JPH07134437A - Electrostatic charge image developer composition - Google Patents

Abstract

(57) [Summary] [Structure] Polyester resin as the main component of the binder resin,
Further, an electrostatic image developer composition comprising a toner containing esteramidoamine and / or a salt thereof, and a carrier composed of the toner and a porous amorphous iron powder having irregularities on the surface. [Effect] It is possible to prevent toner scum formation on the carrier surface over a long life of the developer while ensuring low-temperature fixability, and stably maintain carrier resistance and charge amount.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry type two-component developer used for developing an electrostatic latent image in an image forming apparatus such as a laser printer or a dry type electrostatic copying machine, and more particularly to a toner scum of a carrier. The present invention relates to an electrostatic charge image developer composition in which the carrier resistance charge amount can be maintained at a constant value for a long period of time by maintaining a high value to maintain high image quality.

[0002]

2. Description of the Related Art An electrophotographic method used in an image forming apparatus such as a laser printer or a dry electrostatic copying machine is disclosed in U.S. Pat. Nos. 2,221,776, 2,297,691 and 2,357. , 809 and the like, the photoconductive insulating layer is uniformly charged (charging step), and then the layer is exposed to dissipate the charge in the exposed area and electrostatically. A latent image is formed (exposure step), and the electrostatic latent image is visualized by adhering charged fine powder, so-called toner (developing step), and the obtained visible image is transferred onto a transfer material such as transfer paper. The image is transferred (transfer step) and then permanently fixed (fixing step) by heating, pressure or other appropriate means.

The developing methods applied to these electrophotographic methods are roughly classified into a dry developing method and a wet developing method. The former method further includes a method using a one-component developer and a method using a two-component developer composed of a toner and a carrier. As the two-component developer, a magnetic brush developing method using a magnetic powder carrier (US Pat. No. 2,786,439) and a cascade developing method using a somewhat rough bead carrier are used depending on the type of a toner conveying system. (US Pat. No. 2,618,551) and the like.

As the toner applied to these developing methods, a binder such as a styrene-acrylate copolymer resin (polystyrene resin), a polyester resin, or an epoxy resin is used in a binder resin, a coloring agent such as a dye or a pigment, and a charge. 1-8 by mixing and dispersing various functional additives such as control agents and wax.
A fine powder pulverized to about 0 μm is generally used.
Such a two-component developer is generally required to have long life, that is, stability and maintainability of image quality in continuous development. For that purpose, it is necessary to maintain the charge amount and the developer resistance between the toner and the carrier particles within an appropriate range, and it is most desirable that the initial charge amount and the resistance do not change even in the latter half of the long run.

For the purpose of maintaining a stable charge amount and resistance of these developers, conventionally, the design and selection of a binder resin, a charge control agent and other additives have been studied from the toner side, while the carrier side has been studied. However, various studies have been made on the oxidation treatment method of iron powder, the constituent materials such as ferrite and magnetite, the surface shape of these magnetic powders, the coating material and the treatment method thereof. Particularly when developing at a high speed, a large amount of developer is required, and a large force is required to stir the developer. Therefore, the developer is deteriorated due to repeated collisions between the developer and the stirring member of the developing device. Becomes remarkable.

In order to reduce the deterioration of the developer, a stirring torque is reduced by using a porous amorphous iron powder called "sponge" as a carrier to reduce the bulk specific gravity. There is. When the developing speed is high, carriers near the photoconductor are likely to be charged up during development, and the edge effect of the solid black portion tends to be large, but this phenomenon also occurs in the case of porous irregular iron powder. Since the contact point between particles can be increased by the interposition of particles, and there is a secondary effect such that the effect of bias can be improved and the substantial development electric field strength can be increased, carriers with this type of structure are pseudo-conductive. It is suitable for high-speed printers and copiers that use the security method.

