JPS635352A - Charge imparting material for electrostatic image development - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved electrostatic charge characteristics of a toner by incorporating a reaction product of diorganotin oxide and boric acid or organoboric acid to at least the surface of the titled material. CONSTITUTION:The carrier type electric charge imparting material is obtd. by dissolving the reaction product of diorganotin oxide and boric acid or organoboric acid in a solvent, followed by dispersing it, and by dispersing the carrier of iron powders to the obtd. dispersion, followed by agitating it in a ball mill, and subsequently, drying the mixture until the solvent is completely removed, and by disassembling the obtd. weak cohesive material. Thus, the titled material which does not decrease the electrostatic charge and does not disorder a latent image by repeating a development, is obtd. The titled material facilitates the electrostatic charge, without injuring a color tone of the color toner.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention improves the function of imparting charge to toner used for developing electrostatic images in electrophotography, electrostatic recording, electrostatic printing, etc. The present invention relates to a material or member having a fixed shape, that is, a charge imparting material (herein, the word "material" is used to include granular materials in addition to members having a regular shape).

[Prior art] Conventionally, electric f-1 photo υ: U.S. Patent No. 2,297,
Various methods are described in Japanese Patent Publication No. 691-, Japanese Patent Publication No. 42-23910, and Japanese Patent Publication No. 43-24748. An electrostatic latent image is formed by applying a charge to the insulating layer and irradiating the insulating layer with a light image, and then the latent image is developed and visualized using a fine powder called toner using this technique, and if necessary, it is printed on paper. After a powder image is transferred to a surface such as a surface, the zigzag is determined by applying force, pressure, a solvent, a vapor, or the like.

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

] Depending on the type of carrier that conveys the toner, component-based developing methods include mag-based developing methods that use iron powder carriers.
/ ' }There are the brush method, the casket method using bead carriers, the fur brush method using fur, etc.

In addition, those belonging to the one-component development method include toner particles f
Powder kraut method using atomized IEI, contact development method (also called contact development or toner development) in which toner particles f- are brought into direct contact with the electrostatic latent image surface for development.
, Jumping development method, in which toner particles are not brought into direct contact with the electrostatic latent image surface, but are charged and flown toward the latent image surface by the electric field of the electrostatic latent image; There is the MagneDry method, which develops by contacting the LM image surface.

Toners used in these development methods have traditionally been dyes in natural or synthetic resins. A fine powder containing pigments is used. For example, particles obtained by dispersing a coloring agent in a binder resin such as polystyrene and pulverizing the particles to about 1 to 30 μm are used as toner. Furthermore, magnetic toners containing magnetic particles such as gnetite 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 toner as described in 1- is usually
It is used mixed with carrier grains such as crow beads and iron powder.

Also, the toner is f
Me 1F or negative charge is selected by IJ-.

In order to charge the toner, it is possible to use only the triboelectric properties of the resin, which is a component of the toner.
This method uses toner. Since the electroconductivity is low, the image obtained by development is easily fogged and becomes unclear. Therefore, in order to impart desired triboelectric chargeability to the toner, charge control agents such as dyes and pigments that enhance chargeability are added to the toner.

However, in order to impart chargeability to the toner by adding these additives, these additives must be exposed to some extent on the surface of the toner. Therefore, these additives fall off from the toner surface due to the friction of the toner, collision with the carrier, friction with the electrostatic latent image holder, etc. Contamination of the body, for example a photoreceptor belt or a tram, etc. may occur. As a result, the charging property deteriorates, and as the development operation is repeated, the deterioration progresses, the image density decreases, fine line reproducibility decreases, fog increases, etc., which become practical problems.

The problems noted in L are the toner binder and {i? This can be improved by improving the affinity and dispersibility of additives such as dyes and pigments that impart electrical properties or charge control agents; however, surface treatment to increase the affinity for these additives may lead to electrical properties. In many cases, if the shear is applied strongly and dispersed finely, the proportion of the additive that appears on the surface of the toner decreases, and there is a tendency for the 11''1 conductivity to not be sufficiently applied. Therefore, there are very few additives that can impart 1 and 2 electric properties to toner to a sufficient extent, and only a few have been put into practical use.Especially for monochrome images. However, in order to obtain a color image, it is preferable that the charge control agent added to the toner be colorless, and in this case, there are almost no practically satisfactory charge control agents.

