JP2003195567A - Electrostatic charge image developing color toner and manufacturing method therefor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red color toner, especially a magenta toner which has excellent coloring power and hue, shows stable electrification properties even if environment such as temperature and humidity is changed and has excellent color reproducibility as a result, whose electrification quantity is not varied while the toner is used even when it is applied to a negatively chargeable toner and which shows satisfactory and stable print image quality and to provide a manufacturing method for the red color toner, especially the magenta toner. <P>SOLUTION: An electrostatic charge image developing color toner containing at least a binder resin and a coloring agent is characterized in that the coloring agent is an organic pigment having a structure represented by formula 1. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color toner for developing an electrostatic charge image for developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing and the like, and a method for producing the same.

[0002]

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

The properties required of such color toners are that the image after printing has a vivid color-forming property and that it exhibits excellent transparency in color overlapping when multicolor printing is performed. It has clear color reproducibility without color turbidity, or an overhead projector (hereinafter,
There is a demand for color reproduction characteristics such as displaying a clear color without turbidity when a color image obtained by transferring and fixing on a sheet (referred to as OHP) is projected on a screen.

Further, as a method for fixing a toner image, a heat roll fixing method is widely and generally used, and good fixing property and offset resistance at that time are also important characteristics required for color toners. is there. In recent color copiers or printers, the processing speed has been increased, the fixing temperature has become lower, and the fixing time has become shorter.
It is required to fix with lower energy and to have offset resistance.

Generally, the composition of a color toner comprises a binder resin and a colorant, and various other additives.
As the binder resin, polystyrene, styrene-
(Meth) acrylic acid ester copolymer, styrene-butadiene copolymer, polyester, epoxy resin, coumarone indene resin and the like are generally used.

Conventionally, many techniques have been disclosed for such color toners, and in particular for magenta or red color toners, JP-A-51-24234.
JP-A-59-165069 and JP-A-62-296167 disclose magenta toners using quinacridone pigments and JP-A-62-296167 disclose magenta toners using various monoazo pigments.

By the way, in the magenta toner which has been conventionally used, the organic pigment such as C.I. I. PIGMENT RED 122,
Alternatively, a lake pigment such as C.I. I. PIGMENT R
ED 57: 1 has mainly been used. The former has a good hue and excellent blue color reproducibility,
Poor dispersibility in the toner resin and poor coloring power.
Therefore, it is necessary to increase the content in the toner in order to perform printing with a target density, and as a result, there is a drawback that the charging characteristics of the toner are likely to become unstable. In particular, the pigment tends to be positively charged, and when applied to a negatively charged toner, there is a problem that the charge amount is reduced during use.

In the latter case, although the coloring power is good, the Ca salt structure is adopted, so that the latter has a hygroscopic property and the charging characteristics of the toner are easily affected by the environment. In addition, C.I. I. PIGMENT RED 57:
No. 1 gives a clear magenta color when it is used as a printing ink, but when it is used as a toner, it tends to be a yellow magenta color. I. PIGME
It was inferior to NT RED 122.

From such a background, in the toner field, it has excellent coloring power and hue, and exhibits stable charging characteristics even when the environment such as temperature and humidity changes, and as a result, color reproducibility is obtained. Further, it has been desired to obtain a red color toner, particularly a magenta toner, which has excellent charge stability and does not fluctuate in charge amount during use even when applied to a negatively chargeable toner, and which exhibits good and stable print image quality.

[0010]

The object of the present invention is to have excellent coloring power and hue, and to exhibit stable charging characteristics even when the environment such as temperature and humidity changes, and as a result, color reproduction is achieved. Another object of the present invention is to provide a red color toner, particularly a magenta toner, which has excellent properties and does not fluctuate in charge amount during use even when applied to a negatively chargeable toner and exhibits good and stable print image quality. Another object of the present invention is to provide a method for producing a red color toner, especially a magenta toner, which satisfies the above characteristics.

[0011]

The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides an electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the colorant is an organic pigment having a structure of the following <Formula 1>. To provide toner. <Formula 1>

[Chemical 2]

The present invention also provides a color toner in which the organic pigment having the structure of <Formula 1> is previously dispersed using a part of a binder resin and then diluted and dispersed using the binder resin. It provides a method.

