JPH05333601A - Electrostatic charge image developing toner - Google Patents

Abstract

PURPOSE:To obtain a sharp image good in thin line reproducibility and clear in halftone by allowing the toner to adsorb a specified organic compound or infiltrating the toner with it. CONSTITUTION:The electrostatic charge image developing toner is formed by allowing the toner to adsorb the organic compound or infiltrating the toner with the compound represented by formula I in which M<2+> is a cation. Resin particles small in size are used as the starting material and those obtained by polymerizing at least one kind of vinyl monomer by an optional method are preferably used. In this case, a dispersion deposition polymerization method capable of easily obtaining resin particles small in size and narrow in grain diameter distribution is advantageous, thus permitting a sharp image to be obtained and the toner to be given stable and uniform electric chargeability, though it is small in size, by using this organic compound as a charge controller, and the toner to be simple in manufacturing process and low in cost.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image, and more particularly to developing an electrostatic charge image in electrophotography, electrostatic recording, electrostatic printing, etc. A suitable dry toner.

[0002]

2. Description of the Related Art In dry electrophotography, an electrostatic latent image is generally formed on a photosensitive member, which is developed with a dry toner, and then the toner image is transferred onto a copy paper and then heat fixing (often, " The heat roller fixing "is performed) to obtain a copy image. As is well known, the dry toner used in this method contains a binder resin and a colorant as main components, and optionally contains additives such as a charge control agent and an anti-offset agent.

By the way, as a method for producing a dry toner, a kneading and pulverizing method is generally used. This is because the binder resin and the colorant (dye, pigment, etc.) raw materials for toner are mixed by stirring with a mixer, and the mixture is heated and melted and kneaded with a two-roll, three-roll, kneader, etc. After being cooled by rolling, it is roughly pulverized by a mixer, pulverizer, hammer mill or the like, finely pulverized by an air jet mill or the like, and further classified by air force to obtain toner fine particles.

This kneading and pulverizing method is the most general method, but a drawback is that the manufacturing process is long and complicated. Further, there is a problem of dispersibility between the binder resin and the dye / pigment, the charge control agent, the release material, etc. in the kneading, and a problem such as a change in the physical properties of the binder resin due to heat history, shearing force, etc. This greatly affects the manufacturability and physical properties of the toner. Furthermore, the particle size distribution of the toner obtained by the kneading and pulverization method is broad, and the coarse powder and the fine powder have a great influence on the image quality. In order to make the particle size distribution of the toner sharp, it is necessary to classify and remove the excessive particle size particles, resulting in momentum, deterioration of yield, and cost increase. In addition, in recent years, there has been a movement to further reduce the toner particle size in response to higher image quality in copying. In such a case, however, it is necessary to repeat the pulverization step in the kneading pulverization method, and the yield also deteriorates. However, the current situation is that cost increases cannot be avoided.

Then, as a method for producing a toner which does not require a crushing step, for example, JP-B-47-51830, JP-B-51-14895, JP-A-53-17735,
JP-A-53-17736 and JP-A-53-17737
A method based on a polymerization method has been proposed, as described in the official gazette of the publication. In this method, a composition obtained by adding a water-insoluble monomer, a colorant, an additive, a surfactant and a water-soluble polymerization initiator to an aqueous solution is suspended by high-speed shearing stirring with a homomixer or the like, and polymerized. Is. The toner manufactured by this method has a spherical particle shape and is excellent in fluidity as compared with the toner obtained by the pulverization method. Further, there is an advantage that the manufacturing process is simple and the manufacturing cost is low.

However, in the method of producing a toner by the suspension polymerization method, the problem of the suspension state of the monomer composition in the production process becomes a problem. That is, the physical properties of the toner such as the particle size distribution and the charging are greatly changed due to the difference in the dispersion state and the stirring state of the colorant, the additive and the like, and it is practically difficult to control the production conditions. In particular, pigments (typically "carbon black" can be mentioned) have an action of inhibiting polymerization, and therefore, a method of performing surface treatment or the like of the pigment and then polymerizing is proposed, but it also increases the cost. Dispersibility is a big issue. The particle size distribution is sharper than that of the toner obtained by the pulverization method, but the particle size is not necessarily uniform. At present, whether or not a uniform particle size is obtained is greatly influenced by the dispersion state, manufacturing conditions and the like.

