JPS61272758A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a developer stable in triboelectrificationd amt. and sharp and uniform in a distribution of triboelectrification amt. by incorporating an org. tin compd. having at least one alkoxy group directly combined with a tin atom. CONSTITUTION:The org. tin compd. having at least one alkoxy group directly combined with the tin atom has sufficient triboelectrifiability, and when it is contained in a toner, it serves as a good charge controller capable of providing a developer superior in electrophotographic characteristics. It is important for the charge controller itsels to have high triboelectrifiability, and at the same time, to exist on the surface of each toner particle in a large amt. in order to exhibit superior characteristics, and it is effective to raise the organic property of the org.tin oxide in order to enhance the compatibility of this oxide with resins. The triboelectrifiability of the org. tin oxide can be maintained and the compatibility with resins can be remarkably improved by reacting this oxide with alcohol.

Description

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

[Prior Art] Conventionally, as an electrophotographic method, U.S. Patent No. 2,297.69
1, Special Publication No. 42-23910, and Special Publication No. 43
Various methods are described in Japanese Patent No. 24748, etc., but these methods basically apply a uniform electrostatic charge to a photoconductive insulating layer and irradiate the insulating layer with a light image to remove the electrostatic charge. A latent image is formed, and then the latent image is developed and visualized using a fine powder called toner using the technology, and the powder image is transferred to paper or the like as necessary, and then fixed by heat, pressure, or solvent vapor. It is something to do.

The developing methods applied to these electrophotographic methods include:
Broadly speaking, there are dry development methods and wet development methods. The former method is further divided into 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 beads as a carrier, and a fur brush method using fur, depending on the type of carrier for conveying the toner.

In addition, those belonging to the -component type development method include a powder cloud method in which toner particles are sprayed, and a contact development method (contact development, or (also referred to as toner 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; and magnetic conductive method. There is the MagneDry method, which develops by bringing a 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 304 particles are used as toner. As the magnetic toner, one containing magnetic particles such as magnetite is used. In the case of a system using a so-called two-component developer, the toner is usually mixed with carrier particles such as glass beads and iron powder. Further, the toner is made to hold a positive or negative charge depending on the polarity of the electrostatic latent image to be developed.

In order to make the toner hold an electric charge, it is also possible to use the triboelectricity of the resin that is a component of the toner, but since the toner's chargeability is small with this method, the image obtained by development is prone to fogging and is unclear. Become something. Therefore, in order to impart desired triboelectrification properties to toners, dyes and pigments that impart electrostatic properties, as well as charge control agents, are added.

Charge control agents known in the art today include the following:

(1) As a device that controls toner to be positively charged
1 There are the following substances.

Nigrosine, azine dyes containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1986), basic dyes (e.g. C,1,Ba5ic Yellow2 (C,1,4
1000), C,1,Ba5ic Yellow 3
,C,1,Ba5ic Red 1 (C,1,4
5160), C, 1, Ba5ic Red 9 (C
, 1,42500).

C11, Ba5ic Violet 1 (C,1,
42535), C, 1, Ba5fc Violet
3 (C, 1, 42555).

C,1,Ba5ic Violet 10(C,1
, 45170), C, 1, Ba5ic Violet
14 (C, 1, 42510), C, 1, Ba5ic
Blue 1 (C, 1, 42025), C, 1
, Ba5ic Blue 3 (C, 1,5100
5), C, 1, Ba5ic Blue 5 (C,
Z, 42140).

C,1,Ba5ic Blue 7 (C,1,4
2595), C, 1, Ba5ic Blue 9
(C,1,52015),C,1,Ba5ic Bl
ue 24 (C, 1, 52030), C, 1, Ba5
ic Blue 25 (C, 1, 52025), C
,1,Ba5ic Blue 26(C,1,44
045), C, 1, Ba5ic Green 1
(C, f, 42040), C, 1, Ba5ic-Gre
en 4 (C, 1, 42000).

C, 1,42510, 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, ferrocyanide, etc.), C
,1,5olventBlack 3 (C,I,
26150), Hanzai Z Law (:.

(C,1,11680), C,1,Mordlant
Blackll, C, 1, Pigment
Black 1, Gilt Night, Asphalt, etc.

Quaternary ammonium salts, such as pencil methyl-hexadecyl ammonium chloride, decyl-trimethyl ammonium chloride, organotin compounds such as dibutyltin oxide, metal salts of higher fatty acids, glass, mica, inorganic fine powders such as zinc oxide, EDTA , metal complexes of acetylacetone, etc., vinyl polymers containing 7-mino groups, and polyamine resins such as condensation polymers containing amine groups.

(2) The following substances can be used to control the negative chargeability of toner.