The present invention will be described in detail below. The electrostatic toner image developing color toner of the present invention contains at least a binder resin and an organic pigment having the structure of <Formula 1>, and the binder resin does not impair the object of the present invention. If there is no particular limitation, it can be used. Specific examples include vinyl copolymer resins such as polystyrene resin, styrene acrylic resin, or styrene butadiene resin, and further polyester resin, epoxy resin, butyral resin, xylene resin, coumarone indene resin, and the like. However, among these, vinyl-based copolymer resins and polyester resins are preferable, and polyester resins can be particularly preferably used because they have a good balance of fixability, offset resistance, transparency, and the like.

The polyester resin is synthesized by dehydration condensation of polybasic acid and polyhydric alcohol. Examples of polybasic acids include terephthalic acid, isophthalic acid, phthalic anhydride, trimellitic anhydride, pyromellitic acid, aromatic carboxylic acids such as naphthalenedicarboxylic acid, or maleic anhydride, fumaric acid, succinic acid, alkenyl. Examples thereof include aliphatic carboxylic acids such as succinic anhydride and adipic acid, and alicyclic carboxylic acids such as cyclohexanedicarboxylic acid. These polybasic acids can be used alone or in combination of two or more. Among these polybasic acids, it is preferable to use aromatic carboxylic acids.

Examples of the polyhydric alcohol include aliphatic diols such as ethylene glycol, triethylene glycol, propylene glycol, hexanediol, neopentyl glycol, glycerin, trimethylolpropane and pentaerythritol, or cyclohexanediol, 1, Examples thereof include alicyclic diols such as 4-cyclohexanedimethanol and hydrogenated bisphenol A, or aromatic diols such as ethylene oxide adducts of bisphenol A and propylene oxide adducts of bisphenol A. These polyhydric alcohols can be used alone or in combination of two or more. Among these polyhydric alcohols, aromatic diols and alicyclic diols are preferable, and aromatic diols are more preferable.

In addition, a monocarboxylic acid and / or a monoalcohol is further added to a polyester resin obtained by polycondensation of a polycarboxylic acid and a polyhydric alcohol,
The acid value of the polyester resin can be adjusted by esterifying the hydroxyl group and / or the carboxyl group at the polymerization end.

Examples of the monocarboxylic acid used for such purpose include acetic acid, acetic anhydride, benzoic acid, trichloroacetic acid, trifluoroacetic acid, propionic anhydride and the like. Further, as the monoalcohol, for example, methanol, ethanol, propanol, octanol,
2-ethylhexanol, trifluoroethanol, trichloroethanol, hexafluoroisopropanol, phenol and the like can be mentioned.

The polyester resin can be produced by subjecting the polyhydric alcohol and the polycarboxylic acid to a condensation reaction according to a conventional method. For example, the polyhydric alcohol and the polycarboxylic acid are blended in a reaction vessel equipped with a thermometer, a stirrer, and a downflow condenser, and heated at 150 to 250 ° C. in the presence of an inert gas such as nitrogen, By-produced low-molecular compounds are continuously removed from the reaction system, the reaction is stopped when the physical properties reach a predetermined value, and the reaction product is cooled to obtain a desired reaction product.

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

In such a polycondensation reaction, in order to produce a crosslinked polyester resin, a polybasic acid having three or more carboxyl groups in one molecule or an anhydride thereof and / or one molecule is used. A synthetic raw material in which a polyhydric alcohol having 3 or more hydroxyl groups is essential may be used.

As the vinyl-based copolymer which can be used in the present invention, a styrene- (meth) acrylic acid ester copolymer resin is preferable. Examples of the styrene monomer include styrene, α-methylstyrene, vinyltoluene, dimethylaminomethylstyrene and the like.