In view of these considerations, we aim to achieve the first goal of charging the toner with goo characteristics not only by using toner additives, but also by using carriers that come into contact with the toner during the development process.
It is also proposed that conveyance, regulation, or friction members such as sleeves and tractor blades (in this specification, these are collectively referred to as "charged materials") can be used to charge toner by improving their J-characteristics. has been done. In other words, in this specification, the term "charged goo material" refers to a material that comes into contact with the toner during or prior to the development process to add a commercial charge to the toner necessary for development or to add an auxiliary charge to the toner. It is a material or member that can be obtained with J-L.

This method of actively applying charge to the toner using a charged material eliminates the need to add additives to the toner to improve its charging characteristics, so it is possible to solve the problems mentioned above. For example, contamination sources such as carrier particles and photoreceptors are effectively reduced, so that repeated development operations do not reduce chargeability or disturb the latent image. Furthermore, it can be easily applied without damaging the color tone of the color toner. It can be powered.

``Problems that IJ is trying to solve: Core-loading materials such as cocarriers, sleeves, and doctor blades not only have a strong electrical charging ability;
It must be durable and able to withstand friction with toner. For example, it is desired that the carrier be used for a long period of time without being replaced, and the sleeve is required to have the same level of durability as the main body of the developing machine.

The purpose of the present invention is to solve the above-mentioned problems by using a charged battery!
The aim is to provide one material.

A further object of the present invention is to provide a charge imparting material that applies an appropriate load to toner.

A further object of the present invention is to provide a charged academic material whose performance does not deteriorate even after long-term use.

A further object of the present invention is to provide a load-imparting material that provides images with excellent fine line reproducibility and gradation.

The purpose of ZARANIKI 9:ψ is to provide a charge imparting material suitable for charging color toner.

[Means and actions to solve problems] Kiba IJI
As a result of research aimed at achieving the above-mentioned purpose, the following inventors have arrived at the following invention.

That is, the present invention is a charge imparting material for developing an electrostatic image, characterized in that it has a reaction product of diorganotin oxide and boric acid or organoboronic acid on at least its surface.

The diorganotin oxide used to obtain the reaction product used in the present invention is not particularly limited, but a group that increases the charge density of tin atoms is preferable. For example, specific examples of organo groups include alkyl groups such as methyl group, ethyl group, t-butyl group, octyl group, and lauryl group; cyclic alkyl groups such as cyclohexyl group and cyclobentyl group;
It is a derivative whose basic skeleton is an aryl group such as a phenyl group, a naphthyl group, an anthryl group, a heptaralkyl group such as a benzyl group, a phenylethyl group, or the above-mentioned substituents,
The two organo groups may be the same or different.

Furthermore, there are no particular restrictions on organoboronic acids. Well-known examples of organic organoboronic acids include alkylporonic acids such as methylporonic acid, ethylporonic acid and n-butylporonic acid, and arylporonic acids such as phenylporonic acid and naphthylboronic acid.

The reaction between the diolucanotin dioxide and the onolecanoporonic acid is carried out as follows.

Using BTX (henzene, toluene, xylene) as a solvent, equimolar amounts of diorganotin oxide and organoboronic acid are reacted under heating at approximately 100°C. At the end of the reaction, water is produced in an equimolar amount as that of the original '1 used. When

The average particle size of the compound is generally 10 to 0.01 μm, particularly 2 to 0.01 μm, although it depends on the form of the charged academic material to which it is applied.
It is preferable to provide the charged material with a grain size of 1 lLm.

