JP3137738B2 - Toner for developing electrostatic images - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic image in electrophotography, electrostatic recording and the like. The present invention relates to a colorant among them, and further relates to a toner that dyes powder particles with the colorant.

[0002]

2. Description of the Related Art In recent years, in order to improve the image quality and durability of an electrophotographic system, the toner has a small particle size, a sharp particle size distribution,
Sufficient coloring power and uniform charge control are required. The toner for electrostatic charge development is usually manufactured by melt-kneading a thermoplastic resin and a colorant, pulverizing, and then classifying. In the case where the toner manufactured in this way is intended to obtain a small particle size and a narrow particle size distribution, the production capacity and the yield are significantly reduced, and the cost is increased, as well as the smaller the particle size, Poor toner charging characteristics due to uneven dispersion of the charge control agent and the colorant occur. In addition, the surface shape of the particles obtained by the pulverization has considerably many protrusions, and the particles easily adhere to the carrier or the member for thinning the toner. Further, there is a disadvantage that an expensive charge control agent or the like which originally exhibits a function on the toner surface is also contained in the toner, resulting in high cost.

[0003] Therefore, many proposals have been made regarding a toner which provides high image quality and high durability and a method for producing the same. For example, it is known to form a nucleus particle containing a color pigment and a charge control agent by a suspension polymerization method in Japanese Patent Publication No.
No. -14895 and Japanese Patent Publication No. 47-51830, this method is difficult to remove a dispersion stabilizer or the like adhering to the surface, and is liable to cause charging deterioration. It is difficult to stably produce a product having a sharp particle size and a sharp particle size distribution. It has been proposed in Japanese Patent Publication Nos. 57-494 and 56-13945 to form core particles containing a pigment and a charge controlling agent therein by a spray granulation method. It is very difficult to control the particle size and requires classification after granulation, or it is effective in preventing the occurrence of offset (development that transfers to the plastic sheet when the formed fixed toner image is stored over the plastic sheet). It has a disadvantage that a high-molecular resin cannot be used.

On the other hand, as a method for obtaining a uniform particle diameter, a seed polymerization method in which particles are formed and then particles are grown by polymerization, or a dispersion method in which a monomer is a good solvent but a polymer is polymerized using a solvent which is a poor solvent. Polymerization methods are known, but these polymerization methods can provide resin particles with a sharp particle size distribution and small particle size, but it is difficult to add carbon black and other colorants internally. There is. For example, JP-A-61-18965 discloses a method of forming a coating layer such as a colorant on the surface of a dispersed polymer particle using a jet mill apparatus, and JP-A-63-2075, JP-A-63-23166 and JP-A-63-23166. 63-2440
No. 57 proposes a method of embedding a pigment in a thermoplastic resin by applying mechanical strain to it.However, such a method does not provide sufficient coloring power, and the toner is affected by the colorant present on the surface. There are problems such as poor fixability and occurrence of offset. Further, JP-A-50-46333, JP-A-61-228458, JP-A-63-106667, and JP-A-1-103631 each propose a method of dyeing resin particles in a dye solution. Those colored by this method are dyed up to the inside of the resin with a dye, and therefore have a small amount of the dye present on the surface of the resin particles, so that the method is preferable in that the fixability and the anti-offset property are good. However, no dye exhibiting sufficient coloring power was found in this dyeing method.

[0005]

SUMMARY OF THE INVENTION The present invention provides an electrophotographic toner in which the above-mentioned disadvantages are improved. A first object of the present invention is to provide a stable toner using a colorant having excellent dispersibility and excellent fastness to heat and light. A second object of the present invention is to provide a dyed toner having excellent reliability. A third object is to provide a low-cost toner having high image quality and high durability by using a toner having a sharp particle size distribution and a small particle size.

