JPS63284563A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a stable image, irrespective of environmental conditions, such as temperature and humidity, by incorporating a specified compound in a resin component in an amount of 0.01-10wt.% of the resin. CONSTITUTION:The electrostatic charge image developing toner contains, in an amount of 0.01-10wt.% of the resin component, one of the compounds represented by formulae I and II in which R<1> is 1-18C alkyl, alkenyl, aralkyl, or aryl; R<2> is H, halogen, nitro, or 1-18C alkoxy; R<3> is H, halogen, nitro, carboxy, anilido, or 1-18C alkyl, alkenyl, aralkyl, aryl, alkoxy, or carboxy ester; each of X and Y is -O-, -COO-, -S-, or -NR<4>-; R<4> is 1-4C alkyl; M is Sc, Ti, Va, Mn, Ni, or Zn; A is H, Na, K, ammonium, or organic ammonium; lis 1 or 2; each of m and n is 1, 2, or 3, and when plural substituents are present, each may be same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a toner for developing electrostatic latent images in electrophotography, electrostatic recording, and the like.

[Prior Art] In toner for developing electrostatic images, it is not possible to obtain a certain level of charging performance with the binder resin used alone, so dyes, pigments, etc. are used to control the toner to have the desired triboelectric charging performance. Addition of a charge control substance has been carried out.

Today, the ones that have been put into practical use in the relevant technical field are:
Nigrosine-based dyes are used to impart or control positive charge to the toner, and Japanese Patent Publication No. 45-26478 and Japanese Patent Publication No. 55-427 are used to impart or control negative charge to the toner.
Examples include metal-containing compounds shown in Publication No. 52 and the like. In terms of the ability to impart charge to toner particles, these compounds have particularly excellent properties among charge control substances that have been proposed to date, and they also produce images that are sufficient for practical use in conventional copying machines. We were able to provide a toner that gives you the best results.

[Problems to be solved by the invention] However, as electrophotography and electrostatic recording media become more personalized, faster, and more multifunctional, it is important to understand that electrophotography and electrostatic recording media are becoming more personalized, faster, and more multifunctional. There is a need for toners that can provide images with higher density, no fogging, high resolution, clear contrast, or excellent gradation reproducibility. Various development methods have been used, including not only normal development and analog development, but also reversal development, digital development, and low-potential development, and it is required to provide toner that provides high image quality for any development method. ing.

With miniaturization and personalization, products have been used in harsh environments such as high temperature and high humidity in tropical regions, low temperature and low humidity in inland regions, and in places without air conditioning, making them stable under any environment. must be provided with high-quality images. Furthermore, by increasing the speed, it is necessary to withstand use in large quantities at one time and continuous use over long periods of time, and to stably provide high-quality images.

On the other hand, the performance required of toner is not limited to developability.
Various raw materials have been used to improve fixing properties, anti-offset properties, cleaning properties, and anti-blocking properties. As a result, the amount of triboelectric charge of low-quality materials changes significantly, and the ability of charge control agents to simply "impart" or increase charge is insufficient, and it is difficult to "control" the amount of charge on toner to a constant level. It should not interfere with the other performance requirements and listed above, but rather should support it.

Toner is required to be controlled so that it is triboelectrically charged to a constant amount even during long-term use under any environment, and as a result, to provide stable high image quality. Therefore, conventional toners are no longer able to satisfy the various requirements mentioned above, and there is a need for improvement in charge control agents.

An object of the present invention is to provide a toner that provides a stable image without being affected by the environment such as temperature and humidity.

Another object of the present invention is to provide a toner that is highly durable and always provides stable images even when used continuously for a long period of time.

Still another object is to provide a toner that provides images with high resolution and fine line reproducibility.

Yet another object is to provide a toner that consistently provides high density, fog-free images.

Still another object is to provide an image that accurately represents delicate images and clearly represents images such as graphics.

Still another object is to provide a toner that can be used in both low-speed and high-speed machines.

Still another object is to provide a toner that does not deteriorate in performance even when left for a long period of time.

[Means and effects for solving the problems] The present invention has the following features:
The toner for developing electrostatic images is characterized in that it contains 0.01 to 10 parts by weight of a compound represented by the following general formula (I) or general formula (II) based on 100 parts by weight of the resin component.