Metal complex salts of monoazo dyes described in Japanese Patent Publications No. 41-20153, No. 43-27586, No. 44-6387, No. 45-26478, etc., #open/closed 50-133
Dye and pigments such as nitrofumic acid and its salts or C,I, 14645 described in No. 338, Japanese Patent Publication No. 1983-
No. 42752, Special Publication No. 58-41508, Special Publication No. 1987
Metal complexes such as Co, Cr, and Fe of salicylic acid, naphthoic acid, and guicarboxylic acid, which may have mono- or dialkyl groups, and sulfonated copper phthalocyanine pigments described in Japanese Patent Publication No. 7384 and Japanese Patent Publication No. 59-7385, etc. , styrene oligomers with nitro groups and halogens, chlorinated paraffins, melamine resins, etc.

Many of these charge control agents are derived from dyes and pigments.
Generally, they have a complex structure, and many of them have strong coloring properties.

Recently, there are some newly proposed products that are different from these, but none have superior overall performance to those based on dyes and pigments, and dyes are still used, although they are still unsatisfactory.

These are usually added to a thermoplastic resin, thermally melted and dispersed, finely pulverized, adjusted to a suitable particle size as required, and used.

These dyes used as charge control agents have complex structures, inconsistent properties, and poor stability.In addition, they decompose during hot kneading (9) due to mechanical impact and friction.

It is easy to decompose or change in quality due to changes in temperature and humidity conditions, and tends to cause a phenomenon in which charge controllability deteriorates.

Therefore, when a toner containing these dyes as a charge control agent is used for development in a copying machine, as the number of copies increases, the charge control agent decomposes or changes in quality, which may cause deterioration of the toner during durability. Furthermore, since it is extremely difficult to uniformly disperse these charge control agents in thermoplastic resins, they pose the fatal problem of causing a difference in the amount of frictional charge between toner particles obtained by pulverization. have. For this reason, various methods have been used to achieve more uniform dispersion6.For example, basic nigrosine dyes are used by forming salts with higher fatty acids in order to improve the compatibility with thermoplastic resins. 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, fogging, 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 of 1 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 developers. Many of the charge control agents are hydrophilic, and due to poor dispersion in these resins, the dye is exposed on the toner surface when the dye 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 conventional charge control agents are used in toner,
Variations occur in the amount of charge generated on the surface of toner particles between toner particles, between toner and carrier, or between toner and a toner carrier such as a sleeve,
Problems such as development fog, toner scattering, carrier contamination, etc. are likely to occur, and these problems become noticeable when copying is repeated many times, resulting in a result that is practically unsuitable for copying machines.

Furthermore, under high humidity conditions, the transfer efficiency of toner images decreases significantly, making many toner images unusable.Even at room temperature, when the toner is stored for a long time, the charge used 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 toners, long-term use may cause the charge control agents to adhere to the surface of the photoreceptor or promote the adhesion of toner, adversely affecting latent image formation (filming phenomenon). There are many things that have a negative effect on the cleaning process of a copying machine, such as those that cause scratches on the surface of the photoreceptor or cleaning members such as cleaning blades, or accelerate wear of these members.

Furthermore, when conventional charge control agents are used in toner, there are many that have a large effect on the thermal melting properties of the toner and degrade fixing performance.In particular, they worsen high-temperature offset performance and cause problems on copy paper during heat roll fixing. There are some that increase the stickiness of the rollers and others that reduce the durability of the rollers.

As described above, there are many problems with conventional charge control agents, and there is a strong demand in the technical field to improve these, 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.

[Problem that the invention seeks to solve]

An object of the present invention is to provide a new technique for controlling charge of toner that overcomes such problems.

An object of the present invention is to stabilize the amount of triboelectric charge between toner particles, between toner and carrier, or between toner and a toner carrier such as a sleeve in the case of -component development, and to ensure that the distribution of triboelectricity is sharp and uniform. The object of the present invention is to provide a developer that can control the amount of charge suitable for the developing system used.

Yet another object is to provide a developer that provides faithful development and transfer of the latent image, ie, toner adhesion in background areas during development.

To provide a developer that does not cause fog or toner scattering around the edges of a latent image, provides high image density, and has good halftone reproducibility.

Yet another purpose is to keep the developer flowing continuously over long periods of time.
1. To provide a developer that maintains its initial characteristics even when used, and does not cause toner aggregation or change in charging characteristics.

Another objective is to develop a developer that reproduces stable images that are not affected by changes in temperature and humidity, especially a developer that has high transfer efficiency and does not cause scattering or transfer failure during transfer at high or low humidity. On offer.

Still another object is to provide a bright chromatic developer.

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

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

Still another object is to provide a developer that has good fixing properties, particularly a developer that does not have problems such as high-temperature offset.

[Means and effects for solving the problems] The present invention provides S
At least one alkoxy group directly bonded to the n atom
A toner for developing an electrostatic image is characterized by containing an organic tin compound having seeds.

The present inventors have discovered that an organotin compound having at least one alkoxy group directly bonded to a Sn atom has sufficient triboelectric charging properties, and when contained in a toner, provides a developer with excellent electrophotographic properties. The present invention was achieved by discovering that it is a high quality charge control agent.

