JPH05181316A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain the toner, which has the excellent fastness against heat and light and of which grain diameter is small and in which distribution of grain diameter is sharp and which can obtain the high image quality and which has the improved durability, by including the specified compound in the coloring agent. CONSTITUTION:In the electrostatic charge image developing toner mainly composed of thermoplastic resin and the coloring agent, the coloring agent includes the compound expressed by a formula I. In the formula, D represents a formula II; X hydrogen atom, syano group, alkyl group having 1-4 of carbon, alkoxyl group, chlorine atom, bromine atom, fluorine atom or acetokyl group; Y hydrogen atom, syano group, alkyl group having 1-4 of carbon, alkoxyl group, chlorine atom, bromine atom, fluorine atom, -NHCOCH3, -NHCOC2H5, -NHCOC3H7, -NHSO2CH3; R1, R2 alkyl group, alkenyl group, hydroxyalkyl group, alkokyalkyl group, phenokyalkyl group or the like; and R3 hydrogen atom, syano group, nitro group, chlorine atom, bromine atom, fluorine atom or the like.

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 charge image in electrophotography, electrostatic recording and the like. The present invention relates to a colorant, and more particularly to a toner for dyeing powder particles with the colorant.

[0002]

2. Description of the Related Art In recent years, in order to improve image quality and durability of electrophotographic systems, toner particles have a smaller particle size and 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 them, and then classifying them. When it is attempted to obtain a toner having a small particle size and a narrow particle size distribution, the toner produced in this manner has a significantly reduced production capacity and yield, and the cost is high. Poor toner charging characteristics may occur due to uneven distribution of the charge control agent and the colorant. In addition, the surface shape of the particles obtained by pulverization has many protrusions, and fusion with the carrier or the toner thinning member is likely to occur. Furthermore, since an expensive charge control agent or the like that originally exerts a function on the toner surface is also contained inside the toner, there is a drawback that the cost becomes high.

[0003] Therefore, many proposals have been made regarding a toner that provides high image quality and high durability and a method for manufacturing the toner. For example, it is possible to form a core particle containing a color pigment and a charge control agent therein by a suspension polymerization method.
No. 14895 and Japanese Examined Patent Publication No. 47-51830, this method is difficult to remove the dispersion stabilizer or the like adhering to the surface and easily causes electrostatic deterioration, and is small in polymerization contained inside. It is difficult to stably produce a material having a particle size and a sharp particle size distribution. Further, it is proposed in JP-B-57-494 and JP-B-56-13945 to form core particles containing a pigment and a charge control 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 offset (development in which the formed fixed toner image is transferred to the plastic sheet when stored overlaid on the plastic sheet) It has the drawback of not being able to use various polymer resins.

On the other hand, as a method for obtaining a uniform particle size, a seed polymerization method in which particle species are formed and then particles are grown by polymerization, or a dispersion in which a monomer is a good solvent but a polymer is a poor solvent is used for polymerization. Polymerization methods are known, but although these polymerization methods can obtain resin particles with a sharp particle size distribution and small particle diameters, it is difficult to internally add carbon black and other colorants, so various conventional proposals have been made. There is. For example, JP-A-61-18965 discloses a method of forming a coating layer such as a coloring agent on the surface of dispersed polymer particles using a jet mill apparatus, JP-A-63-2075, JP-A-63-23166 and JP-A-63-23166. 63-2440
57, a method of embedding a pigment in a thermoplastic resin by applying a mechanical strain is proposed, but such a method does not provide sufficient coloring power, and the colorant present on the surface affects the toner. There are problems such as poor fixability and occurrence of offset. Further, JP-A-50-46333, JP-A-61-228458, JP-A-63-106667, JP-A 1-103631 each propose a method of dyeing resin particles in a dye solution, The one colored by this method is dyed even inside the resin with a dye. Therefore, since the amount of the dye present on the surface of the resin particles is small, the fixing property and the offset resistance are good, and this is a preferable method. However, no dye showing 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 drawbacks have been improved. A first object of the present invention is to provide a toner having good stability using a colorant having excellent dispersibility and fastness to heat and light. A second object of the present invention is to provide a dyed type toner having excellent reliability. A third object is to provide a high image quality and high durability toner at low cost 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 charge image containing a thermoplastic resin and a colorant as main components, the colorant is at least one compound represented by the following general formula (I). A toner for developing an electrostatic charge image, which comprises:

[Chemical 1] 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, -N
_{HCOC 2 H 5, -NHCOC 3 H} 7, represents _{-NHSO 2 CH 3, R 1,} R 2, R 6 is an alkyl group, an alkenyl group,
Hydroxyalkyl group, alkoxyalkyl group, phenoxyalkyl group, cyanoalkyl group, chloroalkyl group, bromoalkyl group, acyloxyalkyl group, alkoxycarbonyloxyalkyl group, benzoyloxyalkyl group, phenoxycarbonyloxyalkyl group,
It represents 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 represents a hydrogen atom, a cyano group, a nitro group, a chlorine atom, a bromine atom, a fluorine atom, a trifluoromethyl group, an alkyl group or an alkoxy group, and R ₄ and R ₅ represent a hydrogen atom, an alkyl group, a cyano group, a nitro group. Represents a group, chlorine atom, bromine atom or fluorine atom)

Further, according to the present invention, in the toner for developing an electrostatic charge image containing a thermoplastic resin and a colorant as main components, the colorant is a compound represented by the following formula (II). A developing toner is provided.

[0008]

[Chemical 2] (In the formula, R ₇ and R ₈ are alkyl groups having 1 to 4 carbon atoms, cyano groups, hydroxyl groups, lower alkoxy groups, lower alkoxycarbonyloxy groups, lower alkylcarbonyloxy groups, lower alkoxycarbonyl groups, phenoxy groups, chloro groups. Represents a lower alkylcarbonyloxy group, a chlorine atom, a bromine atom, a lower alkylamino group or a lower alkyl group substituted with an allyloxycarbonyl group, a cyclohexyl group, a benzyl group or an allyl group, and R ₉ represents a methyl group or an ethyl group. R ₁₀ is a hydrogen atom and has 1 carbon atom.
Represents an alkyl group, a lower alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group represented by 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 powder particles containing the thermoplastic resin as a main component are dyed with a compound of the formula (I) or (II). Further, the present invention is characterized in that the thermoplastic resin is a polyester resin. Further, in the present invention, the powder particles containing the thermoplastic resin as a main component are spherical particles and have a volume average particle diameter Dv of 3 to 9 μm, and a ratio Dv / Dp of the volume average particle diameter Dv and 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 releasing substance is provided on the toner surface.

The compound represented by the general formula (I) of the present invention is produced as follows by a known method. 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 the solution of the coupling component represented by V) and conducting a coupling reaction.

[0011]

[Chemical 3] [D and R ₁ , R ₂ , X and Y in Formula (III) and Formula (IV) are defined by
According to (I). More specific examples of the compound of formula (I) thus obtained include those shown in Table 1.

[0012]

[Table 1] Table 1

The compound represented by the formula (II) of the present invention 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 conducting the coupling reaction.

[0014]

[Chemical 4] [R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R _{12 of} Formula (V) and Formula (VI)]
And R ₁₃ conform to the 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, a polyester resin, an epoxy resin, a polyurethane resin or a polymer or copolymer 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 Methyl ketone, N-vinyl pyrrolidone, N-vinyl pyridine, ethylene, propylene, butadiene, etc. are mentioned.

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 and a polyester resin, a high image quality can be obtained. A color toner for use is obtained.