On the other hand, when the carrier is made porous, the low surface energy coating agent on the convex portions of the particles is peeled off by repeated use thereof, and the fine powder of the toner generated in the developing device becomes the nucleus, and a thin film called toner scum is formed. Is formed, and the convex portion that becomes a contact point becomes high resistance with the passage of time, and the developing bias through the magnetic brush is hard to reach near the surface of the photoconductor, so the image density is lowered and especially the solid black portion can be reproduced. There is a problem of disappearing. Further, especially in high-speed copying machines and printers, low-temperature fixing property of toner is required, but in a developing tank which is continuously heated to 50 ° C. or higher, the low-temperature fixing toner is thermally fused to the convex portion and solidified. It was a condition that the low temperature fixing property and the long life property required were in conflict with each other.

FIGS. 1A, 1B, and 1C show the mechanism of toner scum generation. The carrier is a core 1 made of porous iron powder having irregularities, and a conductive material covering the surface of the core 1. It consists of a sex coat material 2. And
In the initial state shown in (a), the toner 3 is filled in the concave portion of the core 1 and does not exist in the convex portion, and this convex portion serves as a contact point between adjacent carriers. However, as shown in (b), the coating material 2 existing on the convex portion is peeled off due to abrasion due to repeated use of the carrier, and scumming is likely to occur. As shown in (c), the toner scum 3a due to the toner 3 is generated in this portion. It is formed.

As is well known, each carrier bridges between the magnet roller and the photoconductor using the convex portion as a contact point, and supplies the charged toner 3 to the electrostatic latent image formed on the surface of the photoconductor. However, when the resistance of the carrier is increased by the toner scum 3a, the bias from the magnet roller is less likely to be transmitted, and as a result, the amount of the toner 3 supplied to the surface of the photoconductor is reduced, and the above-mentioned decrease in image density is caused. It becomes a factor.

As a material for preventing toner cleaning failure on a carrier having this kind of structure, for preventing the offset phenomenon and for reducing the abrasion of the photoreceptor, conventionally, a suitable amount of stearin is used as a binder. A lubricant such as zinc acid is externally added, and is disclosed in, for example, JP-A-4
As shown in JP-A-6-12680, zinc stearate was externally added to a linear polyester resin as a binder to lubricate the outer surface of the toner particles. According to this, the toner does not easily adhere to the surface of the carrier even if the coating material is consumed in the convex portion, so that it is possible to prevent the image density from being lowered in a long life.

[0011]

However, in practice, a toner to which a lubricant of this kind is added externally is liable to cause lubricant separation, and in particular, the lubricant released from the toner in the transfer step adheres to the surface of the photoconductor, which causes a problem in copying. The lubricant forms an insulating layer on the surface of the photoconductor depending on the continuation of the image, which causes image deterioration such as soiling, and significantly affects the chargeability of the toner itself, resulting in a decrease in the charge amount and an improvement in the fluidity of the developer. There is a problem that the image density decreases due to an increase in developer resistance.

Therefore, in a two-component type developer using a carrier made of porous amorphous iron powder having irregularities on the surface, the carrier resistance and the charge amount can be maintained for a long period of time without impairing the low temperature fixability of the toner. There has been a demand for a developer composition that can be maintained stably.

[0013]

As a result of intensive studies conducted by the present inventors in such a situation, the use of esteramidoamine and / or a salt thereof in a toner makes it possible to maintain low-temperature fixability while maintaining toner scum on the carrier side. The present invention has been completed by finding that an electrostatic charge image developer composition can be obtained in which the carrier resistance and the charge amount can be stably maintained for a long period of time.

That is, the present invention provides an electrostatic charge image developer composition comprising a toner and a carrier made of porous amorphous iron powder having irregularities on the surface thereof, wherein the toner comprises a polyester resin and a binder resin as a main component. And an ester amidoamine and / or a salt thereof, which further comprises an electrostatic charge image developer composition.

The carrier used in the present invention is made of a sponge called a sponge, which has a porous irregular iron powder having irregularities on its surface as a core material and the outer surface of which is coated with a coating agent. As the amorphous iron powder constituting the core, ore reduced iron powder produced by reducing iron ore, mill scale reduced iron powder produced by reducing mill scale, cooling powder by flowing molten metal of steel from pores Examples include atomized spherical atomized iron powder and iron nitride powder obtained by nitriding thin steel pieces and pulverizing and denitrifying. Among these, the bulk specific gravity is 2 to 4 g / c.
m ³ , average particle size 50 to 200 μm, especially 55 to 170
μm is preferable, and the unevenness of each particle is 10 μm.
An amorphous iron powder having pores of m or more is preferable. The iron powder carrier is oxidized by the presence of moisture in the air and Fe ₂ O ₃ (so-called rust) is generated on the surface, so it is covered with a stable oxide thin film with a relatively high resistance by forced oxidation. The electric resistance as a carrier can be adjusted by adjusting the thickness of the thin film depending on the degree.

