JP2997705B2 - Toner for developing electrostatic images - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an electrostatic image developer used for electrophotography, electrostatic printing, and the like, and more particularly, to a negatively chargeable toner for development.

(Prior Art) As disclosed in JP-A-61-147261,
Methods of developing an electrostatic image using toner are roughly classified into a method using a so-called two-component developer in which a toner and a carrier are mixed, and a method using a single-component developer in which a toner is used alone without being mixed with a carrier. There is a method using an agent.

According to the above method, the toner and the carrier are charged with different polarities by agitating and rubbing the toner and the carrier, and an electrostatic image is visualized by the charged toner. , A cascade method using a bead carrier, a fur brush method, and the like.

The latter one-component developing method includes a powder cloud method in which toner particles are sprayed, a contact developing method in which toner particles are brought into direct contact with an electrostatic latent image surface for development (also called touch-down development), and a magnetic method. And an induction developing method in which the conductive toner is brought into contact with the surface of the electrostatic latent image.

As a toner applied to these various developing methods, fine powder in which a coloring agent such as carbon black is dispersed in a binder resin made of a natural resin or a synthetic resin is used. For example, particles obtained by finely pulverizing a dispersion of a colorant in a binder resin such as polystyrene to about 1 to 30 μm are used as toner. Further, those in which a magnetic material such as magnetite is further contained in these components are used as a magnetic toner.

As described above, the toner used in various developing methods has positive or negative charge depending on the polarity of the electrostatic image to be developed.However, to retain the charge in the toner, a toner component is used. Although the frictional charging property of a certain binder resin can be used, in this method, since the charging property of the toner is small, an image obtained by development is easily fogged and becomes unclear. Therefore, in order to impart a desired triboelectric charging property to the toner, a dye, a pigment, or a charge control agent that imparts charging property is added.

A negatively charged toner is used for developing a positive latent image due to a positive charge and a reversal latent image due to a negative charge. Conventionally, as a negative charge control agent for toner, metal complex salts of monoazo dyes, nitrohumic acid and its salts, salicylic acid, naphthoic acid, metal complexes of dicarboxylic acid such as Co, Cr and Fe, sulfonated copper phthalocyanine pigment, nitro There are styrene oligomers, chlorinated paraffins, melamine resins and the like into which groups and halogens have been introduced, but these dyes and resins have complicated structures, inconsistent properties and poor stability. In addition, during thermal kneading, decomposition or mechanical shock, friction, changes in temperature and humidity conditions and the like easily cause decomposition or deterioration, and charge controllability is likely to be degraded. In many cases, chargeability changes depending on the environment. Further, when a conventional toner containing the charge control agent is used for a long period of time, filming on the photoconductor may occur due to poor charging.

Further, polyester resins and epoxy resins have recently been often used as binder resins for toners due to advantages such as resistance to fusing PVC mat and not impairing the original color of the color material of the color toner. However, when a polyester resin or an epoxy resin is used as a binder resin in a toner, the charge amount is low in any case, or the charge amount decreases when used repeatedly even if the charge amount is high, resulting in fogging and toner scattering. There was a problem that it was difficult to use. This is because of the chemical structure of polyester resin and epoxy resin.
It is considered that functional groups such as COOH and -OH groups are present, which hinders maintenance of stable chargeability.

(Problems to be Solved by the Invention) An object of the present invention is to provide friction between a toner and a carrier in the case of a two-component developer and friction between a toner and a charging member such as a developing sleeve or a blade in the case of one-component development. Charging is stable, and the triboelectric charge distribution is sharp and uniform,
An object of the present invention is to provide a toner which has a good charge rising property and environmental stability and can be controlled to a charge amount suitable for a developing method to be used. Yet another object is to provide a vivid color toner. Further, another object of the present invention is to provide a toner in which the toner is used in combination with a carrier coated with a silicone resin to stably charge the toner and the carrier, to provide a sharp and uniform charge distribution of the toner, An object of the present invention is to provide a toner which has a high charge rising speed, is free from background contamination and toner scattering at the time of image formation, and has high fidelity equivalent to an initial image even during continuous use.

