JPH043076A - Electrostatic charge image developing toner - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

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

[Prior art] As a conventional electrophotographic method, U.S. Patent No. 2,297,691
No., Special Publication No. 42-23910 and Special Publication No. 43-2
Various methods are described in Japanese Patent No. 4748 and the like.

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

As toners applied to these dry developing methods, fine powders in which dyes and pigments are dispersed in natural or synthetic resins have conventionally been used. For example, particles obtained by dispersing a colorant in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. Further, in the case of a system using a two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder.

Either toner must have a positive or negative charge depending on the polarity of the electrostatic latent image being developed.

!・In order to attach an electric charge to the toner, it is also possible to use the triboelectricity of the resin that is a component of the toner. However, since the toner's chargeability is small in this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, it is common to add a substance called a charge control agent to the toner in order to further impart triboelectric charging properties.

Now, as charge control agents known in the technical field, negative triboelectric ones include metal complex salts of monoazo dyes, metal complex salts of salicylic acid, metal complex salts of naphthoic acid, metal complex salts of dicarboxylic acids, and copper phthalocyanine. There are application fees, etc.

[Problems to be Solved by the Invention] Many of the charge control agents described above have sufficiently high charge imparting ability, but are colored and cannot be used in color toners. In addition, some control agents tend to contaminate toner carriers such as sleeves or carriers, so toners using these agents have a reduced amount of triboelectric charge as the number of copies is increased, causing a decrease in image density. easy. Further, since the amount of triboelectric charge of some types of control agents varies greatly depending on the binder resin used, there are restrictions on the binder resins or other materials that can be used. Further, although they are excellent in imparting frictional electrification, many of them lack controllability and tend to be excessively charged.

At present, there is a strong demand for the development of a charge control agent that satisfies all of these requirements.

An object of the present invention is to provide an excellent toner using a charge control agent that solves the above problems.

That is, between toner particles or between toner and gear nois,
- A toner that can reproduce a stable image that is stable in the amount of triboelectric charge between the toner and a toner carrier such as a sleeve in the case of component development without being affected by changes in temperature or humidity, and is not affected by changes in environmental conditions. It is to provide.

A further object of the present invention is to provide a developer in which toner is uniformly dispersed or dissolved in a binder resin, toner particles are uniformly charged, and a clear image without fogging is produced.

[Means and effects for solving the problems] The present invention is characterized by the following: 2-hydroxy-1-naphthoic acid,
-Hydroxy-1-naphthoic acid, hydroxyquinoline carboxylic acid in which hydroxy groups and carboxy groups are located adjacent to each other on the quinoline skeleton, compounds in which substituents are introduced into these hydroxynaphthoic acids and hydroxyquinoline carboxylic acids, and linking groups are used. At least one kind selected from dimerized or multimerized compounds is used as a charge control agent.

The negative charging performance of hydroxynaphthoic acid or hydroxyquinolinecarboxylic acid varies depending on the type of substituent, and in order to suppress sublimation and improve charging performance, hydroxynaphthoic acid or hydroxyquinolinecarboxylic acid with a substituent introduced is preferred.

Substituents for hydroxynaphthoic acid or hydroxyquinolinecarboxylic acid include hydroxy group, carboxy group, halogen group, nitro group, trihedroxygenomethyl group, cyano group, sulfoxy group, alkyl group having 1 to 12 carbon atoms, and carbon number 1-12 aryl group, C1-8 alkoxy group,
Aryloxy group having 1 to 12 carbon atoms, amino group having 1 to 12 carbon atoms, acyloxy group having 1 to 12 carbon atoms, 1 to 1 carbon atoms
Examples include an acylamide group having 1 to 12 carbon atoms, a thioxy group having 1 to 12 carbon atoms, a sulfonyl group having 1 to 12 carbon atoms, and a sulfinyl group having 1 to 12 carbon atoms. Hydroxynaphthoic acid or hydroxyquinolinecarboxylic acid having at least one substituent selected therefrom is preferred. Furthermore, two or more substituents may be linked to form a ring structure.

Furthermore, compounds obtained by dimerizing or multimerizing one or more of these hydroxynaphthoic acid compounds or hydroxyquinoline carboxylic acids with a linking group have almost no sublimation property, and are more preferable as charge control agents. .

Linking groups include alkylene, xylylene, sulfinyl, sulfonyl, sulfur, aryl, carbonyl,
Dicarbonyl and the like can be mentioned. In particular - formula (I
) to (■) can be mentioned. Among compounds using these linking groups, dimers using xylylene and methylene are preferred from the viewpoint of ease of synthesis.

