JPH05142856A - Electrophotographic toner - Google Patents

Abstract

PURPOSE:To enhance offset resistance and reduce fixing temperature by containing a polyester resin obtained by condensation polymerization of a specified diol component with an acid component containing a trivalent carboxylic acid and a trimellitic acid therein. CONSTITUTION:A binder resin is a polyester resin obtained by condensing a diol component represented by a formula I with an acid component containing 1-50 mole % of a divalent carboxylic acid or its anhydride represented by a formula II and 10-30 mole % of a trimellitic acid or its anhydride, as a compound selected from the group consisting of dixzalent or more polyhydric carboxylic acids, and acid anhydrides and lower alkyl esters thereof. A releasing agent is a wax selected from the group consisting of free fatty acid eliminated type carnauba waxes, montan ester waxes and acid value rice waxes having acid values of 10-30. In the formulae I and II, R<1> represents an alkylene group, X and Y each represent an integral number in which the average value of the sum is 2-16, R<2> represents a hydrocarbon group having 4-20 carbons, and R<3> has the same meaning as R<2>, or represents hydrogen.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner used for developing an electric latent image in electrophotography, electrostatic printing and the like. Particularly, in the heat roll fixing method, the present invention relates to a toner that is sufficiently fixed at a lower temperature and that does not affect developer characteristics such as charging characteristics even when used for a long time in a developing device.

[0002]

2. Description of the Related Art In the case of a dry method, an electrostatic charge image formed by an electrophotographic method, an electrostatic printing method, an electrostatic recording method or the like is generally developed with a dry toner containing a binder resin and a colorant as a main component. ,
Transferred and fixed on copy paper. Although there are various fixing methods for toner images, the heat roller fixing method is widely used because of its high thermal efficiency and high-speed fixing. When performing high-speed fixing by such a heat fixing method, the toner is required to have good low-temperature fixability (that is, the lower limit fixing temperature is low), and for this reason, a binder resin having a low softening point is required. used. However, when a low softening point resin is contained in the toner, a part of the toner image adheres to the surface of the heat roller at the time of fixing, and this is transferred to copy paper to cause background stain, so-called offset phenomenon and winding phenomenon. It tends to occur (especially when the heat roller temperature is low). Therefore, as means for preventing these phenomena, JP-A-51-143333, JP-A-57-148752, JP-A-58-97056,
In each of the 60-247250 publications, it is proposed to add solid silicone varnish, higher fatty acid, higher alcohol, various waxes, etc. as a release agent, but all of them are more satisfactory while maintaining good low temperature fixing property. It did not show excellent offset resistance and wrapping resistance. Further, conventional polyolefin waxes such as low-molecular weight polyethylene and low-molecular weight polypropylene have good offset resistance, but have insufficient low-temperature fixability and poor dispersibility in a binder resin. There is a lot of so-called filming in which the agent is separated from the toner and adheres to the photoconductor or the developing sleeve, and carrier contamination by the spent toner also occurs, and it is difficult to form a stable and high-quality image for a long time. ..

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to have sufficient offset resistance at the time of fixing, have a low fixing lower limit temperature, and prevent winding around a fixing roll.
Still another object is to provide a toner which is free from scumming and toner scattering and which can obtain an image with high fidelity equivalent to the initial image even when continuously used, and which is suitable for high-speed fixing.

[0004]

In the present invention, a binding resin,
In an electrophotographic toner containing a colorant, a charge control agent and a release agent as main components, a diol component represented by the following general formula (I) as a binder resin for the toner and a divalent or higher polyvalent carboxylic acid or As the compound selected from the group consisting of the anhydride and the lower alkyl ester thereof, 1 to 50 mol% of a divalent carboxylic acid represented by the following general formula (II) or its anhydride and 10% of trimetic acid or its anhydride are used.
A polyester resin obtained by condensing with an acid component containing 30 to 30 mol% of a releasing agent (a) a free fatty acid type carnauba wax having an acid value of 5 or less, and (b) a montan ester wax. , (C) one or more waxes selected from the group of oxidized rice waxes having an acid value of 10 to 30 are used.

[0005]

[Chemical 7]

[0006]

[Chemical 8]

Further, as the colorant, the following (A)
At least one set of red colorant selected from the group combination, at least one kind or one set of blue colorant selected from the group (B), or selected from combination of the group (C) In addition, at least one set of green colorants is used.

(A) Group red colorants CI Pigment Red 48 and CI Pigm
ent Red 57: 1, CI Pigment Red
122, C. I. Pigment Red 112, C. I.
Solvent 49 or CI Pigment Vi
Combination with one of olet38.

Blue colorant of group (B) Colorant of the general formula (III) alone or CI Pigme
ntBlue15 and CI Pigment Red 5
Combination with 7: 1.

[Chemical 9]

Green Coloring Agent of Group (C) The coloring agent of the general formula (III) or CI Pigmen
One of t Blue 15 and CI Pigment
Yellow 17 or CI Solvent Ye
Combination with one of the low 162.

The charge control agent is at least represented by the following formula (I
V), a compound represented by the general formula (V), or a compound represented by the general formula (VI) provides a toner for electrophotography, which is stable and has a chargeability even when used for a long period of time due to environmental changes. It

[0012]

[Chemical 10]

[0013]

[Chemical 11] In the formula, R ₃ , R ₄ and R ₅ are hydrogen or an alkyl group having 1 to 10 carbon atoms or an allyl group, and particularly preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or an allyl group. Here, R ₃ , R ₄ and R ₅ may be the same or different at the same time. Further, Me is zinc, nickel, cobalt, copper,
Or any metal selected from chrome.

[0014]

[Chemical 12] In the formula, x and y are integers, and n = x + y
Is 4 to 8 and R _{1 to} R ₅ and R _{11 to} R ₁₅ are as shown below. R ₁ : a hydrogen atom, an alkyl group having _{1 to 5} carbon atoms, or-
(CH ₂ ) mCOOR ₁₀ (R ₁₀ is a hydrogen atom or a lower alkyl group, m is an integer of 1 to 3) group, R ₂ : a hydrogen atom, a halogen atom, or an optionally branched C 1 to C 12 group. Alkyl group, aralkyl group, -N
_{O 2, -NH 2, -N (} R 7) 2 (R 7 is a lower alkyl _{group), - SO 3 R 8 (} R 8 is a hydrogen atom), phenyl group which may have a substituent group or -Si, _{(CH 3) 3, R 3} , R 4: a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -NH ₂ or _{-N, (R 9) 2 (} R 9 is a lower alkyl group), R ₅ : Hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁₁ : hydrogen atom, alkyl group having 1 to 5 carbon atoms or-
(CH ₂ ) pCOOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, p is a group representing an integer of 1 to 3), R ₁₂ : hydrogen atom, halogen atom, optionally branched carbon number 1-12 alkyl groups, aralkyl groups, -N
_{O 2, -NH 2, -N (} R 17) 2 (R 17 is a lower alkyl _{group), - SO 3 R 18 (} R 18 is a hydrogen atom), phenyl group which may have a substituent group or -Si, _{(CH 3) 3, R 13} , R 14: a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -NH ₂ or _{-N, (R 19) 2 (} R 9 is a lower alkyl group), R ₁₅ : Hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms,

The present invention also provides an excellent electrophotographic developer by mixing the toner with a carrier having a core material coated with a silicone resin.

Next, materials used for the toner of the present invention will be described. The polyester resin used as the binding resin used in the present invention has a higher impact resistance of the resulting resin as the amount of trimellitic acid or its anhydride used increases, but the pulverization during the production of the toner Sex deteriorates. On the other hand, as the amount of the compound represented by the general formula (II) or the anhydride thereof increases, the glass transition point tends to decrease and the storage stability of the toner at high temperature tends to deteriorate. However, trimellitic acid or an anhydride thereof is used in an amount of 10 to 30 mol%, preferably 20 to 30 mol% in the acid component,
By using the compound represented by the general formula (II) or its anhydride in an amount of 1 to 50 mol% in the acid component, the above problems can be suppressed.