As a method of obtaining a toner, a method of kneading and pulverizing a polymer or copolymer of the above resin and the above monomer and a colorant, a polarity control agent, etc., or a method in which the above monomer is combined with a colorant, polarity control, etc. A method of suspension polymerization is also possible, but in the present invention, a method of dyeing particles obtained by a seed polymerization method or a dispersion polymerization method of a monomer with a colorant solution is preferable. As a method for dyeing resin particles with a coloring agent, a method of dispersing and heating a disperse dye and resin particles in water and dyeing, or a solvent dyeing method in which a dye is dissolved in an organic solvent to dye the resin particles in a solvent When dyeing with the colorant of the present invention, solvent dyeing is preferred.

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

The ratio of the resin particles to the colorant is preferably about 3 to 7 wt% with respect to the resin particles, although it depends on the monomer composition of the resin particles, the particle size and the structure of the colorant. 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 another dye in order to adjust the color tone. Examples of these dyes include the following. 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 addition amount of the above dye is at least 1
It should be 0% or more.

A coating layer of a charge control agent or a releasing material may be provided on the surface of the particles thus dyed.

As the charge control agent, nigrosine, an azine dye containing an alkyne group having 2 to 16 carbon atoms (Japanese Patent Publication No.
2-1627), basic dyes such as C.I. I. B
asic Yellow 2 (C.I. 41000), C.I. I.
Basic Yellow 3, C.I. I. Basic Red 1 (C.
I. 45160), C.I. I. Basic Red 9 (C.I.
42500), C.I. I. Basic Violet 1 (C.
I. 42535), C.I. I. Basic Violet 3
(C.I. 42555), C.I. I. Basic Violet1
0 (C.I. 45170), C.I. I. Basic Violet
14 (C.I. 42510), C.I. I. Basic Blu
e 1 (C.I. 42025), C.I. I. Basic Blue
3 (C.I. 51005), C.I. I. Basic Blue
5 (C.I. 42140), C.I. I. Basic Blue
7 (C.I. 42595), C.I. I. Basic Blue
9 (C.I. 52015), C.I. I. Basic Blue 2
4 (C.I. 52030), C.I. I. Basic Blue
25 (C.I. 52025) C.I. I. Basic Blue
26 (C.I. 44045), C.I. I. Basic Green
1 (C.I. 42040), C.I. I. Basic Green
4 (C.I. 42000) and the like, and lake pigments of these basic dyes (as a laker, phosphotungstic acid, phosphomolybdic acid, phosphotungstic acid, tannic acid, lauric acid, gallic acid, ferricyanide) Compound, ferrocyanide, etc.), C.I. I. Solvent Black 3
(C.I. 26150), Hansa Yellow G (C.I.
11680), C.I. I. Mordlant Black 11,
C. I. Pigment Black 1 benzoylmethyl-hexadecyl ammonium chloride, decyl-trimethyl aluminum chloride, or dialkyl tin borate compounds such as dibutyl or dioctyl, guanidine derivatives, vinyl polymers containing amino groups, condensation polymers containing amino groups, etc. Polyamine resins, metal complex salts of monoazo dyes described in JP-B Nos. 41-20153, 43-27596, 44-6397 and 45-26478, and JP-B-55-42752.
No. 54, Japanese Patent Publication No. 54-150080, Japanese Patent Publication No. 58-738
4, metal complexes of salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acids such as Zn, A1, Co, Cr and Fe, and sulfonated copper phthalocyanine pigments described in JP-B No. 4 and JP-B-59-7385.

Examples of the releasing material include low molecular weight polyethylene, low molecular weight polypropylene, low molecular weight polyolefins such as polyethylene oxide, beeswax, carnauba wax,
There are natural waxes such as montan wax, higher fatty acids 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 low molecular weight polyolefins such as polypropylene are preferred.

As a method for coating the above charge control agent or the releasing material, a generally known method can be adopted. For example, if the dyed particles and a charge control agent or a release agent are mixed and adhered by a wet or dry method, and mechanical energy is applied to the mixture, the surface of the powder particles is impregnated with a resin coating colorant, and then 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 blade rotating at a high speed, a method of causing particles to collide with each other or a collision plate in a high-speed air stream. As a concrete driving device, mechanofusion (Hosokawa Micron), type I mill (Nippon Pneumatic Mfg. Co., Ltd.), which lowers the crushing air pressure than in the case of normal crushing, turbo mill (Turbo Kogyo), hybridizer (Nara) Machine Manufacturing Co., Ltd., Cosmomizer (Nara Machinery Manufacturing Co., Ltd.), automatic mortar, etc.