- Formula (I) 1+-CH2← n=1 to 16 - Formula (II) S - General formula (IV) - ■ General formula (V) 1+A r← Ar is phenylene or naphthalene general formula (Vl) C- General formula (■) By dimerizing, there is no sublimation of the engineered acid to hydroxynaf 1 (this makes it possible to select a wider range of temperature conditions during toner production, and toner can be produced under more appropriate conditions). Furthermore, although the cause is unknown, due to dimerization, the amount of charge tends to be higher than that of monomeric hydroxynaphthoic acids.

As compounds similar to hydroxynaphthoic acid, JP-A-63
Japanese Patent No. 33755 discloses a two-component toner containing salicylic acid and a metal salt of a salicylic acid compound.

However, salicylic acid itself has sublimation properties and does not have sufficient negative triboelectric charging properties, so its uses are extremely limited. The present inventors investigated salicylic acid derivatives based on their own ideas and found that the amount of negative triboelectric charging can be increased by introducing a substituent to salicylic acid. However, the charging ability of these salicylic acid derivatives is usable, but it cannot be said to be high, and in order to impart stable development characteristics to the toner, a charge with even higher negative charging performance is required. Control agents are preferred.

Therefore, when we investigated hydroxynaphthoic acids in place of salicylic acid compounds, we found that the monomer sublimes less during toner production than salicylic acids, and the amount of negative triboelectric charge when made into toner is higher than that of salicylic acid compounds. I found it.

In addition, this hydroxynaphthoic acid was
When compared with the hydroxynaphthoic acid complex described in 56, the hydroxynaphthoic acid metal complex is colored, and when used in a color toner, depending on the amount added, it causes color tone inhibition, so there is a limit to the amount added. On the other hand, many of these hydroxynaphthoic acid compounds are
It is considered to be virtually colorless, and the color is so pale that it is difficult to cause color disturbance.

Furthermore, since the hydroxynaphthoic acid of the present invention has improved dispersibility in the binder resin compared to the metal monomer, the triboelectric charging between the toner particles becomes uniform, the generation of oppositely charged particles is suppressed, and fogging does not occur. Furthermore, contamination of toner carriers such as sleeves and carriers could be reduced.

Also, when compared with metal salts of hydroxynaphthoic acid,
Metal salts of hydroxynaphthoic acid have extremely low triboelectrification properties and are difficult to use as charge control agents, whereas this hydroxynaphthoic acid has sufficient negative triboelectrification properties.

In addition, the dependence of the image on the environment is less than that of conventional metal compounds (images with sufficient density can be obtained even under high temperature conditions or low temperature and low humidity conditions. This is because metal complexes have high water absorption properties. However, there is a large difference in the amount of water absorbed in each environment, whereas the corresponding hydroxynaphthoic acid has low water absorption.

Furthermore, hydroxyquinolinecarboxylic acid, in which a hydroxyl group and a carboxyl group are arranged at adjacent positions on the quinonone skeleton, has the same effect as hydroxynaphthoic acid.

As described above, the hydroxynaphthoic acid compounds of the present invention,
A toner containing a hydroxyquinoline carboxylic acid compound, or a compound obtained by dimerizing or multiplying hydroxynaphthoic acid or hydroxyquinoline carboxylic acid using a linking group contains a conventional charge control agent. The inventors have discovered that this toner has superior properties compared to other toners, and have arrived at the present invention.

Next, specific examples of the hydroxynaphthoic acid compounds, hydroxyquinoline carboxylic acid compounds, or dimerized products or multimerized products of hydroxynaphthoic acid or hydroxyquinoline carboxylic acid of the present invention are illustrated below. However, since the structural formula of the multimerized product is not clear, only the raw materials and synthesis method are described.

Compound example R UI'I (]5) (17) Compound obtained by mixing equal moles of 3-hydroxy-2-naphthoic acid and αα dichloroxylene in a chlorobenzene solvent and reacting at high temperature with zinc chloride as a catalyst. .

(18) A compound obtained by mixing 2-hydroxy-1-naphthoic acid and paraformaldehyde (excess) and reacting the mixture at high temperature in xylene solvent with potassium hydroxide as a catalyst.

The aforementioned hydroxynaphthoic acid compounds can be synthesized by known methods. Further, multimerized products such as dimerized products can be synthesized by reacting a hydroxynaphthoic acid compound monomer with a vine compound that serves as a linking group.

For example, compound (11) has 1,4. The target compound is obtained by reacting dihydroxynaphthalene with carbon dioxide gas in an organic solvent using sodium hydride as a catalyst under high temperature and high pressure conditions.