Examples of the (meth) acrylic acid ester monomer include methyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, tertiary butyl (meth) acrylate, octyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate and stearyl (meth) acrylate, alicyclic (meth) acrylates such as cyclohexyl (meth) acrylate, and aromatic (meth) such as benzyl (meth) acrylate Acrylate, hydroxy group-containing (meth) acrylate such as hydroxyethyl (meth) acrylate, phosphoric acid group-containing (meth) acrylate such as (meth) acryloxyethyl phosphate, 2-chloroethyl (meth) acrylate Halogen atom-containing (meth) acrylates such as 2,3-dibromopropyl (meth) acrylate, epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, ether group-containing (meth) acrylates such as 2-ethoxyethyl (meth) acrylate. ) Basic nitrogen atom- or amide group-containing (meth) acrylates such as acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

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

Further, the crosslinking agent may be used in the range of 0.1 to 2% by weight based on the vinyl monomer. Examples of the cross-linking agent include divinylbenzene, divinylnaphthalene, divinyl ether, ethylene glycol di (meth)
Acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like can be mentioned.

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

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

The binder resin used in the present invention preferably has a glass transition temperature (Tg) of 50 ° C. or higher.
Above all, those having a Tg of 55 ° C. or higher are particularly preferable.
If the Tg is 50 ° C. or less, a blocking phenomenon (thermal aggregation) is likely to occur when the toner is stored, transported, or exposed to a high temperature inside the developing device of the machine. Further, the acid value is preferably 1 to 30 mgKOH / g or less.

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

Further, as a full-color toner, in particular,
When color reproducibility during color superposition and transparency when fixed on an OHP sheet are required, the softening point of the resin is
The range of 90 ° C to 130 ° C is preferable, and the range of 95 ° C to 120 ° C is more preferable.

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, a flow tester CFT-500 manufactured by Shimadzu Corporation. Measurement conditions with a flow tester are: piston cross-sectional area 1 cm ² , cylinder pressure 0.98 MPa, die length 1
mm, die hole diameter 1 mm, measurement starting temperature 50 ° C., temperature rising rate 6 ° C./min, sample weight 1.5 g.

In the present invention, the organic pigment having the structure of <Formula 1> is used. By using this pigment, a magenta pigment which has been usually used in conventional toners, such as C.I. I. Pigment Red 57: 1 and quinacridone pigment C.I. I. Pigment Red 12
It is possible to obtain a color toner having excellent coloring power, gradation, resolution, and transfer characteristics as compared with those of No. 2 and the like. Also,
Stable charging behavior is exhibited during continuous printing, and high-quality images with excellent color reproducibility and transparency can be printed.

The amount of the organic pigment having the structure of <Formula 1> used in the present invention is preferably 1 to 50 parts by weight, more preferably 2 to 30 parts by weight, and 2 to 100 parts by weight of the binder resin. A range of 20 parts by weight is especially preferred.

In the present invention, in addition to the organic pigment of <Formula 1>,
Other colorants may be added and used in order to adjust the hue so long as the effects of the present invention are not lost. As such a colorant, well-known ones can be mentioned. For example, as a blue colorant, a phthalocyanine-based C.I. I. P
igment Blue 15-3, an indanthrone type C.I. I. Pigment Blue 60 or the like is a quinacridone-based C.I. I. Pigme
nt Red 122, an azo C.I. I. Pigmen
t Red 22, C.I. I. Pigment Red
23, C.I. I. Pigment Red 31, C.I. I.
Pigment Red 48: 1, C.I. I. Pigme
nt Red 48: 3, C.I. I. Pigment R
ed 57: 1 and the like are azo type C.I.
I. Pigment Yellow 12, C.I. I. P
igment Yellow 13, C.I. I. Pigm
ent Yellow 14, C.I. I. Pigment
Yellow 17, C.I. I. Pigment Ye
low 97, C.I. I. Pigment Yellow
w 155, benzimidazolone-based C.I. I. Pigm
ent Yellow 151, C.I. I. Pigmen
t Yellow 154, C.I. I. Pigment
Yellow 180, etc.

The above-mentioned pigments can be used in combination with the organic pigment of <Formula 1> within the range not impairing the object of the present invention.
For example, a light-colored toner can be obtained by combining it with a yellow pigment, and a blue-violet toner can be obtained by combining it with a cyan pigment. In particular, C.I. I. Pigment Red 122,
C. I. Pigment Red 23, C.I. I. Pi
When used in combination with a bluish red pigment such as gment Red 31, a magenta toner having a vivid magenta color with a coloring power can be obtained.