These compounds can be dissolved or dispersed in a solvent or a dispersion agent together with Ba Ingu resin if necessary, and then applied to the charged material. Apply 711 to one material by dipping, spraying, brushing, etc., or apply B.
When the L material is in the form of carrier particles, it can be mixed with the coating solution described in 12 by immersion and then dried, or by coating with a direct mixture of this and the above-mentioned compound using a fluidizing vent. By forming 41 layers of the above compound on +1 material L, the charged R material of the present invention can be obtained. In addition, charged resins are melt-kneaded directly with pinter resin and extruded and laminated onto f-limbers to provide a coating layer containing the municipal material. You can also get wood. Furthermore, these compounds may be incorporated into a moldable resin and molded into the shape of carrier grains, sleeves, or doctor plates to be used as a loaded goo material. As the binder resin or molding resin, a binder type resin can be used. For example, polystyrene, polyacrylic acid ester, polymethacrylic acid ester, polyacrylonitrile, rubber resins such as imprene and butadiene, polyester, polyurethane, poly7amide, epoxy resin, rosin, polycarbonate, phenolic resin, chlorinated paraffin, Derivatives thereof such as polyethylene, polypropylene, silicone resin, Teflon, copolymers thereof, or mixtures thereof can be used.

These resins can be made to have a crosslinked structure after coating or molding, if necessary, in order to improve the durability of the surface layer of the charge-imparting material.

When using a pinter resin or a molding resin, it is preferable to use the compound in a ratio of 0.5 to 200 parts by weight, particularly 2 to 100 parts by weight per 100 parts by weight of the resin. When coating the surface of a charged q-material, the coating or coating amount of the compound needs to be appropriately controlled;
ffi2 range is good, preferably 0.1 mg/Cm2
~2 B/cm2 is good.

Also, throughout the cases in Chapter L, along with the above compounds,
Ceramic powders such as silica powder, aluminum oxide, cerium oxide, and silicon carbide may be used as the filler. In addition, 4′ of carpon blanks, tin mellowing, etc.
．． An E-adding agent may be used in the conductive A node. Furthermore, in order to prevent the spent toner from accumulating on the sleeve or carrier surface, # type agents such as fatty acid metal salts, hnylidene fluoride, etc. may be used.

All known carriers can be used as the base material of the charge imparting material of carrier type 5f, and metals such as iron, nickel, aluminum, copper, alloys, powders of metal compounds containing metal drunken powders, etc. Particles, even glass, SiC. Ceramic powder or particles such as BaTi02 and SrTi02 are used. Further, examples include those whose surfaces have been treated with a resin, resin powder, or resin powder containing a magnetic material. The average particle diameter is preferably about 20 to 250H.

Furthermore, as a material for charging the electrically charged academic material in the form of a sleeve or doctor blade, metals or alloys such as iron, aluminum, stainless steel, and nickel, non-metallic compounds such as ceramics and plastics, etc. are generally used. The best thing to do is to use something that can be used as a blade.

On the other hand, substantially all toners used in combination with the charge-imparting material of the present invention, such as Yuki, can be effectively used as toners conventionally used for developing electrostatic images. That is, both non-magnetic and magnetic toners can be used. Therefore, if Si L <, the toner is a colored fine particle containing a coloring agent in a stone resin, and may contain magnetic powder as necessary. Additionally, these toners contain small amounts of charge-imparting substances, such as dyes, pigments, etc., for more efficient charge-imparting. Alternatively, it may contain a so-called charge control agent, and a fluidizing agent such as colloidal silicate, an abrasive such as cerium oxide L1, strontium titanate, and silicon carbide, and a lubricant such as metal stearate and vinylidene fluoride. May be included. It may also contain a core conductivity imparting agent such as carbon black, tin oxide, or the like.

As the developing method using the above-described charged material and toner of the present invention, substantially all of the developing methods using a two-component developer or a one-component developer can be used. For example, magnetic brush development method, cascade development method, fur brush development υ:, so-called microtoning development method using magnetic substance-containing resin powder as a carrier, or developing power method using resin powder as a carrier, so-called jump/g development method, Alternatively, there is a jump-nog development method in which non-magnetic toner is developed.