Production examples of the resin used in the present invention will be 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 replaced with nitrogen using nitrogen gas, a solution of azobisisobutyronitrile 0.82 parts dissolved 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 overnight. After decanting to remove the supernatant liquid, 100 parts of methanol was added and stirred for 30 minutes, then filtered and dried to obtain 49 parts of white powder. The volume average particle diameter (Dv) of this powder is 7.36 μm, and the number average particle diameter (D
The ratio Dv / Dp with 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 of Production Example 1,
Polymerization was performed in the same manner as in Production Example 1 except for the above, 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; 4 vinyl pyridine.

Preparation Comparative Example-1 A solution in which 5 parts of polyacrylic acid was dissolved in 150 parts of methanol, the inside of the reaction vessel was replaced with nitrogen using nitrogen gas, and then 52 parts of styrene was dissolved with 0.82 part of azobisisobutylnitr. Was added, and the mixture was stirred at 60 ° C. for 8 hours to carry out dispersion polymerization, allowed to stand at room temperature for 24 hours, decanted to remove the supernatant liquid, added with 100 parts of methanol, stirred for 30 minutes, filtered and dried to give 49 parts of white. A powder was obtained. The volume average particle diameter (Dv) of this powder is 10.08 μm and the number average particle diameter (D
The ratio Dv / Dp with 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-Dodecenyl succinic anhydride 53.4 parts 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 reacted 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. The obtained solid wood finger was pulverized and classified to have a volume average particle diameter of 3 to 9 μm and a Dv / D.
The p was 1.13.

[0031]

EXAMPLES The present invention will be described below with reference to examples. The following parts are all parts by weight [Example 1] Polyester resin (Production Example 10) 100 parts Compound No. 1 of 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 diameter of 8 μm. 3 parts of this toner was mixed with 100 parts of iron powder carrier to obtain a developer. This developer is put in a magnetic brush developing device of a copying machine (FT4060 manufactured by Ricoh Co., Ltd.) to develop an electrostatic latent image formed on a selenium photoreceptor by a usual electrophotographic method, and transfer it to paper and mylar.
After fixing, red images were obtained. As a result of exposing the copied image transferred to paper with a fade meter for 5 hours, no discoloration or fading was observed. The haze of the copied image transferred to Mylar was measured and found to be 25, indicating excellent transparency.

Example 2 No. 1 in Table 1 above. Preparation Example by dissolving 0.5 part of the compound of 3 in 100 parts of methanol under heating-
Dyeing was carried out by adding 10 parts of the resin particles obtained in 1 and stirring under heat reflux for 1 hour. Then, the mixture was cooled to room temperature and suction-filtered to obtain a reddish powder. 10 parts and 3 of these colored resin particles,
After stirring for 5 minutes with 0.1 part of 5 ditert-butyl zinc salicylate in an Auster blender, the number of revolutions was 1 with hybridization NHS-O (Nara Machinery Co., Ltd.)
A red toner was obtained by processing for 5 minutes at 2,000 rpm.
3 parts of this toner was mixed with 100 parts of iron powder carrier, this developer was loaded into a copying machine (FT4060 manufactured by Ricoh Co., Ltd.), and copying was performed to obtain a clear red copied image.
In order to check the sublimation property, a polyester film was brought into close contact with the image surface of this copied image and placed in a thermostat set at 100 ° C. for 5 hours. As a result, the dye sublimated on the polyester film was visually determined, and as a result, the dye was found It didn't move at all. Separately, no discoloration or discoloration was observed as a result of exposing the copied image for 5 hours with a fade meter. Further, in the same manner as in Example-1, the haze was measured by transferring and fixing to Mylar and found to be 18.