When the pigment of <Formula 1> is used in combination with another pigment, the amount of the pigment of <Formula 1> used is preferably 40% by weight or more, more preferably 50% by weight, based on the total amount of the pigment. That is all.

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

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

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

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

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

In the present invention, a charge control agent can be used if necessary. For example, as a positive charge control agent, a nigrosine dye, a triphenylmethane dye, a quaternary ammonium salt, a resin containing a quaternary ammonium group and / or an amino group, or the like is used as a negative charge control agent, a trimethylethane dye, or a metal of salicylic acid. Complex salts, metal complex salts of benzylic acid, copper phthalocyanine, perylene, quinacridone, azo pigments, metal complex salts azo dyes, acid dyes containing heavy metals such as azochrome complexes, calixarene type phenolic condensates, cyclic polysaccharides, carboxyl groups And / or resins containing sulfonyl groups.

In particular, in the present invention, it is desirable to use a colorless charge control agent, and as the negative charge control agent, a metal complex compound of salicylic acid, "Bontron E-84" manufactured by Orient Chemical Co., Ltd., or Hodogaya Chemical Co., Ltd. "TN10
5 "," N4PVP-2481 "manufactured by Clariant Co., Ltd., and TP-302, TP-415, TP-61 having a quaternary ammonium salt structure as a colorless positive charge control agent.
0; (manufactured by Hodogaya Kagaku), Bontron P-51; (manufactured by Orient Kagaku), and Copy Charge PSY (Clariant Japan) are preferably used. Examples of positively chargeable resin type charge control agents containing a quaternary ammonium group and / or amino group include "FCA-201-PS" (Fujikura Kasei Co., Ltd.) and the like.

Among them, the charge control agents that can be particularly preferably used in the present invention include the compounds of the following <formula 2> and the compounds of <formula 3>. <Formula 2>

[0044]

[Chemical 3] (In the formula, R ₁ is quaternary carbon, methine, 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. )

<Equation 3>

[0046]

[Chemical 4] (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 kind of trivalent metal selected from B, Al, Fe, Ti, Co and Cr, and X ⁺ represents a cation).

Specific examples of the compound of formula 2 are:
The following <charge control agent 1> to <charge control agent 3> are available.

<Charge Control Agent 1>

[0049]

[Chemical 5]

<Charge control agent 2>

[0051]

[Chemical 6]

<Charge control agent 3>

[0053]

[Chemical 7]

Further, specific examples of the compound of <formula 3> include <charge control agent 4> and <charge control agent 5> described below.

<Charge Control Agent 4>

[0056]

[Chemical 8]

<Charge Control Agent 5>

[0058]

[Chemical 9]

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.

The manufacturing method for obtaining the toner of the present invention is as follows:
It can be obtained by any known means. For example, a resin, a colorant, and optionally a wax, various additives are melt-kneaded at a melting point (softening point) or higher of the resin, and then pulverized,
It can be obtained by classifying. In order to further develop the effect of the present invention, the pigment of <Formula 1> is dispersed at a high concentration in a part of the binder resin used, and then this dispersion is diluted and dispersed in the binder resin used. And good.

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

The proportion of the binder resin and the colorant in the dispersion having a high pigment concentration is preferably 10 parts by weight to 100 parts by weight with respect to 100 parts by weight of the binder resin.

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

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

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

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

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

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

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

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

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

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

As the core agent of the carrier, iron powder, magnetite, ferrite and the like which are used in the usual two-component developing method can be used, but among them, the true specific gravity is low, the resistance is high, the environmental stability is excellent, and the spherical shape is easy. Ferrite or magnetite having good fluidity is preferably used. The shape of the core agent may be spherical, amorphous or the like, and may be used without any particular problem.
The average particle diameter is generally 10 to 500 μm, but 30 to 80 μm is preferable for printing a high resolution image.

Examples of coating resins for coating these core agents include polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinylcarbazole, polyvinyl ether, polyvinyl ketone, and chloride. Vinyl / vinyl acetate copolymer, styrene / acrylic copolymer, straight silicone resin composed of organosiloxane bond or its modified product, 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.

