JPH07175269A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner excellent in the stability of a compound and dispersibility to a binder resin, free from the deterioration at the time of producing the toner, having excellent static charge characteristic by friction under various environmental condition and capable of stably giving an image of high picture quality by containing a specific compound as a charge controlling agent. CONSTITUTION:The toner contains one or more kind of the compound selected from a group of compounds expressed by a formula I or II. In the formulas I and II, each of A and B represents hydrogen atom, halogen atom, alkoxyl group, carboxyl group, hydroxyl group, ester group, nitro group, amino group, alkylamino group or the like, R represents hydrogen atom, (substituted) alkyl group, (substituted) phenyl group or (substituted) naphthyl group, (m) represents integers of 2-16 and (n) represents integers of 4-8. The content of the charge controlling agent in the toner is generally 0.1-7wt.%, preferably 0.3-5wt.%.

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 containing a specific compound.

[0002]

2. Description of the Related Art In an electrophotographic image forming process, an electrostatic latent image is formed on an inorganic photoreceptor such as selenium, a selenium alloy, cadmium sulfide, or amorphous silicon, or an organic photoreceptor using a charge generating agent and a charge transporting agent. After being formed, it is developed with toner, transferred to paper or a plastic film, and fixed to obtain a visible image.

The photosensitive member has a positive charging property and a negative charging property depending on its constitution. When the printing portion is left as an electrostatic latent image by exposure, it is developed with a toner of opposite sign charging, while the printing portion is discharged. When reversal development is carried out, the development is carried out with a toner having the same sign. A toner is composed of a binder resin, a colorant and other additives, but is generally a charge control agent in order to impart desirable triboelectrification characteristics (charging speed, charging level, charging stability, etc.), temporal stability and environmental stability. Is used. The characteristics of the toner are greatly affected by this charge control agent.

In the case of color toner, a light-colored, preferably colorless charge control agent which does not affect the hue is required. Examples of these light-colored or colorless charge control agents include, for example, JP-B-55-4 for negatively chargeable toner.
No. 2752, JP-A-61-69073, JP-A-61-221756, etc., metal complex salt compounds of hydroxybenzoic acid derivatives, JP-A-57-111.
Aromatic dicarboxylic acid metal salt compounds described in JP-A No. 541 and the like, JP-A-61-141453 and JP-A-62.
-94856 and the like, metal complex salt compounds of anthranilic acid derivatives, USP-4767688, organic boron compounds described in JP-A-1-306861, etc., and JP-A-61-3149. There are biphenol compounds and the like. Further, for positively charging toner, JP-A-57-119364 and JP-A-58-9 are used.
There are quaternary ammonium salt compounds described in JP-A No. 154 and JP-A No. 58-98742.

However, these charge control agents are chromium compounds which may cause environmental problems, may not be completely colorless, or may have a low charge imparting effect, or may have a large amount of reversely charged toner. There are drawbacks such as poor dispersibility and poor compound stability, and none of them have satisfactory performance as a charge control agent.

[0006]

SUMMARY OF THE INVENTION According to the present invention, the stability of the compound is good, the dispersibility in the binder resin is good, there is no deterioration during toner production, and the charging characteristics due to friction are maintained even under various environmental conditions. The present invention provides a toner that always gives a good and high-quality image in a stable manner.

[0007]

The present inventors have found a colorless and stable compound which has good dispersibility with a binder resin and can impart good charging characteristics to a toner. The present invention has led to the invention of excellent toners.

That is, the present invention has the following general formula (1)

[0009]

[Chemical 3] ... (1)

[In the formula, A and B are independently a hydrogen atom, a halogen atom, an alkoxyl group, a carboxyl group, a hydroxyl group, an ester group, a nitro group, an amino group, an alkylamino group, or an alkyl group which may have a substituent. Alternatively, it represents a phenyl group which may have a substituent, and R represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent. Represents a naphthyl group, m
Represents an integer of 2 to 16. ] Alternatively, the general formula (2)

[0011]

[Chemical 4] ... (2)

[In the formula, A and B are independently a hydrogen atom, a halogen atom, an alkoxyl group, a carboxyl group, a hydroxyl group, an ester group, a nitro group, an amino group, an alkylamino group, or an alkyl group which may have a substituent. Alternatively, it represents a phenyl group which may have a substituent, and R represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent. Represents a naphthyl group, n
Represents an integer of 4 to 8. ] The present invention relates to a toner for developing an electrostatic charge image, which comprises one or more compounds selected from the group of compounds represented by the following as a charge control agent.