[0006]

According to the present invention, in a toner for developing an electrostatic image mainly containing a thermoplastic resin and a colorant, the colorant is at least one of the compounds represented by the general formula (I). And a toner for developing an electrostatic image, characterized by comprising:

Embedded image And X represents a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group. Y is a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a chlorine atom, a bromine atom, a fluorine atom, -NHCOCH ₃ -,-
_{NHCOC 2 H 5 -, - NHCOC} 3 H 7 -, - NHSO 2
CH ₃ - represents, R _1, R ₂ is an alkyl group, an alkenyl group, hydroxyalkyl group, alkoxyalkyl group,
Phenoxyalkyl group, cyanoalkyl group, chloroalkyl group, bromoalkyl group, acyloxyalkyl group,
Represents an alkoxycarbonyloxyalkyl group, a benzoyloxyalkyl group, a phenoxycarbonyloxyalkyl group, an alkoxycarbonylalkyl group, a phenoxycarbonylalkyl group, a carbonyl ester alkyl group, a chlorohydroxyalkyl group, an aryl group, a cyclohexyl group or a benzyl group. R ₃ is a hydrogen atom, a cyano group, a nitro group, a chlorine atom, a bromine atom, a fluorine atom,
R ₄ and R ₅ represent a hydrogen atom, an alkyl group, a cyano group, a nitro group, a chlorine atom, a bromine atom or a fluorine atom. )

According to the present invention, there is provided a toner for developing an electrostatic image mainly comprising a thermoplastic resin and a colorant, wherein the colorant is a compound represented by the following formula (II): A developing toner is provided.

[0008]

Embedded image (Wherein R ₇ and R ₈ are an alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a lower alkoxy group, a lower alkoxycarbonyloxy group, a lower alkylcarbonyloxy group, a lower alkoxycarbonyl group, a phenoxy group, a chloro group, A lower alkylcarbonyloxy group, a chlorine atom, a bromine atom, a lower alkyl group substituted with a lower alkylamino group or an allyloxycarbonyl group, a cyclohexyl group, a benzyl group or an allyl group, and R ₉ is a methyl group or an ethyl group Wherein R ₁₀ is a hydrogen atom and has 1 carbon atom
To 4 alkyl group, a lower alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group, R _11,
R ₁₂ and R ₁₃ represent a nitro group, a chlorine atom, a bromine atom, a fluorine atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group)

Further, the present invention is characterized in that the powder particles mainly composed of the thermoplastic resin are dyed with the compound of the formula (I) or (II). Further, the invention is characterized in that the thermoplastic resin is a polyester resin. In the present invention, the powder particles mainly composed of the thermoplastic resin are spherical particles, the volume average particle diameter Dv is 3 to 9 μm, and the ratio Dv / Dp of the volume average particle diameter Dv to the number average particle diameter Dp. Is in the range of 1.00 to 1.15. Further, the present invention is characterized in that a layer containing a charge control substance and a release material is provided on the surface of the toner.

The compound represented by the general formula (I) of the present invention is produced by a known method as follows. That is, the amine component represented by the general formula (III) is diazotized to form the general formula (I
The monoazo compound represented by the general formula (I) is obtained by adding to a solution of the coupling component represented by V) and performing a coupling reaction.

[0011]

Embedded image [D and R ₁ , R ₂ , X and Y in the formulas (III) and (IV) are
Same as (I). More specific examples of the compound of the general formula (I) thus obtained include those shown in Table 1.

[0012]

[Table 1]

The compound of the present invention represented by the formula (II) is produced by a known method as follows. That is, after diazotizing the amine component represented by the formula (V), the formula (V)
The monoazo compound represented by the formula (II) is obtained by adding to the solution of the coupling component represented by I) and causing a coupling reaction.

[0014]

Embedded image [R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R _{12 in the} formulas (V) and (VI)]
And R ₁₃ conform to formula (II). More specific examples of the compound of the general formula (II) thus obtained include those shown in Table 2.

[0015]

[Table 2] Table 2

As the thermoplastic resin used in the present invention, polyester resins, epoxy resins, polyurethane resins and polymers or copolymers of the following monomers can be used. For example, styrene, parachlorostyrene, vinyltoluene, vinyl chloride, vinyl bromide, vinyl fluoride, vinyl acetate, vinyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, (meth)
Propyl acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Lauryl (meth) acrylate, (meth) acrylic acid 2
-Hydroxyethyl, hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, (meth) acrylic acid, vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether, vinyl Examples include methyl ketone, N-vinylpyrrolidone, N-vinylpyridine, ethylene, propylene, butadiene, and the like.