As a coating agent for coating the outer surface of irregular iron powder, it has been conventionally used in electrophotography for the purpose of facilitating charge control and maintaining charge stability at long run and high temperature and high humidity. All known carrier coating agents can be used. Specifically, for example, styrene acrylic resin, polyester resin,
As a polyamide resin, an epoxy resin, or a silicone resin, a silicon acrylic resin, or a fluorine-based resin that plays a role of further increasing the surface lubricity, various fluorocarbons can be mentioned. Specific examples of the fluorocarbon include vinylidene fluoride, trifluoroethalene, tetrafluoroethylene, tetrafluoroethylene, hexafluoropropylene and the like homopolymers or copolymers. More specifically, tetrafluoroethylene-hexafluoropropylene copolymer, vinylidene fluoride-trifluoroethylene copolymer, vinylidene fluoride-tetrafluoropropylene copolymer and the like can be mentioned. Of these, a fluororesin using ethylene tetrafluoride or vinylidene fluoride as one of the monomers is preferable.

Further, the above-mentioned fluororesin can be used by being mixed with inorganic fine particles such as alumina, graphite, molybdenum disulfide, bronze or the like in order to improve electric characteristics or wear characteristics. Firing and binding can be performed at a temperature near the melting point. Furthermore, a polyamide resin or an epoxy resin can be added to the adhesive to improve the adhesive strength of the fluororesin to the surface of the irregular iron powder and to impart durability.

As a coating method, the above resins are dispersed in a dispersion medium such as methyl ethyl ketone or tetrahydrofuran, and the carrier is dipped in this dispersion.
Alternatively, it can be obtained by spraying the dispersion medium on the surface of a carrier and subsequently thermosetting at 150 to 300 ° C. The coating amount is preferably 0.5 to 10% by weight, and particularly preferably 1 to 5% by weight, based on the weight of the carrier.

In order to satisfy the thermal property required for fixing, which is an important required property of the toner, the polyester resin, which is a binder resin used for the toner, has a cross-linked structure with at least one trifunctional or higher polyfunctional monomer. Those having a softening point of 95 ° C. or more and 160 ° C. or less by a Koka type flow tester, and the temperature difference between the outflow starting temperature and the softening point is 1
It is preferably 5 to 50 ° C. The Koka type flow tester is a very effective device for evaluating the binder resin for toner, since the melting behavior of the resin and the like can be measured with good reproducibility at each temperature.

If the softening point is less than 95 ° C., offset resistance,
Blocking resistance is impaired, and if it exceeds 160 ° C., low-temperature fixability is impaired, which is not preferable. Similarly, if the temperature difference between the outflow start temperature and the softening point is less than 15 ° C, the offset resistance and blocking resistance may be impaired, and if it exceeds 50 ° C, the low-temperature fixing property may be impaired, which is not preferable. .

The polyester resin preferably has a glass transition temperature by DSC of 50 ° C. or higher and 80 ° C. or lower. If the temperature is less than 50 ° C, it tends to aggregate and the stability is poor.
If the temperature exceeds ℃, poor fixing tends to occur, and the pulverizability during production is not good, which is not preferable.

The polyester resin used in the present invention is
Alcohol and carboxylic acid, or carboxylic acid ester, carboxylic acid anhydride and the like are synthesized as raw material monomers. Examples of the divalent alcohol component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3.3) -2,
2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.
Alkylene of bisphenol A such as 0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane and polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane Oxide adduct, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentane Examples thereof include diol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A and hydrogenated bisphenol A.

Examples of trihydric or higher alcohol components include sorbitol, 1,2,3,6-hexanetetrol, 1,
4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-
Butanetriol, 1,2,5-pentanetriol,
Examples thereof include glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene.

