JPH02110576A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain the toner which is uniform in triboelectrostatic charge quantity between toner particles and is stable in the triboelectrostatic charge quantity is spite of a change in temp. and humidity by incorporating a metal complex compd. contg. specific quaternary ammonium group-substd. salicylic acid as its ligand. CONSTITUTION:The colorless or pale color metal complex compd. which contains the quaternary ammonium group-substd. salicylic acid as its ligand, is incorporated into the toner. In the formula I, R<1> denotes 1 to 8C alkyl group, aralkyl group, aryl group. W denotes a quaternary ammonium group or org. group having quaternary ammonium group; X<-> denotes anion; M denotes metal ions of Al, Ti, Cr, Fe, and Co; n is 1 or 2. the toner which is stable in the triboelectrostatic charge quantity and has the lower dependency of the triboelectrostatic charge quantity on humidity is obtd. in this way.

Description

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

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297°68
1, Special Publication No. 42-23910, and Special Publication No. 43
Various methods are described in Japanese Patent No. 24748, etc., but in short, these methods provide static charges such as - on a photoconductive insulating layer and irradiate the insulating layer with a light image to generate static electricity. An electrostatic latent image is formed, and then the latent image is developed and visualized using a fine powder called toner in the art, and if necessary, the powder image is transferred to paper or the like, and then heated, pressurized, or by solvent vapor, etc. This is to fix the problem.

The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former is further divided into a method using a two-component developer and a method using a -component developer.

Two-component developing methods include a magnetic brush method using an iron powder carrier, a cascade method using a bead carrier, a fur brush method using fur, etc., depending on the type of carrier for conveying the toner.

In addition, methods belonging to the -component development method include the powder cloud method, in which toner particles are sprayed, and the contact development method (contact development, or toner development method, in which toner particles are brought into direct contact with the electrostatic latent image surface for development. Jumping development method, in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; magnetic conductivity; There is the MagneDry method, which develops by bringing toner into contact with the electrostatic latent image surface.

Conventionally, toners used in these development methods are fine powders in which dyes and pigments are dispersed in natural or synthetic resins. Particles obtained by pulverizing the particles to about 1 to 30 particles are used as toner. As magnetic toners, those containing magnetic particles such as magnetite instead of or in addition to the dyes or pigments described above are used. In the case of a system using a so-called two-component developer, the above toner is usually mixed with carrier particles such as glass beads and iron powder.

Further, the toner is given a positive or negative charge in advance depending on the polarity of the electrostatic latent image to be developed.

In order to charge the toner, it is also possible to use only the triboelectricity of the resin that is a component of the toner, but with this method, the toner's chargeability is small, so the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectric charging properties to the toner, charge control agents such as dyes and pigments that enhance the charging properties are added.

Charge control agents known in the art today include nigrosine dyes, azine dyes (Japanese Patent Publication No. 42-182
7), metal complex salts of monoazo dyes, and copper phthalocyanine pigments. Many of these charge control agents are derived from dyes and pigments, have complex structures, and many have strong coloring properties. Therefore, when these charge control agents are used in color toners, the color sharpness of the toners is impaired.

In addition, recently proposed colorless or light-colored charge control agents include quaternary ammonium salts such as tributylbenzylammonium hydroxynaphthylsulfonic acid;
Examples include organic tin oxides such as dibutyltin oxide, and polyamines such as vinyl polymers containing amino groups and condensation polymers containing amino groups. However, many of these charge control agents are hydrophilic, and the amount of triboelectric charging decreases, especially under high humidity conditions. Also,
If the amount of triboelectric charge does not decrease under high humidity conditions, the amount of triboelectricity will abnormally increase under low humidity conditions. If a toner containing a charge control agent whose triboelectric charge varies significantly depending on humidity is used, the image quality will change due to changes in temperature and humidity, making it extremely difficult to consistently provide images of good quality. .

Therefore, there is a strong demand in this technical field for the development of a colorless charge control agent whose triboelectric charge is less dependent on humidity.

[Problem to be Solved by the Invention 8] An object of the present invention is to provide a new technique for controlling the charge of toner that solves the above-mentioned problems.

An object of the present invention is to ensure that the amount of triboelectric charge between toner particles, between toner and carrier, between toner and toner carrier such as a sleeve in the case of -a development is stable, and is resistant to changes in temperature and humidity. It is an object of the present invention to provide a developer capable of reproducing stable images without being affected by the effects.

A further object of the present invention is to provide a vivid chromatic developer.