Examples of the compound represented by the general formula (II) include n-dodecenyl succinic acid, n-dodecyl succinic acid, i-dodecyl succinic acid, i-octyl succinic acid, n-octyl succinic acid, Examples include n-butyl succinic acid. By introducing these succinic acid derivatives, the fixability as a toner at low temperature is improved. As the remaining acid component compound, usual compounds such as fumaric acid, phthalic acid, isophthalic acid, terephthalic acid, maleic acid and their anhydrides and their lower alkylene esters can be used.

As an example of the diol represented by the general formula (I), polyoxypropylene (2,2)-
2,2-bis (4-hydroxyphenyl) propane, polyoxyester (2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6)-
2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (16) -2,2-bis (4-hydroxyphenyl) propane and the like can be mentioned.

It is also possible to use the following polyhydroxy compound having two or more functional groups in the diol component in an amount of about 5 mol% or less. For example, ethylene glycol, propylene glycol, glycerin, pentaerythritol, trimethylolpropane, hydrogenated bisphenol A, sorbitol or their etherified polyhydroxyl compounds.

In the present invention, a polyol component and a polycarboxylic acid component are usually used in an inert gas atmosphere at 180 to 250.
A polyester resin can be prepared by condensing at a temperature of ° C.

The released free fatty acid type carnauba wax used as a release agent in the toner of the present invention is a free fatty acid released from carnauba wax as a raw material and therefore has an acid value of 5 or less. In addition, the particles are finely crystallized as compared with the conventional carnauba wax, and the dispersed particle diameter in the binder resin is 1 μm or less, and the dispersibility is improved.

The montan ester wax is refined from minerals and becomes fine crystals like the carnauba wax, and the dispersed particle diameter in the binder resin is 1 μm or less, and the dispersibility is improved. In the case of a montan ester wax, the acid value is particularly preferably 5-14.

The oxidized rice wax of the present invention is obtained by air-oxidizing rice bran wax. Acid value is 10-3
It is preferably 0, and when it is less than 10, the lower limit fixing temperature rises and the low temperature fixability becomes insufficient, and when it is more than 30, the cold offset temperature rises and the low temperature fixability also becomes insufficient. The above waxes may be used alone or in combination, and if the wax is contained in an amount of 1 to 15 parts by weight based on the total weight of the toner, the good results shown above can be obtained.

As the red colorant of the present invention, CI Pi
gmentRed 48 (hereinafter, CI Pigment and Solvent numbers are based on the names described in the Color Index 3rd Edition) and CI Pigment Red.
By combining 57: 1, it becomes possible to impart an appropriate charge amount to the toner, which cannot be obtained by the conventional red colorant. The structural formulas of CI Pigment Red 48 and CI Pigment Red 57: 1 are as follows.

[0025]

[Chemical 13]

[0026]

[Chemical 14]

Also, CI Pigment Red 48
The mixing ratio of CI Pigment Red 57: 1 and CI Pigment Red 57: 1 is preferably 9: 1 to 1: 9, and the blending amount of both colorants is 1 to 15 parts by weight with respect to 100 parts by weight of the binder resin. Preferably.

Further, as the red colorant of the present invention, CI Pigment Red 48 and CI Pigm are used.
By using a combination of ent Red 122, a red toner having an appropriate charge amount can be obtained. The structural formula of CI Pigment Red 122 is as follows.

[0029]

[Chemical 15]

In addition, CI Pigment Red 48
The mixing ratio of CI Pigment Red 122 and
It is preferably 9: 1 to 1: 9, and more preferably the compounding amount of both colorants is 1 to 15 with respect to 100 parts by weight of the binder resin.

Furthermore, as the red colorant of the present invention, the above CI Pigment Red 48 and CI Pigment are used.
By using a combination of ment Red 112, a red toner having an appropriate charge amount can be obtained. The structural formula of the CI Pigment Red 112 is as follows.

[0032]

[Chemical 16]

Also, CI Pigment Red 48
The mixing ratio of CI Pigment Red 112 and
It is preferably 9: 1 to 5: 5, and more preferably 1 to 15 with respect to 100 parts by weight of the binder resin.

Further, as the red colorant of the present invention, the above CI Pigment Red 48 and CI Sol are used.
By using a combination of Vent Red 49,
It is possible to obtain a red toner having an appropriate charge amount. In addition,
The structural formula of CI Solvent 49 is as follows.

[0035]

[Chemical 17]

Also, CI Pigment Red 48
The blending ratio of CICI Solvent Red 49 and CICIvent Red 49 is preferably 9: 1 to 1: 9, and the blending amount of both colorants is 1 to 15 relative to 100 parts by weight of the binder resin. Preferably.

Further, as the red colorant of the present invention, the above-mentioned CI Pigment Red 48 and CI Pigment are used.
By using a combination of the Ment Violet 38, a red toner having an appropriate charge amount can be obtained.
The structural formula of CI Pigment Violet 38 is as follows.

[0038]

[Chemical 16] In addition, CI Pigment Red 48 and CI Pi
The blending ratio of gment Violet 38 is 9: 1 to
It is preferably 1: 9, and the blending amount of both colorants is preferably 1 to 15 with respect to 100 parts by weight of the binder resin.

By using the coloring matter represented by the above-mentioned general formula (III) as the blue colorant of the present invention, it is possible to impart an appropriate charge amount to the toner which cannot be obtained by the conventional blue colorant. Is possible. Specific examples of the colored product represented by the general formula (III) include the following.

[0040]

[Table 1] Table 1

Even if these blue colorants are used alone,
You may use together 2 or more types. Further, the blending amount of the colorant is preferably 1 to 15 with respect to 100 parts by weight of the binder resin.

As the blue colorant of the present invention, C.I.
I. Pigment Blue 15 and the above C.I.P.
IGMENT RED 57: 1 in combination, a blue toner having an appropriate charge amount can be obtained. The structural formula of CI Pigment Blue 15 is as follows.

[0043]

[Chemical 19]

Also, CI Pigment Blue 1
5 and CI Pigment Red 57: 1 is preferably 9: 1 to 5: 5, and the amount of both colorants is 1 to 15 parts by weight based on 100 parts by weight of the binder resin. Preferably.

In the present invention, as the green colorant, the colorant represented by the above general formula (III) or Table 1 and CI Pi
gment Yellow 17 and / or CI Sol
By combining the Vent Yellow 162, it becomes possible to impart an appropriate charge amount to the toner, which has not been obtained by the conventional green colorant. In addition, CI Pigme
nt Yellow 17 and CI Solvent Ye
The structural formula of low 162 is as follows.

[0046]

[Chemical 20]

[0047]

[Chemical 21]

The blending ratio of the blue colorant and the yellow colorant of the present invention is preferably 1: 9: 5 to 5, and the blending amount of both colorants is 1 to 100 parts by weight of the binder resin. ~ 1
It is preferably 5.

Further, a combination of the above CI Pigment Blue 15 as the green colorant of the present invention and the above CI Pigment Yellow 17 and / or CI Solvent Yellow 162 as the yellow colorant is used. A proper amount of charge can be used to obtain a green toner.

The blending ratio of the blue colorant and the yellow colorant of the present invention is preferably 1: 9: 5 to 5, and the blending amount of both colorants is 1 to 100 parts by weight of the binder resin. ~ 1
It is preferably 5.

Other colorants used in the present invention include carbon black, lamp black, iron black, ultramarine blue,
Nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, pigment Any conventionally known dye or pigment may be used alone or in combination.

The compounds represented by the above general formulas (IV), (V) and (VI) impart a negative chargeability to the toner and at the same time,
The effect of suppressing the change in the charging property of the toner with respect to the change in the environment is shown. The addition amounts of the compounds represented by the general formulas (IV), (V), and (VI) are as described below, but when the amount is less than the appropriate range, a sufficient negative charge amount can be imparted to the toner. On the contrary, when the amount is large, the charge control agent may be detached from the surface of the toner during continuous use in the developing device, and the charge amount may change greatly. The compounding amount of the compound represented by the general formula (IV) is 0.1 based on 100 parts by weight of the binder resin.
It is preferably ˜5 parts by weight.