Therefore, as another means for eliminating the drawbacks of the above-mentioned polymerization method, for example, JP-A-56-154738, JP-A-59-61844, JP-A-61-22845 and JP-A-63-106667 are disclosed. As described in the above publication, a method is proposed in which resin spherical particles containing no colorant or the like are first synthesized and then obtained as colored particles. However, in this method, the post-treatment on the obtained resin spherical particles becomes important. That is, a method for obtaining appropriate colored particles,
A method of obtaining particles having an appropriate charge and a method of obtaining particles having an appropriate cleaning performance are important.

Of these, charge control is extremely important as a toner characteristic, and therefore various proposals have been made to improve the toner characteristic. For example, Japanese Patent Application Laid-Open No. 62-209541 discloses a method of fixing a charge control agent on the surface of fine particles by mechanical energy to the outside of the particle, and Japanese Patent Application Laid-Open No. 63-198070 discloses resin particles on the surface of a fine particle and charging. Each method of fixing the control agent to the outside of the particles by mechanical energy has been proposed. However, in the method of fixing the charge control agent to the surface of the fine particles by mechanical energy, it is difficult to fix the charge control agent uniformly because the particle size distribution of the fine particles is wide. If the thermal characteristics are different, there is a drawback that the fixing characteristics of the fine particles are obstructed. Further, even in the method of fixing the resin particles and the charge control agent to the surface of the particles by mechanical energy, it is difficult to uniformly fix the physical properties of the resin particles and the charge control agent having different compositions and properties, and it is difficult to control the charge. That is, the present situation is that a toner having a small particle size and a narrow particle size distribution and having sufficiently uniform and stable triboelectric charging properties has not yet been found.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a small particle size toner having a narrow particle size distribution which solves the problems found in the conventional methods. It is an object of the present invention to provide a method for producing a dry toner which is a toner excellent in halftone reproducibility and photographic reproducibility, has uniform charging and is stable, has a convenient manufacturing process, and is inexpensive.

[0010]

The first of the toners for developing an electrostatic charge image of the present invention is that the resin particles have the following general formula:

[Chemical 1] It is characterized by adsorbing or permeating an organic compound represented by.

The second of the electrostatic image developing toners of the present invention is
Resin particles obtained by adsorbing or permeating an organic compound represented by the above general formula in a hydrophilic organic liquid, and then subjecting the organic compound to mechanical collision to fix the organic compound on the surface of the resin particles. It is characterized by

In the first and second toners of the present invention, it is advantageous that the resin particles are dispersed and precipitation-polymerized in a hydrophilic organic liquid by a polymer dispersant which dissolves in the organic liquid. is there.

The inventors of the present invention have conducted many studies on dry type toners, but have adsorbed or permeated a specific organic compound having a charge controllability on resin particles in a wet type (in a hydrophilic organic liquid). It was confirmed that the toner obtained by the above can sufficiently meet the above-mentioned problems. The present invention is based on this.

The present invention will be described in more detail below. In the dry toner (electrostatic image developing toner) of the present invention, the organic compound represented by the general formula of the above chemical formula 1 is used as a charge control agent, which is uniformly adsorbed or penetrated into the resin particles. It has a uniform and stable charging performance even though it has a small particle size, and the manufacturing process is simple and the cost is low.

By the way, in the toner of the present invention, resin particles having a small particle diameter are used as a starting material, and the resin particles are obtained by polymerizing at least one vinyl monomer by an arbitrary method. It is desirable to have one. However, in this case, the dispersion precipitation polymerization method is advantageous as the polymerization method. This is because resin particles having a small particle size and a narrow particle size distribution can be easily obtained.