The present invention basically comprises a binder resin, a colorant, and the compound represented by the general formula (1) or (2) according to the present invention, but as a method for producing the toner of the present invention, , A method in which these mixtures are kneaded under melting of a binder resin with a heating mixer, cooled, then coarsely pulverized, finely pulverized, and obtained by classifying, dissolving these mixtures in a solvent, atomizing by spraying, and drying, How to get by classifying,
There is a method in which the colorant or the charge control agent represented by the general formula (1) or (2) is dispersed in the suspended monomer particles to obtain it by a polymerization method.

The content of the charge control agent of the present invention in the toner is generally 0.1 to 7% by weight, preferably 0.
It is 3 to 5% by weight. As the binder resin, polystyrene, styrene-methacrylic acid ester copolymer, styrene-propylene copolymer, styrene-butadiene copolymer, acrylic resin, styrene-maleic acid copolymer, olefin resin, polyester, epoxy resin, polyurethane Resin, polyvinyl butyral, etc. alone or
Can be mixed and used.

As the colorant, carbon black is generally used for black toner, and the following colorants can be used for color toner. Examples of yellow colorants include C.I. I. Pigment Yellow 1, C.I. I.
Pigment Yellow 5, C.I. I. Pigment Yellow 1
2, C.I. I. Pigment Yellow 17, an azo organic pigment, an inorganic pigment such as ocher, or C.I. I. Solvent Yellow 2, C.I. I. Solvent Yellow 6, C.I. I. Solvent Yellow 14, C.I. I. Solvent Yellow 19
Oil-soluble dyes, etc.,

Examples of magenta colorants include C.I. I. Pigment Red 57, C.I. I. Pigment Red 57: 1, an azo pigment, C.I. I. Pigment Violet 1, C.I.
I. Pigment Red 81, a xanthene pigment such as C.I.
I. Pigment Red 87, C.I. I. Butt Red 1,
C. I. Pigment Violet 38 or C.I. I. Solvent Red 19, C.I. I. Solvent Red 49, C.I. I. Cyan colorants such as oil-soluble dyes such as Solvent Red 52 include C.I. I. Pigment Blue 1 and the like, C.I. I. Pigment Blue 15, C.I. I. Pigment Blue 17 or a phthalocyanine pigment such as C.I. I. Solvent blue 2
5, C.I. I. Solvent Blue 40, C.I. I. Known colorants such as oil-soluble dyes such as Solvent Blue 70 can be used.

In A and B represented by the general formulas (1) and (2) according to the present invention, the alkoxyl group is an alkoxyl group having 1 to 12 carbon atoms, and the ester group is -CO.
OX (wherein X represents an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent) group and an alkylamino group have an alkylamino group having 1 to 8 carbon atoms and a substituent. The optional alkyl group represents an alkyl group which may have a substituent having 1 to 12 carbon atoms. Further, as the substituent of the alkyl group which may have a substituent, a phenyl group, an acetyl group, an amino group, a nitro group, a hydroxyl group, a halogen atom and an alkoxyl group having 1 to 8 carbon atoms are shown. Examples of the phenyl group that may be used include an alkyl group having 1 to 12 carbon atoms, an acetyl group, an amino group, a nitro group, a hydroxyl group, a halogen atom, and an alkoxyl group having 1 to 8 carbon atoms.

In R represented by the general formulas (1) and (2) according to the present invention, the alkyl group which may have a substituent is an alkyl group which has 1 to 16 carbon atoms and may have a substituent. Represents The substituent of the alkyl group which may have a substituent is an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a heterocyclic residue having a nitrogen atom or an oxygen atom, or a halogen atom. As the substituent of the phenyl group which may have a substituent, an alkoxyl group having 1 to 8 carbon atoms, an alkyl group having 1 to 8 carbon atoms, an acetyl group,
Hydroxyl group, carboxyl group, nitro group, carbon number 1
~ 8 alkylamino group, amino group or halogen atom. Examples of the substituent of the naphthyl group which may have a substituent include a hydroxyl group, a carbonyl group, a nitro group, an alkyl group having 1 to 8 carbon atoms, a carbamoyl group and a halogen atom.

