JPS61145560A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a toner uniform, stable, and easily controllable in the amt. to be triboelectrified, prevented from flocculation during storage, and also superior in fixability, etc., by incorporating a specified org. tin compd. as a charge controller in the toner. CONSTITUTION:The electrostatic charge image developing toner is obtained by incorporating as the charge controller a tin compd. represented by the formula shown on the right, R being aralkyl optionally substd. by a group, such as halogen or NH2, together with a synthetic binder resin, and a colorant, etc., thus permitting this charge controller to be good in dispersibility in polymers, prevented from filming trouble, and the toner contg. it to stably form an image high in density, good in halftone reproducibility, without being affected by change of temp. and humidity, and further, a sharp color image, too.

Description

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

11. Conventionally, as an electrophotographic method, U.S. Patent No. 2.297.69
No. 1, Japanese Patent Publication No. 42-23910.

Various methods are described in Japanese Patent Publication No. Sho 43-24748, etc., but these methods basically involve applying a uniform electrostatic charge onto a photoconductive insulating layer and irradiating the insulating layer with a light image. An electrostatic latent image is formed by doing this, and then the latent image is developed and visualized using a fine powder called toner in the art, and if necessary, after transferring the powder image to paper etc., heating,
Fixing is performed by pressurization or solvent vapor.

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 the 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; and 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. Finely pulverized particles of about 1 to 30 IL 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 impart a charge to the toner, Z is a component of the toner.
It is also possible to utilize only the triboelectricity of the resin, but in this method, the toner has a low chargeability, so the image obtained by development is likely to fog and become unclear. 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 today in fields such as electrophotography include the following.

(1) Things that control the toner to be positively charged Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983), basic dyes (e.g. C, 1, B
a5ic Yellow 2 (C, 1,4100G)
, G, 1. Ba5ic Yellow 3, C, 1,
Ba5ic Red l (C, 1, 45180),
C, 1, Basic Red 9 (C, 1, 4250
0), C, I.

Ba5ic Violet 1 (C, 1, 42535)
, C,1,Ba5ic Violet3(C,I,
42555), C,l-Ba5ia Violet
10 (C,1,45170), C,1,Ba5ic
Violet 14 (C, 1, 42510), C, I
.

Ba5ic Blue 1 (C, 1, 42025)
,C,1,Ba5ic Blue 3(C,1,5
1005), C,1,Ba5ic Blue 5(
C, I, 42140), C31, Ba5ic Bl
ue 7 (C, 1, 42595), C, 1, Ba5i
c Blue 9 (C, 1, 52015), C, 1
, Ba5ic Blue 24 (G, 1.5203
0), C,1,Ba5ic Blue25(C,1,
52025), C,1,Ba5ic Blue2B(
C,1,44045), C,1,Ba5ic Gr
een 1 (C, 1, 42040), C, 1, B
a5ic Green 4 (C, 1,42000)
, C, 1,45170, etc.), lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten-molybdic acid, tannic acid, lauric acid, gallic acid, ferricyanide). compounds, ferrocyanides, etc.), C, I.

5olvent Black 3 (C, 1, 28150
), Hansa Yellow G (C, 1,1188G), C
, iMordant Black 11, G, I.

Pigment Black 1, Gilt Night,
asphalt etc.

Quaternary ammonium salt 1 For example, benzylmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, organic tin compounds such as dibutyltin oxide, metal salts of higher fatty acids, inorganic fine powders such as glass, mica, zinc oxide, etc., EDTA, Metal complexes of acetylacetone, etc.

Polyamine resins such as vinyl polymers containing amine 7 groups and condensation polymers containing amine groups.

(2) A device that controls toner to be negatively charged
No. 0153, No. 43-27596, No. 44-8397
A metal complex salt of a heptanoazo dye described in No. 45-26478.

Co of salicylic acid, naphthoic acid, and guicarboxylic acid described in Japanese Patent Publications No. 55-42752, No. 58-41508, No. 59-7384, No. 59-7385, etc.
, Cr, Fe, etc. metal complexes.

Sulfonated copper phthalocyanine pigment.

Styrene oligomers with nitro groups and halogens introduced, chlorinated paraffins, melamine resins, etc.