The compound represented by the general formula (V) is Cla.
rk, J .; L. Kao, H; J. Amer. Che
m. Soc. 70 , 2151 (1948). For example, a zinc salt can be obtained by adding and mixing 2 mol of sodium salicylate salt (including sodium salt of salicylic acid derivative) and 1 mol of zinc chloride in a solvent, heating and stirring. This metal salt is a white crystal, and does not show coloring even when dispersed in a binder resin. Metal salts other than zinc salts can also be produced according to the above method. The compounding amount of the present compound is 0.1 to 10 parts by weight, preferably 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

The compound represented by the general formula (VI) is referred to as (n) arene compound, and it is synthesized from phenol and aldehyde as raw materials in high yield particularly when a concentrated alkali is used. The amount of the compound of the general formula (VI) added is 0.5 to 5 parts by weight, preferably 1 to 5 parts by weight, based on the whole toner. Specific examples of the compound represented by the general formula (VI) are shown in Tables 2 to 4
However, the present invention is not limited to this example.

[0055]

[Table 2] Table 2

[Table 3] Table 3

[Table 4] Table 4

Further, the toner of the present invention contains a magnetic material and can be used as a magnetic toner. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, metals such as iron, cobalt, and nickel, or aluminum of these metals,
Examples thereof include alloys with metals such as cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten and vanadium, and mixtures thereof.

These ferromagnetic materials have an average particle size of 0.1 to 2 μm.
It is desirable that the amount is about 20 to 200 parts by weight with respect to 100 parts by weight of the resin component, and particularly preferably 40 to 150 parts by weight with respect to 100 parts by weight of the resin component.

Further, the toner of the present invention may be mixed with additives as required. Examples of the additive include a fluororesin, a lubricant such as zinc stearate, or an abrasive such as cerium oxide or silicon carbide, a fluidity-imparting agent such as colloidal silica or aluminum oxide, an anti-caking agent, or carbon black. , Tin oxide, and other conductivity-imparting agents, and low-molecular-weight polyolefins and other fixing aids.

The present invention provides an excellent electrophotographic developer by mixing the toner as a core material with a carrier coated with a silicone resin. In this case, by coating the surface of the carrier core particles with a silicon resin containing conductive fine powder, the advantages of the conventional silicon resin-coated carrier are maintained in the same manner, and by imparting conductivity to the carrier, The charge accumulation phenomenon can be effectively suppressed.

In the present invention, the carrier core particles coated with the silicone resin may be those conventionally known, for example, ferromagnetic metals such as iron, cobalt and nickel,
Examples thereof include alloys and compounds such as magnetite, hematite, and ferrite, and glass beads. The average particle size of these core particles is usually 10 to 1000 μm, preferably 30 to 500 μm.
m. The amount of silicon resin used is usually 1 to 10% by weight based on the carrier core particles.

The silicone resin used in the present invention may be any conventionally known silicone resin, for example, commercially available KR261, KR271, KR272, KR275, manufactured by Shin-Etsu Silicone Co., Ltd.
KR280, KR282, KR285, KR251, K
R155, KR220, KR201, KR204, KR
205, KR206, SA-4, ES1001, ES1
001N, ES1002T, KR3093, SR2100, SR2101, SR210 manufactured by Toray Silicone Co., Ltd.
7, SR211O, SR2108, SR2109, SR
2115, SR2400, SR2410, SR241
1, SH805, SH806A, SH840 and the like are used. As the method of forming the silicone resin layer,
The silicon resin may be applied to the surface of the carrier core particles by a method such as a spraying method or a dipping method. The coating layer composition is prepared by adding conductive fine powder to a silicone resin solution and dispersing with a mixer.

The fine powder dispersed in the coating layer is 0.01 to 5.0.
Particle size of about μm is preferable, and silicone resin 10
It is preferable to add 2 to 30 parts by weight to 0 parts by weight, and most preferably 5 to 20 parts by weight. Carbon black is most preferable as the conductive fine powder. As the carbon black, conventionally known carbon black may be used, and examples thereof include contact black, furnace black and thermal black.

[0063]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. All parts are parts by weight.

Production Example 1 of Polyester Resin Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 900 parts Fumaric acid 130 parts n-Dodecenyl succinic anhydride 53.4 parts Hydroxine 0.1 part to glass The mixture was placed in a flask and heated to 230 ° C. in an electric heating mantle, and the reaction was performed while stirring in a nitrogen stream. The acid value when the water generated by the reaction stopped flowing out was 1.5. Further, 63.5 parts of trimellitic anhydride was added and the reaction was carried out for about 8 hours, and when the acid value reached 20, the reaction was terminated. The softening point of the obtained resin was 120 ° C.

Production Example 2 of Polyester Resin Polyoxypropylene (2) -2,2-bis (4-hydroxyphenyl) propane 650 parts Fumaric acid 120 parts Isododecenyl succinic anhydride 53.4 parts at 220 ° C. as in Production Example 1. Reacted. Furthermore, the softening point of the resin obtained by adding 79.0 parts of trimellitic anhydride and reacting at 200 ° C. was 120 ° C.

Production Example 3 of Polyester Resin Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 490 parts Terephthalic acid 188 parts n-Dodecenyl succinic anhydride 26.8 parts Diisopropyl orthotitanate 0.8 parts 195 parts of polyoxyethylene (2) -2,2-bis (4-hydroxyphenyl) propane were reacted at 230 ° C. for about 5 hours in the same manner as in Production Example 1 and further 78.8 parts of trimellitic anhydride were added at 200 ° C. The reaction was performed for 4 hours, and further under reduced pressure for 2 hours. The softening point of the resin is 115 ° C,
The acid value was 33.

Comparative Example of Production of Polyester Resin Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 490 parts Terephthalic acid 204.3 parts Diisopropyl orthotitanate 0.8 parts Polyoxyethylene (2) -2 195 parts of 2-bis (4-hydroxyphenyl) propane were reacted at 230 ° C. for about 5 hours in the same manner as in Production Example 1, and 78.8 parts of trimellitic anhydride were added at 200 ° C., and the reaction was continued for about 4 hours, and further under reduced pressure. And reacted for 2 hours. The softening point of the resin is 115 ° C,
The acid value was 34.

Example 1 Polyester resin (made in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 5 parts Carbon black (Mitsubishi Carbon Co. # 44) 12 parts Chromium-containing azo system Dye (S-34, manufactured by Orient Chemical Co., Ltd.) 2 parts The mixture having the above composition is sufficiently stirred and mixed in a Henschel mixer, and then heated and melted at a temperature of 80 to 110 ° C. for about 40 minutes on a roll mill, and cooled to room temperature to obtain the product. The kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. This toner 3
To 100 parts of the carrier, 97 parts of 100 to 200 mesh ferrite carrier coated with silicone resin was mixed by a ball mill to obtain a two-component developer. Next, a plain paper copier equipped with a Teflon coated roller as a fixing roller (Ricoh FT-703
When the developer was set to 0) and a continuous copy test was performed at a heat roller temperature of 130 ° C., a good image was obtained not only at the initial stage but also after copying 100,000 sheets without causing the phenomenon of offset or winding. Neither filming on the photosensitive member nor the developing sleeve was observed. As a fixing test, hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured by the following evaluation methods, and good results as shown in Table 5 were obtained. Further, when the state of the spent toner due to the toner of the carrier was observed after 100,000 sheets, the spent toner due to the toner of the carrier was not observed.