The compounds (1) and (2) of the present invention can be easily prepared by a known method. Specific examples of the compound according to the present invention that can be used as the charge control agent include the following.

Compound No. (1)

[Chemical 5]

Compound No. (2)

[Chemical 6]

Compound No. (3)

[Chemical 7]

Compound No. (4)

[Chemical 8]

Compound No. (5)

[Chemical 9]

Compound No (6)

[Chemical 10]

Compound No. (7)

[Chemical 11]

Compound No (8)

[Chemical 12]

Compound No. (9)

[Chemical 13]

Compound No. (10)

[Chemical 14]

Compound No. (11)

[Chemical 15]

Compound No. (12)

[Chemical 16]

Compound No. (13)

[Chemical 17]

Compound No (14)

[Chemical 18]

Compound No. (15)

[Chemical 19]

Compound No. (16)

[Chemical 20]

Compound No. (17)

[Chemical 21]

Compound No (18)

[Chemical formula 22]

Compound No (19)

[Chemical formula 23]

Compound No (20)

[Chemical formula 24]

Compound No (21)

[Chemical 25]

Compound No (22)

[Chemical formula 26]

Compound No (23)

[Chemical 27]

Further, the toner may be used as an additive in the toner.
For the purpose of carrier protection, toner fluidity improvement, thermal / electrical / physical property adjustment, resistance adjustment, softening point adjustment, and fixability improvement, hydrophobic silica, metal soap, fluorine-based surfactant, Dioctyl phthalate, wax, tin oxide, conductive zinc oxide and the like are used if necessary.

When the toner of the present invention is used as a two-component developer, as a carrier, fine glass beads, iron powder, ferrite powder, a binder type carrier of resin particles in which magnetic particles are dispersed or a polyester resin on the surface, Fluorine resin,
A resin-coated carrier coated with an acrylic resin, a silicone resin, or the like is used. Further, the toner of the present invention exhibits excellent performance even when used as a one-component toner.

[0045]

EXAMPLES The present invention will be specifically described below with reference to examples. Parts in the examples represent parts by weight.

Example 1 1 part of (Compound No (1)), 5 parts of carbon black, and 94 parts of styrene-ethylhexyl methacrylate copolymer were kneaded by a heating mixer, cooled, and coarsely crushed by a hammer mill. Finely pulverize with a jet mill and then classify 1
A black toner of 0 to 12 μm was obtained. When this toner was mixed with an iron powder carrier in a weight ratio of 4: 100 and shaken, the toner was negatively charged, and the charge amount was measured by a blow-off powder charge amount measuring device (manufactured by Toshiba Chemical Co., Ltd.). Was -21 μc / g. When this toner was used and an image was produced by a modified commercial copying machine, a clear image was obtained at the initial stage and after copying 10,000 sheets.

Example 2 (Compound No (12)) 1 part, carbon black 5 parts,
Styrene-ethylhexyl methacrylate copolymer 94
The parts were kneaded with a heating mixer, cooled, and coarsely crushed with a hammer mill. It was finely pulverized with a jet mill and then classified to obtain a black toner of 10 to 12 μm. When this toner was mixed with an iron powder carrier in a weight ratio of 4: 100 and shaken, the toner was negatively charged, and the charge amount measured by a blow-off powder charge amount measuring device was -18 μc / g.
When this toner was used and an image was produced by a modified commercial copying machine, a clear image was obtained at the initial stage and after copying 10,000 sheets.

Example 3 1 part of (Compound No (1)), 5 parts of Spylon Blue 2BNH (product of Hodogaya Chemical Co., Ltd.) which is a copper phthalocyanine oil-soluble dye, and 94 parts of styrene-butyl methacrylate copolymer are heated. Kneading with a mixing device,
After cooling, it was roughly crushed with a hammer mill. It was finely pulverized with a jet mill and then classified to obtain a blue toner of 10 to 12 μm. When this toner was mixed with an iron powder carrier in a weight ratio of 4: 100 and shaken, the toner was negatively charged, and when measured with a blow-off powder charge amount measuring device, the charge amount was −.
It was 23 μc / g. When this toner was used and an image was produced by a modified commercial copying machine, a clear image was obtained at the initial stage and after copying 10,000 sheets.