In the case of dimerized products, for example, compound (1) can be obtained by reacting 3-hydroxy-2-naphthoic acid with α,a-dihalogenoxylylene in a chlorobenzene solvent using zinc chloride as a catalyst. be able to.

In the present invention, methods for incorporating hydroxynaphthoic acid, hydroxyquinolinecarboxylic acid, dimerized products or multimerized products thereof into the toner include a method of adding them inside the toner and a method of adding them 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, when internally added, it is preferably 0 parts per 100 parts by weight of the binder resin.
．． It is used in an amount of 1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight. When externally added, the amount is preferably 0.01 to io parts by weight per 100 parts by weight of the resin.

When externally added, it is particularly preferable to fix or embed the binder resin or colorant near the surface of the fine particles by mechanical impact.

First, as a pretreatment, the charge control agent (particles (B)) is dispersed and rubbed against the colored fine particles (particles (A)) so that it adheres to the colored fine particles by electrostatic force and van der Waals force. - Numerically, a mixer with high-speed stirring blades is used, but any mixer with mixing and dispersion functions may be used. Alternatively, a crusher, vibrating mill, etc. may be used with reduced impact force.

In order to make this pretreatment dispersion more uniform, a fluidity imparting agent, a lubricant, a conductivity imparting agent, etc. may be added as a dispersion aid, if necessary.

Furthermore, the dimerized or multimerized products of hydroxynaphthoic acid and hydroxyquinolinecarboxylic acid of the present invention can be prepared using conventionally known charge control methods such as alkyl salicylic acid complex salts, metal complex salts of monoazo dyes, boron compounds, and sulfonic acid pendant resins. It can also be used in combination with other agents.

Further, in the toner of the present invention, fine silica powder can be externally added to the toner. As the silica fine powder, silica fine powder manufactured by a dry method or a wet method can be used.

The dry method mentioned here is a method for producing fine silica powder produced by vapor phase oxidation of a silicon halide compound. For example, this method utilizes a thermal decomposition oxidation reaction of silicon tetrachloride gas in oxygen and hydrogen, and the basic reaction formula is as follows.

5iCf! 4+ 2 H2+ 02→SiO□+4 H
C4' Also, in this manufacturing process, for example, it is also possible to obtain a composite fine powder of silica and other metal oxides by using other metal halide compounds such as aluminum chloride or titanium chloride together with a silicon halide compound. Also includes.

On the other hand, various conventionally known methods can be applied to produce the silica fine powder used in the present invention by a wet method.

For example, the decomposition of sodium silicate with an acid can be expressed by the general reaction formula (the reaction formula is omitted below): Na2O.X5iOz+HCj' 10HzO=SiOz
・nHzO+NaCj) Other methods include decomposition of sodium silicate with ammonia salts or alkali salts, generation of alkaline earth metal silicate from sodium silicate and then decomposition with acid to form silicic acid, and ionization of sodium silicate solution. There are methods such as using exchange resin to produce silicic acid, and using natural silicic acid or silicate.

The silica fine powder referred to herein can be any of anhydrous silicon dioxide (silica) and other silicates such as aluminum silicate, sodium silicate, potassium silicate, magnesium silicate, and zinc silicate.

Among the above silica fine powders, the specific surface area due to nitrogen adsorption measured by the BET method is 30 m"/g or more (especially 50 to 40 m"/g).
0m2/g) is preferable.

Furthermore, the silica fine powder used in the present invention may be treated with a silane coupling agent or a treatment agent such as an organosilicon compound for the purpose of hydrophobization, if necessary, and a known method may be used. , treated with the above-mentioned treatment agent that reacts with or physically adsorbs the silica fine powder. Examples of such treatment agents include hexamethyldisilazane, trimethylsilane, trimethylchlorosilane, trimethylethoxysilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allyl phenyldichlorosilane, and benzyldimethylchlorosilane. Silane, bromomethyldimethylchlorosilane, α-chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane, triorganosilylmercaptan, trimethylsilylmercaptan, triorganosilylacrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, Dimethyldimethoxysilane, diphenyljethoxysilane, hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1
, 3-diphenyltetramethyldisiloxane, and dimethylpolysiloxane having 2 to 12 siloxane units per molecule and containing one Si-bonded hydroxyl group in each unit located at the end. These may be used alone or in a mixture of two or more.

Finally, the degree of hydrophobicity of the treated silica fine powder was determined to be 30 as measured by methanol titration test.
When the developer is hydrophobized so as to exhibit a value in the range of 80 to 80, the amount of triboelectric charge of the developer containing such fine silica powder becomes sharp and uniformly positive, which is preferable. Here, in the methanol titration test, the degree of hydrophobization of the silica fine powder having a hydrophobized surface is confirmed.