[Fixing Test Evaluation Method] This evaluation method is shown in Tables 5 to 5.
It is common to Table 15. 1. Offset generation temperature: Contamination caused by repeating the operation of fixing the toner image transferred onto the copy paper under the conditions of a roller nip width of 4 mm and a linear velocity of 250 mm / sec while sequentially increasing the heating temperature of the roller with the Teflon-coated roller. Then, the minimum temperature at this time is defined as the cold offset generation temperature, and the maximum temperature is defined as the hot offset generation temperature. 2. Winding temperature: A so-called solid black original is used to transfer toner onto almost the entire surface of copy paper,
Except for gradually lowering the heating temperature of the roller, the fixing operation is repeated as in the case of measuring the offset generation temperature, and the temperature when the copy paper is wrapped around the roller is obtained.

3. Fixing lower limit temperature: Fixing is performed in the same manner as in the measurement of the offset generation temperature, and the temperature when the toner fixing rate reaches 70% by the clock meter is obtained. In the table, the evaluation column shows the overall evaluation, ⊚ and ◯ are good, Δ is bad, and × is out of practical use.

Comparative Example 1 Instead of the free fatty acid type carnauba wax of Example 1, a low molecular weight polypropylene (660P manufactured by Sanyo Kasei Co., Ltd.) was used.
A developer was obtained in the same manner as in Example 1 except that was used, and a continuous copy test was conducted. As a result, a winding phenomenon occurred and a good image was not obtained.

Example 2 Polyester resin (produced in Polyester Resin Production Example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts Carbon black (Mitsubishi Carbon Co. # 44) 9 parts Chromium-containing azo dye (Orient Chemical Co., Ltd., S-34) 2 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 1, and then 80 to 110 ° C. with a roll mill.
After heating and melting for about 40 minutes at room temperature and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. To 3.5 parts of this toner, 96.5 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron Powder Co., Ltd.) was mixed with a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 1, the same good results as in Example 1 were obtained. The fixability of this product was good as shown in Table 5.

Example 3 A developer was obtained in the same manner as in Example 1 except that oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 1. Next, this developer was used in Example 1.
When a continuous copy test was conducted in the same manner as above, good results were obtained. The fixability of this product was good as shown in Table 5.

Comparative Example 2 A developer was prepared in the same manner as in Example 2 except that the montan ester wax of Example 2 was not used, and a continuous copy test was conducted. Occurred and a good image was not obtained.

Comparative Example 3 A polyester resin was prepared in the same manner as in Example 1 except that the polyester resin prepared in Comparative Example 1 was used in place of the polyester resin of Example 1, and a continuous copy test was conducted. , The fixing lower limit temperature was high and the fixing property was insufficient, and a good image was not obtained.

Example 4 A developer was obtained in the same manner as in Example 1 except that the polyester resin prepared in Production Example 2 of polyester resin was used instead of the polyester resin of Example 1. When a continuous copy test was conducted on this developer in the same manner as in Example 1, the same good results as in Example 1 were obtained. The fixability of this product was good as shown in Table 5.

Example 5 A developer was obtained in the same manner as in Example 1 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 1. When a continuous copy test was conducted on this developer in the same manner as in Example 1, good results were obtained. The fixability of this product was good as shown in Table 5.

Example 6 An example except that the polyester resin prepared in Production Example 3 was used in place of the polyester resin of Example 1 and montan ester wax was used in place of the free fatty acid type carnauba wax. A developer was obtained in the same manner as in 1. Next, when this developer was subjected to a continuous copy test in the same manner as in Example 1, good results were obtained as in Example 1. The fixability of this product was good as shown in Table 5.

Comparative Example 4 A developer was obtained in the same manner as in Example 1 except that polypropylene oxide (manufactured by Sanyo Kasei Co., Ltd.) was used in place of the free fatty acid type carnauba wax of Example 1, and a continuous copy test was conducted. However, a wrapping phenomenon occurred and a good image could not be obtained. Further, as shown in Table 5, the low temperature fixability of this product was sufficient, but hot offset occurred and it was not at a practical level.

[0080]

[Table 5] Table 5

Example 7 Polyester resin (made in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Carbon black (Mitsubishi Carbon Co. # 44) 12 parts Table 2 (VI) -1 compound 2 parts After thoroughly stirring and mixing the mixture having the above composition in a Henschel mixer, it is heated and melted at a temperature of 80 to 110 ° C. for about 40 minutes by a roll mill, and cooled to room temperature, and then the obtained kneaded product is obtained. Was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. This toner 3
97 parts of 150-250 mesh iron oxide powder (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) coated with a silicone resin was mixed in a ball mill to obtain a two-component developer. Next, when the above-mentioned developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 130 ° C, and an offset or winding phenomenon occurred. Without saying, of course,
A good image was obtained even after 100,000 copies, and filming on the photoconductor or the developing sleeve was not observed. Also, as a fixing test, hot offset, cold offset,
When the wrapping occurrence temperature and the fixing lower limit temperature were measured, good results as shown in Table 6 were obtained. Also, 10
After observing the state of the spent toner due to the toner of the carrier after 10,000 sheets, the spent toner due to the toner of the carrier was not observed.

Comparative Example 5 Instead of the released free fatty acid type carnauba wax of Example 7, a low molecular weight polypropylene (660P manufactured by Sanyo Chemical Industry Co., Ltd.) was used.
A developer was obtained in the same manner as in Example 7 except that was used, and a continuous copy test was conducted. As a result, a winding phenomenon occurred and a good image was not obtained.

Example 8 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts Carbon black (Mitsubishi Carbon Co. # 44) 9 parts Table 2 ( Compound of VI) -2 1.5 parts The mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer in the same manner as in Example 7, and then 80 to 110 ° C in a roll mill.
After heating and melting for about 40 minutes at room temperature and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. To 3.5 parts of this toner, 96.5 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron Powder Co., Ltd.) was mixed by a ball mill to obtain a two-component developer. The charge amount of the toner was −19 μc / g. When a continuous copy test was performed using this developer in the same manner as in Example 7, the same good results as in Example 6 were obtained. The fixability of this product was good as shown in Table 6.

Example 9 Except that the released free fatty acid type carnauba wax of Example 7 was replaced with an oxidized rice wax having an acid value of 15 and the charge control agent was replaced with the compound of (VI) -3 in Table 2. A developer was obtained in the same manner as in Example 7. Next, this developer was used in Example 7.
When a continuous copy test was conducted in the same manner as in Example 7, good results were obtained as in Example 7. The fixability of this product was good as shown in Table 6.

Comparative Example 6 A developer was prepared in the same manner as in Example 8 except that the montan ester wax of Example 8 was not used, and a continuous copy test was conducted. Occurred and a good image was not obtained.

Comparative Example 7 A polyester resin was prepared in the same manner as in Example 7 except that the polyester resin produced in Comparative Example 1 was used instead of the polyester resin in Example 7, and a continuous copy test was conducted. , The fixing lower limit temperature was high and the fixing property was insufficient, and a good image was not obtained.

Example 10 Example 10 was repeated except that the polyester resin prepared in Production Example 2 of Polyester Resin was used in place of the polyester resin of Example 7 and the charge control agent was replaced with the compound of (VI) -4 in Table 2. A developer was obtained in the same manner as in 7. Toner charge is-
It was 19.0 μc / g. The following developer was used in Example 7
When a continuous copy test was conducted in the same manner as above, good results were obtained. The fixability of this product was good as shown in Table 6.

Example 11 Sazol wax H1 manufactured by Sazol Co. was used in place of the carnauba wax of Example 7, and a charge control agent shown in Table 2 was used.
A developer was obtained in the same manner as in Example 7, except that (VI) -5 in Table 3 was used instead of (VI) -1. Next, this developer was subjected to a continuous copy test in the same manner as in Example 7, and good results were obtained. The fixability of this product was good as shown in Table 6.

Example 12 Polyester resin (made in Polyester resin production example 3) 85 parts Montane ester wax (acid value 12.0) 3 parts Carbon black (Mitsubishi Carbon Co. # 44) 9 parts Table 3 ( VI) -6 1.5 parts was treated in the same manner as in the example to obtain a toner having a particle size of 5 to 20 μm. Silicone resin (SR-2
411; manufactured by Toray Silicone Co., Ltd.) was mixed with 97 parts of 100-250 mesh ferrite carrier in a ball mill to obtain a two-component developer. The toner charge amount is -18.
It was 5 μc / g. Hereinafter, using this developer, Example 7
When a continuous copy test was conducted in the same manner as in, good results were obtained as in Example 7. The fixability of this product was good as shown in Table 6.