The acid component is a carboxylic acid component and is a divalent monomer such as maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid and adipine. Acid, sebacic acid, azelaic acid, malonic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, n-dodecylsuccinic acid,
Isododecyl succinic acid, n-octenyl succinic acid, n-
Examples thereof include octyl succinic acid, isooctenyl succinic acid, isooctyl succinic acid, and anhydrides or lower alkyl esters of these acids.

As the trivalent or higher carboxylic acid component, 1,
2,4-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,
5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropane, 1,
2,4-cyclohexanetricarboxylic acid, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, empole trimer acid, and their acid anhydrides, lower alkyl esters, etc. Can be mentioned.

Such polyester resin can be synthesized by a usual method. Specifically, the reaction temperature is 170 to 25
The reaction is performed at 0 ° C and a reaction pressure of 5 mmHg to atmospheric pressure (optimum temperature,
The pressure is determined by the reactivity of the monomer), and the reaction may be terminated when the above-mentioned physical properties are achieved.

Further, as the binder resin, polyamide, polyester polyamide resin, etc., which are compatible with the above polyester resin, can be mixed in an appropriate amount and used.

The ester amidoamine and / or its salt used in the present invention functions as a scum preventing agent for lowering the surface resistance of the toner and preventing toner scum on the carrier.

The ester amidoamine is a tertiary amine compound having an amide group and a carbonyloxy group in the molecule and is preferably a compound represented by the following general formula (1).

[0030]

[Chemical 2]

These esteramidoamines are obtained by cyanoalkylating an alkylamide, hydrogenating this, reacting an intermediate obtained by hydrolysis with a fatty acid, and esterifying it, and in particular, the following compounds ( 2) ~
(4) is preferred.

[0032]

[Chemical 3]

(In the formula, R ⁴ represents an alkyl group having 1 to ⁴ carbon atoms, R ⁵ and R ⁶ each represent an alkyl group having 11 to 21 carbon atoms, and R ⁷ represents an alkyl group having 12 to 22 carbon atoms. And n is 2 or 3.)

More preferred is hydroxyethylmethylpropylenediamine-esteramide (H
EMPDA-EA) can be mentioned. HEMPD
A-EA is the following general formula (5) obtained by esterifying hydroxyethylmethylamine by cyanoethylation and adding fatty acid to hydroxyethylmethylpropylenediamine obtained by hydrolysis.

[0035]

[Chemical 4]

(In the formula, R ⁸ and R ⁹ each represent an alkyl group having 16 to 18 carbon atoms).

Next, as a salt of esteramidoamine,
Examples thereof include those obtained by neutralizing the esteramidoamine represented by the general formula (1) with an acid, and particularly those obtained by neutralizing the HEMPDA-EA represented by the above formula (5) with an acid. Examples of the salt include hydrochloride, quaternary ammonium salt and the like.

These esteramidoamines and salts thereof may be used alone or in combination of two or more kinds. In addition, these esteramidoamines and /
Alternatively, as a method for adding the salt to the binder resin, a melt-kneading method, that is, either an internal addition method or an external addition method can be adopted, and in any method, these are compatible with the polyester resin which is the binder resin. As a result, a long-chain alkyl group is exposed on the surface of the toner to reduce the surface resistance of the toner. The amount of esteramidoamine and / or its salt added to the binder resin is 0.5 to 5.0.
%, Especially 0.7 to 2.0% by weight is preferred. If it is less than 0.1% by weight, the function as an anti-scum agent cannot be achieved, and if it exceeds 5.0% by weight, adhesion to the photoreceptor is caused, which is not preferable.

Next, various additives used for preparing the toner according to the present invention will be described. In addition to the components described above, a charge control agent, a colorant, and if necessary, a fluidity improver, a cleaning improver, and a release agent are added to the toner.