The "methanol titration test" specified herein for evaluating the degree of hydrophobicity of the treated silica fine powder is carried out as follows. 0.2g of silica fine powder sample in a capacity of 250m
50 mjl of water in the Erlenmeyer flask of R! Add to. Methanol is titrated from the burette until all of the silica is wetted. At this time, the solution in the flask is constantly stirred with a magnetic stirrer. The end point is observed when the entire amount of fine silica powder is suspended in the liquid, and the degree of hydrophobization is expressed as the percentage of methanol in the liquid mixture of methanol and water when the end point is reached.

Coloring agents used in the present invention include carbon black, lamp black, iron black, ultramarine, nigrosine dyeing, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa yellow G, rhodamine 6G, calco oil blue chrome yellow, Conventionally known dyes and pigments such as quinacridone, benzidine yellow, rose bengal, triarylmethane dyes, monoazo dyes, and disazo dyes and pigments can be used alone or in combination.

Examples of the resin used in the present invention include monopolymers of styrene and its substituted products such as polystyrene, poly-p-chlorostyrene, and polyvinyltoluene;
-Chlorstyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-methyl chloromethacrylate copolymer Polymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer , styrenic copolymers such as styrene-acrylonitrile-indene copolymers; polyvinyl chloride, phenolic resins, naturally modified phenolic resins, natural resin-modified maleic resins, acrylic resins, methacrylic resins, polyvinyl acetate, silicone resins, polyesters Resin, polyurethane, polyamide resin, furan resin, epoxy resin, xylene resin, polyvinyl butyral, terpene resin, coumaron indene resin,
Petroleum-based resins can be used.

Further, crosslinked styrenic copolymers are also preferred binder resins.

Examples of comonomers for the styrene monomer in the styrenic copolymer include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, and methacrylate. Acid, monocarboxylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide, etc. or substituted products thereof; e.g., maleic acid, butyl maleate , dicarboxylic acids having double bonds, such as methyl maleate, dimethyl maleate, etc.; vinyl esters, such as vinyl chloride, vinyl acetate, vinyl benzoate; such as ethylene, propylene, butylene, etc. Vinyl monomers such as ethylene olefins; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone; vinyl ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl isobutyl ether; Can be used alone or in combination.

As the crosslinking agent, compounds having two or more polymerizable double bonds are mainly used, such as aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; for example, ethylene glycol diacrylate,
Carboxylic acid esters having two double bonds such as ethylene glycol dimethacrylate and 1,3-butanediol dimethacrylate; divinyl compounds such as divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; and three or more vinyl Compounds having groups can be used alone or as a mixture.

In addition, when using a pressure fixing method, it is possible to use a binder resin for pressure fixing toner, such as polyethylene,
Examples include polypropylene, polymethylene, polyurethane elastomer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ionomer resin, styrene-butadiene copolymer, styrene-isoprene copolymer, linear saturated polyester, and paraffin.

Further, the toner for developing an electrostatic image of the present invention can also be used as a magnetic toner by containing a magnetic material. Magnetic materials used include iron oxides such as magnetite, γ-iron oxide, ferrite, and iron-rich ferrite; metals such as iron, cobalt, and nickel, or combinations of these metals with aluminum, cobalt, copper, lead, magnesium, and tin. , zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, alloys with metals such as vanadium, and mixtures thereof. It is desirable that these magnetic materials have an average particle size of about 0.1 to lpm, preferably about 0.1 to 0.5 μm, and the amount contained in the magnetic toner is 100% of the binder resin component.
40 to 150 parts by weight, preferably 60 to 150 parts by weight
It is 120 parts by weight.

In the magnetic toner using the charge control agent of the present invention, a toner having a volume average particle diameter of 3 to 15 μm can be used.

In particular, magnetic toner particles having a particle size of 5 μm or less are 12 μm or less.
~60% by number, 1 to 33% by number of magnetic toner particles having a particle size of 8 to 12.7 μm, and 16pm
Magnetic toner particles having a particle size of 2.0% by volume or less are contained, and the volume average particle size of the magnetic toner is 4 to 1 OIi
, +o is more preferable from the viewpoint of development characteristics.

The particle size distribution of toner can be measured by various methods.
In the present invention, it is appropriate to use a Coulter counter.

