any binder resin can be used without particular limitation as long as it does not impair the object of the present invention. Specifically, a polystyrene-based resin, a styrene- (meth) acrylic acid ester copolymer resin, or a vinyl-based copolymer resin such as a styrene-conjugated diene copolymer resin, a polyester resin, an epoxy resin, Examples thereof include butyral resin, xylene resin, coumarone indene resin, and hybrid resin obtained by combining the above resins. Among them, vinyl-based copolymer resin, polyester resin, and epoxy resin are preferable, and fixability and resistance A polyester resin can be particularly preferably used because it has a good balance of offset property, transparency and the like.

The polyester resin preferably used in the present invention includes (A) a dibasic or more polybasic acid and / or acid anhydride and / or a polybasic acid compound (B) divalent selected from lower alkyl esters thereof. It is obtained by dehydration condensation of the above polyhydric alcohol by a usual method.

Examples of the polybasic acid and / or acid anhydride having a valence of 2 or more 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.

The following compounds may be mentioned as polyhydric alcohols having two or more valences. For example, as the divalent aliphatic alcohol, (a) ethylene glycol, polyethylene glycol,
Propylene glycol, tripropylene glycol, butanediol, pentanediol, hexanediol,
Examples include neopentyl glycol, cyclohexanedimethanol, ethylene oxide-propylene oxide random copolymer diol, ethylene oxide-tetrahydrofuran copolymer diol, and the like.

As the divalent aromatic diol,
The following compound (b) which is an alkylene oxide adduct of bisphenol A may be mentioned. (B) Polyoxyethylene- (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene- (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 and the like.

Further, as the polyhydric alcohol having a valence of 3 or more, (c) 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 ，
Trihydric or higher alcohol such as 5-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 or copolymer of vinyl compound having epoxy group, epoxidized resorcinol-acetone condensate, partially epoxidized polybutadiene,
There are semi-dry or dry fatty acid ester epoxy compounds and the like.

As the polyester resin used in the present invention, a polybasic acid compound selected from a divalent polybasic acid and / or an acid anhydride and / or a lower alkyl ester thereof and a divalent aliphatic polyhydric alcohol are used. As the main constituent, further, if necessary, a polybasic acid compound having a valence of 3 or more, or a polyester resin crosslinked or branched with a polyhydric alcohol having a valence of 3 or more described in the component (c) is used. Is more preferable. In that case, when the compound (b) is used as the polyhydric alcohol, it is preferably 0 to 30 mol% in all alcohol components,
It is more preferably from 0 to 10 mol%. Above all, it is particularly preferable not to use the compound (b) at all.

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.

When a polyester resin is used as the binder resin of the toner for developing an electrostatic image of the present invention, the most preferable embodiment is that the compound (b) is not used as the polyhydric alcohol component and a divalent polybasic acid and And / or a linear polyester resin obtained by reacting a polybasic acid compound selected from an acid anhydride and / or a lower alkyl ester thereof with a divalent aliphatic alcohol, and a (b) compound as a polyhydric alcohol component. A polybasic acid compound selected from a divalent polybasic acid and / or an acid anhydride and / or a lower alkyl ester thereof, which is not used, and a crosslinked polyester resin obtained by reacting a divalent aliphatic alcohol and an epoxy resin. This is the case when they are used together. A toner using such a resin as a binder resin has good fixing performance at low temperatures and excellent offset performance at high temperatures.

The softening point of the binder resin used in the present invention is preferably in the range of 90 to 180 ° C., and 95
More preferably, it is in the range of ˜160 ° C. If the temperature is lower than 90 ° C, offsetting at high temperature tends to occur,
If it exceeds 0 ° C, the fixability at low temperatures tends to deteriorate.

The softening point of the resin in the present invention is defined by the T1 / 2 temperature measured by using a constant load extrusion type capillary rheometer, Flow Tester 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, the sample weight was 1.5 g.

Further, the glass transition temperature of the binder resin 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 JIS K7121.
It is defined as the extrapolated glass transition onset temperature obtained by the measurement according to. Shimadzu DSC-60 was used for the measurement.

The acid value is preferably 1 to 30 mgKOH / g, more preferably 1 to 20 mgKOH / g. The hydroxyl value is 10 to 100 mg KO.
H / g is preferred, and 10-60 mg KOH /
More preferably, it is 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.