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

In this case, the material of the charging member of the developing device is not particularly limited as long as it is used under normal conditions. For example, aluminum, stainless steel, urethane rubber,
A developing sleeve made of silicon rubber, aluminum, stainless steel, duralumin, copper, or a layer thickness regulating member in which urethane rubber or silicon rubber is attached to them can be preferably used.

When the color toner for developing an electrostatic image of the present invention exerts its effect when used as a non-magnetic one-component developing toner, the developing device is preferably constructed of a developing sleeve and a layer thickness regulating member. And either one is aluminum,
The most effective combination (development sleeve / layer thickness regulating member) is a combination of urethane rubber or silicon rubber developing sleeve and stainless layer thickness regulating member, or stainless steel developing. It is a combination of a sleeve and a layer thickness regulating member made of urethane rubber or silicon rubber.

[0079]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples. In the following, the numerical values in the composition table represent "parts by weight". An example of synthesizing the binder resin used for preparing the toner is shown below. (Synthesis Example 1) Naphthalenedicarboxylic acid 87 parts by weight Terephthalic acid 249 parts by weight Diethylene glycol 26 parts by weight Neopentyl glycol 104 parts by weight Ethylene glycol 50 parts by weight Tetrabutyl titanate 2.5 parts by weight The above raw materials are made of glass and have a four-necked mouth of 2L. The flask was charged with a thermometer, a stir bar and a nitrogen introduction tube, reacted in an electric heating mantle heater at 240 ° C. for 10 hours under a normal pressure nitrogen stream, and then depressurized successively to continue the reaction 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 101 ° C. The obtained polymer (hereinafter referred to as resin A) was a colorless solid, had an acid value of 7, and a glass transition temperature of 70 according to the DSC measurement method.
The softening point was 102 ° C.

(Synthesis Example 2) terephthalic acid 315 parts by weight diethylene glycol 21 parts by weight cyclohexanedimethanol 144 parts by weight ethylene glycol 50 parts by weight tetrabutyl titanate 2.5 parts by weight Reaction similar to that in Resin Synthesis Example 1 using the above raw materials. I went. The obtained polymer (hereinafter referred to as resin B) was a colorless solid, had an acid value of 9, a glass transition temperature of 60 ° C. according to the DSC measurement method, and a softening point of 97 ° C.

Synthesis Example 3 Polyoxyethylene- (2.0) -2,2-bis (4-hydroxyphenyl) propane 64 parts by weight Isophthalic acid 16 parts by weight Terephthalic acid 16 parts by weight Maleic anhydride 0.6 Parts by weight dibutyltin oxide 0.06 parts by weight or more of the raw materials are placed in a glass 2-liter four-necked flask, equipped with a thermometer, a stir bar and a nitrogen inlet tube, and heated in an electric heating mantle heater under normal pressure nitrogen stream to give 230 After the reaction at 24 ° C. for 24 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 99 ° C.

The obtained polymer (hereinafter referred to as resin C)
Is a colorless solid having an acid value of 7, a glass transition temperature of 62 ° C. by a DSC measurement method, and a softening point of 101 ° C.

(Synthesis Example 4) terephthalic acid 332 parts by weight isophthalic acid 332 parts by weight polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 700 parts by weight trimethylolpropane 80 parts by weight ethylene Glycol 75 parts by weight Tetrabutyl titanate 3 parts by weight The above composition was placed in a four-necked flask equipped with a stirrer, a condenser and a thermometer, and the mixture was heated to 240 ° C. under a nitrogen gas stream while removing water produced by dehydration condensation. For 10 hours at normal pressure. Thereafter, the pressure was sequentially reduced and the reaction was continued at 10 mmHg. The reaction is tracked by the softening point, and the softening point is 1
The reaction was terminated when the temperature reached 51 ° C. The resulting polymer (hereinafter referred to as resin D) has a softening point of 153 ° C. and an acid value of 4, D
The Tg according to the SC measurement method was 65 ° C.