In this polymerization method (dispersion precipitation polymerization method), a polymer dispersant which is soluble in the organic liquid is added to the hydrophilic organic liquid, which is further dissolved in the organic liquid, but the polymer produced is After the step of polymerizing by adding one or more vinyl monomers that swell or hardly dissolve in the organic liquid, or during the process, the seed particle dispersion liquid has the same or other hydrophilicity as the organic liquid. This is a process of growing seed particles by adding a vinyl monomer diluted with an organic liquid. Here, the dispersion precipitation polymerization method will be described in the following (i) and (ii).

(I) Production of seed particles Seed particles are previously synthesized in a hydrophilic organic liquid. At this time, the polymer dispersant that dissolves in the hydrophilic organic liquid is 0.1 to
The amount of vinyl monomer is 10% by weight, and the amount of vinyl monomer is 50 times or less that of the polymer dispersant. When the amount of the vinyl monomer is 50% by weight or less with respect to the hydrophilic organic liquid, it is easy to obtain polymer particles having a narrow average particle size distribution of 0.1 to 10 μm. However, the target particle size,
Depending on the polymer dispersant, vinyl monomer and hydrophilic organic liquid used, it is also possible to carry out the treatment outside the above range as appropriate.

(Ii) Growth reaction In this method, polymer particles having an average particle size of 10 μm or less and a narrow particle size distribution are synthesized once by the above-mentioned polymerization (formation of seed particles). When a vinyl monomer is further added to the system under a condition that radical polymerization occurs and particles are not coalesced or aggregated, seed particles once formed can be grown while maintaining their distribution. It is desirable to add the vinyl monomer or the vinyl monomer solution during the nucleus particle growth reaction when the polymerization rate becomes 10% or more after the generation of the nucleus particles starts. The second stage growth reaction may be started after the polymerization reaction of is completely completed. Further, the growth reaction may be performed after purifying the nuclear particle polymerization reaction liquid and removing unreacted vinyl monomer, coarse particles, and fine particles. Therefore, the term “at the time when the polymerization rate of the core particles reaches 10% or more” does not only mean that the core particle polymerization reaction is continuing, but also the time of purification after the completion of the core particle polymerization reaction. It includes.

Appropriate conditions are selected for the growth reaction in order to prevent the particles from coalescing. Regardless of the type of polymer, most of the growing polymer is dissolved or swollen in the vinyl monomer used for the growth reaction, and has tackiness and adhesiveness. When these particles collide with each other by the action of stirring, Brownian motion, etc. and exceed the upper limit of being stabilized by the polymer dispersant, they coalesce and agglomerate to promote enlargement of the particles and expansion of the particle size distribution.

Therefore, in order to allow the polymerization to proceed while maintaining the particle size distribution of the seed particles, it is necessary to consider the frequency of collision between the particles and to make the seed particles hydrophilic before adding the vinyl monomer. It is necessary to adjust the concentration to 15% by weight or less with respect to the volatile organic liquid. However, if the seed particle concentration is too low, coalescence between particles is suppressed, but the amount of newly generated particles becomes extremely large (though this can be separated later), 2 to 10 wt. It is preferably in the concentration range of%.

Here, the meaning of "growth (progress of polymerization) while maintaining the particle size distribution" means that the ratio of the volume average particle size of the obtained polymer particles to the expected growth volume average particle size is 1.10. It means that The expected growth volume average particle diameter is defined as follows. In the formula, the weight of the vinyl monomer effectively used in the growth reaction is the weight of the added vinyl monomer excluding the unreacted one and the one not added to the growth reaction (newly generated particles). is there. The amount of unreacted vinyl monomer can be determined by gas chromatography or the weight of the recovered particles, and the weight of the newly generated particles can be determined separately from the grown particles by gravity sedimentation or centrifugal sedimentation in the liquid.

In order to prevent coalescence due to stickiness of the seed particles during the reaction, the concentration of the vinyl monomer also has an appropriate range, and the vinyl monomer during the growth reaction is 25% by weight of the hydrophilic organic liquid.
The following is preferable. However, if the concentration of the vinyl monomer is too dilute, coalescence of the particles can be suppressed, but the growth rate of the particles cannot be high, the productivity is poor, and the polymerization rate is slow. It is good to do in the range of%. In order to prevent the concentration of the vinyl monomer to be added with respect to the entire system from being lowered or raised too much, a means of appropriately adjusting the addition rate according to the reaction rate is used.