Comparative Example 8 A developer was obtained in the same manner as in Example 7 except that oxidized polypropylene (manufactured by Sanyo Kasei Co., Ltd.) was used in place of the carnauba wax of Example 7, and a continuous copy test was conducted. Occurred and a good image was not obtained. Further, as shown in Table 6, the low-temperature fixability was sufficient, but hot offset occurred and the fixability was not at a practical level.

Comparative Example 9 A developer was obtained in the same manner as in Example 7 except that a chromium oxynaphthoate complex was used in place of the charge control agent in Example 7.
When a copy image was produced, fogging occurred on the background portion of the image, and a good image could not be obtained.

Example 13 Instead of the charge control agent of Example 7, the compound (VI) -7 of Table 3 was used.
A developer was obtained in the same manner as in Example 7 except that was used, and a copy image was obtained, and a good image was obtained. But,
As shown in Table 6, the initial charge amount was -18.0 µc / g, but after copying 100,000 copies, it was -14 µc / g, which tended to be slightly decreased.

[0093]

[Table 6] Table 6

Example 14 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 1 6 parts CIPigmennt Red 57: 1 4 parts After thoroughly stirring and mixing the mixture of composition in a Henschel mixer, it is heated and melted at a temperature of 80 to 110 ° C. for about 40 minutes by a roll mill, and after cooling to room temperature, the obtained kneaded product is pulverized and classified to a particle size of 5 to 20 μm. A red toner having a particle size was obtained. To 3 parts of this toner, 97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, a plain paper copier equipped with a Teflon coated roller as a fixing roller (Ricoh FT-703
When the developer was set to 0) and a continuous copy test was performed at a heat roller temperature of 130 ° C., a good image was obtained not only at the initial stage but also after copying 100,000 sheets without causing the phenomenon of offset or winding. Neither filming on the photosensitive member nor the developing sleeve was observed. As a fixing test, hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured, and good results as shown in Table 7 were obtained. Also, when observing the state of spent toner due to the toner of the carrier after 100,000 sheets,
No spent toner by the toner of the carrier was observed.

Comparative Example 10 Instead of the free fatty acid type carnauba wax of Example 14, low molecular weight polypropylene (660 manufactured by Sanyo Kasei Co., Ltd.) was used.
A developer was obtained in the same manner as in Example 14 except that P) was used, and a continuous copy test was conducted. As a result, a winding phenomenon occurred and a good image was not obtained.

Example 15 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CIPigmennt Red 48: 2 6 parts CIPigmennt Red 57: 1 4 parts Formula ( Compound of IV) 2 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 14, and then 80 to 110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 14, the same good results as in Example 14 were obtained. The fixability of this product was good as shown in Table 7.

Example 16 Example 1 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 14.
A developer was obtained in the same manner as in 4. Next, a continuous copy test was conducted on this developer in the same manner as in Example 14,
Good results were obtained as in Example 14. The fixability of this product was good as shown in Table 7.

Comparative Example 11 A developer was prepared in the same manner as in Example 15 except that the montan ester wax of Example 15 was not used, and a continuous copy test was carried out. Occurred and a good image was not obtained.

Comparative Example 12 A polyester resin was prepared in the same manner as in Example 14 except that the polyester resin produced in Comparative Example 1 was used instead of the polyester resin in Example 14, and a continuous copy test was conducted. , The fixing lower limit temperature was high and the fixing property was insufficient, and a good image was not obtained.

Example 17 A developer was obtained in the same manner as in Example 14 except that the polyester resin prepared in Polyester Resin Production Example 2 was used instead of the polyester resin in Example 14. When a continuous copy test was conducted on this developer in the same manner as in Example 14, good results were obtained. The fixability of this product was good as shown in Table 7.

Example 18 A developer was obtained in the same manner as in Example 14 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 14. When a continuous copy test was conducted on this developer in the same manner as in Example 14, good results were obtained. The fixability of this product was good as shown in Table 7.

Example 19 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 3 6 parts CIPigmennt Red 57: 1 4 parts general A developer was obtained in the same manner as in Example 14 except that 2 parts of the compound of the formula (V) in which Me was Zn was used. Next, this developer was subjected to a continuous copy test in the same manner as in Example 14, and good results were obtained. The fixability of this product was good as shown in Table 7.

Comparative Example 14 A developer was prepared in the same manner as in Example 15 except that a chromium oxynaphthoate complex was used instead of the compound of formula (IV) in Example 15, and a continuous copy test was conducted. However, some toner fogging occurred on the background portion of the image, and a good image could not be obtained.

Comparative Example 14 CIP was used instead of CI Pigmennt Red 57: 1 in Example 14.
A developer was prepared in the same manner as in Example 14 except that igmennt Red 239 was used, and a continuous copy test was conducted. As a result, some toner fogging occurred on the background of the image, and a good image was not obtained. It was

[0105]

[Table 7] Table 7

Example 20 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 1 6 parts CIPigmennt Red 122 4 parts After thoroughly stirring and mixing the mixture in a Henschel mixer, heat and melt it for about 40 minutes on a roll mill at a temperature of 80 to 110 ° C., cool to room temperature, and then pulverize and classify the kneaded product to obtain a particle size of 5 to 20 μm. Toner was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, as a fixing test, hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured, and favorable results as shown in Table 8 were obtained. Further, when the state of the spent toner due to the toner of the carrier was observed after 100,000 sheets, the spent toner due to the toner of the carrier was not observed.

Example 21 Polyester resin (made in Polyester Resin Production Example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CIPigmennt Red 48: 2 6 parts CIPigmennt Red 122 4 parts Formula (IV) 2 parts of the compound of the above, as in Example 20, thoroughly agitating and mixing in a Henschel mixer, and then 80-110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was carried out in the same manner as in Example 20 using this developer, good results were obtained. The fixability of this product was good as shown in Table 8.

Example 22 Example 2 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 20.
A developer was obtained in the same manner as in 0. Next, this developer was subjected to a continuous copy test in the same manner as in Example 20, and good results were obtained. The fixability of this product was good as shown in Table 8.

Example 23 A developer was obtained in the same manner as in Example 20 except that the polyester resin prepared in Production Example 2 of polyester resin was used instead of the polyester resin of Example 20. When a continuous copy test was conducted on this developer in the same manner as in Example 20, good results were obtained. The fixability of this product was good as shown in Table 8.

A developer was obtained in the same manner as in Example 20, except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 20. When a continuous copy test was conducted on this developer in the same manner as in Example 20, the same good results as in Example 20 were obtained. The fixability of this product was good as shown in Table 8.

Example 25 Polyester resin (made in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 3 6 parts CIPigmennt Red 122 4 parts General formula ( A developer was obtained in the same manner as in Example 20, except that 2 parts of the compound of V) having Me as Zn was used. Next, this developer was subjected to a continuous copy test in the same manner as in Example 20, and good results were obtained. The fixability of this product was good as shown in Table 8.

[0112]

[Table 8] Table 8

Example 26 Polyester resin (prepared in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 1 6 parts CIPigmennt Red 112 4 parts After thoroughly stirring and mixing the mixture in a Henschel mixer, heat and melt it for about 40 minutes on a roll mill at a temperature of 80 to 110 ° C., cool to room temperature, and then pulverize and classify the kneaded product to obtain a particle size of 5 to 20 μm. Toner was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copier (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. In addition, when a hot offset, a cold offset, a winding occurrence temperature and a fixing lower limit temperature were measured as a fixing test, good results as shown in Table 9 were obtained. Further, when the state of the spent toner due to the toner of the carrier was observed after 100,000 sheets, the spent toner due to the toner of the carrier was not observed.