(Synthesis Example 5) Styrene 368.5 parts by weight Butylmethacrylate 119.5 parts by weight Acrylic acid 12.0 parts by weight Benzoyl peroxide 5.0 parts by weight Thermometer, glass airflow introducing pipe, vacuum resistant 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 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. Reaction is 65 ℃
The temperature was raised to 130 ° C. in order to complete the reaction after 10 to 12 hours, and the polymerization was completed. 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 are connected to the Claisen distillation tube, and the outlet of the condenser is connected to an eggplant-shaped flask via a suction adapter. The vacuum adapter is connected to the vacuum adapter via a manometer and trap with a rubber tube for pressure reduction, and the preparation for vacuum distillation is 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 ° C xylene or possibly unreacted monomer begins 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 (E1)) was placed in a stainless steel pan in a molten state at high temperature, cooled to room temperature and then crushed. The polymer (E1) thus obtained had a softening point of 119 ° C. by a ball and ball method, a calibration curve using monodisperse polystyrene as a standard substance, and a number-average molecular weight of about 12,000 as measured by GPC (gel permeation chromatography). The molecular weight was about 30,000.

This polymer (E1) was crushed into small pieces having a side of 5 mm or less, 300 parts of which were weighed and charged into a 1-volume four-neck round bottom flask. The flask was equipped with a high-speed stirring device, a thermometer, and a drying tube filled with silica gel, and heating was started by a mantle heater. The charged resin gradually melted, and when the temperature was further raised, it became a completely mucous state.
3.7 parts of calcium hydroxide (corresponding to approximately 0.5 equivalents of all free carboxyl groups contained in the polymer (E1)) while slowly stirring the high-speed stirring device and intensifying the stirring when the temperature reached 160 ° C. Gradually add over 20 minutes,
The reaction was performed at a liquid temperature of 150 to 195 ° C. for 10 hours. After the reaction, the high temperature melt was spread on a stainless steel pan, cooled to room temperature and then crushed to obtain a calcium metal chlorinated polymer (hereinafter referred to as polymer (E)). The softening point of the polymer (E) is 1
At 48 ° C., Tg = 63 ° C.

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

<Production Example of Processed Pigment> (Processed Pigment 1) 650 parts by weight of Resin A Organic pigment of Formula 1 350 parts by weight or more of raw materials were mixed with a Henschel mixer, and then kneaded with a heated two-roll mill. After cooling, coarse pulverization was performed to prepare a processed pigment 1 having a pigment content of 35%.

(Processed Pigment 2) Processed Pigment 2 was prepared in exactly the same manner as Processed Pigment 1 was prepared except that Resin A was used as Resin B in the preparation of Processed Pigment 1.

(Processed Pigment 3) Processed Pigment 3 was prepared in exactly the same manner as Processed Pigment 1 was prepared except that Resin A was used as Resin C in the preparation of Processed Pigment 1.

(Processed Pigment 4) Processed Pigment 4 was prepared in exactly the same manner as Processed Pigment 1 except that Resin A was used as Resin D in the preparation of Processed Pigment 1.

(Processed Pigment 5) Processed Pigment 5 was produced in exactly the same manner as Processed Pigment 1 except that Resin A was used as Resin E in the production of Processed Pigment 1.

(Processed Pigment 1 for Comparison) In the processed pigment 1 above, C.I. was used instead of the organic pigment of <Formula 1>. I. Comparative Processed Pigment 1 was obtained in the same manner except that Pigment Red 122 was used.

(Processed Pigment 2 for Comparison) In the processed pigment 1, the C.I. I. Comparative Processed Pigment 2 was obtained in the same manner except that Pigment Red 57: 1 was used.

Example 1 93 parts by weight of Resin A, <Formula 1>
Pigment (Carmine 190 (manufactured by Arimoto Kagaku)) 4
Parts by weight, charge control agent (compound of <charge control agent 4>,
1 part by weight of LR-147 (manufactured by Japan Carlit Co., Ltd.), 2 parts by weight of carnauba wax (refined carnauba wax No. 1, acid value 5, manufactured by Celarica NODA Co., Ltd.) are mixed with a Henschel mixer, and a biaxial kneader is used. Melt and knead with, cool and finely pulverize with a jet mill, classify and average particle size 8.0μm
Toner of

Next, for 100 parts by weight of this toner, 1 part by weight of silica "NAX50" manufactured by Nippon Aerosil and "RY
By externally adding 1 part by weight of "-200", a magenta toner of Example 1 was obtained.