Organic tin oxide is known to be a charge control agent itself, as reported in Japanese Patent Publication No. 57-29704, but it still has problems with affinity with resins and dispersibility in resins. It has been discovered that dispersion and compatibility with resins can be improved by allowing alcohol to act on organic tin oxide.

In order for a certain substance to exhibit excellent properties as a charge control agent for toner for developing electrostatic images, it is important that the substance itself has a large triboelectric charging ability and that a large number of wheels exist on the surface of the toner. Although organic tin oxide itself has sufficient triboelectric charging ability, it can be combined with organic tin oxide such as dibutyltin oxide or dioctylthione oxide and a resin having a polar group (for example, a carboxyl group commonly used as a binder resin for toner). In combination with styrene-acrylic acid resins), the charge controllability may be completely lost. It was discovered that it does not need to be type 2 packing (\S・=0) like organic tin oxide. We also discovered that increasing the organicity of organic tin oxide is effective in improving the compatibility of organic tin oxide with resin, and by reacting organic tin oxide with alcohol, we can maintain the triboelectric charging ability of organic tin oxide and improve its compatibility with resin. It can be used as a charge control agent for color toners. In addition, the hygroscopicity, which is one of the problems of other conventionally used charge control agents, can be significantly improved.

is not limited at all, but examples include dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, diisopropyltin oxide, bis(2-7minooctyl)tin oxide. , bis(2-tolyloctyl)tin oxide, optionally branched or substituted dialkyltin oxide; dicyclohexyltin oxide, dicyclopentyltin oxide, dicyclooctyltin oxide, bis(2-7minocyclohexyl ) tin oxide.

Dicycloalkyltin oxide which may have a substituent such as bis(2-methylcyclohexyl)tin oxide:
Diphenyltin oxide, ditolyltin oxide, dinaphthyltin oxide, bis(0-phenylphenyl)tin oxide, bis(2-methyl-4-ethylnaphthyl)
Diaryltin oxide which may have a substituent such as tin oxide, bis(4-aminophenyl)tin oxide, di-α-anthryltin oxide, di-β-anthryltin oxide, di-α-anthryltin oxide, etc. ; dibenzyltin oxide, bis(4-methylbenzyl)tin oxide, diphenylethyltin oxide, bis(4-methylbenzyl)tin oxide;
dialkyltin oxide which may have a substituent such as -isopropylphenylethyl)tin oxide, dinaphthylethyltin oxide; divinyltin oxide, diisopropenyltin oxide, diallyltin oxide, bis(2-aminobutenyl)tin oxide, etc. Examples include dialkenyl tin oxides which may have branched chains or substituents.

Further, there are no particular limitations on the alcohol that can be used in the present invention, and specific examples include aliphatic monohydric alcohols such as methanol, ethanol, tent-butyl alcohol, octyl alcohol, and lauryl alcohol; Ethylene glycol, 1.3-7'ropanediol, 1.2-propanediol, 1.4-butanediol, 1.8-octanediol.

1.4-dodecanediol, 1.4-tetracosanediol, 2-amino-1,4-butanediol, 2-ethyl-1,4-hexanediol, styrene glycol,
Dihydric alcohols such as 4-aminostyrene glycol, 2-isopropylstyrene glycol, 1,2-cyclohexyldiol; glycerin, trimethylolpropane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,2,6-hexane Diol, 1, 1,
1-) Trihydric alcohols such as lis(hydroxymethyl)propane and 2,2-bis(hydroxymethyl)butanol-3: tetramethylolmethane, 1,2,4°5-
There are tetrahydric alcohols such as pentanetetraol and 1,2,3,4-butanetetraol.There are zero or more alcohols.There are tetrahydric alcohols such as 1,2,3,4-butanetetraol.

The above alcohols are aliphatic alcohols, but as long as they are aliphatic alcohols, they may be either saturated alcohols or unsaturated alcohols, and may have substituents. Compounds to which a hydroxyl group is directly added can also be used in the same manner as the aliphatic alcohols mentioned above.

In the present invention, a compound in which a hydroxyl group is directly added to an aromatic ring is referred to as an aromatic alcohol.