The charge control agent is not particularly limited, and the type of the control agent can be set by the positively charged toner and the negatively charged toner. The positively charged toner may be one or two of all positively chargeable charge control agents conventionally used for electrophotography.
More than one seed is used. Specific examples include imidazole derivatives such as "PLZ-2001" and "PLZ-800".
1 "(above, manufactured by Shikoku Kasei Co., Ltd.); triphenylmethane derivative such as" COBY BLU PR "(manufactured by Hoechst), quaternary ammonium compound such as" TP-4 ".
15 "," TP-4040 "(Hodogaya Chemical Co., Ltd.);" Bontron P-51 "(Orient Chemical Co., Ltd.)," Cop "
y Charge pxvP435 "(manufactured by Hoechst), cetyltrimethylammonium bromide and the like; polyamine resins such as" AFP-B "(manufactured by Orient Chemical Co.) and the like.

As the negatively chargeable toner, one kind or two or more kinds are used from all the negatively chargeable charge control agents known to be conventionally used for electrophotography. Specific examples include metal-containing azo dyes such as "Barry First Black 3804", "Bontron S-32", "Bontron S-34", "Bontron S-36" (all manufactured by Orient Chemical Co., Ltd.), and "Eisenspir". Ron Black TVH "
(Manufactured by Hodogaya Chemical Co., Ltd.); copper phthalocyanine dye, alkyl-derivatized complex of salicylic acid, for example, "Bontron E-8"
4 "(manufactured by Orient Chemical Co., Ltd.); quaternary ammonium salt,
For example, “CopyCharge NX Vp434”
(Manufactured by Hoechst) and the like.

It is also possible to use a main charge control agent in combination with a charge control agent of opposite polarity, and the amount of charge control agent of opposite chargeability is set to 1/2 or less of the amount of charge control agent of main chargeability. If you do 5
Even if development is continuously performed on ten thousand or more sheets, the density does not decrease and a good visible image can be obtained. These charge control agents are contained in the binder resin in an amount of 0.1 to 8.0% by weight, particularly 0.2.
It is preferable to add the compound in an amount of ˜5.0 wt%.

As the coloring agent, a chromatic dye or a pigment such as carbon black which develops black color, or grafted carbon black obtained by coating the surface of carbon black with a resin is used, and all known ones can be used. It is not particularly limited. There are three primary colors other than black, yellow, magenta, and cyan. For example, yellow has CI Solvent Yellow 21, CI Solvent Yellow 77, CI Pigment Yellow 12, and C.I.
I. Disperse Yellow 164 and the like. For magenta, CI Solvent Red 49, CI Solvent Red 128, CI Pigment Red 13,
CI Pigment Red 48.2, CI Disperse Red 11 and the like. For cyan, CI Solvent Blue 21, CI Solvent Blue 94,
C. I. Pigment Blue 15.3 and the like. These colorants are preferably added in an amount of 0.01 to 20% by weight, particularly 1 to 10% by weight, based on the total amount of the toner.

If necessary, a fluidity improver, a cleaning improver, etc. can be used in the toner of the present invention. As the fluidity improver, for example, silica, alumina, titanium oxide, barium titanate, magnesium titanate, calcium titanate, strontium titanate,
Zinc oxide, silica sand, clay, mica, wollastonite, diatomaceous earth, chromium oxide, cerium dioxide, red iron oxide, antimony trioxide, magnesium oxide, zirconium oxide, barium sulfate, barium carbonate, calcium carbonate, silicon carbide, silicon nitride Examples thereof include fine particles of silica, and fine silica powder is particularly preferable.

As the cleaning property improver, in addition to the esteramidoamine and / or its salt added to the toner exhibiting its function, fine particles of fluorine-based polymer and fine particles of silicone resin can be used. . The fluidity improver and the cleaning improver are added in an amount of 0.01 to 1.0% by weight with respect to the toner in order to prevent the effect of the esteramidoamine and / or its salt used as a scum inhibitor from being lowered. It is preferable.

A release agent may be used in the toner of the present invention, if necessary, for the purpose of improving offset resistance in heat roller fixing. As the release agent, fatty acid, fatty acid metal salt, fatty acid ester, partially saponified fatty acid ester, polyolefin, higher alcohol,
Paraffin wax, amide wax, polyhydric alcohol ester, silicon varnish, aliphatic fluorocarbon,
Any one or more kinds of offset preventing agents such as silicone oil may be contained.

Various additives other than the above may be added to the toner of the present invention. For example, as an additive for adjusting the developing property, for example, fine particle powder of a polymer of methyl methacrylate is used. In addition, a small amount of carbon black can be used for toning and resistance adjustment.