On the other hand, it is preferable that the vinyl monomer to be added is not added as it is but diluted with a hydrophilic organic liquid to some extent and then added. The added vinyl monomer diffuses into the system, but the diffusion speed is not considered to be particularly fast compared with the time for particles to aggregate and coalesce. Therefore, it is preferable to use a pre-diluted vinyl monomer in order to maintain the particle size distribution.
It is advisable to add it in an amount of not more than wt%. The vinyl monomer added in this way may be the same vinyl monomer as that used to produce the seed particles or a different vinyl monomer, and the growth reaction can be carried out using two or more kinds. However, the polymer or copolymer to be purified must not be dissolved in the hydrophilic organic liquid.

Of course, the hydrophilic organic liquid for diluting the seed particles and diluting the vinyl monomer during the growth reaction is not limited to the same one used for the production of the seed particles. Rather, in order to prevent the seed particles from coalescing with each other, it may be preferable to select one that is farther from the SP value of the seed particle polymer than the hydrophilic organic liquid used to produce the seed particles. However, if they are too far apart, the number of newly generated particles will extremely increase and the frequency of aggregation of particles will increase, so caution is required.

A polymer dispersant can also be added to the dispersion liquid of the seed particles or the vinyl monomer to be added during the growth reaction, so that the stabilizing effect of the particles can be enhanced and aggregation can be prevented.
It is also a major feature of this dispersion precipitation polymerization method that particles can be grown while maintaining a sharper particle size distribution by repeating the process of nuclei particle growth several times rather than once.

By the dispersion precipitation polymerization method described above, the ratio of the volume average particle diameter to the number average particle diameter is 1.15 or less, the volume average particle diameter is 1 to 20 μm, and the particle diameter distribution is small. Narrow resin particles are obtained.

The hydrophilic organic liquid used as a diluent for the monomers used in the formation of the seed particles and the growth reaction of the seed particles includes, for example, methyl alcohol, ethyl alcohol,
Denatured ethyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, tert-
Butyl alcohol, sec-butyl alcohol, ter
t-amyl alcohol, 3-pentanol, octyl alcohol, benzyl alcohol, cyclohexanol,
Alcohols such as furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerin, diethylene glycol; methyl cellosolve, ethyl cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. Representative examples thereof include ether alcohols and the like. These organic liquids can be used alone or as a mixture of two or more kinds.

It should be noted that when an organic liquid other than alcohols and ether alcohols is used in combination with the above-mentioned alcohols and ether alcohols, under the conditions that the polymer particles of the organic liquid are not soluble. It is possible to change the SP value in various ways and change the polymerization conditions to suppress the size of particles to be generated, coalescence of seed particles and generation of new particles. In this case, the organic liquid used in combination includes hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene and xylene;
Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, tetrabromoethane; ethers such as ethyl ether, dimethyl glycol, trioxane, tetrahydrofuran; acetals such as methylal and diethyl acetal; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexane Such as ketones; butyl formate, butyl acetate, ethyl propionate, cellosolve acetate etc .; acids such as formic acid, acetic acid, propionic acid etc .; nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide, dimethyl Sulfur- and nitrogen-containing organic compounds such as formamide; other water is also included.

Polymerization is carried out in the presence of sulfate ion, nitro ion, phosphate ion, chlorine ion, sodium ion, potassium ion, magnesium ion, calcium ion, and other inorganic ions in a solvent composed mainly of these hydrophilic organic liquids. You may do it. Also at the start of polymerization,
During the polymerization, the type and composition of the mixed solvent can be changed from the final stage of the polymerization to adjust the average particle size, particle size distribution, drying conditions and the like of the polymer particles produced.