[Wherein, R1 represents alkyl, alkenyl, aralkyl, or aryl having 1 to 18 carbon atoms, R2 represents hydrogen, halogen, nitro, or alkoxy having 1 to 18 carbon atoms, and R3 represents hydrogen, halogen, Represents nitro, carboxyl, anilide, or alkyl, alkenyl, aralkyl, aryl, alkoxy or carboxy ester having 1 to 18 carbon atoms. X, Y is 10-
, -000-, -3-, Mata represents -NR4- (R4 is alkyl having 1 to 4 carbon atoms), N is scandium,
It represents titanium, vanadium, manganese, nickel or zinc, A represents hydrogen, sodium, potassium, ammonium or organic ammonium, p represents 1 or 2, m, n represents 1, 2 or 3. In addition, when it has multiple substituents, each may be the same or different. As a result of extensive research into toners that can be stably negatively charged under any environment and provide stable images over a long period of time, the present inventors have found that toners containing the compound represented by general formula (I) I found that it was particularly good. That is, the compound represented by the general formula (I) used in the present invention is thermally and temporally stable, has low hygroscopicity, and when incorporated into a toner, a toner with excellent electrophotographic properties even under low humidity. The present invention was achieved by discovering that it is a high-quality charge control agent that gives the following properties.

Further, since some compounds represented by the general formula (I) have weak coloring power, they can be used in combination with other colorants for color toners.

Further, the toner containing the compound represented by the general formula (I) used in the present invention has good dispersion in the resin, and can be used between toner particles or between the toner and the carrier, and between the toner and the sleeve in the case of -component development. It has been found that the amount of triboelectric charge between the toner and the toner carrier is stable, the distribution of the amount of triboelectricity is sharp and uniform, and the amount of charge can be controlled to be suitable for the developing system used.

Methods for incorporating the compound represented by general formula (I) used in the present invention into the toner include a method of adding it inside the toner and a method of adding it externally. The amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method, including the dispersion method, and is not uniquely limited. However, it is preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the binder resin. In addition, when externally added, 0.
01 to 10 parts by weight is preferred.

The compound represented by general formula (I) used in the present invention is
It is obtained by treating a metallizable azo compound with a metallizing agent by a known method, and the counter ion can be changed depending on the subsequent treatment conditions.

For example, by diazotizing 4-methyl-6-chloro-2-aminephenol, coupling it with β-naphthol, treating it with an inorganic manganese salt, filtering it at pH 3 or below, and washing the precipitate until the pH reaches 6-7. , compound (1) is obtained.

Compound (1) Other specific examples of the compound include the following, which are synthesized in a similar manner.

Compound (2) Compound (3) Compound (4) The compounds used in the present invention can also be used in combination with conventionally known charge control agents.

As the colorant used in the present invention, any suitable pigment or dye can be used. For example, known dyes and pigments such as carbon black, iron black, phthalocyanine blue, ultramarine blue, quinacridone, and benzidine yellow are used.

The binder resin used in the present invention includes styrene, 0-
Methylstyrene, m-methylstyrene, p-methylstyrene, p-methoxystyrene, p-phenylstyrene,
p-Chlorstyrene, 3,4-dichlorostyrene, p-
Ethylstyrene, 2,4-dimethylstyrene, p-n
-butylstyrene, p-tert-butylstyrene,
Styrene and its M conductors such as p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene; ethylene, propylene, butylene , ethylenically unsaturated monoolefins such as isobutylene; unsaturated polyolefins such as butadiene; vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide, and vinyl fluoride; Vinyl esters; methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, methacrylate α- phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.
Methylene aliphatic monocarboxylic acid esters; methyl acrylate, ethyl acrylate, n-butyl acrylate,
Isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid
Acrylic acid esters such as 2-ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate; Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, and vinyl isobutyl ether; Vinyl methyl ketone, vinyl hexyl ketone, and methyl Vinyl ketones such as isopropenyl ketone;
N-vinyl compounds such as N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, and N-vinylpyrrolidone; vinylnaphthalenes; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; acrylic acid, methacryl Acid, vinyl compound derivatives having a carboxyl group such as maleic acid and fumaric acid; Hafester such as maleic acid Hafester and fumaric acid Hafester; Malein m
Monopolymers, copolymers, polyesters, polyurethanes, epoxy resins, polyvinyl butyral, rosins, modified rosins, terpene resins, phenolic resins, fats that are vinyl compounds such as anhydrides, maleic esters, fumaric ester a conductors; etc. Group or alicyclic hydrocarbon resins, aromatic petroleum resins, haloparaffins, paraffin waxes, etc. can be used alone or in combination.