Example 4 1 part of (Compound No (1)), 5 parts of carbon black, and 94 parts of styrene-ethylhexyl methacrylate copolymer were kneaded by a heating mixer, cooled, and coarsely crushed by a hammer mill. Finely pulverize with a jet mill and then classify 1
A black toner of 0 to 12 μm was obtained. This toner was mixed with a silicon coating carrier at a weight ratio of 4: 100, and when shaken, the toner was negatively charged, and the charge amount measured by a blow-off powder charge amount measuring device was −14 μm.
It was c / g. When this toner was used and an image was produced by a modified commercial copying machine, a clear image was obtained at the initial stage and after copying 10,000 sheets.

Example 5 (Compound No (14)) 1 part, carbon black 5 parts,
Styrene-ethylhexyl methacrylate copolymer 94
The parts were kneaded with a heating mixer, cooled, and coarsely crushed with a hammer mill. It was finely pulverized with a jet mill and then classified to obtain a black toner of 10 to 12 μm. This toner was mixed with an acrylic coating carrier in a weight ratio of 4: 100 and shaken to negatively charge the toner, and the charge amount measured by a blow-off powder charge amount measuring device was −18 μm.
It was c / g. When this toner was used and an image was produced by a modified commercial copying machine, a clear image was obtained at the initial stage and after copying 10,000 sheets.

Example 6 1 part of (Compound No. (11)), 60 parts of magnetic iron powder and 100 parts of styrene-acrylic copolymer were kneaded by a heating mixer, cooled, and coarsely crushed by a hammer mill. It was finely pulverized with a jet mill and then classified to obtain a black toner of 10 to 12 μm. When an image was produced by a modified commercial copying machine using this one-component toner, a clear image quality could be obtained even at the initial stage and after copying 10,000 sheets.

Examples 7 to 15 The same procedure as in Example 1 was repeated except that the compounds shown in Tables 1 and 2 were used instead of the compound No. (1) of Example 1 and Tables 1 to 1 were used.
The results shown in 2 were obtained.

[0053]

[Table 1]

[0054]

[Table 2]

[0055]

The toner containing the compound of the present invention as a charge control agent has good environmental resistance and stability over time. As a result, it is a toner for developing a high-quality electrostatic charge image, which is free from copy stains. Further, since the charge control agent itself is white or substantially colorless (does not affect the coloring of the colorant), it is possible to select any colorant according to the hue required for the color toner. It is also characterized by not hindering the original hue of dyes and pigments.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kayoko Watanabe 45 Miyukigaoka, Tsukuba City, Ibaraki Prefecture Hodogaya Chemical Industry Co., Ltd. Tsukuba Research Institute (72) Keiko Iwasa 45 Miyukigaoka, Tsukuba City, Ibaraki Prefecture Tsuchiya Chemical Industry Co., Ltd. Tsukuba Research Center

Claims (1)

[Claims] 1. The following general formula (1): (1) [wherein A and B independently have a hydrogen atom, a halogen atom, an alkoxyl group, a carboxyl group, a hydroxyl group, an ester group, a nitro group, an amino group, an alkylamino group, or a substituent. Represents a good alkyl group or a phenyl group which may have a substituent, R represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent Optionally represents a naphthyl group, and m represents an integer of 2 to 16. ] Or, the general formula (2): (2) [wherein A and B independently have a hydrogen atom, a halogen atom, an alkoxyl group, a carboxyl group, a hydroxyl group, an ester group, a nitro group, an amino group, an alkylamino group, or a substituent. Represents a good alkyl group or a phenyl group which may have a substituent, R represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a substituent Optionally represents a naphthyl group, and n represents an integer of 4 to 8. ] One or two or more compounds selected from the group of compounds represented by the following are contained as charge control agents, an electrostatic image developing toner.