[Means and effects for solving the problems] The present invention is characterized by a positive triboelectric electrostatic charge image developer containing at least one colorless or light-colored metal complex compound represented by the following general formula [I]. It is in the toner for use.

(In the formula, RI represents an alkyl group, aralkyl group, or aryl group having 1 to 8 carbon atoms, W represents a quaternary ammonium group or a group having a quaternary ammonium group, X- represents an anion, 0M represents Aj ), Ti.

Represents a metal ion of Cr, Fe, Go, and n is 1 or 2. ) [I] In consideration of ease of production, the intermediate substitution R1 and position n of W are the 3rd or 5th position with respect to the carboxyl group of the aromatic ring.
Preferably.

The organic group having a quaternary ammonium group represented by W is (
2) and (3).

R3, R4,)is represents hydrogen, an alkyl group, an aralkyl group, or an aryl group that may have a substituent. Considering ease of production, hydrogen or C1~(zo is preferable;
Hydrogen or 01-C8 is more preferred, and R3. R
4 and R5 may be the same or different, and may form a ring structure.

Examples of R6 include hydrogen, an alkyl group, and an aralkyl group.

In consideration of ease of production, hydrogen or C1-C2O is preferable, and hydrogen or C1-C8 is more preferable.

Examples of the linking group R2 include an alkylene group, an aralkylene group, and an arylene group, which may have a substituent.

Also, it is not necessary, considering the ease of manufacturing, C1~
C2O is preferable and Cl-Cs is more preferable. Furthermore, the linking group R2 may have a functional group in its main chain. In that case, R2 can be represented as shown in (4).

-R-Y-R8- (4) The linking groups R1 and R8 represent an alkylene group, an aralkylene group, or an arylene group which may have a C1 to C8 substituent, and R1 may be omitted. Y represents a functional group or 01
-C8 alkyl group). Considering ease of production, the number of functional groups is 10-9.

X- represents an anion, F-, C1)-, halogen ion such as Br-, sulfate ion, -BFn, -PF6,
-5iF6 or No+02n'-, PW+20n3-
Inorganic anions such as heteropolyacid anions can be exemplified. Further, organic i-ions such as bililinium ion, organic sulfonic acid ion, organic phosphorous ion, carboxylic acid ion, phenol ion, and tetraphenylboron anion can be exemplified. The substituent in the anion and anion preferably has 1 to 28 carbon atoms, and has 1 to 28 carbon atoms.
-10 is more preferred.

Although the positive triboelectric charging mechanism of the metal complex salt compound described above is not necessarily clear, it is thought that the introduction of a quaternary ammonium group into the bulky metal complex plays an important role in the positive triboelectric charging property.

The metal complex of salicylic acid or alkylsalicylic acid shown in Japanese Patent Publication No. 55-42752 exhibits negative chargeability, however, as a result of intensive study, the present inventor introduced a quaternary ammonium group on the salicylic acid or alkylsalicylic acid coordination. We have found that salicylic acid metal complexes can be positively charged by doing this.

As a positively charged metal complex, JP-A-60-98443
A metal complex having an azo group-containing group as a ligand is known from Japanese Patent No. 3, but this complex is colored and difficult to use as a charge control agent for color. However, the quaternary ammonium group-substituted lithylate metal complex of the present invention is colorless or so light that it can be considered substantially colorless, and when used in a color developer, it can form color images with excellent colors. can do.

Further, the metal complex salt compound of the present invention is thermally stable and has low hygroscopicity, so that it has positive triboelectric charging properties that are less dependent on humidity. Therefore, when the metal complex salt compound of the present invention is contained in a developer, it becomes a high-quality charge control agent that provides a developer with stable electrophotographic properties.

Specific examples of the metal complex salt compound of the present invention are illustrated below.

(Hereinafter, blank spaces) The toner of the present invention can be obtained by blending the metal complex compound as described above into a toner (colored fine powder) containing a binder resin and a colorant as essential components. As for the blending form, there is a so-called internal addition form in which the compound is encapsulated in the toner uniformly or in a capsule form, and a so-called internal addition form in which the compound is mixed and attached to the toner.

Any of the so-called externally added forms can be adopted.

When internally added, the amount of the metal complex compound to be 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.
Although not limited to boat fishing, it is preferably used in an amount of o, i to 20 parts by weight (more preferably 0.5 to 10 parts by weight) based on 100 parts by weight of the binder resin.