In other words, the measuring device is Coulter counter TA.
-Using an IT type (manufactured by Coulter), an interface (manufactured by Nikkaki) that outputs the number distribution and volume distribution and CX-
1 A personal computer (manufactured by Canon) is connected, and the electrolyte is approximately 1% Na (J') using primary sodium chloride.
Prepare the aqueous solution. For example, ■5OTON■-■ (manufactured by Coulter Engineering, Inc. Japan) can be used. The measurement method is 100 to 150 m of the electrolytic aqueous solution.
A surfactant, preferably an alkylbenzenesulfonate salt, is added in an amount of 0.1 to 51 mg as a fractionating agent to ρ, and the sample to be measured is added in an amount of 2 to 20 mg. The electrolytic solution in which the sample was suspended was dispersed for about 1 to 3 minutes using an ultrasonic disperser, and then dispersed using the Coulter Counter TA-II model using a 100 pm aperture, based on the number of particles.
The particle size distribution of particles of ~404 tm is measured and converted to determine the particle size distribution of the toner.

Furthermore, the toner of the present invention can be mixed with a carrier to form a two-component i.
- It can also be used as a ner. As the carrier that can be used in the present invention, known carriers can be used, such as iron powder, ferrite powder, magnetic powder such as nickel powder, glass beads, etc., and carriers whose surfaces are treated with resin etc. Those who have done so will be listed. Further, as the resin for coating the carrier surface, styrene-acrylic ester copolymer, styrene-methacrylic ester copolymer, acrylic ester copolymer, methacrylic ester copolymer,
Silicone resins, fluorine-containing resins, polyamide resins, ionomer resins, polyphenylene sulfide resins, etc., or mixtures thereof can be used.

The toner of the present invention may contain additives, if necessary. Examples of additives include lubricants such as zinc stearate, abrasives such as cerium oxide and silicon carbide, flow agents such as aluminum oxide, anti-caking agents, and conductivity imparters such as carbon black and tin oxide. There is a drug.

Further, fine powder of a fluorine-containing polymer such as fine powder of polyvinylidene fluoride is also a preferable additive from the viewpoint of fluidity, polishability, charging stability, and the like.

In addition, in order to improve mold releasability during hot roll fixing, waxy substances such as low molecular weight polyethylene, low molecular weight polypropylene, microcrystalline wax, carnauba wax, Sasol wax, paraffin wax, etc.
It is also one of the preferred embodiments of the present invention to add about 5% by weight to the toner.

In manufacturing the toner according to the present invention, the toner constituent materials as described above are thoroughly mixed using a ball mill or other mixer, and then kneaded (kneaded) using a hot kneader such as a hot roll kneader or an extruder, and then cooled and solidified. After that, it is preferable to obtain the toner by mechanical crushing and classification.Another method is to obtain the toner by dispersing the constituent materials in a binder resin solution and then spray drying; or from the core material or shell material. In the so-called microcapsule toner consisting of
Methods such as a method of incorporating a predetermined material into the core material, the shell material, or both can be applied.

Furthermore, it is possible to apply a polymerization toner production method in which a monomer to constitute a binder resin is mixed with a predetermined material to form an emulsified suspension and then polymerized to obtain a toner.

Furthermore, the toner according to the present invention can be produced by sufficiently mixing desired additives with a mixer such as a Henschel mixer, if necessary.

The toner of the present invention can be used in any conventionally known development process for visualizing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, and the like.

[Examples] Hereinafter, the present invention will be specifically explained using Examples, but these are not intended to limit the present invention in any way.

Note that all parts in the following formulations are parts by weight.

Add 2 parts by weight of hydroxynaphthoic acid compound or hydroxyquinoline carboxylic acid to 100 parts of East 11 resin, knead,
It was crushed and classified to obtain a powder. Powder 0,5 in iron powder carrier
The mixture was mixed for 3 minutes at a carrier ratio of 9.5, and the amount of charge was measured by a suction method.

The results of the amount of charge are shown in Table 1.

The charge amount of the sodium salt of compound (5) was evaluated in the same manner as in Example 1.

Bamoic acid disodium salt (manufactured by Aldrich Chemical Co.) -4.2 μc/g From these results, it is clear that when the hydroxynaphthoic acid of the present invention is made into a metal salt, its effect is lost.

After thoroughly mixing the above materials in a blender, they were kneaded in a twin-screw kneading extruder set at 150°C.

The obtained mixed material was cooled, coarsely pulverized with a cutter mill, and then finely pulverized with a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Furthermore, using the Coanda effect, the obtained classified powder was strictly classified and removed at the same time using a multi-division classifier (Nippon Steel Mining Co., Ltd. Elbow Jet Classifier) to remove ultra-fine powder with a volume average particle size of 7.9.
A fine powder of μm size was obtained.

100 parts of the obtained fine powder was added with silica fine powder (BET specific surface area: 300
m2/g) was added and mixed using a Henschel mixer to obtain a toner.

Next, 5 parts of the obtained toner were mixed with 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 μm to prepare a developer.