Examples of aromatic alcohols that can be used in the present invention include phenol, p-cresol, m-cresol, O-
Phenol derivatives such as cresol, aminophenol, 0-phenylphenol, resorcinol, hydroquinone, p-chlorophenol; α-naphthol, β-naphthol, 2-methyl-α-naphthol, 4-amino-α-
Naphthol ga forms such as naphthol, 3-chloro-α-naphthol, 5-7 minnow β-naphthol, 4-hydroxy-α-naphthol; α-anthrol, 4-ethyl-α-anthrol, 5-amino-α - Antrol,
Aromatic monoalcohols such as anthrol derivatives such as β-anthrol, 8-isopropyl-β-antrol; catechol derivatives such as catechol, 3-methylcatechol, 4-7minocatechol, 4-hydroxycatechol, 1.2 -dihydroxynaphthalene, 1,2-dihydroxy-3-methylnaphthalene, 1,2-dihydroxy-4-aminonaphthalene, 1゜2.4-trihydroxynaphthalene, 2.3-dihydroxynaphthalene, 1
-Ethyl-2,3-dihydroxynaphthalene, 5-amino-2°3-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 3-amino-1,8-dihydroxynaphthalene, 5-isopropyl-1°8-dihydroxynaphthalene, etc. Dihydroxynaphthalene derivative; 1,
2-dihydroxyanthracene, 4-methyl-1,2-
Dihydroxyanthracene, 5-amino-1,2dihydro 1xyanthracene, 2,3-dihydroxyanthracene, l-isopropyl-2,3-dihydroxyanthracene, 1,9-dihydroxyanthracene, 2-amino-1,9-dihydroxyanthracene ,1
, 9.5-)lihydroxyanthracene, 8-chloro-
Alcohols of 0 or more, such as aromatic dialcohols such as dihydroxyanthracene derivatives such as 1,9-dihydroxyanthracene, are just one example; as long as it is an alcohol, it does not matter if it is aliphatic, aromatic, monovalent or polyvalent. .

Examples of the chemical structure of the reaction product of organic tin oxide and alcohol in the present invention include the following.

The following compound examples are shown for each monovalent, divalent, trivalent or tetravalent alcohol, but as a charge control agent, 5n-0
Although it depends on the charge density of the bond and does not depend on the valence of the alcohol, it is preferable to use an alcohol that does not leave unreacted hydroxyl groups in the reaction product. Good development characteristics.

(b-7) cH3 Eyelid (b-11) (b-12) (c-1) (c-2) Sn ( (c-3) (c-5) (c-6) (c-7) ( c-8) (d-1) (d-2) (d-3) (d-4) (d-5) (d-6) (e-1) (e-2) (e-3) ( e-4) (e-5) n3 (e-10) (f-1) (f-2) (f-3) (f-4) (f-5) h2 (H3 (f-9) (f-10) (f-11) (f-13) (f-14) Shi3r17 (f-15) Organotin compounds in which an alkoxy group is directly bonded to the Sn atom can be synthesized by the following method. .

That is, benzene, toluene, or xylene (selected depending on the reaction temperature) is used as a solvent, and the alcohol to be reacted with the corresponding disubstituted organotin oxide is mixed at a molar ratio (organotin oxide/alcohol) of 0.4 to 0.5 (monohydric alcohol). ', o, a~1 (dihydric alcohol), 0.8~l or 1.3~1.5 (trihydric alcohol), 0.8~1,
1.3-1.5. Also, disperse with 1.8 to 2.0 (tetrahydric alcohol), continue to reflux this solution for 1 hour to 10 hours,
Organic tin alkoxide is synthesized by the dehydration reaction of alcohol and organic tin oxide. The solution is filtered and washed with hot benzene, hot toluene, or hot xylene to obtain the desired product. The completion of the reaction means that in the infrared absorption spectrum of the product, the absorption around 1700 cm due to 5n=o completely disappears, and the absorption at around 1700 cm due to 3l-o-c is newly added.
It is preferable to confirm by the appearance of absorption near loocm-1.

Methods for incorporating the above compound into the developer include a method of adding it inside the developer and a method of adding it externally. When internally added, the amount of these compounds used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner manufacturing method, including the dispersion method, and is not uniquely limited. However, it is appropriate to use 0.1 to 20 parts by weight, preferably 0.2 to 20 parts by weight, per 100 parts by weight of the binder resin.
It is used in a range of 10 parts by weight (more preferably 0.5 to 5 parts by weight).

In addition, when externally added, 0.0 parts by weight per 100 parts by weight of resin.
1 to 10 parts by weight is preferred.

Further, conventionally known charge control agents can be used in combination with the charge control agent of the present invention as long as they do not impede the object of the present invention.

Colorants used in the present invention include carbon black, lamp black, iron black, and ultramarine blue.

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, and disazo dyes and pigments can be used alone or in combination.

The binder resin used in the present invention includes polystyrene,
Monopolymers of styrene and its substituted products such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymers, styrene-propylene copolymers,
Styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer Coalescence, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene- Vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene- Maleic acid copolymer.

Styrenic copolymers such as styrene-maleic acid ester copolymers: polymethyl methacrylate, polymethyl methacrylate, polyvinyl chloride.

Polyvinyl acetate, polyethylene, polypropylene, polyester, polyurethane, polyamide, epoxy resin,
Polyvinyl butyral, polyacrylic acid resin, rosin,
Modified rosin.