Since the polyester resin has a sharp softening temperature and high transparency, it is excellent as a resin for a color image toner for superimposing colors. By combining the dye of the present invention with a polyester resin, high image quality can be obtained. Color toner is obtained.

As a method for obtaining a toner, a method of kneading and pulverizing a polymer or copolymer of the above-mentioned resin and the above-mentioned monomer with a colorant or a polarity control agent, or a method of mixing the above-mentioned monomer together with a colorant or polarity control, etc. Although a method of suspension polymerization is possible, in the present invention, a method of dyeing a monomer obtained by a seed polymerization method or a dispersion polymerization method with a colorant solution is preferable. As a method of dyeing resin particles with a colorant, a method of dispersing a disperse dye and resin particles in water to heat and dye, or a method of dissolving the dye in an organic solvent and dyeing the resin particles in a solvent is used. However, when dyeing using the coloring agent of the present invention, solvent dyeing is preferred.

As the solvent used here, general-purpose organic solvents can be used, and alcohol solvents such as methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, i-butyl alcohol and t-butyl alcohol are used. Solvents are preferred, and depending on the solubility of the resin, it is also possible to add another solvent to the alcohol solvent and dye with a mixed solvent, or dye with a system to which a surfactant or an alcohol-soluble polymer is added.

The ratio of the resin particles to the colorant depends on the monomer composition, the particle size of the resin particles and the structure of the colorant, but is preferably about 3 to 7% by weight based on the resin particles. The amount of the solvent is preferably about 3 to 10 times the weight of the resin particles.

The colorant of the present invention may be used alone, or may be used in combination with other dyes to adjust the color tone. The following are mentioned as these dyes. CI SOLVENT YELLOW (6,9,17,31,35,100,102,105), CI SOLVENT orange (2,7,13,14,66), CI SOLVENT RED (5,16,17,18,19,22,23,143,145,146,1
49,150,151,157,158), CI SOLVENT VIOLET (31,32,33,37), CI SOLVENT BLUE (22,63,78,83-86,91,94,95,104), CI SOLVENT GREEN (24,25), CI SOLVENT BROWN ( In the case of the present invention, the amount of the dye is at least 1
It needs to be 0% or more.

A coating layer of a charge controlling agent or a release material may be provided on the surface of the dyed particles.

Examples of the charge control agent include nigrosine, an azine dye having an alkyne group having 2 to 16 carbon atoms (Japanese Patent Publication No. Sho.
No. 2-1627), basic dyes such as C.I. I. B
asic Yellow 2 (CI.41000), C.I. I.
Basic Yellow 3, C.I. I. Basic Red 1 (C.I.
I. 45160), C.I. I. Basic Red 9 (CI.
42500), C.I. I. Basic Violet 1 (C.I.
I. 42535), C.I. I. Basic Violet 3
(CI. 42555), C.I. I. Basic Violet1
0 (CI. 45170), C.I. I. Basic Violet
14 (CI. 42510), C.I. I. Basic Blue
1 (CI. 42025), C.I. I. Basic Blue
3 (CI. 50005), C.I. I. Basic Blue 5
(C.I. 42140), C.I. I. Basic Blue 7
(CI. 42595), C.I. I. Basic Blue 9
(CI. 52015), C.I. I. Basic Blue 24
(CI. 52030), C.I. I. Basic Blue 2
5 (CI52025) C.I. I. Basic Blue 2
6 (CI44045), C.I. I. Basic Green1
(C.I. 42040), C.I. I. Basic Green 4
(CI.42000) and the like, and lake pigments of these basic dyes (as a lake-forming agent, phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, tannic acid,
Lauric acid, gallic acid, ferricyanide, ferrocyanide, etc.), C.I. I. Solvent Black 3 (C.I.
I. 26150), Hansa Yellow G (CI.116)
80), C.I. I. Mordant Black 11, C.I. I.
Pigment Black 1 benzoylmethyl-hexadecylammonium chloride, decyl-trimethylaluminum chloride, or a dialkyltin borate compound such as dibutyl or dioctyl, a guanidine derivative,
Polyamine resins such as amino group-containing vinyl polymers and amino group-containing condensation polymers,
-20153, 43-27596, 44-6
Nos. 397 and 45-26478, metal complex salts of monoazo dyes described in JP-B-55-42752, JP-B-54-415080, JP-B-58-7384, and JP-B-59-7385. Of salicylic acid, dialkylsalicylic acid, naphthoic acid and dicarboxylic acid
Metal complexes such as n, A1, Co, Cr, and Fe; and sulfonated copper phthalocyanine pigments.