[0048]

The toner of the present invention thus obtained is mixed with a carrier for a dry two-component developer to form a toner scum on the surface of the carrier for a long life of the developer while ensuring low temperature fixing property. The toner of the present invention is suitable for a developer using a high-speed conductive pseudo two-component developing method.

[0049]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. Further, the composition ratios shown below are expressed in parts by weight unless otherwise specified. An example of producing a binder resin and a toner used in the present invention and an example of producing a coated carrier particularly suitable for the present invention are also shown below.

Resin Production Example 1 Polyoxypropylene (2.2) -2,2-bis (4-)
Hydroxyphenyl) propane 740 g, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 300 g, dimethyl terephthalate 466
g, isododephenyl succinic anhydride 80 g, 1,2,4
114 g of tri-n-butylbenzenetricarboxylate was placed in a glass 2-liter four-necked flask together with an ordinary esterification catalyst, and a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen introducing tube were attached, and in an electric heating mantle heater. 210 ° C normal pressure under nitrogen flow, 210 latter half
The reaction proceeded while stirring at a reduced pressure of ℃. The obtained polyester resin had an acid value of 2.8 KOHmg / g and a hydroxyl value of 28.
0KOHmg / g, Koka type flow tester, softening temperature 13
It was 8.7 ° C. Let the said resin be binder resin (1).

Resin Production Example 2 Polyoxypropylene (2.2) -2,2-bis (4-)
Hydroxyphenyl) propane 551 g, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 463 g, fumaric acid 191 g, 1,
189 g of 2,4-benzenetricarboxylic acid and 3 g of dibutyltin oxide were placed in a glass 3-liter four-necked flask, a thermometer, a stainless steel stirring rod, a downflow condenser and a nitrogen introduction tube were attached, and a nitrogen stream was generated in an electric heating mantle heater. The reaction proceeded while stirring at 210 ° C. in the first half. The degree of polymerization was traced from the softening point according to ASTM E28-51T, and the reaction was terminated when the softening point reached 137 ° C. The acid value of the polyester resin is 20.4 KOHmg
/ G, and the hydroxyl value was 21.0 KOHmg / g. Let the said resin be binder resin (2).

Example 1

[Table 1] Binder resin (1) 88.2 parts Carbon black “Regal 330R” 7 parts Positively chargeable charge control agent “Bontron N-07” (manufactured by Orient Chemical Co.) 2 parts Positively chargeable charge control agent “TP -415 "(manufactured by Hodogaya Chemical Co., Ltd.) 1 part Esteramidoamine" HEMPDA-EA "(manufactured by Kao Corporation) 1.8 parts *: HEMPDA-EA is the one represented by the general formula (5), Industrially, esteramide amine 80 to 84% shown in (5), intermediate (monoamide) 12 to 15
%, Fatty acids (C18: 55%, C16: 45%) 4.6
It is a composition containing -5% and decomposing at 240 or more at 63 ° C.

After thoroughly mixing the above raw materials with a Henschel mixer, they were melt-kneaded with a twin-screw extruder equipped with a barrel cooling device, cooled and coarsely crushed, then pulverized with a jet mill, and further using an air classifier. And classify, average particle size 11 μm
To obtain positively chargeable toner 1.

Example 2 1.8 parts of the esteramidoamine of Example 1 was converted into esteramidoamine hydrochloride "HEMPDA-EA-HCl" (8
(0% purity product) The same procedure was performed except that the amount was changed to 1.8 parts to obtain a positively chargeable toner 2. In addition, "HEMPDA-EA-
"HCl" is represented by the following formula.

[0055]

[Chemical 5]

(In the formula, R ⁸ and R ⁹ have 16 to 18 carbon atoms.
Represents the alkyl group of

Example 3

[Table 2] Binder resin (2) 90.5 parts Carbon black "Regal 400R" (manufactured by Cabot) 8 parts Negatively chargeable charge control agent "Aizen spirone rack T-77" (manufactured by Hodogaya Chemical Co., Ltd.) 1 .5 copies

To 100 parts of the above toner, "HEMP
1.8 parts of "DA-EA" was externally added and mixed and attached using a Henschel mixer to obtain a negatively chargeable toner 3.