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

Example 1 100g of a reaction product of dibutyltin oxide and boric acid was dissolved and dispersed in MEKlu, and an iron powder carrier (particle size:
250-400mesh) I kg was dispersed and stirred in a hole mill for about 30 minutes.

After drying this iron powder carrier mixture and completely removing the solvent, light agglomerations are loosened, and the carrier-like charge according to the present invention is applied! I got chi wood.

Separately, a toner was prepared according to the following formulation without adding any charge control agent.

Styrene 100 parts by weight (n
Product name: Raven 3500 (manufactured by Capot Co., Ltd.) The above materials were kneaded, pulverized, and classified to have a particle size of 1 to 30 IL+++.

This toner and the carrier were mixed in an m ratio of 10:100 to prepare a developer.

The amount of triboelectric charge of this developer was measured by the Bloch method and was found to be -1'2.8 pc/g.

When this developer was used to produce images on a Canon MP-5000 copying machine, there was no change in image density even after a durability test of 50,000 sheets, and fine line reproducibility and gradation were good. . Also, there was no force bulge. Example 2 Polymethyl methacrylate resin 10 in xylene IJJ
0g of the solution was dissolved, and 50g of a reaction product of dicyclohexyltin oxide and boric acid was added thereto. This was mixed with the same iron powder carrier as in Example 1 and dried to obtain a carrier having a charge imparting effect.

When this was used and combined with toner in the same manner as in Example 1, the amount of triboelectric charge of the toner was -13. It becomes 1gc/g,
When this was used to produce images, the resulting images showed good image density, fine line reproducibility, and gradation, and no blurring, even after a 50,000-sheet durability test. Example 3 Polymethyl methacrylate tree 11F+ in 1U of xylene
A solution was prepared by dissolving lOOg and mixing 50g of a reaction product of dibenzyltin oxide and methylporonic acid. Dip a developing sleeve (made of stainless steel) for Canon IP-400RE in this solution, and place 0.
A coating of 1 mg/cm2 to 0.81 Ilg/cm2 was applied. This sleeve was placed in the original developing machine.

The toner was prepared according to the following recipe using a general kneading and pulverizing method.

Styrene-butyl methacrylate 100 parts by weight MW = 300,000 Hina molding agent 4 parts by weight (trade name: PE-130 manufactured by Ni-Hoechst) Magnetic powder
60 parts by weight (product name BL
-200: manufactured by Titan Kogyo Co., Ltd.) The prepared toner had a particle size of lpm to 30 gm.

Using this toner, an image printing durability test was conducted using Canon NP-400RE.

After 50,000 sheets of durability, there was no change in the image from the beginning, fine line reproducibility and gradation were good, and there was no fog.

Also, when the surface potential on the sleeve was measured, it was -33v.
It was confirmed that the toner was completely negatively charged.

[Effects of the Invention] As described above, according to the present invention, a charge-adding agent for applying a load to an electrostatic charge image developing toner having a compound having a specific structure as a charge control agent on the surface thereof is provided. material is provided. In particular, the compound of the present invention not only exhibits excellent charge controllability and stability against heating or moisture absorption, but also has the ability to coat the surface of a charged material or to mix it into a material. By allowing the presence of ``f!!'', etc., a good electrically charged material with excellent durability against friction with toner can be obtained. Therefore, if this electrically charged material is present in the river, only toner can be produced. By mixing a charged 1-1 agent into the 2-electrode material, a wood-like improvement 54 can be obtained to address the various problems encountered when improving the 2-electrode properties.

Claims (4)

[Claims] (1) A charge-imparting material for developing electrostatic images, characterized in that it has a reaction product of diorganotin oxide and boric acid or organoboronic acid on at least its surface. (2) The charge imparting material for developing an electrostatic image according to claim 1, which is in the form of carrier particles. (3) The charge imparting material for developing an electrostatic image according to claim 1, which is in the form of a cylindrical sleeve. (4) Claim 1 in the form of a doctor blade
A charge imparting material for developing an electrostatic image as described in 2.