Example 27 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CIPigmennt Red 48: 2 6 parts CIPigmennt Red 112 4 parts Formula (IV) 2 parts of the compound of the above. Similarly to Example 26, the mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer, and then 80-110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. Using this developer, a continuous copy test was conducted in the same manner as in Example 26, and good results were obtained. The fixability of this product was good as shown in Table 9.

Example 28 Example 2 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 26.
A developer was obtained in the same manner as in 6. Next, this developer was subjected to a continuous copy test in the same manner as in Example 26, and good results were obtained. The fixability of this product was good as shown in Table 9.

Example 29 A developer was obtained in the same manner as in Example 26 except that the polyester resin prepared in Production Example 2 of polyester resin was used in place of the polyester resin of Example 26. When a continuous copy test was conducted on this developer in the same manner as in Example 26, good results were obtained. The fixability of this product was good as shown in Table 9.

Example 30 A developer was obtained in the same manner as in Example 26 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 26. When a continuous copy test was conducted on this developer in the same manner as in Example 26, good results were obtained. The fixability of this product was good as shown in Table 9.

Example 31 Polyester resin (made in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 3 6 parts CIPigmennt Red 122 4 parts General formula ( A developer was obtained in the same manner as in Example 26 except that 2 parts of the compound of V) in which Me was zinc was used. Next, when this developer was subjected to a continuous copy test in the same manner as in Example 26, good results were obtained as in Example 26. The fixability of this product was good as shown in Table 9.

[0119]

[Table 9] Table 9

Example 32 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CI Pigmennt Red 48: 1 6 parts CISolvent Red 49 4 parts After thoroughly stirring and mixing the mixture in a Henschel mixer, heat and melt it with a roll mill at a temperature of 80 to 110 ° C for about 40 minutes, and after cooling to room temperature, the obtained kneaded product is pulverized and classified to have a particle size of 5 to 20 μm. Toner was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copier (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, as a fixing test, hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured, and good results as shown in Table 10 were obtained. Also, when observing the state of spent toner due to the toner of the carrier after 100,000 sheets,
No spent toner by the toner of the carrier was observed.

Example 33 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CI Pigmennt Red 48: 2 8 parts CISolvent Red 49 2 parts Formula (IV) 2 parts of the compound of the above. Similarly to Example 32, the mixture having the above composition was sufficiently stirred and mixed in a Henschel mixer, and then 80-110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 32, good results were obtained. The fixability of this product was good as shown in Table 10.

Example 34 Example 3 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the free fatty acid-type carnauba wax obtained in Example 32.
A developer was obtained in the same manner as in 2. Next, a continuous copy test was conducted on this developer in the same manner as in Example 32, and good results were obtained. The fixability of this product was good as shown in Table 10.

Example 35 A developer was obtained in the same manner as in Example 32 except that the polyester resin prepared in Polyester Resin Production Example 2 was used in place of the polyester resin of Example 32. When a continuous copy test was conducted on this developer in the same manner as in Example 32, good results were obtained. The fixability of this product was good as shown in Table 10.

Example 36 A developer was obtained in the same manner as in Example 32 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 32. When a continuous copy test was conducted on this developer in the same manner as in Example 32, good results were obtained. The fixability of this product was good as shown in Table 10.

Example 37 Polyester resin (made in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 3 6 parts CIPigmennt Solvent Red 49 4 parts General formula A developer was obtained in the same manner as in Example 32 except that 2 parts of the compound (V) in which Me was Zn was used. Next, a continuous copy test was conducted on this developer in the same manner as in Example 32, and good results were obtained. The fixability of this product was good as shown in Table 10 below.

[0126]

[Table 10] Table 10

Example 38 Polyester resin (prepared in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigment Red 48: 1 6 parts CIPigment Violet 38 4 parts After thoroughly stirring and mixing the mixture in a Henschel mixer, heat and melt it with a roll mill at a temperature of 80 to 110 ° C for about 40 minutes, and after cooling to room temperature, the obtained kneaded product is pulverized and classified to have a particle size of 5 to 20 μm. Toner was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copier (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. In addition, when a hot offset, a cold offset, a winding occurrence temperature and a fixing lower limit temperature were measured as a fixing test, good results as shown in Table 11 were obtained. Also, when observing the state of spent toner due to the toner of the carrier after 100,000 sheets,
No spent toner by the toner of the carrier was observed.

Example 39 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CIPigmennt Red 48: 2 8 parts CIPigment Violet 38 3 parts Formula (IV) 2 parts of the compound of the above. The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 38, and then 80-110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. Using this developer, a continuous copy test was conducted in the same manner as in Example 38, and good results were obtained. The fixability of this product was good as shown in Table 11.

Example 40 Example 3 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 38.
A developer was obtained in the same manner as in 8. Next, a continuous copy test was conducted on this developer in the same manner as in Example 38, and good results were obtained. The fixability of this product was good as shown in Table 11.

Example 41 A developer was obtained in the same manner as in Example 38 except that the polyester resin prepared in Production Example 2 of polyester resin was used in place of the polyester resin of Example 38. When a continuous copy test was conducted on this developer in the same manner as in Example 38, good results were obtained. The fixability of this product was good as shown in Table 11.

Example 42 A developer was obtained in the same manner as in Example 38 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 38. When a continuous copy test was conducted on this developer in the same manner as in Example 38, good results were obtained. The fixability of this product was good as shown in Table 11.

Example 43 Polyester resin (prepared in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Red 48: 3 6 parts CIPigmennt Solvent Red 49 4 parts General formula A developer was obtained in the same manner as in Example 38 except that 2 parts of the compound (V) in which Me was Zn was used. Next, when this developer was subjected to a continuous copy test in the same manner as in Example 38, good results were obtained as in Example 38. The fixability of this product was good as shown in Table 11 below.

[0133]

[Table 11] Table 11

Example 44 Polyester resin (prepared in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue colorant (III) -1 3 parts in Table 1 above After thoroughly stirring and mixing the mixture of composition in a Henschel mixer, it is heated and melted at a temperature of 80 to 110 ° C. for about 40 minutes by a roll mill, and after cooling to room temperature, the obtained kneaded product is pulverized and classified to a particle size of 5 to 20 μm. A toner having a particle size was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the above-mentioned developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 130 ° C, and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, when hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured as a fixing test, good results as shown in Table 12 were obtained. Further, when the state of the spent toner due to the toner of the carrier was observed after 100,000 sheets, the spent toner due to the toner of the carrier was not observed.

Comparative Example 15 Instead of the free fatty acid-type carnauba wax of Example 44, a low molecular weight polypropylene (660 manufactured by Sanyo Kasei Co., Ltd.) was used.
A developer was obtained in the same manner as in Example 44 except that P) was used and a continuous copy test was conducted. As a result, a winding phenomenon occurred and a good image was not obtained.

Example 45 Polyester resin (prepared in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts Blue colorant (III) -1 3 parts of Table 1 ( Compound of IV) 2 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 44, and then mixed with a roll mill at 80 to 110.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was performed using this developer in the same manner as in Example 4, good results were obtained. The fixability of this product was good as shown in Table 12.

Example 46 Example 4 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the free fatty acid type carnauba wax of Example 44.
A developer was obtained in the same manner as in 4. Next, this developer was subjected to a continuous copy test in the same manner as in Example 43, and good results were obtained. The fixability of this product was good as shown in Table 12.

Comparative Example 16 A developer was prepared in the same manner as in Example 45 except that the montan ester wax of Example 45 was not used, and a continuous copy test was conducted. Occurred and a good image was not obtained.

Comparative Example 17 A polyester resin was produced in the same manner as in Example 44 except that the polyester resin produced in Comparative Example 1 was used in place of the polyester resin of Example 44, and a continuous copy test was conducted. , The fixing lower limit temperature was high and the fixing property was insufficient, and a good image was not obtained.

Example 47 A developer was obtained in the same manner as in Example 4 except that the polyester resin prepared in Production Example 2 of polyester resin was used in place of the polyester resin of Example 44. When a continuous copy test was conducted on this developer in the same manner as in Example 44, good results were obtained. The fixing properties of this product are shown in Table 1.
It was good as shown in 2.