However, as mentioned above, the use of conventional charge control agents still has many problems that need to be improved. That is,
Many of these charge control agents are derived from dyes and pigments, and generally have complex structures, inconsistent properties, poor stability, and strong coloring properties. Recently, there are some products that have been proposed that are different from the above-mentioned ones, but none of them exceeds dye- and pigment-based ones in terms of overall performance, and although they have many disadvantages as listed below, In most cases, dye and pigment-based charge control agents are used.

In other words, these charge control agents are usually added to a thermoplastic resin, which also serves as a binder resin, and are contained in a toner prepared through processes such as hot melt dispersion, pulverization, and classification. In the manufacturing process, the above-mentioned dye and pigment-based charge control agents often cause problems. For example, as mentioned above, these charge control agents have poor stability as substances, and may decompose during hot kneading. It is easy to decompose or change in quality due to mechanical shock, friction, changes in temperature and humidity conditions, etc., and it is easy to cause a phenomenon in which charge controllability is reduced, and toners containing these dyes and pigments as charge control agents are not used in copying machines. When developed, the number of copies increases! /'s, the charge control agent may decompose or change in quality, causing toner deterioration during repeated copying operations.

Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they pose the fatal problem of causing differences in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used in the past to achieve more uniform dispersion. However, unreacted fatty acids or salt dispersion products are often exposed on the toner surface and contaminate the carrier or toner carrier, causing a decrease in the fluidity of the toner, fog, and a decrease in image density. It becomes. Alternatively, in order to improve the dispersion of these charge control agents into the resin, a method has also been adopted in which charge control agent powder and resin powder are mechanically pulverized and mixed in advance and then hot melt-kneaded. However, the inherent poor dispersion cannot be avoided, and at present, sufficient uniformity of charge has not yet been obtained for practical use.

Furthermore, there is a problem in that most of the substances generally known as charge control agents are dark in color and cannot be incorporated into bright chromatic color developers.

Furthermore, many charge control agents are hydrophilic, and due to poor dispersion in these resins, dyes are exposed on the toner surface when the toner is crushed after melt mixing. Therefore, when the toner is used under high humidity conditions, there is a problem that a good quality image cannot be obtained because these charge control agents are hydrophilic.

In this way, when a conventional charge control agent is used in a toner, it can be used between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve.
This causes variations in the amount of charge generated on the surface of toner particles, which tends to cause problems such as development fog, toner scattering, and carrier contamination, and these problems become more noticeable when a large number of copies are made. The result is practically unsuitable for copying machines.

Furthermore, under high-temperature conditions, the transfer efficiency of toner images decreases significantly, making many toner images unusable.Even at room temperature and humidity, when the toner is stored for a long time, Due to the instability of the control agent, it often undergoes deterioration and becomes unusable due to poor charging properties.

Furthermore, when conventional charge control agents are used in toner, after long-term use, the charge control agents themselves adhere to the surface of the photoreceptor, or their presence promotes toner adhesion (occurrence of filming phenomenon). This often causes inconveniences in the cleaning process of the copying machine, such as adversely affecting latent image formation, causing scratches on the surface of the photoreceptor or cleaning members such as the cleaning blade, or accelerating abrasion of the members.

Furthermore, when conventional charge control agents are used in toner, they often have a large effect on the thermal melting properties of the toner and reduce fixing performance.In particular, they worsen high-temperature offset performance, and when heat roll fixing is performed, paper, etc. There are disadvantages such as increased clinging to the roller and reduced durability of the roller.

As described above, conventional charge control agents have many problems, and there is a strong demand in the technical field to solve these problems, and although many improvement techniques have been proposed so far, The reality is that nothing that is comprehensively satisfactory in practical terms has yet been found.

A general object of the present invention is to provide a new technique for toner charge control that overcomes these problems.

A more specific object of the present invention is to stabilize the amount of triboelectric charge between toner particles, between a toner and a carrier, or between a toner and a toner carrier such as a sleeve in the case of component development;
Another object of the present invention is to provide a toner that has a sharp and uniform triboelectric charge distribution and can be controlled to a charge amount suitable for the developing system used.

Another purpose is to develop and transfer the latent image with a developer that is faithful to the latent image, i.e., toner adhesion in the background area during development, to prevent fogging and around the edges of the latent image.
, there is no toner scattering and high image density is obtained.
The objective is to provide a toner with good halftone reproducibility.

Still another object is to provide a toner that maintains its initial characteristics even when used continuously over a long period of time, and that does not agglomerate or change its charging characteristics.