Similarly, the resin, colorant (or processed pigment), charge control agent and WAX having the composition shown in Table 1 were thoroughly mixed in a Henschel mixer, melt-kneaded in a biaxial kneader, and cooled. Then, the toner was manufactured by pulverizing and classifying, and the external addition process was performed in the same manner as in Example 1 to obtain toners of Examples 2 to 8 and Comparative Examples 1 to 4.

[0097]

[Table 1]

The abbreviations in Table 1 are as follows. Moreover, a part represents a weight part. -P. R. 122; C.I. I. Pigment Red 122
(Fastogen Super Magenta R
"Dainippon Ink and Chemicals, Inc.") ・ P. R. 57: 1; C.I. I. Pigment Red 57:
1 (Symuller Brilliant Carmi
n 6B 285 “manufactured by Dainippon Ink and Chemicals, Inc.”) PETB: pentaerythritol tetrabehenate ester carnauba wax; refined carnauba wax No. 1
(Acid value 5, manufactured by Celarica NODA Co., Ltd.)-PPWAX; Viscole 660P (polypropylene wax "manufactured by Sanyo Kasei")-E-84; Bontron E-84 (metal complex compound of salicylic acid "manufactured by Orient Chemical Co., Ltd.")

(Evaluation of Toner in Table 1) The toner of the commercially available non-magnetic one-component developing type printer (“IPSIO Color 2000” manufactured by Ricoh Co., Ltd.) was removed from the cartridge and the washed cartridge is shown in Table 1. The toners of Examples and Comparative Examples were filled, and 10000 sheets were continuously printed at an image density of 5%. In order to evaluate the stability of printed images against changes in environmental conditions, 25 ° C, 50% and 32 ° C,
A continuous printing test was carried out under two environments of 85%.

(1) Image density / background stain / charge amount The image density and background stain of printed matter are determined by the Macbeth densitometer RD-
It was measured at 918. The background stain was obtained by subtracting the white paper density before printing from the white background density after printing. When the difference was less than 0.01, it was evaluated as ◯, when it was 0.01 to less than 0.03 as Δ, and when it was 0.03 or more as ×. In addition, the charge amount of the print toner is measured by a suction type small charge amount measuring device Mode210H.
It measured using S (made by Trek).

(2) Toner drop and toner scattering After printing 10,000 sheets, the toner does not spill from the developing sleeve mounted in the cartridge (toner drop) or scatter around the developing device (toner scatter) and stain the inside of the machine. A state is ○, a small amount of toner is dropped, or a state where toner scattering is recognized is △, a large amount of toner is dropped,
Alternatively, the state in which toner scattering was recognized was determined as x.

(3) OHP Transparency Using the above printer, an unfixed image was formed on an OHP sheet, and the unfixed image was fixed at 140 ° C. by the fixing unit used in the above fixing / offset test. .

The OHP sheet prepared by the above procedure was projected on a white screen with an overhead projector to evaluate the sharpness. Evaluation is done visually,
A clear and good projection image with good transparency was evaluated as ◯, a case where the transparency was a little lacking and a little turbidity was evaluated as Δ, and a opaque blackish projection image was evaluated as x.

The results at 25 ° C. and 50% are shown in Table 2 and 3.
The results at 2 ° C. and 85% are shown in Table 3.

[0105]

[Table 2]

[0106]

[Table 3]

Example 9 85 parts by weight of resin D, 12 parts by weight of processed pigment 4, 1 part by weight of TP-415 (manufactured by Hodogaya Kagaku) having a quaternary ammonium salt structure as a charge control agent, carnauba wax (purified carnauba wax) No. 1, acid value 5,
(Cerarica NODA Co., Ltd.) 2 parts by weight are mixed with a Henschel mixer, melt-kneaded with a biaxial kneader, cooled, finely pulverized with a jet mill, and classified to produce a toner having an average particle size of 8.0 μm. did.

Next, to 100 parts by weight of this toner, 1 part by weight of silica "TG820F" manufactured by Cabot Specialty Chemicals, Inc. was added,
A positively chargeable magenta toner of Example 9 was obtained. Then
5 parts by weight of this toner and 95 parts by weight of a ferrite carrier coated with a silicone resin and having an average particle size of 80 μm were mixed by a ball mill to obtain a two-component developer.