Examples include terpene resins, phenolic resins, aliphatic or alicyclic hydrocarbon resins, aromatic petroleum resins, chlorinated paraffins, paraffin waxes, etc., which can be used alone or in combination. As binder resins particularly suitable for pressure fixing, the following can be used alone or in combination. Polyolefins (low molecular weight polyethylene, low molecular weight polypropylene, polyethylene oxide,
Polytetrafluoroethylene, etc.), epoxy resin, polyester resin, styrene-butadiene copolymer (monomer ratio 5
~30:95-70), olefin copolymers (ethylene-acrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer.

ethylene-vinyl chloride copolymer, ethylene-vinyl acetate copolymer, ionomer resin), polyvinylpyrrolidone, methyl vinyl ether-maleic anhydride copolymer, maleic acid-modified phenol resin, phenol-modified terpene resin.

Further, when the toner of the present invention is used as a two-component developer, it is mixed 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, Examples include magnetic powders such as ferrite powder and nickel powder, glass peas, and those obtained by treating the grain surface of these with resin or the like.

Furthermore, the toner of the present invention can further contain a magnetic material and be used as a magnetic toner. The magnetic materials contained in the magnetic toner of the present invention include iron oxides such as magnetite, hematite, and ferrite, iron, cobalt, and nickel. metals such as aluminum, cobalt, copper, lead,
Yagnesium, tin, zinc, antimony, beryllium,
Examples include alloys of metals such as bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, and vanadium, and mixtures thereof.

These ferromagnetic materials preferably have an average particle size of about 0.1 to 2 pots, 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 in an amount of about 20 to 200 parts by weight per 100 parts by weight of the resin component. The amount is 40 to 150 parts by weight.

Further, the toner of the present invention may be mixed with additives as required. Examples of additives include lubricants such as Teflon and summer lead stearate, abrasives such as cerium oxide and silicon carbide, or colloidal silica, etc. 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 polyethylene.

To prepare the toner for developing an electrostatic image according to the present invention, the charge control agent according to the present invention is mixed with a vinyl or non-vinyl thermoplastic resin, a pigment or dye as a coloring agent, a magnetic material as necessary, Additives, etc. are thoroughly mixed using a ball mill or other mixer, and then melted, kneaded, and kneaded using a heat kneader such as a heated roll, niegu, or extruder to make the resins compatible with each other. Alternatively, a toner having an average particle size of 5 to 20 IL can be obtained by dispersing or dissolving the dye, cooling and solidifying it, and then crushing and classifying it. Alternatively, the toner can be obtained by dispersing the material in a binder resin solution and then spray drying it, or by mixing a specified material with the monomers that should constitute the binder resin to form an emulsified suspension and then polymerizing it. Methods such as the polymerization method toner manufacturing method obtained can be applied.

Toners produced by these methods can be used for developing to visualize electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc. by any conventionally known means, and can be used for any development purpose such as electrophotography, electrostatic recording, electrostatic printing, etc. Regardless of whether the development is reverse development or reverse development, the following excellent effects can be achieved.

That is, the amount of frictional charge between toner particles is uniform, and the amount of charge can be easily controlled. In addition, the toner is extremely stable, with no variation or decrease in the amount of triboelectric charge due to deterioration during use. Therefore, the above-mentioned problems such as development fog, toner scattering, and contamination of electrophotographic photosensitive materials and copying machines are eliminated, and since the toner of the present invention is extremely superior, for example, during storage, which was a major problem in the past. It is a toner that can withstand long-term storage without causing phenomena such as toner aggregation, clumping, and low-temperature flow, and also has excellent abrasion resistance, fixing properties, and adhesion properties of one toner and one image.

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.

Furthermore, 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.

Next, the present invention will be explained based on examples.

In addition, "1 part" indicates "part by weight."

Example 1 Styrene/butyl methacrylate (80/20) copolymer 100 parts (weight average molecular weight Mw: approximately 300,000) Carbon black 5 parts Low molecular weight polyethylene wax 2 parts Reaction of dibutylthionoxide and 1,4-butanediol 2 parts After mixing the above ingredients well with a blender.

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 tons. Obtained.

A developer was prepared by mixing 5 parts of the fine powder with 95 parts of iron powder carrier having an average particle size of 50 to 80 IL.

Next, by a conventionally known electrophotographic method,
A negative electrostatic charge 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 had a sufficiently high density, no fog, no toner scattering around one image, and a good image with high resolution was obtained.

Further, during durability, 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 in the fixing process at this time, and at the end of the 30°,000-sheet durability test, I observed the fuser and found that there were no scratches or damage to the rollers, and there was almost no dirt from offset toner, so there were no practical problems at all. There wasn't.

Furthermore, when the environmental conditions were set to 35° C. and 85%, the image density was almost unchanged from normal temperature and humidity, and a clear image was obtained without fogging or scattering.

Next, a transferred image was obtained at 15° C. and 10% low temperature and humidity, and the image density was sufficiently high.

Even solid black was developed and transferred extremely smoothly, resulting in an excellent image with no splatters or hollow spots.