This developer was applied to a commercially available color electrophotographic copying machine CLC-1 (
A copying test was conducted using Canon (manufactured by Canon).

As a result, under an environmental condition of 23° C./60%, a bright black image with an image density of 1.43 was obtained from the initial stage, and an image with sufficient density was obtained even after 20,000 copies were made.

Next, when a copying test was conducted under environmental conditions of 15° C./10%, an image with a high density of 1.42 was obtained from the initial stage. Furthermore, even under the environmental conditions of 32°C/85%, the concentration of 1.
45 good images were obtained.

The same procedure as in Example 2 was carried out except that 5 parts of carbon black in Mitate ■ Example 2 was changed to 4 parts of copper phthalocyanine pigment (C, I, Pigment Blue 15:3), with a volume average particle diameter of 82IL1.
A fine powder of No. 11 was obtained, and silica was further mixed therein to obtain a toner.

Next, the same carrier as in Example 2 was mixed in the same ratio,
It was used as a developer.

This developer was subjected to a copying test in the same manner as in Example 2. As a result, under the environmental conditions of 23° C./60%, a good blue image with a density of 1.41 and no fog was obtained from the beginning. Sufficient images were obtained even after copying 20,000 copies.

Copying tests were also conducted under environmental conditions of 35°C/85% and 15°C/10%, and good results were obtained as in the case of 23°C/60%.

叉J1凱A Fine powder with a volume average particle size of 8.0 μm was obtained in the same manner as in Example 2, except that 5 parts of carbon black in Example 2 was changed to 4 parts of a quinacridone pigment (C, 1, Pigment Red 122). , further mixed with silica to obtain a toner.

Next, the same carrier as in Example 2 was mixed in the same ratio,
It was used as a developer.

This developer was subjected to a copying test in the same manner as in Example 2. As a result, under the environmental conditions of 23° C./60%, a good magenta image with a density of 1.43 and no fog was obtained from the beginning. No deterioration in image quality was observed even after 20,000 copies were made.

Copying tests were also conducted under environmental conditions of 35°C/85% and 15°C/10%, and good results were obtained as in the case of 23°C/60%.

Mitate 1j 5 parts of carbon black in Example 2 was mixed with yellow pigment (C
, 1, Pigment Yellow 17) A fine powder having a volume average particle size of 8.11 was obtained in the same manner as in Example 2 except that the amount was changed to 5 parts, and silica was further mixed to obtain a toner.

Next, the same ratio as in Example 2, 100 parts of carrier and 6 parts of toner, were mixed to form a developer.

This developer was subjected to a copying test in the same manner as in Example 2. As a result, under the environmental conditions of 23° C./60%, a good yellow image with a density of 1.43 and no fog was obtained from the beginning. No deterioration in image quality was observed even after 20,000 copies were made.

Copying tests were also conducted under environmental conditions of 35°C/85% and 15°C/10%, and good results were obtained as in the case of 23°C/60%.

A full-color image was obtained using the black, cyan, magenta, and yellow developers used in Examples 2 to 4, and a bright full-color image with excellent color mixing and gradation was obtained. .

(3 parts of Compound Example (7) The above materials were thoroughly mixed in a blender, and then kneaded in a twin-screw kneading press set at 130°C.

The obtained mixed material was cooled, coarsely pulverized with a cutter mill, and then finely pulverized with a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Furthermore, ultrafine powder was classified and removed from the obtained classified powder using a multi-division classifier using the Coanda effect (Elbowjet classifier manufactured by Niroku Mining Co., Ltd.) to obtain a fine powder with a volume average particle diameter of 8.2H.

100 parts of the obtained fine powder was added with silica fine powder (BET specific surface area: 300
6 parts of m''/gl O were added and mixed in a Henschel mixer to form a toner.

Next, 5 parts of the obtained toner were mixed with 100 parts of a styrene-acrylic coated ferrite carrier having an average particle size of 65 μm to prepare a developer.

This developer was applied to a commercially available color electrophotographic copying machine CLC-1 (
A copying test was conducted using Canon (manufactured by Canon).

As a result, under an environmental condition of 23° C./60%, a clear black image with an image density of 1.41 was obtained from the initial stage, and an image of good quality was obtained even after copying 1H sheets.

Next, a copying test was conducted under environmental conditions of 15°C/10% (at 7), a high density image of 1641 was obtained from the beginning.
444, an image of sufficient quality was obtained.

After mixing the above ingredients well in a blender.

The mixture was kneaded using a twin-screw kneading extruder set at 140°C.