Example 3 Resin 10 obtained in Production Example 2
Part was dispersed in 35 parts of methanol and the internal temperature was kept at 50 ° C.
No. 0.5 part of the compound of 10 was added little by little, stirred for 8 hours, cooled to room temperature and filtered to obtain a blue colored powder. 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 and dried to give a blue powder. After wax is attached to the surface, 3,5 ditertiary butyl salicylate zinc 0.1
After stirring for 5 minutes with an Oaster blender, a blue toner was obtained by processing with Hybridization NHS-O (manufactured by Nara Machinery Co., Ltd.) at a rotation speed of 10,000 rpm for 5 minutes. 3 parts of this toner was mixed with 100 parts of an iron powder carrier, and this developer was copied in the same manner as in Example 1 to obtain a clear blue copy image. Further, as a result of a repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were stably maintained during the test was obtained.

[Examples 4 to 8] Using the resins and colorants shown in Table 4, colored powders dyed under the same conditions as in Example-3 were obtained. Thereafter, this 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 dyeing amount, light resistance, and sublimation property of these toners.

[Comparative Examples 1 and 2] Oil-soluble dyes other than the present invention (solvent yellow 14, solvent blue 25) were used for dyeing under the same conditions as in Example-3, and the results are shown in Table 4. ..

[0036]

[Table 4] Table 4

The evaluation methods in Table 4 are as follows. Dyeing amount: 0.1 g of the dyed substance 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. Light resistance; Xenon tester (Shimadzu XW-15
0) was used for light irradiation for 10 hours, and then visually determined. ◯: There is almost no color change before and after irradiation. X: There is a color change before and after irradiation. Sublimation; 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: Sublimation is not recognized. B: Sublimation is recognized. Transparency: It is expressed by the haze degree of the toner image transferred to Mylar.

Example 9 Resin 10 obtained in Production Example 6
Part was dispersed in 35 parts of methanol and the internal temperature was kept at 50 ° C.
No. 16 parts of compound 0.4 parts, yellow # 818 (manufactured by Yamamoto Kasei) 0.17 parts and PS Red G (Mitsui Dye Kagaku) 0.1 parts were added little by little, stirred for 8 hours, cooled to room temperature, filtered and black. A powder colored in red was obtained. 10 parts of this colored powder is dispersed in 100 ml of ion-exchanged water, and carnauba wax emulsion (solid content 20
%) 1 part at a time, stirred at room temperature for 1 hour, filtered and dried to deposit wax on the black powder, and then with 0.1 part of metal-containing azo dye (S-34 manufactured by Orient Chemical Co., Ltd.). Was stirred and mixed with an Auster blender for 5 minutes, and then treated with Hybridization NHS-0 (manufactured by Nara Machinery Co., Ltd.) at a rotation speed of 10,000 rpm for 5 minutes to obtain a black toner. 3 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 to obtain a black clear copy image. Furthermore, as a result of a repeated copying test of 10,000 sheets using this developer,
Even during the test, a copy image in which the line image and the photographic image were well maintained was obtained stably.

Example 10 Polyester Resin (Production Example 10) 100 Parts No. 2 in Table 2 A mixture consisting of 5 parts of the compound of 1 and 3 parts of 5,5 zinc di-t-tert-butylsalicylate was heated and kneaded with a hot roll to obtain a toner having a volume average particle diameter of 8 μm. This toner was mixed in 3 parts with 100 parts of an iron powder carrier, and this developer was used in Example 1.
When copied in the same manner as above, a clear blue copy image was obtained.