Example 2 A developer was obtained in the same manner as in Example 1, except that 3 parts of the reaction product of dicyclohexyltin oxide and glycerin was used instead of 2 parts of the reaction product of dibutyltin oxide and 1.4-butanediol. , development, transfer, and fixing were performed to obtain an image in the same manner.

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

Example 3 Instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol, 3.4 parts of dioctyltin oxide and
A developer was obtained in the same manner as in Example 1, except that 5 parts of the reaction product with -dimethylcatechol was 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.

Example 4 Developed in the same manner as in Example 1 except that 2 parts of the reaction product of dibutyltin oxide and 1,2-cyclohexyldiol were used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. 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.

Comparative Example 1 A developer was obtained in the same manner as in Example 1, except that 2 parts of dibutyltin oxide was used, and an image was obtained in the same manner by performing development, transfer, and 1° fixing.

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

In addition, after io and oooo copies were printed during durability, the toner material formed a thin strip-like film on the surface of the photoreceptor and began to appear as lines on the image. This is 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, and there was difficulty in peeling it off from the roller.

When images were obtained under conditions of 35° C. and 85%, the image density decreased and fogging, scattering, and roughness increased. Transfer efficiency was also low.

When an image was obtained under conditions of 15° C. and 10%, the image density was low, and there were severe scattering, fogging, and roughness, and transfer omissions were noticeable.

Example 5 Styrene/butyl methacrylate (80/20) copolymer 100 parts (weight average molecular weight Mw: approximately 350,000) Triiron tetroxide EFT-50060 parts (manufactured by Toda Kogyo) Low molecular weight polypropylene wax 2 parts dibutyltin oxide 1. Reactant with 4-butanediol 2 parts The above materials were thoroughly mixed in a blender, and then kneaded with two rolls heated to 150°C.

After the kneaded material was left to cool naturally, it was roughly pulverized using a 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 IL. Ta.

Next, 0.0 parts of hydrophobic colloidal silica (manufactured by Nippon Aerosil Co., Ltd.) surface-treated with aminosilane was added to 100 parts of the fine powder.
Four parts were mixed in a sample mill to prepare a -component magnetic toner.

When this toner was applied to a commercially available copying machine (trade name NP-1502, manufactured by Canon Co., Ltd.) and an image was produced, good results almost the same as those of Example 1 were obtained.

Example 6 The same procedure as in Example 5 was carried out except that 3 parts of the reaction product of dichlorohexyltin oxide and glycerin was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. A developer was obtained, and development, 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.

Example 7 Example a except that in Example 5, 5 parts of the reaction product of dioctyltin oxide and 4,5-dimethylcatechol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. A developer was obtained in the same manner as in -5, and development, 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.

Comparative Example 2 Development was carried out in the same manner as in Example 5, except that 2 parts of Nigrosine Base EX (manufactured by Orient Chemical Industry Co., Ltd.) was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol in Example 5. An image was obtained in the same manner. At room temperature, there was little fog, but the image density was low, line drawings were scattered, and solid blacks were noticeably rough.

In addition, the filming phenomenon and problems in the fixing process during durability were almost the same as those in Comparative Example 1.
.

When an image was obtained under conditions of 35° C. and 85%, the image density was low and fogging, scattering, and roughness increased, making it unusable. Transfer efficiency was also low. 15℃,
When an image was obtained under 10% conditions, the image density was low;
Scattering, fogging, and roughness were severe, and transfer omissions were noticeable.

Comparative Example 3 The developer was prepared in the same manner as in Example 5, except that 3 parts of dioctyltin oxide was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. An image was obtained in the same manner. The results are shown in Tables 1 and 2, and fog and roughness were noticeable.

Example 8 Styrene/butyl acrylate 100 parts (80/2
0) Copolymer (weight average molecular weight MW: approx. 300,000) Copper phthalocyanine blue pigment 5 parts Low molecular weight polypropylene wax 2 parts Reactant of dibutyltin oxide and 1.4 butanediol 2 parts The above materials were mixed well with a blender. Thereafter, 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 particles with a particle size of 5 to 20I.
A fine powder of L was obtained.

Next, 50 g of magnetic particles having a particle size of 50 to 80 IL were mixed with 100 parts of the fine powder to prepare a developer.

When images were developed using this developer and the developing method shown in FIG. 1, good images exhibiting a bright blue color were obtained after 1,500 images were developed.

Even if the toner/carrier is 10g to 150g,
There was almost no change in image density.

To explain this developing method, in FIG. 1, l is an electrostatic image carrier, 2 is a toner carrier, 3 is a hopper, 52 is a magnetic brush using a mixture of carrier and toner, 58
5 is a toner thickness regulating blade, 50 is a fixed magnet, 6 is a developing bias, and 5 is a toner, that is, a toner carrier 2.
The magnetic brush 52 formed on the top is circulated by rotating the toner carrier 2, and takes in the toner in the hover of 3 and coats it in a thin layer uniformly on the toner carrier 2. Next, the toner carrier 2 and the electrostatic image are transferred. The holding member 1 is opposed to the holding member 1 with a gap larger than the thickness of one toner layer, and the toner 5 on z is developed by flying onto the electrostatic charge image on 1.