Another objective is to provide a toner that reproduces stable images unaffected by changes in temperature and humidity, and especially toner that has high transfer efficiency and does not cause scattering or transfer omissions during transfer at high or low humidity. be.

Still another object is to provide a bright chromatic toner.

Still another object is to provide a toner with excellent storage stability that maintains its initial characteristics even during long-term storage.

Still another object is to provide a toner that does not stain, abrade, or scratch the electrostatic latent image surface and is easy to clean.

Still another object is to provide a toner having good fixing properties, especially a toner that does not suffer from high temperature offset or the like.

l Mitate 1j The toner for developing electrostatic images of the present invention was developed to achieve the above-mentioned object, and more specifically, it contains a binder resin, a colorant, and an organic tin represented by the following general formula It is characterized by containing a compound.

(However, R in the formula represents an aralkyl group or a substituted aralkyl group.) That is, the present inventors found that the organotin compound represented by the above general formula has excellent dispersibility in resin and can be contained in toner. It not only exhibits excellent charge control properties when used, but also is stable over time, has low moisture absorption, and is colorless or light-colored due to its woody properties, which are extremely effective in achieving the above objectives. The present invention was completed based on the discovery that this material has unique characteristics.

The present invention will be explained in more detail below. In the following description, "parts" and "%" expressing quantitative ratios are based on weight unless otherwise specified.

In the present invention, the organic tin compound used as a charge control agent is one in which R in the above general formula is an aralkyl group or a substituted aralkyl group, and the substituent includes a lower alkyl group, a halogen group, an amine group, etc. It will be done.

More specifically, representative examples of the organic tin compound represented by the above general formula include the following.

[Compound Examples] -1-C1 These organic tin compounds are synthesized by a Grignard reaction.For example, Compound 11 in Example (3) above is synthesized by the following method.

p-Methylbenzyl chloride (e.g., manufactured by Tokyo Kasei Kogyo Co., Ltd.) is dissolved in diethyl ether, reacted with metallic magnesium, Grignard reagent (stannic chloride is added to this solution, and bis(P-methylbenzyl)- Obtaining tin dichloride This is then treated with sodium hydroxide to obtain bis(p-methylbenzyl)-tin oxide as a white precipitate.

Generally, organotin compounds have an average particle size of lθ~0.01
It is preferable to prepare the toner with a particle size in the range of 7L%, particularly 2 to 0.1%.

The toner of the present invention can be obtained by blending the above-described organic tin compound into a toner (colored fine powder) containing a binder resin and a colorant as essential components. As for the form of compounding, there is a so-called internal addition form where it is included in the toner uniformly or in a capsule form, and a form where it is mixed and attached to the toner.
Any of the so-called externally added forms can be adopted.

When internally added, the amount of organic tin compound 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 generally limited. Although not necessarily limited to 100 parts by weight of the binder resin, it is preferably used in an amount of 0.01 to 20 parts by weight (more preferably 1 to 10 parts by weight).

In addition, when externally added, 0.
01 to 10 parts by weight is desirable.

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 for the toner, monopolymers of styrene and its substituted products such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers, and styrene-p-chlorostyrene copolymers are used.
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
-Methyl chlormethacrylate 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,
Styrenic copolymers such as styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, and styrene-maleic acid ester 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, phenolic resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin , paraffin wax, etc., and 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, poly(4)) 7-ethylene, etc.), epoxy resins, polyester resins, styrene
Butadiene copolymer (monomer ratio: 5-30:95
~70), olefin copolymers (ethylene-acrylic acid copolymers, ethylene-acrylic ester copolymers, ethylene-methacrylic acid copolymers, ethylene-methacrylic ester copolymers, ethylene-vinyl acetate copolymers.

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 blue, nigrosine dye, aniline blue, 'phthalocyanine blue, phthalocyanine green, Handy Yellow G, Rhodamine 6G Lake, Calco Oil Blue, Chrome Yellow, Quinacridone, Penjigin Yellow,
Conventionally known dyes and pigments such as rose bengal, triallylmethane dyes, monoazo dyes, disazo dyes and pigments can be used alone or in combination. Furthermore, the toner of the present invention can further contain a magnetic material and 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 and ferrite; iron oxides such as iron, cobalt, and nickel; Metals or these metals and aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium,
Examples include alloys with metals such as manganese selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 JL, and are contained in the toner in an amount of about 20 to 200 parts by weight per 100 parts by weight of the resin component, particularly preferably 100 parts by weight of the resin component. 150 parts by weight of 4ON.