Examples of the releasing material include low-molecular-weight polyolefins such as low-molecular-weight polyethylene, low-molecular-weight polypropylene, polyethylene oxide, beeswax, carnauba wax, and the like.
Examples include natural waxes such as montan wax, higher fats such as stearic acid, palmitic acid and myristic acid, metal salts of higher fatty acids, and higher fatty acid amides. These may be used alone or in combination of two or more, but a low molecular weight polyolefin such as polypropylene is preferred.

As a method for coating the above-mentioned charge controlling agent or release material, a generally known method can be adopted. For example, the dyed particles and a charge control agent or a release agent are mixed and adhered in a wet or dry system, and by applying mechanical energy to the mixture, a resin-coated colorant is driven into the surface of the powder particles and coated. Good. Here, the method of applying mechanical energy includes a method of applying a grinding force, a method of applying an impact force to a mixture by a high-speed rotating blade, and a method of causing particles to collide with each other or particles in a high-speed air stream. Specific driving devices include Mechanofusion (Hosokawa Micron), an I-type mill (Nippon Pneumatic Industries), a device in which the grinding air pressure is lower than in the case of normal grinding, a turbo mill (Turbo Kogyo), a hybridizer (Nara) Machine Works), a cosmomizer (Nara Machine Works), an automatic mortar, and the like.

The production examples of the resin used in the present invention are described below. Production Example 1 15 parts of polyacrylic acid was dissolved in 150 parts of methanol,
After the inside of the reaction vessel was purged with nitrogen gas using nitrogen gas, a solution prepared by dissolving 0.82 part of azobisisobutyronitrile in 52 parts of styrene was added, and the mixture was stirred at 60 ° C. for 8 hours to carry out dispersion polymerization and left at room temperature for 24 hours. After the supernatant was removed by decantation, 100 parts of methanol was added, followed by stirring for 30 minutes, followed by filtration and drying to obtain 49 parts of a white powder. The volume average particle size (Dv) of this powder is 7.36 μm and the number average particle size (Dv)
The ratio Dv / Dp to p) was 1.09, and the particle size distribution was sharp.

Production Examples 2 to 9 The following monomers were used in place of styrene in Production Example 1,
Otherwise, polymerization was carried out in the same manner as in Production Example 1, and the results shown in Table 3 were obtained.

[0028]

[Table 3] Table 3 However, St; styrene, n-BMA; n-butyl methacrylate, 2-EHMA; 2-ethylhexyl methacrylate, nBA; n-butyl acrylate, MA; methyl acrylate, AA; acrylic acid, 4VPy;

Production Example 10 5 parts of polyacrylic acid was dissolved in 150 parts of methanol, and the inside of the reaction vessel was replaced with nitrogen by using nitrogen gas. Then, a solution of 0.82 part of azobisisobutyl nitrite dissolved in 52 parts of styrene was added. The mixture was stirred at 60 ° C. for 8 hours to carry out dispersion polymerization, left at room temperature for 24 hours, decanted to remove the supernatant, 100 parts of methanol was added, and the mixture was stirred for 30 minutes, filtered, dried and dried to obtain 49 parts of a white powder. I got The volume average particle diameter (Dv) of this powder is 10.08 μm and the number average particle diameter (Dv)
The ratio Dv / Dp to p) was 1.35.