Comparative Example 1 A positively chargeable toner 4 was obtained in the same manner as in Example 1 except that the binder resin (1) was changed to 90 parts by weight, except for "HEMPDA-EA".

Comparative Example 2 To 100 parts of the toner of Comparative Example 1 was added zinc stearate S.
Z-DF-2F (manufactured by Sakai Chemical Co., Ltd., average particle size 3 μm) 0.
Three parts were externally added and attached using a Henschel mixer to obtain a positively charged toner 5.

Coated Carrier Production Example 1 Sponge iron powder “Copy Pow” having an average particle diameter of 160 μm
der CS105-175 "(Hoganas AB
(Manufactured by Daikin Industries, Ltd.), 1000 parts by weight of vinylidene fluoride-tetrafluoroethylene copolymer [VT50 (manufactured by Daikin Industries, Ltd.),
Copolymer molar ratio 80:20] 50 parts and epoxy resin [Epicoat 1001 (manufactured by Mitsubishi Petrochemical Co., Ltd.)] 20 parts 10 parts
A dispersion liquid prepared by dispersing it in 00 parts of methyl ethyl ketone was spray-coated on the surface of 1000 parts of conductive graphite-filled sponge iron powder using a rolling fluidized bed coating device so that 1 part remained as a coating layer. Then
After further drying, it was heat-treated in an electric furnace at 200 ° C. for 30 minutes to obtain a coated carrier 1.

Coated Carrier Production Example 2 The vinylidene fluoride-tetrafluoroethylene copolymer VT50 and the epoxy resin Epicoat 1001 in the coated carrier production example 1 were straight silicon resin KR.
-71 (manufactured by Shin-Etsu Chemical Co., Ltd.) was performed in the same manner except that the coated carrier 2 was obtained.

Test Example For 100 parts by weight of the coated carrier 1, Examples 1 and 2 were used.
Alternatively, 3 parts by weight of each of the toners 1, 2, 4 and 5 obtained in Comparative Examples 1 and 2 was mixed to prepare a positively charged developer, and 100 parts by weight of the coated carrier 2 was obtained in Example 3. 3 parts by weight of Toner 3 was mixed to prepare a negatively chargeable developer. These developers are fixed by the reversal phenomenon for positively charged developers and the normal rotation phenomenon for negatively charged developers by using a modified copier with OPC belt (Fuji Xerox, FX1075). Property test, and a long-run test of 100,000 sheets in a normal environment (23 ° C., 50% RH), developer charge amount, carrier resistance, image and toner scum on carrier surface FE / SEM (manufactured by JEOL Ltd.) The observation results of No. 1 were evaluated by the method described below.

(1) Evaluation of charge amount The device used for evaluation of the charge amount is a blow-off type charge amount measuring device, and this device is a specific charge measuring device equipped with a Faraday cage, a capacitor and an electrometer. The measuring method is as follows. W (g) (about 3.0 g) of the developer taken out from the developing tank is put into a brass measuring cell equipped with a stainless steel mesh of 325 mesh (the size can be appropriately changed so that carrier particles do not pass). I put it in. Next, from the suction hole,
Suction was performed for 90 seconds at a pressure indicating a flow meter of 3 liter / minute to remove only the toner from the cell. The voltage of the electrometer 90 seconds after the start of suction was set to V (volt). Here, if the electric capacity of the capacitor is C (μF), the specific charge Q / m of this toner is obtained by the following equation.

[0065]

## EQU1 ## Q / m (μc / g) = C × V / m

Here, m is the weight of the toner contained in the development in W (g), and T is the weight of the toner in the developer.
(G), where D (g) is the weight of the developer, the toner density of the sample is expressed as T / D × 100 (%), and m is calculated by the following formula.

[0067]

## EQU2 ## m (g) = W × T / D

(2) Evaluation of carrier resistance When the charge amount was measured in (1), the carrier remaining on the stainless steel mesh of the blow-off type charge amount measuring device was measured by a dynamic carrier resistance measuring device (C-meter Epping).
1 cc was measured with a measuring spoon attached to a cell (manufactured by GmbH), and dynamic carrier resistance was measured using a condenser with a magnetic force of 630 gauss, preliminary stirring for 63 seconds, applied voltage of 12 V, and 10000 pF.