Example 48 A developer was obtained in the same manner as in Example 44 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 44. When a continuous copy test was conducted on this developer in the same manner as in Example 44, good results were obtained. The fixability of this product was good as shown in Table 12.

Example 49 Polyester resin (prepared in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue colorant (III) -3 4 parts in Table 1 General A developer was obtained in the same manner as in Example 44 except that 2 parts of the compound of the formula (V) in which Me was Zn was used. Next, this developer was subjected to a continuous copy test in the same manner as in Example 44, and good results were obtained. The fixability of this product was good as shown in Table 12 below.

Comparative Example 18 A developer was prepared in the same manner as in Example 43 except that a chromium oxynaphthoate complex was used instead of the compound of formula (IV) in Example 43, and a continuous copy test was conducted. However, some toner fogging occurred on the background portion of the image, and a good image could not be obtained.

Comparative Example 19 A developer was prepared in the same manner as in Example 44 except that the following compounds were used in place of the colorant exemplified compound 2 of Example 44, and a continuous copy test was conducted. A small amount of toner fogging occurred on the background portion of the image, and a good image could not be obtained.

[0145]

[Table 12] Table 12

Example 50 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Blue 15 5 parts CIPigmennt Red 57: 1 1 part After thoroughly stirring and mixing the mixture in a Henschel mixer, heat and melt it with a roll mill at a temperature of 80 to 110 ° C for about 40 minutes, and after cooling to room temperature, the obtained kneaded product is pulverized and classified to have a particle size of 5 to 20 μm. Toner was obtained. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, when hot offset, cold offset, wrapping occurrence temperature and fixing lower limit temperature were measured as a fixing test, good results as shown in Table 13 were obtained. Also, when observing the state of spent toner due to the toner of the carrier after 100,000 sheets,
No spent toner by the toner of the carrier was observed.

Example 51 Polyester resin (made in Polyester Resin Production Example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CIPigmennt Blue 15 5 parts CIPigmennt Red 57: 1 1 part Formula (IV) 2 parts of the compound of the above, in the same manner as in Example 50, thoroughly stirring and mixing in a Henschel mixer, and then 80-110 by a roll mill.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 50, good results were obtained. The fixability of this product was good as shown in Table 13.

Example 52 Example 5 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 50.
A developer was obtained in the same manner as in 0. Next, this developer was subjected to a continuous copy test in the same manner as in Example 50, and good results were obtained. The fixability of this product was good as shown in Table 13.

Example 53 A developer was obtained in the same manner as in Example 50 except that the polyester resin prepared in Production Example 2 of polyester resin was used in place of the polyester resin of Example 50. When a continuous copy test was conducted on this developer in the same manner as in Example 50, good results were obtained. The fixability of this product was good as shown in Table 13.

Example 54 A developer was obtained in the same manner as in Example 50 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 50. When a continuous copy test was conducted on this developer in the same manner as in Example 50, good results were obtained. The fixability of this product was good as shown in Table 13.

Example 55 Polyester resin (prepared in Polyester resin production example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue coloring compound (III) -3 2 parts in Table 1 CI Pigmennt Yellow 17 5 parts A developer was obtained in the same manner as in Example 50 except that 2 parts of the compound of the general formula (V) in which Me was Zn was used. Next, this developer was subjected to a continuous copy test in the same manner as in Example 50, and good results were obtained. The fixability of this product was good as shown in Table 13.

[0152]

[Table 13] Table 13

Example 56 Polyester resin (prepared in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue colorant (III) -1 2 parts C in Table 1 I. Pigment Yellow 17 5 parts After thoroughly stirring and mixing the mixture having the above composition in a Henschel mixer, the mixture is heated and melted at a temperature of 80 to 110 ° C for about 40 minutes on a roll mill, cooled to room temperature, and the obtained kneaded product is obtained. It was crushed and classified to obtain a toner having a particle size of 5 to 20 μm. This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. To 3 parts of this toner, 97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the above-mentioned developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 130 ° C, and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, when a hot offset, a cold offset, a winding occurrence temperature and a fixing lower limit temperature were measured as a fixing test, good results as shown in Table 14 were obtained. Further, when the state of the spent toner due to the toner of the carrier was observed after 100,000 sheets, the spent toner due to the toner of the carrier was not observed.

Comparative Example 20 Instead of the free fatty acid type carnauba wax of Example 56, a low molecular weight polypropylene (660 manufactured by Sanyo Kasei Co., Ltd.) was used.
A developer was obtained in the same manner as in Example 56 except that P) was used, and a continuous copy test was conducted. As a result, a winding phenomenon occurred and a good image was not obtained.

Example 57 Polyester resin (produced in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts Blue colorant (III) -2 in Table 1 1.5 parts CISolvent Yellow 162 5 parts Compound of general formula (IV) 2 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 56, and then mixed with a roll mill at 80 to 110.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 56, good results were obtained. The fixability of this product was good as shown in Table 14.

Example 58 Example 5 except that the oxidized free wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 56.
A developer was obtained in the same manner as in 6. Next, this developer was subjected to a continuous copy test in the same manner as in Example 56, and good results were obtained. The fixability of this product was good as shown in Table 14.

Comparative Example 21 A developer was prepared in the same manner as in Example 57 except that the montan ester wax of Example 57 was not used, and a continuous copy test was conducted. Occurred and a good image was not obtained.

Comparative Example 22 Polyester Resin Production A polyester resin prepared in Comparative Example 1 was used in place of the polyester resin of Example 56, and a developer was prepared in the same manner as in Example 56, and a continuous copy test was conducted. , The fixing lower limit temperature was high and the fixing property was insufficient, and a good image was not obtained.

Example 59 A developer was obtained in the same manner as in Example 56 except that the polyester resin prepared in Polyester Resin Production Example 2 was used instead of the polyester resin of Example 56. When a continuous copy test was conducted on this developer in the same manner as in Example 56, good results were obtained. The fixability of this product was good as shown in Table 14.

Example 60 A developer was obtained in the same manner as in Example 56 except that the polyester resin prepared in Production Example 3 was used instead of the polyester resin in Example 56. A continuous copy test was conducted on this developer in the same manner as in Example 56.
Good results were obtained as in No. 6. The fixability of this product was good as shown in Table 14.

Example 61 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue colorant (III) -3 2 parts in Table 1 CI Pigmennt Yellow 17 6 parts Using 2 parts of the compound of the general formula (V) in which Me is Zn, a developer was obtained in the same manner as in Example 56. Next, this developer was subjected to a continuous copy test in the same manner as in Example 56, and good results were obtained. The fixability of this product was good as shown in Table 14 below.

Comparative Example 23 A developer was prepared in the same manner as in Example 56 except that a chromium oxynaphthoate complex was used instead of the compound of formula (IV) in Example 56, and a continuous copy test was conducted. However, some toner fogging occurred on the background portion of the image, and a good image could not be obtained.

Comparative Example 24 Instead of CI Solvent Yellow 162 of Example 57, CI
A developer was prepared in the same manner as in Example 57 except that Pigment Yellow 1 was used, and a continuous copy test was conducted. As a result, some toner fogging occurred on the background portion of the image, and a good image was not obtained. It was

[0164]

[Table 14] Table 14

Example 62 Polyester resin (made in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts CIPigmennt Blue 15 1.5 parts CIPigmennt Yellow 17 5 parts A mixture of the above composition After thoroughly stirring and mixing in a Henschel mixer, heat and melt with a roll mill at a temperature of 80 to 110 ° C for about 40 minutes, cool to room temperature, pulverize and classify the resulting kneaded product, and toner with a particle size of 5 to 20 μm. Got This toner 3
97 parts of iron oxide powder carrier of 150 to 250 mesh (TEFV manufactured by Nippon Iron and Powder Co., Ltd.) was mixed in a ball mill to obtain a two-component developer. Next, when the developer was set in a plain paper copying machine (FT-7030 manufactured by Ricoh) equipped with a Teflon-coated roller as a fixing roller, a continuous copy test was conducted at a heat roller temperature of 190 ° C., and an offset or winding phenomenon occurred. Without fail, a good image was obtained not only in the initial stage but also after copying 100,000 sheets, and filming on the photoconductor or the developing sleeve was not observed. Further, as a fixing test, hot offset, cold offset, winding occurrence temperature and fixing lower limit temperature were measured, and good results as shown in Table 15 were obtained. Also, when observing the state of spent toner due to the toner of the carrier after 100,000 sheets,
No spent toner by the toner of the carrier was observed.