In particular, binder resins for toners used in pressure fixing systems include low molecular weight polyethylene, low molecular weight polypropylene, ethylene-vinyl acetate copolymers, ethylene-acrylic acid ester copolymers, higher fatty acids, polyamide resins, polyester resins, etc. can be used alone or in combination.

Furthermore, when the toner of the present invention is used as a two-component developer, it is mixed with carrier powder.

All known carriers can be used in the present invention, such as magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, etc., and carriers whose surfaces have been treated with resin, etc. Things can be given.

Furthermore, the toner of the present invention is capable of developing while applying an alternating electric field between the developer carrier and the latent image carrier in the development region of the developer carrier facing the latent image carrier for holding the latent image. In an image forming method in which an image is developed with a non-magnetic toner, magnetic particles having a true specific gravity of 6 or less and coated with an electrically insulating resin increase the amount of magnetic particles present in the development area of a developer carrier. A magnetic brush is formed so that the amount of non-magnetic toner is 5 to 100 mg/cm2, and non-magnetic toner is transferred between the latent image carrier and the surface of the developer carrier and the surface of the magnetic brush formed on the surface of the developer carrier in the development area. It is also used in an image forming method characterized by developing a latent image while reciprocating.

Further, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, magnetite, and ferrite, and iron oxides containing other metal oxides;
Metals such as Fe, Go, and Ni, or these metals and AR, Co, and Cu.

Pb, Mg, Ni, Sn, Zn, Sb, B
e, Bi, Cd, Ca, Mn.

Examples include alloys with metals such as Se, Ti, W, and V, and mixtures thereof. These ferromagnetic materials have an average particle size of 0.1 to 2. Is I OK with LLI around 11? Magnetic properties when applying 3e are coercive force 20-150?3e, saturation magnetization 5
0 to 200 emu/g (preferably 50 to 10100
e/g), residual magnetization of 2 to 20 emu/H is desirable, and the amount contained in the toner is 100% of the resin component.
20 to 200 parts by weight, particularly preferably 40 parts by weight
~150 parts by weight.

The toner of the present invention may be mixed with additives if necessary. Examples of additives include lubricants such as Teflon, polyvinylidene fluoride, and fatty acid metal salts; or cerium oxide,
Abrasive agents such as strontium titanate and silicon carbide; or fluidity imparting agents such as colloidal silica and alumina, and anti-caking agents; or conductivity imparting agents such as carbon black and tin oxide; or fixing aids such as low molecular weight polyethylene, etc. 0.5 to 5 w of waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, and Sasol wax are used to improve mold release properties during hot roll fixing.
It is also possible to add about t%.

In manufacturing the toner according to the present invention, the constituent materials are sufficiently mixed using a ball mill or other mixer, and then
A method of obtaining by thoroughly kneading using a heat kneader such as a hot roll, niegu, extruder, etc., cooling and solidifying, and then mechanically crushing and classifying, or dispersing the constituent materials in a binder resin solution and then spray drying. A polymerization toner production method in which the monomers to constitute the binder resin are mixed with predetermined materials to form an emulsified suspension and then polymerized; In the microcapsule toner, a method of containing a predetermined material in the core material, the shell material, or both can be applied.

In the toner of the present invention, the acid value of the soluble components of the toner is preferably 50 or less, more preferably 25 or less. When the acid value of the soluble component of the toner is below the above, the charge control effect of the compound of general formula (I) used in the present invention works most effectively, exhibiting better developability and producing high quality. Can you give an image of it? Acid value is 50
If it exceeds 100%, the amount of charge becomes excessive under low humidity, resulting in a decrease in developability.

In the present invention, the acid value is a numerical value expressed in mg of potassium hydroxide required to neutralize 1 g of a sample, and is measured as follows.

2 g of the soluble component is dissolved in 200 g of a mixed solvent of toluene/ethanol = 271, and titrated with a 0.11XM potassium solution using phenolphthalein as an indicator.