Further, the toner of the present invention may be mixed with additives other than those mentioned above, if necessary. Examples of additives include lubricants such as Teflon and leaden stearate, and fluids such as colloidal silica and aluminum oxide. Examples include conductivity imparting agents, anti-caking agents, conductivity imparting agents such as carbon black and tin oxide, and fixing aids such as low molecular weight polyethylene.

In order to produce the toner for developing an electrostatic image according to the present invention, the organic tin 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. After thoroughly mixing materials, additives, etc. with a ball mill or other mixer, heat rolls and a kneader are used.
Pigment or dye is dispersed or dissolved in the resin by melting and kneading using a heat kneader such as an extruder, and after cooling and solidifying, it is crushed and classified to obtain an average particle size of 5 to 20. You can get toner for tiles. ′
□Alternatively, the material is dispersed in a binder resin solution and then spray-dried, or the monomer that should constitute the binder resin is mixed with the specified material to form an emulsified suspension and then polymerized. Methods such as a polymerization method for producing toner to obtain a toner can be applied.

Furthermore, as described above, the toner of the present invention can also be obtained by externally adding a charge control agent to a toner that has been formed by removing all or part of the charge control agent.

Toners prepared by these methods can be used for developing to visualize electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means.

1. As described above, the toner of the present invention containing an organic tin compound as a charge control agent has a uniform amount of frictional charge between toner particles, can easily control the amount of charge, and is free from deterioration during use. This is an extremely stable toner with no variation or decrease in the amount of triboelectric charge. This eliminates problems such as development fog, toner scattering, and contamination of electrophotographic materials and copying machines, as described above, and also reduces toner aggregation, clumping, and low-temperature fluidity during storage, which were major problems in the past. It is a toner that can be stored for a long time without causing any problems, and the toner image has excellent abrasion resistance, fixing properties, and adhesion properties.

These excellent effects of the toner are further magnified when used in a repetitive transfer copying system in which the operations of charging, exposure, development, and transfer are successively repeated. Further, since there is little color disturbance caused by the charge control agent, it is possible to form color images with excellent colors when used as a color electrophotographic toner.

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

11% styrene/butyl acrylate copolymer (100 parts)
80/20) (Weight average molecular weight Mw: approximately 300,000) Carbon black (Mitsubishi #44) 10 parts Unbalanced molecular weight polyethylene wax 2 parts Organotin compound of Example (1) 2 parts After mixing the above materials well in a blender, The mixture was kneaded using two rolls heated to 150°C. After the kneaded material was allowed to cool naturally, it was roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain particles with a particle size of 5 to 20. A fine toner powder was obtained.

For 100 parts of iron powder gear 9f with an average particle size of 50 to 804,
A developer was prepared by kneading 5 parts of the above toner.

Further, the amount of triboelectric charge of the toner in the developer was measured by a conventional blow-off method.

Next, by a conventionally known electrophotographic method,
A negative electrostatic image was formed, and this was powder-developed using the above-mentioned developer using a magnetic brush method to create a toner image, which was transferred to plain paper and heat-fixed. The resulting transferred image has a density of 1.
34, which was sufficiently high, and there was no fogging at all, and a good image with high resolution was obtained with no toner scattering around the image. Transfer images were continuously created using the above developer and durability was examined, and the transferred images after 30,000 copies were also completely dull compared to the initial images.

Further, during the durability test, the above-mentioned filming phenomenon related to toner on the photoreceptor was not observed at all, and no problems were found in the cleaning process. Also, there were no troubles during the fixing process, and at the end of the 30,000-sheet durability test,
When the fuser was inspected, there were no scratches or damage to the rollers, and there was almost no staining due to offset toner, so there were no practical problems at all.

In addition, when the environmental conditions were set to 35℃ and 85%, the image density was 1.22, a value that was almost unchanged from room temperature, and clear images were obtained without fogging or scattering, and the durability was 30,000 copies. There was almost no change until 15℃ at the 0th order.
, when a transferred image was obtained at a low temperature and low humidity of 10%,
The image density was as high as 1.38, and solid black was developed and transferred extremely smoothly, resulting in an excellent image with no splatters or hollow spots. A durability test was conducted under these environmental conditions. Although copies were made continuously and intermittently, the density variation was ±0.2 up to 30,000 copies, which was sufficient for practical use.