In the toner for electrostatic image development of the present invention, various known release agents such as polypropylene wax, polyethylene wax, polyamide wax, Fischer-Tropsch wax and other polyolefin waxes and / or modified polyolefins 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 waxes containing higher fatty acid ester compounds and / or aliphatic alcohol compounds, waxes derived from natural products such as carnauba wax, rice wax, scale wax, montan ester wax 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 release agent is preferably selected according to the binder resin used in combination. When a release agent having poor dispersibility in the binder resin is selected, the release agent is more likely to be exposed on the surface of the toner particles, and the fluidity of the toner is likely to decrease. Further, in the pulverizing step in the toner manufacturing process, the release agent is easily released, the amount of the release agent contained in the toner is reduced, and the fixing / offset performance is easily deteriorated. Furthermore, in the process of developing the toner, the released release agent easily causes scumming and scattering,
The image quality is likely to deteriorate. If the dispersion in the binder resin proceeds excessively or if the release agent is compatible with the resin, the fixing / offset performance tends to deteriorate. For these reasons, it is preferable to select a release agent that is appropriately dispersed in the binder resin, and the particle size of the release agent dispersed in the binder resin is preferably in the range of 0.01 to 5 μm,
The range of 1 to 3 μm is more preferable.

A preferred combination of the binder resin and the release agent used in the present invention is, when a polyester resin or an epoxy resin is used, a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound as a release agent. When a vinyl-based copolymer is used, the combination is a combination of a polyolefin wax and / or a modified polyolefin wax.

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, the releasing agent may adhere to a charging member such as a blade or a carrier, which may cause instability in charging performance and deterioration in image quality. 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. However, these values are different for the same reason as 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 weight, preferably 1 to 5 parts by weight 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 weight, the offset resistance tends to be impaired, and if the amount is more than 15 parts by weight, the fluidity of the toner tends to deteriorate, and the sticking to the charging member tends 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 toner for developing an electrostatic charge image of the present invention can be obtained by a very general production method without depending on a specific production 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.

Next, there is a method of finely pulverizing with a mechanical pulverizer such as a turbo mill or kryptron, an air pulverizer such as a spiral jet mill, a counter jet mill, a collision plate jet mill, etc., and classifying with a wind classifier or the like. 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, JP-A-8-62891 and the like. 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 weight, preferably 0.1 to 3% by weight, based on the toner.

When the electrostatic image developing toner of the present invention is used in a two-component developing system, the following carriers can be used. As the core 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, polyvinylcarbazole, 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.

[0089]

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. In addition, the resin obtained in each synthesis example was treated with tetrahydrofuran (T
The molecular weight of the THF-soluble component obtained by filtering the solution that had been left in HF) for 12 hours was measured. For the analysis, a gel permeation chromatography (GPC) method was used, and the molecular weight was calculated from a calibration curve prepared using standard polystyrene. GPC device: Tosoh Corp. HLC-8120 GPC column: Tosoh Corp. TSK Guardcolu
mn SuperH-H TSK-GEL Super
HM-M3 coupling concentration: 0.5 wt% Flow rate: 1.0 ml / min The THF insoluble content is 1 g of the sample powder placed on a cylindrical filter paper, and the residue on the filter paper after refluxing for 8 hours with THF as a solvent in a Soxhlet extractor Calculated from Acid value is JIS K690
1 and Tg were measured according to JIS K7121.

(Resin 1) -Terephthalic acid: 664 parts by weight-Ethylene glycol: 75 parts by weight-Polyoxypropylene- (2.2) -2.2-bis (4-hydroxyphenyl) propane: 700 parts by weight-Tri Methylol propane: 80 parts by weight Tetrabutyl titanate: 3 parts by weight The above materials were placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer, and 4 parts by weight of tetrabutyl titanate was added under a nitrogen gas stream. While removing water produced by dehydration condensation, the reaction was carried out at 240 ° C. for 10 hours under normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point, and the reaction was terminated when the softening point reached 145 ° C. The obtained polyester resin is
Mn: 5450, Mw: 152200, softening point: 147
C, acid value is 5.8, Tg by DSC measurement method is 63 ° C,
The THF insoluble content was 3%.