The obtained kneaded material was cooled and coarsely pulverized using a cutter mill, and then finely pulverized using a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Furthermore, the obtained classified powder was strictly classified and removed at the same time using a multi-division classifier (elbow jet classifier manufactured by Niroku Mining Co., Ltd.) that utilizes the Coanda effect, and the volume average particle size was 8.7μ.
A fine powder of m was obtained.

Silica fine powder (BET specific surface area 200
+n''/g) was added and mixed in a Henschel mixer to obtain a magnetic toner.

When this toner was applied to a commercially available copying machine (trade name: NP-6650 manufactured by Canon ■) under an environmental condition of 23°C/60%, the image density was 1.36, and the image was clear with no fog or roughness. A great image was obtained. Furthermore, when 5H sheets were continuously copied and durability performance was examined, a good image with an image density of 1.34, which was comparable to the initial image, was obtained. In addition, when we measured the amount of triboelectric charge of the toner on the developing sleeve, it was -11.4 μc/g at the initial stage, and -11.1 gc/g after 50,000 copies were made, with no contamination of the sleeve being observed. There wasn't.

Next, a copying test was conducted under 15° C./10% environmental conditions, and similarly high-density and good-quality images were obtained. 5
Similarly, good results were obtained in a continuous copying test of 10,000 sheets.

When the same copying test and continuous copying test were conducted under the environmental conditions of 35° C./85%, good results were obtained.

Medicine] 1. Compound example (3) in Example 8 and 2 parts of compound example (9)
A fine powder having a volume average particle diameter of 8.6 μm was obtained in the same manner as in Example 8 except that the amount of the mixed powder was changed to 3 parts and the kneading temperature was changed to 130° C.

To 100 parts of this fine powder, a silica fine powder fBET which was hydrophobized with dimethyldichlorosilane had a specific surface area of 200 m.
2/g) was added and mixed in a Henschel mixer to obtain a magnetic toner.

When this toner was applied to a commercially available copying machine (product name NP-6650 manufactured by Canon ■) and a copying test was conducted under environmental conditions of 23℃/60%, the image density was as high as 1.34, and there was no fogging or roughness. A clear image with no blemishes was obtained. Subsequently, when 30,000 sheets were continuously copied and durability performance was examined, the image density was 1.
32, and a good image comparable to the initial image was obtained. Further, the amount of triboelectric charge of the toner on the developing sleeve did not change much between the initial stage and after 30,000 copies were made, and almost no sleeve contamination was observed.

Then, when a copying test was carried out under an environmental condition of 15° C./10%, similarly high density and good quality images were obtained.

Similarly good results were obtained in a continuous copying test of 30,000 copies.

The same copying test and continuous copying test were conducted under environmental conditions of 35° C./85% and good results were obtained.

Combine the above ingredients in a blender (after mixing).

The mixture was kneaded using a twin-screw kneading extruder set at 130°C.

The obtained mixed material was cooled, coarsely pulverized with a cutter mill, and then finely pulverized with a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Furthermore, fine powder and coarse powder were classified and removed from the obtained classified powder using a multi-division classifier that utilizes the Coanda effect (Nippon Steel Mining Co., Ltd.'s Elbow Jet Classifier), and the volume average particle size was 11.9 parts.
A fine powder was obtained.

Silica fine powder (BET specific surface area 200 m2/
g) 0.4 part was added and mixed in a Henschel mixer to obtain a magnetic toner.

This toner was applied to a commercially available copying machine (product name NP-6650).

When a copying test was carried out under the environmental conditions of 23℃/60% using a Canon product, the image density was as high as 1.33.
Clear images without fog or roughness were obtained. Subsequently, 30,000 sheets were continuously copied and the durability performance was examined. The image density was 1.31, and a good image comparable to the initial image was obtained.

Then, when a copying test was carried out under an environmental condition of 15° C./10%, similarly high density and good quality images were obtained.

Similarly, good results were obtained in a continuous copying test of 30,000 sheets.

The same copying test and continuous copying test were conducted under environmental conditions of 35° C./85% and good results were obtained.

After thoroughly mixing the above materials in a blender, they were kneaded in a twin-screw kneading extruder set at 140°C.

The obtained mixed material was cooled, coarsely pulverized with a cutter mill, and then finely pulverized with a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Further, fine powder was classified and removed from the obtained classified powder using a multi-division classifier (Elbow Jet classifier manufactured by Nippon Steel Mining Co., Ltd.) using the Coanda effect to obtain a fine powder with a volume average particle diameter of 12.1 m. .

100 parts of the obtained fine powder was added with a CBET specific surface area of 200 m of silica fine powder hydrophobized with dimethyldichlorosilane.
2/g) was added and mixed using a Henschel mixer to obtain a toner.