Using the above-mentioned two-component developer with a commercially available laser beam printer (with a selenium photosensitive member),
When continuous printing was performed on 10000 sheets at 50%, a printed matter with high density and no background stain was obtained. No trace of toner scattering was found inside the machine. Furthermore, 10000 sheets were printed under the conditions of 32 ° C. and 85%, but as in the previous term, high density printed matter with high image quality without scumming was continuously obtained, and the inside of the machine No toner stain was generated.

Example 10 A toner was manufactured in the same manner as in Example 9 except that the resin D in Example 9 was changed to the resin E, and the processed pigment 4 was changed to the processed pigment 5. The particle size of the obtained toner was 8.1 μm. Silica was externally added to this toner in the same manner as in Example 9 to produce the positively chargeable magenta toner of Example 10. Further, a two-component developer was prepared in the same manner as in Example 9, and the commercially available laser beam printer (with a selenium photosensitive member) was used at 25 ° C. and 50%.
And, continuous printing of 10,000 sheets was performed under the conditions of 32 ° C. and 85%. As a result, as in the case of Example 9, a high-density printed matter with high image quality without background stains was continuously obtained, and stains due to toner inside the machine did not occur.

Comparative Example 5 Processed Pigment 4 in Example 9
A toner was manufactured in the same manner as in Example 9 except that the comparative processed pigment 1 was used. The particle size of the obtained toner is 8.2μ.
It was m. Silica was externally added to this toner in the same manner as in Example 9 to produce a positively chargeable magenta toner of Comparative Example 5. Further, a two-component developer was prepared in the same manner as in Example 9, and a commercially available laser beam printer (with a selenium photosensitive member) was used to obtain 10,000 sheets under the conditions of 25 ° C., 50%, 32 ° C., and 85%. Was continuously printed. As a result, printed matter with a low image density was obtained from the initial stage of printing, and toner scattering was observed inside the machine. Especially 32 ° C, 8
Under the condition of 5%, the image density was low and the toner scattering was also severe.

Comparative Example 6 Processed Pigment 4 in Example 9
A toner was manufactured in the same manner as in Example 9 except that Comparative processed pigment 2 was used. The particle size of the obtained toner is 8.0μ.
It was m. Silica was externally added to this toner in the same manner as in Example 9 to produce a positively chargeable magenta toner of Comparative Example 6. Further, a two-component developer was prepared in the same manner as in Example 9, and a commercially available laser beam printer (with a selenium photosensitive member) was used to obtain 10,000 sheets under the conditions of 25 ° C., 50%, 32 ° C., and 85%. Was continuously printed. As a result, scumming was found from the beginning of printing, and toner was scattered inside the machine. Especially 32 ° C, 85%
Under the conditions described above, the background stain was severe and the toner was often scattered.

[0113]

The color toner for developing electrostatic images of the present invention has excellent coloring power and hue, and exhibits stable charging characteristics even when the environment such as temperature and humidity changes. Therefore, it is possible to provide a red color toner, particularly magenta toner, which has excellent color reproducibility, does not change the charge amount, and exhibits good and stable print image quality. The above characteristics are particularly remarkable when the electrostatic charge image developing color toner of the present invention is a negatively chargeable toner.

Claims (6)

[Claims] 1. An electrostatic charge image developing toner containing at least a binder resin and a colorant, wherein the colorant is an organic pigment having a structure of the following <formula 1>. . <Formula 1> 2. The color toner for developing an electrostatic image according to claim 1, wherein the binder resin is a polyester resin and / or a vinyl copolymer resin. 3. The color toner for developing an electrostatic charge image according to claim 1, further comprising a release agent. 4. The color toner for developing an electrostatic charge image according to claim 3, wherein the release agent is a wax containing a higher fatty acid ester compound and / or an aliphatic alcohol compound. 5. The color toner for developing an electrostatic charge image according to claim 1, further comprising a charge control agent. 6. A method for producing a color toner, wherein the organic pigment having the structure of <Formula 1> is previously subjected to a dispersion treatment using a part of a binder resin, and then diluted and dispersed using a binder resin.