(Resin 2) -Terephthalic acid: 664 parts by weight-Propylene glycol: 152 parts by weight-Cyclohexanedimethanol: 145 parts by weight-Neopentyl glycol: 150 parts by weight The above materials were set with a stirrer, a condenser and a thermometer. Place in a 2-liter four-necked flask, and under a nitrogen gas stream, 4
While adding tetrabutyl titanate in parts by weight and removing water generated by dehydration condensation, the reaction was carried out at 200 ° C. for 20 hours under normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 5 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 90 ° C. The molecular weight of the obtained polyester is M
It was n: 2520 and Mw: 6200. Softening point: 95
° C, acid value: 6.8, Tg in DSC measurement method: 53
It was ° C.

(Resin 3) -Terephthalic acid: 664 parts by weight-Neopentyl glycol: 120 parts by weight-Ethylene glycol: 150 parts by weight-Propylene glycol: 61 parts by weight-Epiclon 830 (Dainippon Ink and Chemicals, bisphenol F type) Epoxy resin): 19.3 parts by weight, Cardura E: 20 parts by weight The above materials were placed in a 2 liter four-necked flask equipped with a stirrer, a condenser and a thermometer and placed under a nitrogen gas stream for 4 days.
g of tetrabutyl titanate was added, and the reaction was carried out at 240 ° C. for 12 hours under normal pressure while removing water produced by dehydration condensation. After that, the pressure was sequentially reduced and the reaction was continued at 30 mmHg. The reaction was followed by the softening point according to ASTM E28-517, and the reaction was terminated when the softening point reached 200 ° C. The obtained polyester resin has Mn: 5
2,800, Mw: 165,100, THF insoluble matter 7.
4%, softening point: 203 ° C, acid value: 9.3, Tg: 6
It was 7.2 ° C.

(Resin 4) -isophthalic acid: 116 parts by weight-terephthalic acid: 166 parts by weight-trimellitic anhydride: 38 parts by weight-diethylene glycol: 26 parts by weight-neopentyl glycol: 104 parts by weight-ethylene glycol: 50 parts by weight Parts-Tetrabutyl titanate: 2.5 parts by weight or more of the raw materials were placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stir bar and a nitrogen inlet tube, and under an atmospheric pressure nitrogen stream in an electric heating mantle heater. After reacting at 240 ° C. for 10 hours, the pressure was sequentially reduced and the reaction was continued at 10 mmHg. 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 polyester resin is a colorless solid and has an acid value:
4, Tg: 72 ° C, softening point: 151 ° C.

(Resin 5) -Styrene: 380 parts by weight-Butylmethacrylate: 120 parts by weight-Divinylbenzene: 10 parts by weight-Benzoyl peroxide: 5 parts by weight Thermometer, glass air flow introducing tube, vacuum-proof sealing device A 2-volume four-necked round bottom flask equipped with a stirring rod and a water-cooled Dimroth condenser was charged with 500 parts of xylene, the above-mentioned monomers and all of the initiators. 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 (hereinafter referred to as polymer (a)) was placed in a stainless steel pan in a molten state at high temperature, cooled to room temperature and then crushed. The obtained polymer has a softening point: 145 ° C, Tg: 61 ° C, M
It was n: 8,000 and Mw: 21,000.

(Black Colorant Used in Examples) Colorant 1; Black Colorant (Battleship Gr)
ay No. 6; Shepherd Color Co
Coloring agent 2; Black coloring agent (Chocolate Bro)
wn No. 20; Shepherd Color C
made by company)

(Production of Comparative Colorant 1) Average Diameter 0.2 μm
m and a magnetizing value of 85.0 emu / g, 100 g of granular magnetite particle powder was added to 0.26 mol of TiOSO.
₄ was dispersed and mixed in an aqueous solution containing ₄ 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 black particle powder (Comparative Colorant 1).
The particle size of this black particle powder was 0.25 μm.
In addition, X-ray diffraction revealed that the particles were Fe ₂ TiO ₃ and Fe ₂
It was confirmed that the composition was a mixed composition with an O ₃ —FeTiO ₃ solid solution.

Example 1 <Manufacture of Toner> 78 parts by weight of resin 1 18 parts by weight of colorant 1 1 part by weight of compound (3-1) 3 parts by weight of refined carnauba wax No. 1 powder (made by Kato Yoko) Part Henschel mixer was used to prepare a mixture of the above raw materials, and the mixture was temporarily stored in the 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 stock 1 100 parts by weight HVK2150 0.5 part by weight Obtained toner base 1 and the above hydrophobic silica are mixed by a Henschel mixer, and then sieved to obtain Example 1.
Toner was obtained.