(Means for Solving the Problems) As a result of intensive studies, the present inventors have found that in a toner containing a binder resin, a colorant and a charge control agent as main components, the following general formula (I) or (II) By incorporating at least one of the fluorine-containing compounds shown as a charge control agent, a negatively chargeable toner for an electrostatic image, which improves the above-mentioned conventional disadvantages, could be obtained.

However, R ₁ ; H, an alkyl group having 1 to 10 carbon atoms, an aryl group m, n; a positive integer However, R ₁ ; an alkyl group, an aryl group n; a positive integer Further, the negatively chargeable toner charge control agent for electrostatic image development is a fluorinated compound represented by the above general formula (I) or (II). When at least one kind and a metal-containing azo dye were included as a charge control agent, a toner having better negative chargeability was obtained, and good results were obtained even when the binder resin was a polyester resin or an epoxy resin.

In the present invention, typical specific examples of the compound of the above general formula used as a charge control agent include the following, all showing a white or pale yellow image.

The amount of the compound used as the charge control agent in the present invention is determined by the type of the binder resin, the presence or absence of the additives used as necessary, and the toner production method including other dispersion methods. Although not limited, it is preferable that the binder resin 100
It is used in the range of 0.1 to 20 parts by weight with respect to parts by weight.
If the amount is less than 0.1 part by weight, the negative band property of the toner is insufficient, which is not practical. If it exceeds 20 parts by weight, the chargeability of the toner is too large, the electrostatic attraction with the carrier increases, and the fluidity of the developer decreases and the image density decreases.

As the metal-containing azo dye used as the negative charge control agent together with the fluorine-containing compound represented by the general formula (I) or (II), any of the currently commercially available metal-containing azo dyes can be used. For example, there are Eizen Spiron Black TRH and Eizen Color T-37, 77 manufactured by Hodogaya Chemical Co., Ltd., and Bontron S-32, 34, 40, 44 manufactured by Orient Chemical Co., but are not limited thereto.

Examples of the binder resin used in the present invention include styrene such as polystyrene, poly p-chlorostyrene, and polyvinyl toluene, and a monomer of a substituent thereof, styrene-
p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene -Butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-
Chloromethyl methacrylate 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-maleic acid copolymer, styrene-maleic acid ester copolymer, etc. Styrene copolymer, 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, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax And the like, and can be used alone or as a mixture.

Further, as examples of binder resins particularly suitable for pressure fixing, the following resins can be used alone or in combination.
That is, polyolefin (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide, polyfluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer 5 to 30:95 to 7
0), olefin copolymer (ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl chloride copolymer, Ethylene-vinyl acetate copolymer, ionomer resin), polyvinyl pyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin, and the like.

Further, particularly, the polyester resin used in the present invention is obtained by condensation polymerization of an alcohol and a carboxylic acid. Examples of the alcohol include polyethylene glycol, diethylene glycol, triethylene glycol,
Diols such as 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol, 1,4-butynediol, 1,4-bis (hydroxymethyl) cyclohexane, bisphenol A, Etherified bisphenols such as hydrogenated bisphenol A, polyoxyethylenated bisphenol A and polyoxypropylene bisphenol A, and dihydric alcohol units obtained by substituting these with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms , Other dihydric alcohol units, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaethritol, dipentaethritol, tripentaethritol, sucrose, 1 , 2,4
-Butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxy Examples thereof include trihydric or higher polyhydric alcohol monomers such as methylbenzene. Further, as the carboxylic acid used to obtain the polyester resin, for example, palmitic acid, stearic acid, monocarboxylic acids such as oleic acid,
Maleic acid, fumaric acid, mesaconic acid, citraconic acid,
Itaconic acid, glutaconic acid, phthalic acid, isophthalic acid,
Terephthalic acid, cyclohexanedicarboxylic acid, succinic acid, adipic acid, sebacic acid, malonic acid and the like. Divalent organic acid monomers obtained by substituting these with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, anhydrides of these acids, dimers of lower alkyl esters and linoleic acid, and other divalent Organic acid monomer, 1,2,4-benzenetricarboxylic acid, 1,
2,5-benzenetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid,
1,2,4-naphthalenetricarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2-methylenecarboxypropanetetra (methylenecarboxyl ) Methane, 1,2,7,
Examples include tri- or higher-valent polycarboxylic acid monomers such as 8-octanetetracarboxylic acid embol trimer acid and anhydrides of these acids.