Next, 8 parts of the obtained toner were mixed with 100 parts of an acrylic coated ferrite carrier having an average particle size of 65 ILm to prepare a developer.

This developer is applied to a commercially available copying machine (product name NP-6650゜(
When a copying test was carried out under the environmental conditions of 23° C./60% using Canon Co., Ltd., an image with a good image quality of 1.32 was obtained. Using the above developer, 5,000 sheets were continuously copied and the durability was examined. As a result, good images comparable to the initial images were obtained.

Next, copying tests were conducted under environmental conditions of 15° C./10% and 35° C./83%, and similarly good results were obtained.

(Low molecular weight polypropylene 4 parts After mixing the above materials well in a blender,
The mixture was kneaded using a axial kneading extruder.

The obtained mixed material was cooled, coarsely pulverized with a cutter mill, and then finely pulverized with a pulverizer using a jet stream.
The obtained finely pulverized powder was classified using a fixed wall type wind classifier.

Furthermore, fine powder was classified and removed from the obtained classified powder using a multi-division classifier using the Coanda effect (Elbowjet classifier manufactured by Hikaku Mining Co., Ltd.) to obtain a fine powder with a volume average particle diameter of 11°9ILm.

To 100 parts of this fine powder, 1011.0 parts of the compound example and 0.3 parts of fine silica powder were mixed in a Henschel mixer to perform pretreatment.

Next, processing was performed using the apparatus shown in FIG. 1 under the conditions of a minimum gap of 1 mm, a blade circumferential speed of 60 m/see, and a processing time of 5 minutes. When the treated product was observed under an electron microscope, it was observed that the toner was partially adhered to and embedded in the surface of the toner. Furthermore, the adhesion rate was measured and found to be 93%. Further, 100 parts of this treated material was treated with silica fine powder CBET, which was hydrophobized with hexamethyldisilazane, with a specific surface area of 300 m''/
g) 0.4 part was added to obtain a toner.

This toner was applied to a commercially available copying machine (product name NP-6650).

When a copying test was carried out under the environmental conditions of 23° C./60% using Canon (manufactured by Canon), a clear image with an image density of 1.33 and no roughness or roughness was obtained. Furthermore, when we checked the durability performance by continuously copying 20,000 sheets, we found that the image density was 1.3.
A good image comparable to the initial image was obtained.

Next, a copying test was conducted under an environmental condition of 15°C/10%.
Similarly, images with high density and good quality were obtained. Similarly, good results were obtained in a continuous copying test of 20,000 sheets.

Furthermore, the same copying test was carried out under the environmental conditions of 35°C and 785%.
A continuous copying test was conducted and the results were good.

(The following is a blank space) Table [Effects of the Invention] As described above, the hydroxynaphthoic acid compounds and hydroxyquinoline carboxylic acid compounds of the present invention, or their dimerization or multimerization using continuous groups, are used as charge control agents. The toner containing the compound has a sufficient amount of triboelectric charge, and the amount of triboelectricity between the toner particles is uniform, giving a good image without fogging. In addition, since contamination of toner carriers such as sleeves and carriers by the charge control agent is reduced, even after a large number of copies are made, images with sufficient a degree can be stably obtained and the density is stable. Furthermore, since image density is less dependent on temperature and humidity, it provides images of excellent quality under a wide range of environmental conditions.

Further, since toner manufacturing conditions can be set widely, toner materials other than the charge control agent can be selected from a wide range.

Furthermore, it can be used in color toners because there is little color tone disturbance caused by the charge control agent.

[Brief explanation of the drawing]

FIG. 1 is an explanatory diagram schematically showing an example of an apparatus for fixing and embedding a specific compound used in the present invention on the surface of toner particles. 1... Rotating shaft 2... Rotor 3... Dispersion vane 4... Rotating piece (blade) 5... Partition disk 6... Casing 7... Liner
8... Impact part 9... Entrance chamber IO...
- Outlet chamber 11...Return path 12...Product take-out section 13...Raw material input valve 14...Blower 1
5...jacket

Claims (2)

[Claims] (1) 2-hydroxy-1-naphthoic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, 8-hydroxy-1-naphthoic acid, hydroxy group and carboxy group are adjacent on the quinoline skeleton Contains at least one selected from hydroxyquinolinecarboxylic acids arranged in matching positions, compounds in which substituents have been introduced to these hydroxynaphthoic acids and hydroxyquinolinecarboxylic acids, and compounds dimerized or multimerized using linking groups. A toner for developing electrostatic images characterized by: (2) Claim (1) characterized in that it contains a dimerized compound using xylylene or methylene as a continuous group.
) toner for developing electrostatic images.