Thereafter, toners of Examples 2 to 10 and Comparative Examples 1 and 2 were produced with the formulations shown in Table 1 in the same manner as in Example 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) PR; COPY BLUE PR (manufactured by Clariant,
Triphenylmethane dye) -Epoxy resin; Epicron 7050 (Epoxy resin manufactured by Dainippon Ink and Chemicals, Inc., softening point 126 ° C) -St / Bu resin; commercially available styrene-butadiene copolymer styrene: butadiene = 89:11 Mn: 12,400, Mw: 88,500, softening point: 1
35 ° C, Tg: 56 ° C

<Toner Tests 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 weight. The following tests were performed using each developer.

(Printing endurance test) A commercially available high-speed printer (220 sheets of A4 paper / minute) was used to continuously print 100,000 sheets, and 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%.
The results are shown in Table 2.

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 results are shown in Table 2.

The charge amount was measured by using a blow-off charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.) by collecting the toner from the developing device. The results are shown in Table 2.

(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 3. 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 3.

(Measurement of True Specific Gravity) The true specific gravity of the toner was measured with an air-comparison type pycnometer 930 (Beckman). The results are shown in Table 3.

(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 3.

[0109]

[Table 2]

[0110]

[Table 3]

Example 11 <Manufacture of Toner> 87 parts by weight of resin 4 18 parts by weight of colorant 2 parts by weight of compound (6-3) 2 parts by weight of purified carnauba wax No. 1 powder (made by Kato Hiroyuki) 3 parts by weight Part Henschel mixer, the above raw materials are mixed, 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, for 100 parts by weight of this toner, 1 part by weight of silica "NAX50" manufactured by Nippon Aerosil and "RY
Example 11 by externally adding 1 part by weight 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 11 to obtain toners in Examples 12-5 and Comparative Examples 3-4.

[0114]

[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 removed from the cartridge, and the washed cartridge was used as an example 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 / Amount of Charge) 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.

[0118]

[Table 5]

[0119]

Effect of the Invention C. I. Pigment Black
The toner for developing an electrostatic charge image of the present invention using a colorant containing 12 shows stable charging behavior even during long-term use or printing of a large number of copies, has no background stain, and has no fluctuation in image density. It can be performed.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H005 AA01 AA06 CA08 CA14 CA21                       CA22 CA25 CA28 CA30 DA02                       DA03

Claims (6)

[Claims] 1. A toner for developing an electrostatic charge image, comprising a binder resin and a colorant dispersed therein, wherein the colorant is C.I. I.
Pigment Black 12 is a colorant, which is a toner for developing an electrostatic charge image. 2. A nigrosine dye as a charge control agent,
The electrostatic image developing toner according to claim 1, containing at least one selected from a modified nigrosine dye, a triphenylmethane dye, and a compound having a quaternary ammonium salt structure. 3. The compound having a quaternary ammonium salt structure is represented by the formula 1, (Equation 1) _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 2, (Equation 2) _[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, and a heteropolyacid anion containing a molybdenum or a tungsten atom. ] Or Formula 3, (Formula 3) [In formula, m shows 1, 2 or 3, and n shows 0, 1 or 2, M is a hydrogen atom or a monovalent metal ion. X and Z represent 1 or 2, and Y represents 0
Or 1 is shown. Furthermore, when X = 1, Y = 1, Z = 1
Then, when X = 2, Y = 0 and Z = 2. R _{5 to} R
₁₂ is 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 (provided that 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 have 1 to 3 carbon atoms.
0 linear or branched saturated or unsaturated alkyl group, or the general formula _{(-CH 2 -CH 2 -O) n} ,
An oxyethyl group represented by R (wherein 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 group having 5 to 12 carbon atoms; It also represents a polynuclear alicyclic residue, a mononuclear- or polynuclear aromatic residue or an araliphatic residue. ] The toner for developing an electrostatic charge image according to claim 2, which is a compound represented by the formula: 4. Further, as the 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 formula 4, (Formula 4) (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: 5. The binder resin is a polybasic acid compound (B) divalent aliphatic polyvalent compound (B) selected from (A) divalent polybasic acid and / or acid anhydride and / or lower alkyl ester thereof. 5. A polyester resin obtained by reacting a monomer containing alcohol as a main constituent component.
Item 6. The toner for developing an electrostatic charge image according to item. 6. The electrostatic image developing toner according to claim 1, further comprising a higher fatty acid ester compound and / or an aliphatic alcohol compound as a releasing agent.