Furthermore, the epoxy resin used in the present invention is a polycondensate of bisphenol A and epichlorohydrin and the like, for example, epomic R362, R364, R365, R366,
R367, R369 (all manufactured by Mitsui Petrochemical Industries, Ltd.), Epicoat YD-011, YD-012, YD-014, YD-904, YD-017
(Made by Toto Kasei Co., Ltd.), Epikote 1002, 1004, 10
There are commercially available products such as 07 (all manufactured by Shell Chemical Company).

Examples of the coloring agent used in the present invention include carbon black, lamp black, iron black, ultramarine, nigrosine dye, aniline blue, phthalocyanine blue, phthalocyanine green, Hansa Yellow G, rhodamine 6G, lake,
Calco oil blue, chrome yellow, quinacridone,
Any conventionally known dyes and pigments such as benzidine yellow, rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes and pigments can be used alone or in combination.

Further, the toner of the present invention may further contain a magnetic material and be used as a magnetic toner. As the magnetic material contained in the magnetic toner of the present invention, magnetite, hematite, iron oxide such as ferrite, iron, metals such as cobalt nickel or aluminum of these metals, cobalt, copper, lead, magnesium, tin, zinc, Antimony, beryllium, bismuth, cadmium, calcium,
Alloys of metals such as manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof are given.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 20 μm, and are contained in the toner in an amount of about 20 to 200 parts by weight, particularly preferably 100 parts by weight of the resin component. It is about 40 to 150 parts by weight.

Further, the toner of the present invention is used as a two-component developer by mixing with a carrier powder. As the carrier that can be used in the present invention, all known carriers can be used, for example, iron powder, ferrite powder, powder having magnetic properties such as nickel powder, glass beads, and the like, and those obtained by treating their surfaces with a resin or the like. And the like.

Further, the toner of the present invention may optionally contain additives. As additives, for example, Teflon, a lubricant such as zinc stearate or a cerium oxide, an abrasive such as silicon carbide, or, for example, colloidal silica,
Examples include fluidity-imparting agents such as aluminum oxide, anti-caking agents, conductivity-imparting agents such as carbon black and tin oxide, and fixing aids such as low-molecular-weight polyolefin.

〔Example〕

Hereinafter, the present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
All parts are parts by weight.

Example 1 Styrene-2-ethylhexyl acrylate copolymer 100 parts CI Pigment Blue 155 5 parts Charge control agent of Exemplified Compound 1) 2 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer, and then 130 to 140 using a roll mill. The mixture was heated and melted at a temperature of about 30 ° C. for about 30 minutes, cooled to room temperature, and the obtained kneaded product was pulverized and classified to obtain a blue toner having a particle size of 5 to 20 μm.

2.5 to 25 parts of this toner and 100 to 25 coated with silicone resin
97.5 parts of a 0 mesh ferrite carrier was mixed with a ball mill to obtain a developer.

Next, the above developer was set in FT4060 manufactured by Ricoh Co., Ltd., and development was performed. As a result, a good image was obtained, and the image did not change even after copying 100,000 sheets.

When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −19.7 μC / g, which was not much different from the initial value.

In a high humidity environment of 35 ° C and 90% RH,
Even under a low temperature environment of% RH, an image equivalent to that at normal humidity was obtained.

 Also, there was no toner filming on the photoconductor.