A developer was obtained in the same manner as in Example 1, except that 2 parts of nigrosine dye was used instead of 2 parts of the organic tin compound in Example (1) above, and development, transfer, and fixing were carried out in the same manner. I got it.

At room temperature, there was little fog, but the image density was low at 1.06, line drawings were scattered, and solid black was noticeably rough.

I checked the durability, and the density was 0.83 at 30,000 sheets.
and decreased.

Further, during the durability test, after about 10,000 sheets, toner material formed a thin film on the surface of the photoreceptor and began to appear as lines on the image. This is so-called filming, and is thought to be due to the charge control agent changing the lubricity of the toner powder.

Furthermore, during durability, the fixed image tended to get caught up in the fixing roller during the fixing process, making it difficult to peel it off from the roller.

When an image was obtained at 35° C. and 85%, the image density was as low as 0.88, and fogging, scattering, and roughness increased. The transfer efficiency was also as low as 69%.

When an image was obtained under the condition of 15° C. 10%, the image density was as low as 0.91, and there was severe scattering, fogging, roughness, and transfer omissions were noticeable. I tried to take continuous images, but 3
After about 0,000 sheets, the density became 0.53, making it impractical.

1 Breath 1'' Instead of 2 parts of the organotin compound in Example (1) above, Example (2
) A developer was obtained in the same manner as in Example 1, except that 3 parts of the organic tin compound (3 parts) were used, and an image was obtained in the same manner by carrying out development, transfer and fixing.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.

1 example (3 parts) instead of 2 parts of the organotin compound in Example (1) above
) A developer was obtained in the same manner as in Example 1, except that 2 parts of the organic tin compound (2 parts) were used, and an image was obtained in the same manner by performing development, transfer, and fixing.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.

10 mouths Instead of 2 parts of the organotin compound in Example (1) above, Example (4)
) A developer was obtained in the same manner as in Example 1, except that 2 parts of the organic tin compound (2 parts) were used, and an image was obtained in the same manner by performing development, transfer, and fixing.

The detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 1 were obtained.

1 凰1” Styrene/butyl acrylate 100 parts (80/2
0) Copolymer (weight average molecular weight MW: approx. 300,000) 60 parts of triiron tetroxide EFT-50 (manufactured by Toda Kogyo) 2 parts of low molecular weight polypropylene wax 2 parts of the organotin compound of Example (1) Blend the above materials in a blender. After mixing, the mixture was kneaded using two rolls heated to 150°C. After allowing the mixture to cool naturally, it is roughly pulverized using a cutter mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain a fine powder with a particle size of 5 to 20 l. Obtained.

Next, hydrophobic colloidal silica R was added to 100 parts of the fine powder.
0.4 part of -972 (manufactured by Nippon Aerosil Co., Ltd.) was mixed in a sample mill to prepare a -component magnetic toner.

Further, the amount of triboelectric charge of this toner was measured by a conventional blow-off method.

When this toner was applied to a commercially available copying machine (trade name NP-150Z, manufactured by Canon Co., Ltd.) and an image was produced, good results similar to those of Example 1 were obtained.

In Example 5, 3 parts of the organotin compound of Example (2) was used in place of 2 parts of the organotin compound of Example (1).

Other than that, a developer was obtained in the same manner as in Example 5, and an image was obtained in the same manner by performing development, transfer, and fixing.

Detailed results are shown in Tables 1 and 2, and almost the same results as in Example 5 were obtained.

Support 1 In Example 5, a developer was obtained and developed in the same manner as in Example 5, except that 2 parts of the organic tin compound of Example (3) was used instead of 2 parts of the organic tin compound of Example (1). , transfer, and fixing were performed to obtain an image in the same manner.

Detailed results are shown in Tables 1 and 2, and almost the same satisfactory results as in Example 5 were obtained.

kj, JLI mouth A developer was obtained in the same manner as in Example 5, except that 2 parts of dibutyl-tin oxide was used instead of 2 parts of the organotin compound of Example (1), and an image was formed in the same manner. Obtained.

At room temperature and humidity, there is little fog, but the image density is low at 0.81 and the line drawings are scattered.