Further, in the heat fixing toner of the present invention, the molecular weight of the tetrahydrofuran soluble component of the toner is Mn 2,000.
~20,000, M praise is 50,000~5,000,0
00, preferably 50,000 to 3,000,000
It is good that

In the present invention, the values of Mw and Mn were calculated from values measured by gel permeation chromatography. The measurement conditions were as follows: Tetrahydrofuran was used as a solvent at a flow rate of 1 mj/min at a temperature of 25°C, and the sample concentration was 8 m
g/mi' of tetrahydrofuran sample solution to 0.5 m
j) Inject and measure. In addition, the column is 103
In order to accurately measure the molecular weight range of ~2×106, it is recommended to combine multiple commercially available polystyrene gel columns, such as G-Styrage manufactured by Waters.
Combination of R500, 10", 10', 105 and 5bodex A-802, 803, 804 manufactured by Showa Denko
, 805 is a good combination. In measuring the molecular weight of the sample, the molecular weight distribution of the sample was calculated from the relationship between the logarithm value and the count number of a calibration curve prepared using several types of monodisperse polystyrene standard samples. As a standard polystyrene sample for creating a calibration curve, for example, Pressure Ch
emicaj) Go, or Toyo Tsudani Gyo Co., Ltd., with a molecular weight of 6 x 102.2. IX 103,4 X1
03°1.75X 10', 5. IX 104.1.
IX 105.3.9X 105°8.6 X105,
It is appropriate to use a standard polystyrene sample of 2X106.4.48X106 and at least about the 1O point. Further, an RI (refractive index) detector is used as a detector.

In the heat fixing toner that has been roughly kneaded and ground, the tetrahydrofuran insoluble portion of the resin component in the toner is 70 wt.
% or less, preferably 10 to 60 wt%, more preferably 10 to 50 wt%, the compound of general formula (I) used in the present invention is well dispersed in the toner and the charge control effect is effectively exhibited. be done. When the tetrahydrofuran insoluble content is less than 10 wt%, the compound used in the present invention is poorly dispersed, resulting in variations in toner particles.
It has poor durability and may cause problems such as a decrease in density and fogging during use. Moreover, when it exceeds 70 wt%, there are disadvantages such as problems in manufacturing such as poor fixing and insufficient kneading when using the cross-mixing method.

In the present invention, the tetrahydrofuran insoluble content is the proportion of a portion of the polymer that has become insoluble in a solvent. The tetrahydrofuran-insoluble content is defined by the value measured as follows. That is, the toner is kept at a constant weight (W +
g) Weighing and cylindrical filter paper (Toyo Roshi No. 86R)
The polymer is extracted with a Soxhlet extractor, and the soluble components in the polymer are removed with a solvent, and the remaining sample is dried and weighed (W2g).

Let W3 be the weight of solid components such as magnetic material and silica contained in the toner, and the solvent-insoluble content is calculated as follows. For example, tetrahydrofuran is suitable as such a solvent, and extraction was carried out for about 6 hours here.

[Example J Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Note that all parts in the following formulations are parts by weight.

Example 1 After premixing the above materials, they were kneaded with two rolls heated to 150°C, cooled, coarsely pulverized with a cutter mill, pulverized with a pulverizer using a jet stream, and further pulverized with a wind classifier. A fine powder with a volume average particle diameter of 111 Lm was obtained.

Mix this well with 0.4 part of hydrophobic colloidal silica,
Toner N081 was obtained. The physical properties of this toner No. 1 are shown in Table 1.

Commercially available copies of this toner 4! ! (Product name NP-7550
, Canon products) under normal conditions, we were able to obtain high-quality images that were faithful to the original.

Furthermore, as a result of repeated copying tests of 50,000 sheets, good images were obtained stably during the test, and the density was 1.
3 to 1.4 was maintained, no fogging was observed, the reproduction of thin characters was excellent, and no line thinning was observed. Furthermore, under low temperature and low humidity conditions of 15°C and 10% RH, and 30°C and 85% RH.
Similar results were obtained under high temperature and high humidity conditions.

The amount of charge is 1g of toner and iron powder carrier (200/
300mesh) 9g was accurately weighed, thoroughly mixed, and then measured using a blow-off (TB-200 manufactured by Toshiba Chemical Corporation).