Example 2 Polyester resin (Lunaper 1438- manufactured by Arakawa Chemical Co., Ltd.)
6) 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent of Exemplified Compound 1) 1.5 parts The raw material mixture having the above composition is melt-kneaded, cooled, pulverized and classified in the same manner as in Example 1 to obtain a powder having a size of 5 to 25 μm. A black toner having a diameter was obtained.

2.5 to 25 parts of this toner and 100 to 25 coated with silicone resin
97.5 parts of a 0 mesh ferrite carrier was mixed with a ball mill to obtain a developer.

Then, when a copying test was performed using this developer in the same manner as in Example 1, a good image having high sharpness was obtained, and the image did not change even after copying 100,000 sheets.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was −18.8 μC / g, and the charge amount of the toner after 100,000 sheets was copied was −16.6 μC / g, which is almost the same as the initial value. There was no. Further, under a high humidity environment of 35 ° C. and 90% RH and in a low humidity environment of 10 ° C. and 15% RH, images equivalent to those at normal humidity were obtained.

 There was no toner filming on the photoreceptor.

Comparative Example 1 In place of the charge control agent of Exemplified Compound 1) of Example 1,
A developer was prepared and a copy test was performed in the same manner as in Example 1 except that zinc salicylate (E-84 manufactured by Orient Chemical Industries) was used. As the initial image, a clear image without fogging was obtained, but an unclear image with fogging started at around 100,000 sheets, and toner filming was observed on the surface of the photoreceptor.
When an image test was performed in a high-humidity environment of 35 ° C. and 90% RH, the image density was as low as 0.95, and an unclear image with fog was obtained. When the charge amount was measured in the same manner as in Example 1, the initial charge amount was −12.5 μC / g, but after 100,000 sheets, it decreased to −5.5 μC / g.

Example 3 Epoxy resin (R365 manufactured by Mitsui Petrochemical Co., Ltd.) 80 parts Epoxy resin (YD-017 manufactured by Toto Kasei Co., Ltd.) 20 parts CI Pigment Blue 15 5 parts CI Pigment Yellow 17 5 parts Charge control agent of Exemplified Compound 2) 2.5 parts After sufficiently stirring and mixing the mixture having the above composition in a Henschel mixer, the mixture is heated and melted at a temperature of 130 to 140 ° C. for about 30 minutes by a roll mill and cooled to room temperature, and then the obtained mixture is pulverized and classified to have a particle size of 5 to 20 μm. A green toner was obtained. This toner 10
To 0 part, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed by a speed kneader to obtain a toner.

This toner is charged into a developing device as shown in FIG.
When continuous copying was performed and an image test was performed, a good image was obtained. The image did not change even after 50,000 sheets of images were displayed.

The developing method will be described. As shown in the drawing, the toner 6 contained in the toner tank 7 is
, The toner is forcibly brought to the toner supply member 4, and the toner is supplied to the toner supply member 4. Then, the toner taken into the toner supply member 4 is carried to the toner transport member 2 by the rotation of the toner supply member 4 in the direction of the arrow, and
As a result, the toner conveying member 2 strongly rotates in the direction of the arrow, and the toner layer thickness regulating member 3
As a result, a uniform toner thin layer is formed and the toner is triboelectrically charged. Thereafter, the latent image is transported to the surface of the electrostatic latent image carrier 1 which is in contact with or in proximity to the toner conveying member 2, and the latent image is developed.

The electrostatic latent image is formed by applying a negative DC voltage of 800 V to the organic photoreceptor, exposing it to form a latent image, and developing the image reversibly.

In addition, in order to measure the specific charge of the toner on the toner conveying member: Q / M, the toner on the toner conveying member is sucked through a Faraday cage having a filter layer on the outlet side, and trapped in the Faraday cage. The Q / M was measured by a suction method specific charge amount measuring device for measuring the specific charge of the obtained toner, and it was confirmed that the toner was sufficiently charged at -12.4 μC / g.

In addition, the charge amount in running 50,000 sheets was -9.6 μC / g, which was not much different from the initial value.