Production Example 10 Production Example of Polyester Resin Polyoxypropylene (2,2) -2,2-bis (4-hydroxyphenyl) propane 900 parts Fumaric acid 70 parts 60 parts n-Dodecenylsuccinic anhydride 53.4 parts The mixture was placed in a flask and heated to 230 ° C. in an electric heating mantle, and reacted while stirring in a nitrogen stream. The acid value at the time 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 allowed to proceed for about 8 hours. When the acid value reached 20, the reaction was completed. The softening point of the obtained resin was 120 ° C. The obtained solid tree finger is pulverized and classified to have a volume average particle diameter of 3 to 9 μm and a Dv / D
p was obtained as 1.13.

[0031]

The present invention will be described below with reference to examples. The following parts are all parts by weight. Example 1 100 parts polyester resin (Preparation Example 10) 100 parts Compound No. 1 in Table 1 3 parts 3,5 Di-t-tert-butyl zinc salicylate 1 part mixture Was heated and kneaded with a hot roll to obtain a toner having a volume average particle size of 8 μm. Three parts of this toner was mixed with 100 parts of the iron powder carrier to obtain a developer. This developer is placed in a magnetic brush developing device of a copying machine (FT4060 manufactured by Ricoh Company), and the electrostatic latent image formed on the selenium photoreceptor by a normal electrophotographic method is developed and transferred to paper and Mylar.
The images were fixed and red images were obtained. When the copied image transferred to paper was exposed for 5 hours with a fade meter, no discoloration or fading was observed. When the haze of the copied image transferred to Mylar was measured, it was 25 and the transparency was excellent.

[Example 2] No. 2 in Table 1 above. Preparation Example by dissolving 0.5 part of compound 3 in 100 parts of methanol
10 parts of the resin particles obtained in 1 were added, and the mixture was stirred for 1 hour under hot reflux to perform dyeing. Then, the mixture was cooled to room temperature and filtered by suction to obtain a red colored powder. 10 parts of the colored resin particles and 3,
After stirring with 0.1 part of 5 ditertiary butyl zinc salicylate and an Ooster blender for 5 minutes, the number of rotations was 1 at hybridization NHS-O (Nara Machinery).
After processing at 000 rpm for 5 minutes, a red toner was obtained.
Three parts of this toner were mixed with 100 parts of the iron powder carrier, and this developer was loaded into a copying machine (FT4060, manufactured by Ricoh Co.) and copied to obtain a clear red copied image.
In order to examine the sublimation property, a polyester film was brought into close contact with the image surface of the copied image and placed in a thermostat set at 100 ° C. for 5 hours. As a result, the dye subliming on the polyester film was visually determined. It had not migrated at all. Separately, when the copied image was exposed to a fade meter for 5 hours, no discoloration or fading was observed. Further, the haze was measured after transferring and fixing to Mylar in the same manner as in Example-1.

Example 3 Resin 10 obtained in Production Example 2
Was dispersed in 35 parts of methanol, and the internal temperature was maintained at 50 ° C.
No. 0.5 part of the compound of No. 10 was added little by little, and the mixture was stirred for 8 hours, cooled to room temperature and filtered to obtain a blue colored powder. 10 parts of the colored powder is dispersed in 100 ml of ion-exchanged water, 1 part of a carnauba wax emulsion (solid content: 20%) is added little by little to the dispersion, and the mixture is stirred at room temperature for 1 hour, filtered and dried, and dried on a blue powder. After wax was applied to the surface, 0.1% zinc 3,5 di-tert-butylsulfate was added.
The mixture was stirred with an Ooster blender for 5 minutes, and then treated with hybridization NHS-O (manufactured by Nara Machinery) at 10,000 rpm for 5 minutes to obtain a blue toner. Three parts of this toner was mixed with 100 parts of the iron powder carrier, and this developer was copied in the same manner as in Example 1 to obtain a clear blue copied image. Further, as a result of repeatedly performing a copy test on 10,000 sheets using this developer, a copy image in which the line image and the photographic image were favorably maintained during the test was obtained.