Example 63 Polyester resin (made in Polyester resin production example 1) 85 parts Montane ester wax (acid value 12.0) 3 parts CI Pigmennt Blue 15 2 parts CISolvent 162 5 parts Compound 2 of formula (IV) Parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer in the same manner as in Example 62, and then mixed with a roll mill at 80 to 110.
After heating and melting at a temperature of 40 ° C. for about 40 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a toner having a particle size of 5 to 20 μm. 3.5 parts of this toner was mixed with 96.5 parts of a ferrite carrier coated with a silicone resin in a ball mill to obtain a two-component developer. When a continuous copy test was conducted using this developer in the same manner as in Example 62, the same good results as in Example 62 were obtained. The fixability of this product was good as shown in Table 15.

Example 64 Example 6 was repeated except that an oxidized rice wax having an acid value of 15 was used in place of the released free fatty acid type carnauba wax of Example 62.
A developer was obtained in the same manner as in 2. Next, this developer was subjected to a continuous copy test in the same manner as in Example 62, and good results were obtained. The fixability of this product was good as shown in Table 15.

Example 65 A developer was obtained in the same manner as in Example 62 except that the polyester resin prepared in Production Example 2 of polyester resin was used instead of the polyester resin of Example 62. Successive copy tests were conducted on this developer in the same manner as in Example 62, and good results were obtained. The fixability of this product was good as shown in Table 15.

Example 66 A developer was obtained in the same manner as in Example 62 except that the polyester resin prepared in Production Example 3 was used in place of the polyester resin in Example 62. Successive copy tests were conducted on this developer in the same manner as in Example 62, and good results were obtained. The fixability of this product was good as shown in Table 15.

Example 67 Polyester resin (prepared in Polyester Resin Production Example 1) 81 parts Defreeized fatty acid type carnauba wax (acid value 2) 4 parts Blue colorant (III) -3 2 parts in Table 1 CI Pigmennt Yellow 17 5 parts A developer was obtained in the same manner as in Example 62 except that 2 parts of the compound of the general formula (V) in which Me was Zn was used. Next, this developer was subjected to a continuous copy test in the same manner as in Example 62, and good results were obtained. The fixability of this product was good as shown in Table 15.

[0171]

[Table 15] Table 15

[0172]

EFFECT OF THE INVENTION The dry toner of the present invention has sufficient offset resistance and wrapping resistance and can be fixed at a low temperature.
High-speed fixing is possible, and the dispersibility of the release agent in the binder resin is good, so there is little toner filming on the photoreceptor and developing sleeve during development, and there is no carrier contamination by spent toner, and it is stable for a long period of time. Therefore, there is an advantage that a high quality image can be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location G03G 9/08 9/113 G03G 9/08 361 365 9/10 352 (72) Inventor Masanori Suzuki Tokyo 1-3-6 Nakamagome, Ota-ku, Tokyo (72) Inventor Yasutaka Iwamoto 1-3-6 Nakamagome, Tokyo Ota-ku, Tokyo (72) Inventor, Chiharu Mochizuki Nakata, Ota-ku, Tokyo Magome 1-3C6 Inside Ricoh Co., Ltd.

Claims (4)

[Claims] 1. An electrophotographic toner comprising a binder resin, a colorant, a charge control agent and a release agent as main components, wherein the binder resin comprises a diol component represented by the following general formula (I) and a divalent compound. As a compound selected from the group consisting of the above polyvalent carboxylic acids, their anhydrides and their lower alkyl esters, 1 to 50 mol% of a divalent carboxylic acid represented by the following general formula (II) or its anhydride and trimetic acid Or a polyester resin obtained by condensing an anhydride thereof with an acid component containing 10 to 30 mol%, wherein the releasing agent is (a) a free fatty acid type carnauba wax having an acid value of 5 or less; ) Montane ester wax and (c) acid value
An electrophotographic toner comprising at least one wax selected from the group consisting of 10 to 30 oxidized rice waxes. [Chemical 1] [Chemical 2] 2. The colorant is at least one set of red-based colorants selected from the combination of the following (A) group, and at least one type or one set of blue-based colorant selected from the group (B). The toner for electrophotography according to claim 1, which is a colorant or at least one set of green colorants selected from the group (C). (A) Group red colorants CI Pigment Red 48 and CI Pigment
ent Red 57: 1, CI Pigment Red
122, C. I. Pigment Red 112, C. I.
Solvent 49 or CI Pigment Vi
Combination with one of olet38. Blue colorant of group (B) Colorant of general formula (III) alone or CI Pigme
ntBlue15 and CI Pigment Red 5
Combination with 7: 1. [Chemical 3] Green colorant of group (C) The colorant of the general formula (III) or CI Pigmen
One of t Blue 15 and CI Pigment
Yellow 17 or CI Solvent Ye
Combination with one of the low 162. 3. The charge control agent comprises at least the following formula (I
The toner for electrophotography according to claim 1 or 2, which is one of the compounds represented by formula (V), the general formula (V), or the general formula (VI). [Chemical 4] [Chemical 5] In the formula, R ₃ , R ₄ and R ₅ are hydrogen or an alkyl group having 1 to 10 carbon atoms or an allyl group, and particularly preferably hydrogen or an alkyl group having 1 to 6 carbon atoms or an allyl group. Here, R ₃ , R ₄ and R ₅ may be the same or different at the same time. Further, Me is zinc, nickel, cobalt, copper,
Any metal selected from chrome. [Chemical 6] In the formula, x and y are integers, and n = x + y
Is 4 to 8 and R _{1 to} R ₅ and R _{11 to} R ₁₅ are as shown below. R ₁ : a hydrogen atom, an alkyl group having _{1 to 5} carbon atoms, or-
(CH ₂ ) mCOOR ₁₀ (R ₁₀ is a hydrogen atom or a lower alkyl group, m is an integer of 1 to 3) group, R ₂ : a hydrogen atom, a halogen atom, or an optionally branched C 1 to C 12 group. Alkyl group, aralkyl group, -N
_{O 2, -NH 2, -N (} R 7) 2 (R 7 is a lower alkyl _{group), - SO 3 R 8 (} R 8 is a hydrogen atom), phenyl group which may have a substituent group or -Si, _{(CH 3) 3, R 3} , R 4: a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -NH ₂ or _{-N, (R 9) 2 (} R 9 is a lower alkyl group), R ₅ : Hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ₁₁ : hydrogen atom, alkyl group having 1 to 5 carbon atoms or-
(CH ₂ ) pCOOR ₂₀ (R ₂₀ represents a hydrogen atom or a lower alkyl group, p is a group representing an integer of 1 to 3), R ₁₂ : hydrogen atom, halogen atom, optionally branched carbon number 1-12 alkyl groups, aralkyl groups, -N
_{O 2, -NH 2, -N (} R 17) 2 (R 17 is a lower alkyl _{group), - SO 3 R 18 (} R 18 is a hydrogen atom), phenyl group which may have a substituent group or -Si, _{(CH 3) 3, R 13} , R 14: a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, -NH ₂ or _{-N, (R 19) 2 (} R 9 is a lower alkyl group), R ₁₅ : Hydrogen atom, halogen atom, alkyl group having 1 to 3 carbon atoms, 4. An electrophotographic developer obtained by mixing the electrophotographic toner according to claim 1 or 2 with a carrier having a core material coated with a silicone resin.