Further, even under high and low humidity, image quality equivalent to that at normal temperature was obtained. Also, there was no toner filming on the photoconductor.

Example 4 Polyester resin (Lunaper 1447, Arakawa Chemical Co., Ltd.) 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent of Exemplified compound 1) 0.8 part Metal-containing monoazo dye (S-34, Orient Chemical Industries) 2 parts The raw material mixture was melt-kneaded, cooled, pulverized, and classified in the same manner as in Example 1 to obtain a black toner having a particle size of 5 to 25 μm.

2.5 to 100 parts of this toner and 100 to 100% silicone resin
97.5 parts of a 250 mesh ferrite carrier was mixed with a ball mill to obtain a developer.

Then, when a copying test was performed using this developer in the same manner as in Example 1, a good image having high fidelity was obtained, and the image did not change even after copying 100,000 sheets. When the charge amount of the toner was measured by a blow-off method, the initial charge amount was −22.6 μC / g, and the charge amount of the toner after 100,000 sheets was copied was −20.8 μC / g, which was almost the same as the initial value. Was.
In a high humidity environment of 35 ° C and 90% RH, and at 10 ° C and 15% RH
Even under such a low humidity environment, an image equivalent to that at normal humidity was obtained.

 Also, there was no toner filming on the photoconductor.

Comparative Example 2 A toner was prepared and an image test was performed in the same manner as in Example 4 except that the charge control agent of Exemplified Compound 1) was omitted. The initial image was a poor image with some fogging, and the fog increased from around the 5,000th sheet, resulting in an unclear image. When a copy test was performed in a high humidity environment of 35 ° C. and 90% RH, the image density was as low as 0.86, and fogging occurred. When the charge amount was measured in the same manner as in Example 1, the initial charge amount was as low as −10.5 μC / g, and after 5,000 sheets, it was lowered to −1.5 μC / g.

Example 5 100 parts of polyester resin (Lunaper 1447 manufactured by Arakawa Chemical Co., Ltd.) 5 parts of candelilla wax 102 (manufactured by Noda Wax Co., Ltd.) 5 parts CI pigment red 57 5 parts CI pigment red 48 3 parts Charge control agent of exemplified compound 3) 2.5 parts After sufficiently stirring and mixing the mixture of the composition with a Henschel mixer, the mixture is heated and melted at a temperature of 110 to 120 ° C. for about 40 minutes by a roll mill, and after cooling to room temperature, the obtained kneaded material is pulverized and classified to have a particle size of 5 to 20 μm. A red toner was obtained. This toner 10
To 0 part, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed by a speed kneader to obtain a toner. When a copying test was performed using this toner in the same manner as in Example 3, a clear and good image was obtained, and the image did not change even after copying 50,000 sheets. When the charge amount of the toner was measured in the same manner as in Example 3, the initial charge amount was -11.7 μC / g, indicating a sufficient charge, and the charge amount after copying 50,000 sheets was −10.2 μC / g, which was the initial value. And there was little difference.

Further, even under high and low humidity, image quality equivalent to that at normal temperature was obtained. Also, there was no toner filming on the photoconductor.

Examples 6 to 9 Using the charge control agent of the general formula (I) and the toner composition shown in the following table, a toner was prepared in the same manner as in Example 1, and the developer was combined with a carrier as shown in the table. Obtained.
The image properties and chargeability of these developers are also summarized in Table 1.

Example 10 Styrene-2-ethylhexyl acrylate copolymer 100 parts CI Pigment Blue 15 5 parts Charge control agent of Exemplified Compound 19) 3 parts The mixture having the above composition was thoroughly stirred and mixed in a Henschel mixer, and then 130 to 140 using a roll mill. After heating and melting at a temperature of about 30 ° C. for about 30 minutes and cooling to room temperature, the obtained kneaded product was pulverized and classified to obtain a blue toner having a particle size of 5 to 20 μm.

2.5 to 25 parts of this toner and 100 to 25 coated with silicone resin
97.5 parts of a 0 mesh ferrite carrier were mixed with a ball mill to obtain a developer.