Suitable examples of the polymer dispersant used in the production of the seed particles or the production of grown particles include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, Acids such as crotonic acid, fumaric acid, maleic acid or maleic anhydride; an acrylic monomer containing a hydroxyl group, for example β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate.
Γ-hydroxypropyl acrylate, β-hydroxypropyl acrylate, β-hydroxypropyl methacrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3 methacrylic acid
-Chloro-2-hydroxypropyl, diethylene glycol monoacrylic acid ester, diethylene glycol monomethacrylic acid ester, glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide, N-methylol methacrylamide, etc .; with vinyl alcohol or vinyl alcohol Ethers such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether and the like; esters of vinyl alcohol and compounds containing a carboxy group,
For example vinyl acetate, vinyl propionate, vinyl butyrate;
Acrylamide, methacrylamide, diacetone acrylamide or their methylol compounds; acid chlorides such as acrylic acid chloride and methacrylic acid chloride; vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine and the like having a nitrogen atom or a heterocycle thereof A homopolymer or copolymer system of
Polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl Examples thereof include polyoxyethylene type such as phenyl ester and polyoxyethylene nonylphenyl ester; and celluloses such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose. Also,
The hydrophilic monomer and styrene, α-methylstyrene,
Those having a benzene nucleus such as vinyltoluene, derivatives thereof or copolymers such as acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide; further crosslinkable monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Copolymers with allyl methacrylate, divinylbenzene and the like can also be used.

These polymer dispersants are appropriately selected depending on the hydrophilic organic liquid used, the seed of the intended polymer particles, and whether the seed particles are produced or grown particles are produced. In order to prevent the coalescence of the polymer particles in a three-dimensional manner, a polymer having a high affinity for the polymer particle surface and an adsorptive property and a high affinity for the hydrophilic organic liquid and a high solubility is selected. Further, in order to increase the repulsion between the particles in a three-dimensional manner, one having a molecular chain of a certain length, preferably one having a molecular weight of 10,000 or more is selected. However, if the molecular weight is too high, the viscosity of the liquid will remarkably increase, the operability and the agitation property will be deteriorated, and the precipitation probability of the produced polymer on the particle surface will be varied, so that caution is required. Further, it is also effective for stabilization to make a part of the above-mentioned monomer of the polymer dispersant coexist with the monomer constituting the intended polymer particles.

Further, together with these polymer dispersants, metals such as cobalt, iron, nickel, aluminum, copper, tin, lead and magnesium or alloys thereof (particularly preferably having a particle size of 1 μm or less); iron oxide, copper oxide, Fine powders of inorganic compounds of oxides such as nickel oxide, zinc oxide, titanium oxide and silicon oxide; anionic surfactants such as higher alcohol sulfuric acid ester salts, alkylbenzene sulfonates, α-olefin sulfonates and phosphoric acid esters; alkyl Amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazoline and other amine salt types, and alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridium salts, alkyl isoquinonium salts, benzethonium chloride, etc. Class Ammoniu Salt type cationic surfactant;
Nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives; for example, amino acid-type and betaine-type amphoteric surfactants such as alanine-type [eg, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine] When used together, the stability of the produced polymer particles and the improvement of the particle size distribution can be further enhanced.

Generally, the amount of the polymer dispersant used in the production of the seed particles varies depending on the kind of the polymerizable monomer for forming the intended polymer particles, but usually, with respect to the hydrophilic organic liquid,
It is 0.1 to 10% by weight, preferably 1 to 5% by weight.
When the concentration of the polymer dispersant is low, the produced polymer particles have a relatively large particle size, and when the concentration is high, a small particle size is obtained. Even if it is used, it has little effect on reducing the particle size.

The above-mentioned polymer dispersant and inorganic fine powders, pigments, and surfactants added as necessary are, of course, necessary in the production of seed particles, but in the growth reaction. In order to prevent the particles from coalescing with each other, the polymerization may be carried out by allowing the particles to be present in a vinyl monomer solution or seed particle dispersion liquid to be added.