[Embodiment 11] No. 1 in Table 2 above. 0.5 part of the compound of 4 was heated and dissolved in 100 parts of methanol, 10 parts of the resin particles obtained in Production Example-1 was added, and the mixture was stirred under heat reflux for 1 hour for dyeing. Then, the mixture was cooled to room temperature and suction-filtered to obtain a blue-colored powder. After stirring 10 parts of the colored resin particles, 0.1 part of 3,5 zinc ditert-butylsalicylate and 5 minutes with an Oaster blender, a hybridization NHS-O (Nara Machinery Co., Ltd.) was used for 5 minutes at a rotation speed of 10,000 rpm. Processing gave a blue toner. When 3 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, a clear blue copy image was obtained. As a result of a repeated copying test of 10,000 sheets using this developer,
Even during the test, a copied image was obtained in which the line image and the photographic image were well maintained.

Example 12 Resin 1 obtained in Production Example 2
No. 0 in Table 2 was dispersed by dispersing 0 part in 35 parts of methanol and keeping the internal temperature at 50 ° C. 0.5 part of the compound of 10 was added little by little, stirred for 8 hours, cooled to room temperature and filtered to obtain a blue colored powder. 10 parts of this colored powder is added to 100 ml of deionized water
1 part of carnauba wax emulsion (solid content 20%) was added little by little to this dispersion, and the mixture was stirred at room temperature for 1 hour, filtered and dried to deposit the wax on the blue powder, and then 3, 5 Zinc tert-butyl salicylate 0.
After stirring 1 part with an Auster blender for 5 minutes, Hybridization NHS-O (manufactured by Nara Machinery Co., Ltd.)
Was processed at 10,000 rpm for 5 minutes to obtain a blue toner. When 3 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, a clear blue copy image was obtained. Further, as a result of a repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were stably maintained during the test was obtained.

[Examples 13 to 17] Using the resins in Table 2 and the coloring agents in Table 1, colored powders dyed under the same conditions as in Example-12 were obtained. After this, this blue powder Example-1
The same process as in 2 was performed to obtain each colored toner. When 3 parts of each of these toners was mixed with 100 parts of iron powder carrier and this developer was copied in the same manner as in Example 1, a clear copy image was obtained. Further, as a result of a repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were stably maintained during the test was obtained.

Comparative Examples 3 to 4 Oil-soluble dyes other than the present invention (Solvent Yellow 2, Solvent Blue 25) were used for dyeing under the same conditions as in Example-12, but Comparative Example 3 did. 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. Toner was mixed in an amount of 3 parts with 100 parts of an iron powder carrier, and this developer was used in Example 1.
When copying was carried out in the same manner as above, a clear copied image was obtained, but as shown in Table 5, the light resistance was extremely poor.

Comparative Example 5 A blue toner was obtained in the same manner as in Example 11 except that the resin of Production Comparative Example 1 was used in place of the resin of Production Example 1 and the resin of Production Comparative Example 1 was used. When 3 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, a clear blue copy image was obtained. As a result of repeating the copying test, the image became messy after about 5,000 sheets. Dv / Dp, which is a measure of toner particle size distribution, is 1.
It had changed to 50.

Table 5 shows various characteristics of toners and toner images of Examples 13 to 17 and Comparative Examples 3 to 5. The evaluation criteria are the same as in Table 4.

[Table 5] Table 5

Example 18 10 parts of the resin obtained in Production Example 6 was dispersed in 35 parts of methanol and the internal temperature was kept at 50 ° C. 16 compounds 0.
4 parts, 0.17 part of Yellow # 818 (manufactured by Yamamoto Kasei) and 0.1 part of PS Red G (manufactured by Mitsui Dye Kagaku) were added little by little, stirred for 8 hours, cooled to room temperature, filtered and colored black in color. Got the 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 and dried to obtain a black powder. After depositing the wax on the body, 0.1 part of a metal-containing azo dye (S-34, manufactured by Orient Chemical Co., Ltd.) and 5 with an Oaster blender
After stirring and mixing for minutes, the hybridization NHS-
O (manufactured by Nara Machinery Co., Ltd.) was processed at a rotation speed of 10,000 rpm for 5 minutes to obtain a black toner. 3 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 to obtain a black clear copy image. Further, as a result of a repeated copying test of 10,000 sheets using this developer, a copied image in which a line image and a photographic image were stably maintained during the test was obtained.