Next, when a copy test was performed in the same manner as in Example 1 using the above developer, a good image was obtained.
It did not change after 100,000 copies.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -18.2 μC / g, and the charge amount of the toner after 100,000 sheets was copied was −16.7 μC / g, which is a little different from the initial value. Did not.

In a high humidity environment of 35 ° C and 90% RH,
Even under a low humidity environment of% RH, an image equivalent to that at normal humidity was obtained.

 There was no toner filming on the photoreceptor.

Example 11 Polyester resin (Lunaper 1438- manufactured by Arakawa Chemical Co., Ltd.)
6) 100 parts Polypropylene 5 parts Carbon black 10 parts Charge control agent of Exemplified compound 19) 2.5 parts The raw material mixture having the above composition was melt-kneaded, cooled, pulverized and classified in the same manner as in Example 1 to obtain particles of 5 to 25 μm. A black toner having a diameter was obtained.

2.5 to 25 parts of this toner and 100 to 25 coated with silicone resin
97.5 parts of a 0 mesh ferrite carrier was mixed with a ball mill to obtain a developer.

Next, when a copy test was performed using this developer in the same manner as in Example 1, a good image having high sharpness was obtained, and the image did not change even after copying 100,000 sheets.

When the charge amount of the toner was measured by the blow-off method, the initial charge amount was -17.4 μC / g, and the charge amount of the toner after 100,000 sheets was copied was −15.7 μC / g, which is almost the same as the initial value. Did not. Further, under a high humidity environment of 35 ° C. and 90% RH and in a low humidity environment of 10 ° C. and 15% RH, images equivalent to those at normal humidity were obtained.

 There was no toner filming on the photoreceptor.

Example 12 Epoxy resin (R365 manufactured by Mitsui Petrochemical Co., Ltd.) 80 parts Epoxy resin (YD-017 manufactured by Toto Kasei Co., Ltd.) 20 parts CI Pigment Blue 15 5 parts CI Pigment Yellow 17 5 parts Charge control agent of Exemplified Compound 20) 3.5 parts In the same manner as in Example 1 using the mixture having the above composition,
A green toner having a particle size of 20 μm was obtained. To 100 parts of this toner, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed with a speed kneader to obtain a toner. When the charge amount of the toner was measured in the same manner as in Example 3, it was confirmed that the toner was sufficiently charged at -10.1 μC / g. When a copy test similar to that of Example 3 was performed, the charge amount after copying 50,000 sheets was −8.4 μC / g.
And the initial value did not differ much. Further, even under high humidity and low humidity, image quality equivalent to that at normal humidity was obtained. Also, there was no toner filming on the photoconductor.

Example 13 100 parts of polyester resin (Lunaper 1447 manufactured by Arakawa Kasei Co., Ltd.) 5 parts of polypropylene 10 parts of carbon black 10 parts Charge control agent of exemplified compound 19) 1 part Metal-containing monoazo dye (S-34 manufactured by Orient Chemical Industries)
2 parts The raw material mixture having the above composition was melt-kneaded, cooled, pulverized, and classified in the same manner as in Example 1 to obtain a black toner having a particle size of 5 to 25 μm.

2.5 to 25 parts of this toner and 100 to 25 coated with silicone resin
97.5 parts of a 0 mesh ferrite carrier was mixed with a ball mill to obtain a developer.

Next, a copy test was performed using this developer in the same manner as in Example 1. As a result, a good image having high fidelity was obtained, and the image did not change even after copying 100,000 sheets. Also,
When the charge amount of the toner was measured by the blow-off method, the initial charge amount was −20.2 μC / g, and the charge amount of the toner after copying 100,000 sheets was −18.8 μC / g, which was almost the same as the initial value. . In a high humidity environment of 35 ° C and 90% RH, and 10
Even under a low humidity environment of 15 ° C. and 15% RH, an image equivalent to that at normal humidity was obtained. There was no toner filming on the photoreceptor.