Examples 4 to 8 Using the resins and coloring agents shown in Table 4, colored powders dyed under the same conditions as in Example 3 were obtained. Thereafter, the blue powder was treated in the same manner as in Example 3 to obtain respective colored toners. Table 4 shows the results of examining the amount of dyeing, light fastness, and sublimability of these toners.

[Comparative Examples 1-2] Using an oil-soluble dye other than the present invention (Solvent Yellow 14, Solvent Blue 25), dyeing was carried out under the same conditions as in Example 3, and the results are shown in Table 4. .

[0036]

[Table 4] Table 4

The evaluation method in Table 4 is as follows. Dyeing amount: 0.1 g of the dyed product was dissolved in 50 ml of acetone, the absorbance of the absorption spectrum was measured, and the dyeing was determined from the calibration curve of the dye. Xenon tester (Shimadzu XW-15)
After 10 hours of light irradiation using (0), the determination was made by visual observation. ：: Little color change before and after irradiation. X: There is a color change before and after irradiation. Sublimation property; polyester film adhered to powder 7
It was set to 0 ° C. The dye sublimated on the polyester film was placed in a thermostat for 5 hours and visually judged. A: No sublimation is observed. B: Sublimation is observed. Transparency; expressed as haze of the toner image transferred to Mylar.

Example 9 Resin 10 obtained in Production Example 6
Was dispersed in 35 parts of methanol, and the internal temperature was maintained at 50 ° C.
No. 16 parts of the compound 0.4, 0.17 parts of Yellow # 818 (Yamamoto Kasei) and 0.1 parts of PS Red G (Mitsui Dye Chemical) are added little by little, and the mixture is stirred for 8 hours, cooled to room temperature, filtered and blackened. A colored powder was obtained. 10 parts of the colored powder is dispersed in 100 ml of ion-exchanged water, and a carnauba wax emulsion (solid content: 20%) is added to the dispersion.
%) Was added little by little, stirred at room temperature for 1 hour, filtered and dried to deposit a wax on a black powder, and 0.1 part of a metal-containing azo dye (manufactured by Orient Chemical, S-34) was added. Was stirred and mixed in an Ooster blender for 5 minutes, and then treated with hybridization NHS-0 (manufactured by Nara Kikai Seisakusho) at 10,000 rpm for 5 minutes to obtain a black toner. Three parts of this toner was mixed with 100 parts of the iron powder carrier, and this developer was copied in the same manner as in Example 1 to obtain a clear black copied image. Further, as a result of repeated copying test of 10,000 sheets using this developer,
During the test, a copy image in which the line image and the photographic image were well maintained was obtained.

Example 10 Polyester Resin (Production Example 10) 100 parts A mixture consisting of 5 parts of the compound of No. 1 and 1 part of zinc di-t-tert-butylsalicylate was kneaded with a hot roll to obtain a toner having a volume average particle diameter of 8 μm. 3 parts of this toner was mixed with 100 parts of iron powder carrier, and this developer was used in Example 1.
When a copy was made in the same manner as in Example 1, a clear blue copied image was obtained.

[Embodiment 11] No. 11 in Table 2 above. Compound 0.5 was heated and dissolved in 100 parts of methanol, 10 parts of the resin particles obtained in Production Example 1 were added, and the mixture was stirred under heat reflux for 1 hour to perform dyeing. Then, the mixture was cooled to room temperature and filtered by suction to obtain a blue colored powder. After stirring with 10 parts of the colored resin particles, 0.1 part of 3,5 di-tert-butylsalicylate zinc and 0.1 part of Ooster Blender for 5 minutes, hybridization NHS-O (Nara Machinery Co., Ltd.) at 10,000 rpm for 5 minutes. This gave a blue toner. Three parts of this toner was mixed with 100 parts of iron powder carrier, and this developer was copied in the same manner as in Example 1. As a result, a clear blue copied image was obtained. As a result of a repeated copy test of 10,000 sheets using this developer,
During the test, a copy image in which the line image and the photographic image were stably maintained was obtained.