The thickness of one layer of toner is the size of a 52 magnetic brush.

That is, it is controlled by the amount of magnetic particles and 58 regulating blades.

The gap between l and 2 may be made larger than the thickness of the toner layer, and a developing bias of 6 may be applied.

The evaluation results of each example and comparative example are shown in Tables 1 and 2.

Table 1 Table 2 0...Good, OΔ...Slightly good, Δ...Slightly poor, ×...Poor Example 9 Substitute for 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol A developer was obtained in the same manner as in Example 1, except that 2 parts of a reaction product of dibutyltin oxide and trimethylolpropane was used, and then an image was obtained.

The detailed results are shown in Tables 3 and 4, and good images were obtained.

Example 10 A developer was prepared in the same manner as in Example 1, except that 3 parts of a reaction product of dichlorohexyltin oxide and stearyl alcohol was used instead of 2 parts of a reaction product of dibutyltin oxide and 1,4-butanediol. was obtained and then an image was obtained.

The detailed results are shown in Table 3.4, and good images were obtained.

Example 11 Instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol, dicyclohexyltin oxide and 1 part
．． A developer was obtained in the same manner as in Example 1, except that 2 parts of the reaction product with 2.6-hexandriol was used, and then an image was obtained.

The detailed results are shown in Table 3.4, and good images were obtained.

Example 12 Developed in the same manner as in Example 1, except that 2 parts of the reaction product of dibenzyltin oxide and p-cresol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. The agent was obtained and then the image was obtained.

The detailed results are shown in Table 3.4, and good images were obtained.

Example 13 A developer was prepared in the same manner as in Example 5, except that 2 parts of a reaction product of dibutyltin oxide and trimethylolpropane was used instead of 2 parts of a reaction product of dibutyltin oxide and 1,4-butanediol. was obtained and then an image was obtained.

The detailed results are shown in Table 1, 3.4, and good images were obtained.

Example 14 Development was carried out in the same manner as in Example 5, except that 3 parts of the reaction product of dicyclohexyltin oxide and stearyl alcohol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. The agent was obtained and then the image was obtained.

The detailed results are shown in Tables 3 and 4, and good images were obtained.

Example 15 Instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol, dicyclohexyltin oxide and 1 part
．． A developer was obtained in the same manner as in Example 5, except that 3 parts of the reaction product with 2.6-hexandriol was used, and then an image was obtained.

The detailed results are shown in Tables 3 and 4, and good images were obtained.

Example 16 A developer was prepared in the same manner as in Example 8, except that 2 parts of the reaction product of dibutyltin oxide and trimethylolpropane was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. was obtained and then an image was obtained.

The detailed results are shown in Tables 3 and 4, and good images were obtained.

Table 3 0...good, OΔ...slightly good, Δ...slightly poor, ×...defective clothing 4 0...good, OΔ...slightly good, Δ...slightly poor, × ...Bad Example 17 Same as Example 1 except that 5 parts of the reaction product of dibenzyltin oxide and phenol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. A developer was obtained, and then an image was obtained.

The detailed results are shown in Tables 5 and 6, and good images were obtained.

Example 18 Instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol, ditolyltin oxide and 1,2,4
．． A developer was obtained in the same manner as in Example 1, except that 3 parts of the reaction product with 5-pentatetraol was used, and then an image was obtained.

The detailed results are shown in Table 5.6, and good images were obtained.

Example 19 A developer was obtained in the same manner as in Example 1, except that 5 parts of the reaction product of dibutyltin oxide and catechol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. First, an image was obtained.

The detailed results are shown in Tables 5 and 6, and good images were obtained.

Example 20 A developer was prepared in the same manner as in Example 1, except that 7 parts of a reaction product of ditolyltin oxide and tetramethylolmethane was used instead of 2 parts of a reaction product of dibutyltin oxide and 1,4-butanediol. was obtained and then an image was obtained.

The detailed results are shown in Table 5.6, and good images were obtained.

Example 21 A developer was obtained in the same manner as in Example 5, except that 5 parts of the reaction product of dibutyltin oxide and phenol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. , then the image was obtained.

The detailed results are shown in Tables 5 and 6, and good images were obtained.

Example 22 Instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol, ditolyltin oxide and 1,2,4
．． A developer was obtained in the same manner as in Example 5, except that 3 parts of the reaction product with 5-pentatetraol was used, and then an image was obtained.

The detailed results are shown in Tables 5 and 6, and good images were obtained.

Example 23 A developer was obtained in the same manner as in Example 5, except that 3 parts of the reaction product of dibutyltin oxide and catechol was used instead of 2 parts of the reaction product of dibutyltin oxide and 1,4-butanediol. , then the image was obtained.