In addition, when adding externally, 0 parts per 100 parts by weight of resin.
．． 01 to 107 parts by weight is desirable, and as an external addition method, it is particularly preferable to fix by a mechanochemical method.

Note that, if necessary, a conventionally known charge control agent may be used in combination with the charge control agent of the present invention.

As the binder resin of the toner, polystyrene, poly-p-
Monopolymers of styrene and its substituted products such as chlorostyrene and polyvinyltoluene: styrene p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-
Vinyl toluene copolymer, styrene-vinylnaphthalene copolymer F'1, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Coalescence, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene- mullein s
Styrenic copolymers such as co-i polymers, styrene-maleic acid ester copolymers; polymethyl methacrylate, polybutyl methacrylate, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester,
Polyurethane, polyamide, epoxy resin, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin,
Examples include paraffin wax, which can be used alone or in combination.

Further, in order to provide a toner particularly suitable for pressure fixing, the following binder resins can be used alone or in combination.

Polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, oxidized polyethylene, polytetrafluoroethylene, etc.), epoxy resins, polyester resins, styrene
Butadiene copolymer (monomer ratio: 5-30:95-7
0), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.

Colorants include carbon black, lamp black,
Iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 8G, lake, calco oil blue, chrome yellow quinacridone, benzidine yellow,
The coloring agent, which can be used alone or in combination with conventionally known dyes and pigments such as rose bengal, triarylmethane dyes, monoazo dyes, and disazo dyes and pigments, is 1 to 10 parts by weight per 100 parts by weight of the binder resin. Preferably, the toner of the present invention further contains a magnetic material and can be used as a magnetic toner. Examples of the magnetic material contained in the magnetic toner of the present invention include iron oxides such as magnetite, magnetite, and ferrite; Metals such as iron, cobalt, nickel, or these metals and aluminum, cobalt, copper,
Examples include alloys with metals such as lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 µl, particularly 0.1 to 1.0 µl, and are contained in the toner in an amount of about 20 to 100 parts by weight per 100 parts by weight of the resin component. 2
00 parts by weight, particularly preferably 40 to 150 parts by weight per 100 parts by weight of the resin component.

Further, the toner of the present invention may contain additives other than those mentioned above, if necessary.

For example, lubricants such as Teflon and zinc stearate; abrasives such as cerium oxide and silicon carbide; flow agents such as colloidal silica, titanium oxide, and aluminum oxide;
Examples include anti-caking agents; conductivity imparting agents such as carbon black and tin oxide; fixing aids such as low molecular weight polyethylene; and the like.

In particular, positively charged hydrophobic silica treated with amine-modified silicone oil or the like is preferably externally added to the toner.

In order to produce the toner for developing an electrostatic image according to the present invention, the metal complex compound charge control agent according to the present invention is combined with the above-described binder resin, a pigment or dye as a coloring agent, and optionally a magnetic material. Materials, additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted and kneaded using a heat kneader such as a heated roll, niegu, or extruder to make the resins compatible with each other. It is possible to obtain a toner having an average particle size of 5 to 20 mm by dispersing or dissolving it, cooling and solidifying it, and then crushing and classifying it. Alternatively, the material can be obtained by dispersing the material in a binder resin solution and then spray-drying it, or by mixing the specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as a polymerization toner manufacturing method for obtaining a toner, or a method of incorporating the toner into the core and/or shell of a so-called microcapsule toner consisting of a core material and a shell material can be applied.

Furthermore, the toner of the present invention can also be used as a two-component developer, and in that case, the carrier that can be used in the present invention is mixed with a carrier powder.
Known materials can be used, such as magnetic powders such as iron powder, ferrite powder, and nickel powder, glass beads, and those whose surfaces are treated with resin or the like.

The toner or developer produced by the above method is
Any conventionally known means can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc.

[Example] EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, all "r parts" in the following formulations are parts by weight.

Example 1 The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was roughly pulverized with a cutter mill, then pulverized with a fine pulverizer using a shedding air flow, and roughly classified using a wind classifier.
A fine toner powder having an average particle size of 12.6 mm was obtained.Next, 0.4 part of hydrophobic dry silica treated with amino-modified silicone oil was mixed with 100 parts of the fine powder to prepare a toner.

A developer was prepared by mixing 5 parts of the above toner in a ratio of 1:1 to 100 parts of a fluorine acrylic coated ferrite carrier having an average particle size of 85 g.