Example 12 Resin 1 obtained in Production Example 2
0 parts was dispersed in 35 parts of methanol, and the internal temperature was maintained at 50 ° C. 0.5 part of the compound of No. 10 was added little by little, and the mixture was stirred for 8 hours, cooled to room temperature and filtered to obtain a blue colored powder. 10 parts of this colored powder was added to 100 ml of ion exchange water
1 part of a carnauba wax emulsion (solid content: 20%) was added little by little to the dispersion, and the mixture was stirred at room temperature for 1 hour, filtered and dried to deposit wax on a blue powder. Zinc tert-butyl salicylate 0.
After stirring 1 part with an Ooster blender for 5 minutes, hybridization NHS-O (Nara Machinery Co., Ltd.)
For 5 minutes at 10,000 rpm to obtain a blue toner. Three parts of this toner was mixed with 100 parts of iron powder carrier, and this developer was copied in the same manner as in Example 1. As a result, a clear blue copied image was obtained. Further, as a result of repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were well maintained during the test was obtained.

Examples 13 to 17 Using the resins shown in Table 2 and the coloring agents shown in Table 1, colored powders dyed under the same conditions as in Example 12 were obtained. Thereafter, this blue powder Example-1
The same treatment as in Example 2 was performed to obtain each colored toner. Three parts of each of these toners was mixed with 100 parts of the iron powder carrier, and this developer was copied in the same manner as in Example 1. As a result, a clear copied image was obtained. Further, as a result of repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were well maintained during the test was obtained.

Comparative Examples 3 and 4 Using oil-soluble dyes other than the present invention (Solvent Yellow 2, Solvent Blue 25), dyeing was carried out under the same conditions as in Example 12, but Comparative Example 3 was dyed. Comparative Example 4 was not dyed. The colored powder of Comparative Example 3 was treated in the same manner as in Example 12 to obtain a colored toner. Three parts of the toner were mixed with 100 parts of the iron powder carrier, and this developer was used in Example 1.
When a copy was made in the same manner as in Example 1, a clear copied image was obtained, but as shown in Table 5, the light fastness was extremely poor.

Example 8 A blue toner was obtained in the same manner as in Example 11, except that the resin of Production Example 10 having a wide particle size distribution was used instead of the resin of Production Example 1. Three parts of this toner was mixed with 100 parts of the iron powder carrier, and this developer was copied in the same manner as in Example 1. As a result, a clear blue copied image was obtained. As a result of repeated copying tests, the dyeing amount, weather resistance, and sublimability were excellent, but the image was blurred after only about 5,000 sheets. Dv / Dp which is a measure of toner particle size distribution is 1.5
It had changed to 0.

Table 5 shows the properties of the toners and toner images of Examples 13 to 18 and Comparative Examples 3 and 4. The evaluation criteria are the same as in Table 4.

[Table 5]

Examples 18 to 19 10 parts of the resin obtained in Production Example 6 were dispersed in 35 parts of methanol, and the internal temperature was kept at 50 ° C. Compound 16
4 parts, 0.17 part of Yellow # 818 (manufactured by Yamamoto Kasei) and 0.1 part of PS Red G (manufactured by Mitsui Dye Chemicals) are added little by little, and the mixture is stirred for 8 hours, cooled to room temperature, filtered, and black-colored powder. I got a body. 10 parts of this colored powder is dispersed in 100 ml of ion-exchanged water, 1 part of carnauba wax emulsion (solid content: 20%) is added little by little to this dispersion, and the mixture is stirred at room temperature for 1 hour, filtered, dried and dried to obtain a black powder. After attaching wax on the body, 0.1 part of a metal-containing azo dye (manufactured by Orient Chemical Co., S-34) was added to the blender with an osten blender for 5 minutes.
After stirring and mixing for minutes, the hybridization NHS-
O (manufactured by Nara Machinery Co., Ltd.) for 5 minutes at 10,000 rpm to obtain a black toner. Three parts of this toner was mixed with 100 parts of the iron powder carrier, and this developer was copied in the same manner as in Example 1 to obtain a clear black copied image. Further, as a result of repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were maintained favorably during the test was obtained.