The detailed results are shown in Table 5.6, and good images were obtained.

Example 24 A developer was prepared in the same manner as in Example 8, except that 5 parts of a reaction product of dibenzyltin oxide and phenol was used instead of 2 parts of a reaction product of dibutyltin oxide and 1,4-butanediol. and then an image was obtained.

The detailed results are shown in Table 5.6, and good images were obtained.

Table 5 0...good, 0Δ...slightly good, Δ...slightly poor, ×...defective clothing 6 0...good, 0Δ...slightly good, Δ...slightly poor, × ...Poor [Synthesis example] 124g of dibutyltin oxide in 300ml of toluene
and 50 g of 1,4-butanediol were dispersed, and the reaction solution was refluxed for 5 hours to obtain 136 parts of the desired product.The product was washed with hot toluene and dried to obtain a purified product. .

In addition, the infrared absorption spectrum of the purified product was measured, and the absorption near 1700 cm due to 5n=o completely disappeared,
It was confirmed that a new absorption near 1100 cm-1 caused by 5n-o-c appeared.

Experimental Example 1-a (Invention) Dibutyl tin oxide with an average particle size of 1.5 g and 1 .4
- Mix 10 parts by weight of the reactant with butanediol,
The number of particles dissolved per minute was measured. When the measurement was performed five times, an average of 0.4 aggregates was observed.

Experimental Example 1-b (Comparative Example) The number of aggregates was measured in the same manner as Experimental Example 1-a except that dibutyltin oxide with an average particle size of 1.5 μl was used. Agglomerations were seen. From the results of Experimental Example 1-a and Experimental Example 1-b, it was found that the organic tin compound having an alkoxy group according to the present invention has excellent dispersibility in resin.

Experimental Example 2-a (invention) Styrene-butyl acrylate-butyl maleate hafester copolymer (weight average molecular weight approximately 300,000) 100
7 parts of a reaction product of dibutyltin oxide and 1,4-butanediol were mixed into the mixture, and the mixture was melt-kneaded at a temperature of 150°C for 30 minutes and cooled. The cooled material was easily crushed and could be pulverized.

Experimental Example 2-b (Comparative Example) Mixing and melt-kneading were performed in the same manner as in Experimental Example 2-a except for using dibutyltin and oxide.
After 0 minutes, it became rubbery and was extremely difficult to crush even after cooling.

Experimental Example 3-a (Invention) 100 parts of styrene-butyl acrylate-butyl maleate hafester copolymer (weight average molecular weight approximately 300,000, copolymerization ratio = 70:24:6), dibutyltin oxide and 1, Two parts of the reaction product with 4-butanediol were mixed, melt-kneaded at 150°C, cooled, pulverized, and classified to obtain a powder with a particle size of 5 to 20 μL. When 5 parts of the obtained powder and 95 parts of iron powder carrier of 50 to 80 JL were mixed and triboelectrically charged, the tripo charge of the powder was measured.+
14 p-c/g. Experimental Example 3-b (Comparative Example) 5 to 20 liters of powder was obtained in the same manner as Experimental Example 3-a, except that 2 parts of dibutyltin oxide was used. . Five parts of the obtained powder and 95 parts of a 50 to 80 iron powder carrier were mixed and triboelectrically charged, and then the tripocharge of the powder was measured and found to be -5 gc/g. From this, it was found that dibutyltin oxide does not show positive chargeability depending on the type of resin to be kneaded.

[Effect of the invention] The effects obtained by the present invention are as follows.

(1) The amount of triboelectric charge between toner particles, between toner and carrier, or between toner and toner carrier such as a sleeve in the case of -component development is stable, and the distribution of triboelectricity is sharp and uniform. It is a developer that can control the amount of charge to suit the developing system used.

(2) The developer is capable of faithfully developing and transferring a latent image, maintains its initial characteristics even when used continuously over a long period of time, and does not cause toner aggregation or change in charging characteristics.

(3) A developer that can reproduce stable images that are not affected by changes in temperature and humidity, and that can also produce images in vivid chromatic colors.

(4) The electrostatic latent image surface is not stained, rubbed or scratched, the cleaning process is easy, and the fixing properties are excellent. It is a developer that does not have any problems such as high temperature offset.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of an example of a developing device to which the positively chargeable toner according to the present invention can be applied. 1----------1 electrostatic image carrier, 2--------
---1 toner carrier, 5---------) toner. 50---------One magnet. 52--------1 magnetic brush;

Claims (4)

[Claims] (1) A toner for developing electrostatic images characterized by containing an organic tin compound having positive charge controllability and having at least one alkoxy group directly bonded to an Sn atom. (2) The toner for developing an electrostatic image according to claim 1, wherein the organic tin compound has an electron donating group. (3) The toner for developing electrostatic images according to claim 1 or 2, wherein the organic tin compound has an aralkyl group. (4) The toner for developing electrostatic images according to any one of claims 1 to 3, wherein the organic tin compound has an aryl group.