(3) Evaluation of Image Evaluation was carried out by the following methods with respect to development density and background stain. Image density is Macbeth reflection densitometer RD-914 (M
acbeth Process Measuremen
It was evaluated by the measurement value according to ts). The background stain is whiteness colorimetric color difference meter Z-1001Dp (manufactured by Nippon Denshoku Industries Co., Ltd.)
Then, the whiteness of the surface of the unused paper and the non-image area of the paper after development were measured, and evaluated by the relative comparative value obtained by subtracting the latter from the former.

(4) Evaluation of Fixing Property An image is displayed without applying silicone oil to the fixing part of the above-mentioned copying machine, and the roller temperature is modified so that the temperature can be changed.
The fixing temperature was controlled at 120 ° C to 240 ° C, and the minimum fixing temperature and offset property of the image were evaluated. The minimum fixing temperature here is a reflection thermometer of Macbeth Co. before and after rubbing 5 times back and forth on the image fixed through a fixing stage with a load of 500 g placed on a sand eraser with a bottom surface of 15 mm x 7.5 mm. The optical reflection density is measured by means of, and it means the temperature of the fixing roller when the fixing rate exceeds 70% according to the definition below.

[0071]

[Equation 3]

For all the toners obtained in each of the examples and comparative examples, the target fixing temperature of 180 ° C. or lower, which is the target minimum fixing temperature, can be secured, and no offset occurs even at 240 ° C. .

(5) Occurrence of Scum on Carrier Surface After copying 1 million sheets with the above copying machine, the carrier was taken out, and after separating the toner, it was observed by an electron microscope whether or not toner scum was generated on the convex portion. Table 3 shows the test results of the above (1) to (5). Note that (4)
Since the test result of No. 1 does not cause the offset phenomenon in all toners, it is excluded from the table.

[0074]

[Table 3]

As is clear from the results shown in the above table, in the case where the anti-scum agent of Comparative Example 1 is not added at all, the charge amount is halved, and the resistance value rises to such an extent that measurement becomes impossible. Performance is degraded. This is also verified by the fact that the image density is reduced to about half, the increase of background dust and the occurrence of toner scum. Further, in the case where zinc stearate is externally added as the anti-scum agent in Comparative Example 2, the amount of charge is extremely reduced and the image density is not so much reduced, but the ground stain is extremely increased. This means that zinc stearate in the toner sequentially moves to the photoreceptor side during the transfer process to form an insulating layer on the surface of the photoreceptor, or free zinc stearate improves the fluidity of the developer, and the carrier It is presumed that this is probably because the contacts are made too strong and bias leakage occurs.
On the other hand, when the toners of Examples 1 to 3 are used,
It was confirmed that a long life of up to 1 million sheets can be achieved while satisfying the target low-temperature fixability, and toner scum on the carrier can be satisfactorily prevented. This also means that the esteramidoamine and / or its salt contained in the toner lowers the surface resistance of the toner regardless of internal addition or external addition, and forms a thin film on the metal-exposed convex portions of the carrier. It is presumed that is difficult to adhere to the carrier surface.

[Brief description of drawings]

FIG. 1A to FIG. 1C are schematic views showing a generation mechanism of toner scum.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03G 9/10 311

Claims (5)

[Claims] 1. A toner containing a polyester resin as a main component of a binder resin and further containing ester amidoamine and / or a salt thereof. 2. An ester amidoamine is represented by the following general formula (1): The toner according to claim 1, which is represented by 3. The polyester resin has a softening point of 95 ° C. or higher and 160 ° C. or lower as measured by a Koka type flow tester,
The toner according to claim 1 or 2, wherein the glass transition temperature by DSC is 50 ° C or higher and 80 ° C or lower. 4. An electrostatic charge image developer composition comprising a carrier made of porous amorphous iron powder having irregularities on the surface and the toner according to any one of claims 1 to 3. 5. The electrostatic image developer composition according to claim 4, wherein the irregular iron powder constituting the carrier has an average particle size of 50 to 200 μm and the difference between the irregularities is 10 μm or more. .