The particles initially formed are stabilized by the polymer dispersant distributed in equilibrium in the hydrophilic organic liquid and on the surface of the polymer particles. When it is present in the liquid in a considerable amount, it has a somewhat swollen stickiness, and overcomes the steric repulsive force of the polymer dispersant to agglomerate. Furthermore, when the amount of the monomer is extremely large with respect to the hydrophilic organic liquid, the produced polymer is completely dissolved and does not precipitate unless the polymerization proceeds to some extent. The state of precipitation in this case takes the form of forming a highly sticky lump. Therefore, the amount of the monomer with respect to the hydrophilic organic liquid at the time of producing the particles is naturally limited, and the monomer / hydrophilic organic liquid ratio is about the same although the amount is slightly different depending on the kind of the hydrophilic organic liquid. 1 or less, preferably 1/2 or less is suitable.

The above-mentioned "vinyl monomer" is one which is soluble in a hydrophilic organic liquid, and is, for example, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p. -Ethylstyrene, 2,4
-Dimethylstyrene, pn-butylstyrene, pt
ert-butyl styrene, pn-hexyl styrene,
pn-octylstyrene, pn-nonylstyrene,
pn-decylstyrene, pn-dodecylstyrene,
Styrenes such as p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, acrylic Acid n-octyl, dodecyl acrylate,
Lauryl acrylate, 2-ethylhexyl acrylate,
Stearyl acrylate, 2-chloroethyl acrylate,
Phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, methacrylic acid 2 Α-methyl fatty acid monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate; acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; Vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride, and other vinyl halides, etc., alone or in admixture with each other, and containing 50% by weight or more of these and co-weighing Means a mutual mixture with compatible monomers.

The polymer used in the present invention may be polymerized in the presence of a so-called cross-linking agent having two or more polymerizable double bonds in order to enhance the offset resistance. As the cross-linking agent preferably used, divinylbenzene, divinylnaphthalene and aromatic divinyl compounds which are derivatives thereof, other ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, tert-butyl. Aminoethyl methacrylate,
Tetraethylene glycol dimethacrylate, 1,3-
Examples include all divinyl compounds such as butenediol dimethacrylate and other diethylenic carboxylic acid esters, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and compounds having three or more vinyl groups, which may be used alone or Used in mixtures and the like.

When the growth polymerization reaction is subsequently carried out using the seed particles thus crosslinked, the inside of the growing polymer particles is crosslinked. On the other hand, when the vinyl monomer solution used for the growth reaction contains the above-mentioned cross-linking agent, a polymer whose particle surface is hardened is obtained. For the purpose of adjusting the average molecular weight, polymerization may be carried out in the presence of a compound having a large chain transfer constant. Examples thereof include low molecular weight compounds having a mercapto group, carbon tetrachloride and carbon tetrabromide.

Further, as the polymerization initiator of the monomer,
For example, 2,2'-azobisisobutyronitrile, 2,
Azo polymerization initiators such as 2'-azobis (2,4-dimethylvaleronitrile), peroxide polymerization initiators such as lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate, and potassium persulfate. Such a persulfidic initiator or a system in which sodium thiosulfate, amine or the like is used in combination is used. The concentration of the polymerization initiator is
0.1 to 10 parts by weight is preferable to 100 parts by weight of the vinyl monomer.

The polymerization conditions for obtaining the seed particles are as follows: the concentration of the polymer dispersant and the vinyl monomer in the hydrophilic organic liquid, and the blending ratio, depending on the target average particle size and the target particle size distribution of the polymer particles. Is determined. Generally, the concentration of the polymeric dispersant is set high when the average particle size of the particles is reduced, and the concentration of the polymeric dispersant is set low when the average particle size of the particles is set large. On the other hand, if the particle size distribution is to be made extremely sharp, the vinyl monomer concentration is set low, and if the distribution is relatively wide, the vinyl monomer concentration is set high. When it is used in an amount exceeding 50 times the amount used, it is difficult to obtain particles having an average particle size within ± 25% with a distribution of 90% or more by weight, and it is suitable as a seed particle. Absent.