When this developer was applied to a reprint copying machine (product name NP-5540 manufactured by Canon) and an image was produced, it was found that the temperature was 23°C and 80°C.
The image density was 1.23% under environmental conditions, and a bright magenta image was obtained. In addition, the environmental conditions were set to 35℃ and 8℃.
When it was set to 5%, the image density was 1.18, which resulted in an image with sufficient density.

When a transferred image was obtained at 15° C. and 10% low temperature and low humidity, a good image with a high image density of 1.25 was obtained.

Comparative Example 1 Example 1 except that 4 parts of benzylmethylhexadecyl ammonium chloride was used instead of 4 parts of compound (1).
A developer was obtained in the same manner as above, and images were obtained in the same manner by performing development, transfer, and fixing. At room temperature and humidity, there was little fog, but the image density was low at 1.07, line drawings were scattered, and solid images were noticeably rough. When durability was examined, image density gradually decreased.

When an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.88, and roughness increased.

Example 2 A developer was prepared in the same manner as in Example 1, except that 2 parts of compound (2) was used instead of 4ffffi of compound (1) and 5 parts of phthalocyanine blue pigment was used instead of 10 parts of quinacridone dye, and an image was obtained. Ta. Environmental conditions were 23℃.

At 60%, the image density is 1.25, and at 35°C, 85%
A clear blue image with a density of 1-min was obtained under each environmental condition: 1.20.15°C at 10%, and 1.25 at 10%.

Example 3 The above materials were thoroughly mixed in a blender and then kneaded with two rolls heated to 150°C. After the kneaded material was left to cool naturally, it was roughly pulverized using a Kerr 7 ter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain an average particle size of I1. A fine powder was obtained.

Next, amine-modified silicone oil-treated hydrophobic colloidal silica o,"rm was added to 100 parts of the fine powder and mixed in a Henschel mixer to obtain a -forming magnetic toner.

When this magnetic toner was applied to a commercially available copying machine (product name NP-150 manufactured by Canon ■) and an image was produced, the image density was 1.32.
1.30.15℃ at 5%, 1.36 at 10%
Clear images with sufficient density were obtained under each environmental condition.

Comparative Example 2 A developer was obtained in the same manner as in Example 3, except that 5 parts of triethylbenzylammonium chloride was used instead of 5 parts of compound (5) in Example 3, and an image was obtained in the same manner. It was low at .95, and solid black images were noticeably rough.

Furthermore, when an image was obtained under conditions of 35° C. and 85%, the image density was as low as 0.85, and roughness increased.

Example 4 The above materials were thoroughly mixed in a blender, and then kneaded at 180° C. in a two-wheel kneading extruder in the same direction.

After coarsely pulverizing the mixed material with a cutter mill, pulverizing it with a jet mill and classifying it with an air classifier to obtain an average particle size of 12
．． Next, 1.2 parts of hydrophobic silica treated with amine-modified silicone oil was mixed with 100 parts of the fine toner powder having a particle size of 0 μm to prepare a toner.

Silicon coated ferrite carrier 1 with average grain size of 65 wells
A developer was prepared by mixing 00 parts of the above toner with 3 parts of the toner described above.

This developer was applied to a commercially available Copy 4J1 (trade name NP-554).
0 Canon ■) and applied to the image.

The image density was 1.33 under the environmental conditions of 20° C. and 60%, and a bright black image was obtained. In addition, the environmental conditions were
When the temperature was set to 85% at 5°C and 10% at 15°C, the image density was 1.30.1.37, and images with sufficient density were obtained.

[Effects of the Invention] As described above, the toner containing the metal complex compound of the present invention as a charge control agent has a uniform amount of frictional charge between toner particles, and the amount of charge can be easily controlled. Furthermore, the toner has an extremely stable amount of triboelectric charge even with changes in temperature and humidity. Therefore, problems such as scattering and transfer omission during transfer under high and low humidity are eliminated.

Furthermore, since the charge control agent causes less color tone disturbance, when used in color toners, it is possible to form color images with excellent colors.

Claims (1)

[Claims] (1) A metal complex compound having quaternary ammonium group-substituted salicylic acid as a ligand represented by the following general formula [I],
A toner for developing an electrostatic image, characterized in that it contains at least one kind. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (In the formula, R^1 represents an alkyl group, an aralkyl group, or an aryl group having 1 to 8 carbon atoms. W has a quaternary ammonium group or a quaternary ammonium group. Represents an organic group.X^-
represents an anion. M is Al, Ti, Cr, Fe, C
represents the metal ion of o. n is 1 or 2. )