[0047]

According to the present invention, in a toner for developing an electrostatic image mainly containing a thermoplastic resin and a colorant, (1) a dye having a structure specified in the present invention is used, and (2) a thermoplastic resin component is further used. (3) powder particles mainly composed of a thermoplastic resin are spherical particles having a volume average particle diameter Dv of 3 to 9 μm, and a volume average particle diameter Dv The ratio Dv / Dp of 1.05 to 1.15 is excellent in the fastness to heat and light of a toner image, and a toner having a sharp particle size distribution and a small particle size can be obtained. It is possible to provide a high quality and high durability toner.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ identification code FI G03G 9/097 G03G 9/08 344 (56) References JP-A-4-3172 (JP, A) JP-A-3-121466 ( JP, A) JP-A-64-18152 (JP, A) JP-A-63-318570 (JP, A) JP-A-3-77960 (JP, A) JP-A-3-22964 (JP, A) Hei 4-13664 (JP, A) (58) Fields surveyed (Int. Cl. ⁷ , DB name) G03G 9/08

Claims (6)

(57) [Claims] 1. An electrostatic image developing toner comprising a thermoplastic resin and a colorant as main components, wherein the colorant contains at least one compound represented by the general formula (I). Charge image developing toner. And X represents a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group. Y is a hydrogen atom, a cyano group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, a chlorine atom, a bromine atom, a fluorine atom, -NHCOCH ₃ -,-
_{NHCOC 2 H 5 -, - NHCOC} 3 H 7 -, - NHSO 2
CH ₃ - represents, R _1, R ₂ is an alkyl group, an alkenyl group, hydroxyalkyl group, alkoxyalkyl group,
Phenoxyalkyl group, cyanoalkyl group, chloroalkyl group, bromoalkyl group, acyloxyalkyl group,
Represents an alkoxycarbonyloxyalkyl group, a benzoyloxyalkyl group, a phenoxycarbonyloxyalkyl group, an alkoxycarbonylalkyl group, a phenoxycarbonylalkyl group, a carbonyl ester alkyl group, a chlorohydroxyalkyl group, an aryl group, a cyclohexyl group or a benzyl group. R ₃ is a hydrogen atom, a cyano group, a nitro group, a chlorine atom, a bromine atom, a fluorine atom,
R ₄ and R ₅ represent a hydrogen atom, an alkyl group, a cyano group, a nitro group, a chlorine atom, a bromine atom or a fluorine atom. ) 2. An electrostatic image developing toner comprising a thermoplastic resin and a colorant as main components, wherein the colorant is represented by the following formula (I).
A toner for developing electrostatic images, characterized by being a compound represented by I). (Wherein R ₇ and R ₈ are an alkyl group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a lower alkoxy group, a lower alkoxycarbonyloxy group, a lower alkylcarbonyloxy group, a lower alkoxycarbonyl group, a phenoxy group, a chloro group, A lower alkylcarbonyloxy group, a chlorine atom, a bromine atom, a lower alkyl group substituted with a lower alkylamino group or an allyloxycarbonyl group, a cyclohexyl group, a benzyl group or an allyl group, and R ₉ is a methyl group or an ethyl group Wherein R ₁₀ is a hydrogen atom and has 1 carbon atom
To 4 alkyl group, a lower alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group, R _11,
R ₁₂ and R ₁₃ represent a nitro group, a chlorine atom, a bromine atom, a fluorine atom, a cyano group, an alkyl group having 1 to 4 carbon atoms or a trifluoromethyl group. ) 3. The method according to claim 1, wherein the powder particles mainly composed of the thermoplastic resin are dyed with the compound of the formula (I) or the formula (II). For developing electrostatic images. 4. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polyester resin.
3. The toner for developing an electrostatic image according to item 1. 5. The powder particles mainly composed of the thermoplastic resin are spherical particles having a volume average particle diameter Dv of 3 to 9 μm, a ratio of the volume average particle diameter Dv to the number average particle diameter Dp, /
5. The toner according to claim 1, wherein Dp is in the range of 1.00 to 1.15. 6. The toner for developing an electrostatic image according to claim 1, wherein a layer containing a charge control substance and a release material is provided on the surface. .