[0047]

EFFECT OF THE INVENTION In an electrostatic charge image developing toner containing a thermoplastic resin and a colorant as main components, (1) the dye having the structure specified in the present invention is used, and (2) the thermoplastic resin component is added as described above. (3) Further, the toner is produced by a method of dyeing a structure dye, and (3) the powder particles mainly composed of a thermoplastic resin are spherical particles, and the volume average particle diameter Dv is 3 to 9 μm, and the volume average particle diameter Dv. By adjusting the ratio Dv / Dp of the average particle size Dp to the number average particle size Dp of 1.05 to 1.15, a toner image having excellent fastness to heat and light, a sharp particle size distribution, and a small particle size toner can be obtained. It is possible to provide a high-quality and highly durable toner.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C09B 29/085 B 7306-4H

Claims (6)

[Claims] 1. A toner for developing an electrostatic charge image containing a thermoplastic resin and a colorant as main components, wherein the colorant contains at least one compound represented by the following general formula (I). Toner for developing electrostatic images. 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, -N
_{HCOC 2 H 5, -NHCOC 3 H} 7, represents _{-NHSO 2 CH 3, R 1,} R 2, R 6 is an alkyl group, an alkenyl group,
Hydroxyalkyl group, alkoxyalkyl group, phenoxyalkyl group, cyanoalkyl group, chloroalkyl group, bromoalkyl group, acyloxyalkyl group, alkoxycarbonyloxyalkyl group, benzoyloxyalkyl group, phenoxycarbonyloxyalkyl group,
It represents 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 represents a hydrogen atom, a cyano group, a nitro group, a chlorine atom, a bromine atom, a fluorine atom, a trifluoromethyl group, an alkyl group or an alkoxy group, and R ₄ and R ₅ represent a hydrogen atom, an alkyl group, a cyano group, a nitro group. Represents a group, chlorine atom, bromine atom or fluorine atom. ) 2. A toner for developing an electrostatic charge image comprising a thermoplastic resin and a colorant as main components, wherein the colorant is represented by the following formula (I
A toner for developing an electrostatic image, which is a compound represented by I). (In the formula, R ₇ and R ₈ are alkyl groups having 1 to 4 carbon atoms, cyano groups, hydroxyl groups, lower alkoxy groups, lower alkoxycarbonyloxy groups, lower alkylcarbonyloxy groups, lower alkoxycarbonyl groups, phenoxy groups, chloro groups. Represents a lower alkylcarbonyloxy group, a chlorine atom, a bromine atom, a lower alkylamino group or a lower alkyl group substituted with an allyloxycarbonyl group, a cyclohexyl group, a benzyl group or an allyl group, and R ₉ represents a methyl group or an ethyl group. R ₁₀ is a hydrogen atom and has 1 carbon atom.
Represents an alkyl group, a lower alkoxy group, a chlorine atom, a bromine atom, a fluorine atom or an acetoxy group represented by R ₁₁ ,
R _12, R ₁₃ represents a nitro group, a chlorine atom, a bromine atom, a fluorine atom, a cyano group, an alkyl group or a trifluoromethyl group having 1 to 4 carbon atoms. ) 3. The powder according to claim 1, wherein the powder particles containing the thermoplastic resin as a main component are dyed with a compound of formula (I) or formula (II). Toner for developing electrostatic images. 4. The thermoplastic resin according to claim 1, wherein the thermoplastic resin is a polyester resin.
The toner for developing an electrostatic image as described in 1. 5. The powder particles containing the thermoplastic resin as a main component are spherical particles having a volume average particle diameter Dv of 3 to 9 μm, and a ratio of the volume average particle diameter Dv to the number average particle diameter Dp, Dv. /
The electrostatic charge image developing toner according to claim 1, claim 2, claim 3 or claim 4, wherein Dp is in the range of 1.00 to 1.15. 6. A toner for developing an electrostatic charge image according to claim 1, wherein a layer containing a charge control substance and a releasing substance is provided on the surface. ..