The seed particles are produced by completely dissolving the polymer dispersant in the hydrophilic organic liquid, and then using one or more kinds of vinyl monomers, a polymerization initiator, and other inorganic fine powder, an interface, if necessary. 30-300 by adding activator, dye, pigment, etc.
With normal stirring at rpm, preferably at low speed,
Moreover, by using a turbine-type stirring blade rather than a paddle-type stirring blade, stirring is performed at a speed such that the flow in the tank is uniform, while heating to a temperature corresponding to the decomposition rate of the initiator used and polymerization is performed. Be done. Since the temperature at the initial stage of polymerization has a great influence on the particle size to be generated, it is desirable to raise the temperature to the polymerization temperature after adding the monomer, and to dissolve the initiator in a small amount of solvent and add it. At the time of polymerization, it is necessary to sufficiently expel oxygen in the air in the reaction vessel with an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles are likely to be generated.

In order to carry out the polymerization in the high polymerization rate region, 5 to 40
Polymerization time is required, but the polymerization rate can be increased by stopping the polymerization in the state of the desired particle size and particle size distribution, by sequentially adding the polymerization initiator, and by conducting the reaction under high pressure. be able to. After the polymerization is completed, unnecessary fine particles, residual monomers, polymer dispersants, etc. are removed by operations such as sedimentation, centrifugation, decantation, etc., and then the polymer slurry is collected and washed to adjust the spherical particle size. Polymerized particles (in a solvent) can be obtained. Here, after washing, filtration and spray drying are carried out to obtain spherical polymer particle powder having a uniform particle diameter. Further, by repeating the growth reaction, it is possible to obtain more uniform large-sized particles.

In the present invention, the small particle size resin particles, preferably the resin particles obtained by the above-mentioned polymerization step, are usually colored by a dyeing method. The dye is usually prepared by using a saturated solution of the dye, and the solvent used for preparing the saturated dye solution is the hydrophilic organic liquid used in the polymerization step. Therefore, the resin particles (polymerized particles) obtained in the polymerization step can be dyed in a polymer slurry state without drying. In dyeing, polymer particles are dispersed in a saturated dye solution of a hydrophilic organic liquid, and heating and stirring are performed. It is considered that during this dyeing process, the polymer particles are swollen in the heated organic solution, and the dye molecules dissolved in the liquid are adsorbed in the particles.

The dyes used here include disperse dyes, vat dyes, metal-containing dyes, oil-soluble dyes, and the like, and specific examples thereof include the following (in the parentheses, CI No. Represents). Acid Yellow 11 (18820), 135, 161 Acid Orange 1 (13091), 7 (15510), 19 (146
90), 20 (14600), 28 (16240), 74 (18745), 122 Acid Red 6 (14680), 8 (14900), 51 (454
30), 52 (45100), 80 (68215), 87 (45380), 92 (45410) Acid Violet 78 (12205), 82, 93 Acid Blue 9 (42090), 102 (50320), 104
(42735), 117 (17055), 120 (26400), 229, 234 Acid Green 3 (42085), 7 (42055), 9 (4210
0), 12 (13425), 16 (44025), 19 (20440), 44 (61590), 7
5,76 Acid Brown 13 (10410), 46, 231, 232, 2
94, 295, 296 Acid Black 112, 118, 119, 121, 154, 1
55 Basic Yellow 1 (49005), 2 (41000), 11 (480
55), 14, 36 Basic Orange 15 (46045), 21 (48035) Basic Red 2 (50240), 9 (42500), 12 (480
70), 37 Basic Violet 1 (42535), 3 (42555), 10 (451
70), 14 (42510) Basic Blue 1 (42025), 3 (51004), 5 (4214
0), 7 (42595), 9 (52015), 24 (52030), 25 (52025), 26 (4
4045) Direct Yellow 12 (24895), 24 (22010), 26 (2
5300) Direct Orange 6 (23375), 8 (22130), 26 (291
50) Direct Red 1 (22310), 4 (29165), 28 (221
20) Direct Green 1 (30280) Direct Brown 2 (22311), 44 (35005), 58 (22
340), 59 (22345), 106 (36200) Disperse Yellow 3 (11855), 31 (48000) Disperse Orange 1 (11080), 3 (11005), 11 (607
00), 45 Disperse Red 1 (11110), 4 (60755), 5 (1121)
5), 7 (11150), 11 (62015), 12, 13 (11115), 15 (6071
0), 17 (11210) Disperse Blue 1 (64500), 3 (61505), 6 (6205
0), 7 (62500), 43, 44, 52, 68 Solvent Yellow 16 (12700), 21 (18690), 56 (1
1021), 61 Solvent Orange 1 (11920), 2 (12100), 5 (1874
5: 1), 6 (18736: 1), 14 (26020), 37, 40, 45 (11700) Solvent Red 1 (12150), 8 (12715), 23 (261
00), 30 (27291), 49 (45170: 1), 81, 82, 83, 84, 100 (1
2716) Solvent Violet 8 (42535: 1), 21 Solvent Blue 2 (42563: 1), 12 (62100), 5
5,73 Solvent Brown 20 These dyes may be used alone or in combination of two or more.