Example 14 100 parts of polyester resin (Lunapelle 1447 manufactured by Arakawa Chemical Co., Ltd.) 5 parts of candelilla wax 102 (manufactured by Noda Wax Co., Ltd.) 5 parts CI pigment red 57 5 parts CI pigment red 48 3 parts Charge control agent of exemplified compound 21) 2.5 parts After the mixture of the composition is sufficiently stirred and mixed by a Henschel mixer, the mixture is heated and melted at a temperature of 110 to 120 ° C. for about 40 minutes by a roll mill, and after cooling to room temperature, the obtained kneaded material is pulverized and classified to a particle size of 5 to 20 μm. Red toner was obtained. This toner
To 100 parts, 3 parts of silicon carbide (particle size: 2 μm) and 0.1 part of hydrophobic colloidal silica were sufficiently stirred and mixed by a speed kneader to obtain a toner. When a copy test was performed using this toner in the same manner as in Example 3, a clear and good image was obtained, and the image did not change even after copying 50,000 sheets. When the charge amount of the toner was measured in the same manner as in Example 3, the initial charge amount was −9.8 μC / g, indicating a sufficient charge, and the charge amount after copying 50,000 sheets was −8.3 μC / g. There was little difference between g and the initial value. In addition, image quality equivalent to that at normal humidity was obtained in both high and low humidity. Also, there was no toner filming on the photoconductor.

Examples 15 to 18 Toners were prepared in the same manner as in Example 1 with the toner compositions shown in the following table using the charge control agent of the general formula (II), and a developer was obtained in combination with the carrier. Table 2 also summarizes the image properties and chargeability of these developers.

(Effects) As described above, the toner for developing an electrostatic image of the present invention uses the above-mentioned specific compound as a charge controlling agent, so that even after continuous copying, an image having the same quality as the initial image can be obtained. As a result, a toner having stable negative triboelectric chargeability can be obtained. Further, a toner having good dispersibility in a binder resin and excellent environmental stability can be obtained, and a clear color image can be obtained. In particular, when the fluorine-containing compound and the metal-containing azo dye are used in combination as the charge control agent, the stability of the negative charge property can be increased. Further, the toner for developing an electrostatic image of the present invention can impart sufficient charge stability to a binder resin having an unstable charge such as polyester or epoxy resin, and thus can be used as a color toner or a low-temperature fixing toner.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a developing device using the non-magnetic one-component toner of the present invention useful for carrying out the method of the present invention. 1 .... Electrostatic latent image carrier, 2 .... Toner conveying member, 3 ....
Toner layer thickness regulating member, 4... Toner supply member, 5... Stirring blade, 6... Toner, 7.

Continuation of the front page (72) Inventor Chiharu Mochizuki 1-3-6 Nakamagome, Ota-ku, Tokyo Inside Ricoh Co., Ltd. (56) References JP-A-55-76353 (JP, A) JP-A-1-235959 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) G03G 9/08-9/097

Claims (4)

(57) [Claims] 1. A toner mainly comprising a binder resin, a colorant and a charge control agent, wherein at least one fluorine-containing compound represented by the following general formula (I) or (II) is contained as a charge control agent. A negatively chargeable toner for electrostatic charge development. Provided that R ₁ : H, an alkyl group having 1 to 10 carbon atoms and an aryl group, m and n are positive integers However, R ₁ : alkyl group, aryl group n: positive integer 2. The negatively chargeable toner for developing an electrostatic image according to claim 1, wherein the binder resin of the toner contains at least one of a polyester resin and an epoxy resin. 3. A toner mainly comprising a binder resin, a colorant and a charge control agent, wherein at least one of the fluorine-containing compounds represented by the above general formula (I) or (II) and a metal-containing azo dye are used. A negatively charged toner for developing an electrostatic image, characterized in that it is contained as a charge control agent. 4. The negatively chargeable toner for developing electrostatic images according to claim 3, wherein the binder resin of the toner contains at least one of a polyester resin and an epoxy resin.