The solid black was noticeably rough. I checked the durability, but it was 30
,000 sheets, the temperature decreased to 0.48.

Furthermore, the above-mentioned filming phenomenon during durability and problems in the fixing process were almost the same as those in Comparative Example 1 and were undesirable.

When the image was obtained at 35°C and 85%, the image density was 0.
．． 72, and fogging, scattering, and roughness increased, making it unusable.

The transfer efficiency was also as low as 63%.

When an image was obtained under the condition of 15° C. 10%, the density of one image was as low as 0.73, and there was severe scattering, fogging, roughness, and transfer omissions were noticeable. Continuous image output was performed, but 30
．． The density was 0°59 after printing 000 sheets, making it unusable.

Li1” Styrene/butyl acrylate 100 parts (80/2
0) Copolymer (average molecular weight Mw: approx. 300,000) Copper phthalocyanine blue agent 5 parts Low molecular weight polypropylene wax 2 parts Organotin compound of Example (1) 2 parts Mix the above materials thoroughly in a blender and heat to 150°C. The mixture was kneaded using two rolls. After the kneaded material is left to cool naturally, it is coarsely pulverized using a mill, then pulverized using a pulverizer using a jet stream, and further classified using an air classifier to obtain fine toner powder with a particle size of 5 to 20 l. I got a body.

Further, the amount of triboelectric charge of the toner was measured by a conventional blow-off method.

Next, 50 parts of carrier iron powder having a particle size of 50 to 80 fiL was mixed with 100 parts of the toner to prepare a developer.

Transfer this developer to the developer container l of the developing device shown in the attached drawing.
, and a developing operation was performed. That is, in this device, a cylindrical toner carrier 2 made of stainless steel with a roughened surface is housed in the lower opening of the container l so as to substantially close the lower opening, and the toner carrier 2 is moved at a circumferential speed of 66 m in the direction of the arrow a.
Rotated at m/sec. On the other hand, at the outlet of the sleeve 2 of the container 1 on the downstream side in the rotational direction, there is a distance of 2004 m from the sleeve surface.
An iron blade 3 with its tip placed at the position is placed, and a fixed magnet 4 is placed inside the sleeve z, and its main magnetic pole, the N pole, is connected to the line connecting this to the center of the sleeve and the center of the sleeve. It was arranged so that the angle θ with the tip of the blade 3 was 30°. Under these conditions, as the sleeve 2 rotates, a magnetic brush 5 is formed in the container 1 by the carrier iron powder contained in the developer, and this magnetic brush 6 absorbs the toner distributed preferentially above the magnetic brush 5. 6 is taken up and supplied to the surface of the sleeve 2 while circulating along the periphery of the sleeve 2 below the container 1, forming a thin layer 16 of toner on the surface of the sleeve 2 that has passed through the blade 3.

In this example, the thickness thus formed is approximately 80p.
With a thin toner layer of m, the conventional domes 5 A 7 (
F) Dark area Negative electrostatic images of -600V and -1500V were developed. At this time, the power supply 8 applies a bias voltage with a frequency of 800 Hz, a peak-to-peak value of 1.4 KV, and a center value of 1,300 V. - The voltage was applied between the photosensitive drums 7.

When the image was printed in this way, a good image with a bright blue color was obtained, and even after printing 1500 images, the toner/carrier ratio was 10 parts to 150 parts. No change in image density was observed, and good images were obtained even after printing up to 30,000 sheets while replenishing toner.

Normal temperature-normal humidity (25℃, 60%
RH), high temperature (35℃, 85% RH), low temperature and low humidity (
The evaluation results under various environmental conditions (15° C., 10% RH) are summarized in Tables 1 and 2 below.

[Brief explanation of the drawing]

The drawing is a schematic cross-sectional view of an example of a developing device suitable for applying the toner according to the present invention. 1st life: developer container, 2nd life: toner carrier. 3.O.Doctor blade, 4-.Fixed magnet, 5...
Magnetic brush, 6... Toner, 7... Electrostatic latent image carrier, 16... Thin layer toner. Procedural amendment (method) May 27, 1985

Claims (1)

[Scope of Claims] A toner for developing an electrostatic image, comprising a binder resin, a colorant, and an organic tin compound represented by the following general formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (However, R in the formula represents an aralkyl group or a substituted aralkyl group.)