Example 2 Toner No. 2 having a volume average particle diameter of 12 pm was obtained in the same manner as in Example 1 except that the above materials were used. Toner No. 2
The physical properties of are shown in Table 1.

A developer was prepared by mixing 5 parts of the toner with 100 parts of iron powder carrier having an average particle size of 50 to 80 ILIa. When a 10,000-sheet durability copying test was conducted using a commercially available electronic copying machine (product name NP-5000, Canon product), stable blue high-resolution images were obtained, and no fogging was observed. Ta. Further, at 15°C, 910%RH,
Similar results were obtained when a similar test was conducted at 35° C. and 980% RH.

Example 3 A toner N013 having a volume average particle diameter of 12 μm was obtained in the same manner as in Example 1 except that the above materials were used, and an extruder was used as the kneading device. Table 1 shows the physical properties of toner N093.

Commercially available laser beam printer (product name LBP-CX)
, Canon products), we were able to obtain high-resolution images. As a result of repeatedly printing 3,000 sheets, the density was maintained at 1.30 to 1.40, and no fogging was observed.

Further, in similar tests under various environments of 15° C., 910% RH, and 135° C., 980% RH, excellent images similar to those under the normal environment were obtained.

Comparative Example 1 Toner No. 4 having a volume average particle diameter of 11.5 JLm was obtained in the same manner as in Example 1, except that 2 parts of the following monoazo compound chromium complex was used instead of compound (1). Toner No.
, 4 are shown in Table 1.

As a result of conducting the same copying test as in Example 1, the result was 50.00
Although good images were obtained up to 0 sheets, the density was lower than that of Examples, ranging from 1.1 to 1.2. Another 15°C11
In a low temperature and low humidity environment of 0% RH, the concentration gradually decreases,
After 20,000 copies, the density was 1.0 to 1.1.

Comparative Example 2 Toner No. 5 having a volume average particle diameter of 11.5 m was obtained in the same manner as in Example 3, except that 0.5 part of the monoazo compound chromium complex shown below was used instead of compound (3). Toner N
The physical properties of o and 5 are shown in Table 1.

As a result of conducting the same copying test as in Example 3, the result was 3.000
Good images were obtained up to the first sheet, but the density was lower than that of Example 3, which was 1.2. Furthermore, under an environment of 15° C. and 10% RH, the density was unstable and varied from 1.1 to 1.3, resulting in an image with some fog.

(The following is a blank space) [Effects of the Invention] The toner of the present invention can be used in any conventionally known means for developing electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc. It produces the following excellent effects.

(2) The amount of frictional charge between toner particles is uniform, and the amount of charge can be easily controlled. In addition, the toner is stable because the amount of triboelectric charge does not vary or decrease during long-term continuous use or depending on the environment.

■ It is a toner that is not affected by humidity and provides stable images in both high and low humidity environments.

■ A toner that is not affected by temperature and provides stable images.

■ This toner has excellent durability and consistently produces stable images even after long periods of continuous use.

■ This toner has excellent resolution and consistently produces high-quality images with high density and no fog.

■ Since it has low tinting power, it can also be used in color toners.

■ It is a toner that provides excellent images when developing low-potential latent images.

Claims (1)

[Claims] (1) For 100 parts by weight of the resin component, apply the following general formula (
I) or the compound represented by general formula (II) from 0.01 to
A toner for developing an electrostatic image, characterized in that it contains 10 parts by weight. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) [In the formula, R_1 represents alkyl, alkenyl, aralkyl or aryl having 1 to 18 carbon atoms, R_2 represents hydrogen, halogen, nitro, or alkoxy having 1 to 18 carbon atoms; R_3 represents hydrogen, halogen, nitro,
Represents carboxyl, anilide, or alkyl, alkenyl, aralkyl, aryl, alkoxy or carboxy ester having 1 to 18 carbon atoms. X, Y are -
O-, -COO-, -S-, or -NR^4-(R^
4 represents alkyl having 1 to 4 carbon atoms), M represents scandium, titanium, vanadium, manganese, nickel or zinc, A represents hydrogen, sodium, potassium, ammonium or organic ammonium, and l represents 1 or 2. , and m and n represent 1, 2 or 3. In addition, when it has multiple substituents, each may be the same or different. ]