As described above, the toner of the present invention is characterized in that resin particles are adsorbed or permeated with an organic compound represented by the following general formula in a hydrophilic organic liquid.

[Chemical 1] The organic compounds represented by the above general formula are as shown in Table 1.

[Table 1]

These organic compounds are usually adsorbed or permeated into colored small-sized resin particles. However, since the method of permeating the organic compound into the resin particles is the same as the method of coloring with the dye, the permeation of the compound into the resin particles can be performed not only after coloring the resin particles but also at the same time when coloring. .. Particularly, from the viewpoint of simplifying the process, it is very preferable to carry out the permeation at the time of coloring. Further, the method of adsorbing these organic compounds on the surface of the resin particles, by dissolving the organic compound in a hydrophilic organic liquid, stirring and immersing the resin particles in this, by drying the hydrophilic organic liquid as a solvent to dryness, The organic compound is adsorbed on the particle surface. By dissolving the compound in the hydrophilic organic liquid, it becomes possible to uniformly adsorb the compound on the surface of the resin particles.

Water is considered to be the most common solvent for dissolving the above organic compounds, but most of the organic compounds effective in the present invention are insoluble in water and cannot be used alone. On the other hand, resin particles to be surface-treated, particularly polymerized particles, are polymerized in a hydrophilic organic liquid, the present invention can be carried out in a slurry of polymerized particles, and hydrophilic organic liquid is effective for drying. Therefore, a hydrophilic organic liquid is used as a solvent.

The organic compound used in the present invention has different solubility in a hydrophilic organic liquid depending on its structure. Therefore, in order to improve the solubility of these organic compounds, two or more hydrophilic organic liquids can be mixed and used at the time of adsorption or dyeing. As the mixed solvent, acetone, toluene, methyl ethyl ketone, isopropyl alcohol, butyl alcohol, isobutyl alcohol, n-heptanol, 2-ethyl-1-butanol, n-octanol, 2-ethylhexyl alcohol, n-decanol, dioctyl alcohol, etc. Is. The mixing ratio of these solvents may be such that the resin particles are not dissolved or aggregated but swelled or only a part thereof is dissolved, and 5 to 30 parts by weight is preferable to 95 to 70 parts by weight of methanol. The organic compound used in the present invention is the resin particle 1
It is used in an amount of 0.2 to 10 parts by weight based on 00 parts by weight. 0.
If the amount is less than 2 parts by weight, a sufficient amount of charge cannot be obtained, and if the amount is more than 10 parts by weight, the amount of charge is too high, and the fixability is adversely affected. Preferably 0.3
-6 parts by weight is desirable. Further, when the organic compound is adsorbed on the surface of the resin particles, as a method for drying the hydrophilic organic liquid used as a solvent, evaporation drying, freeze drying,
Drying by heating with a hot plate or the like, heating under reduced pressure by an evaporator or the like can be raised. In either method, it is necessary to completely evaporate the solvent, and pressure reduction, heating, etc. can be performed as necessary. However, the heating temperature must not cause the particles to aggregate, and the glass transition temperature (Tg) of the resin
The following temperatures are desirable.

It is very preferable that the organic compound adsorbed on the surface of the colored resin particles is further subjected to a mechanical impact to fix the compound on the surface of the particles, because the durability of the obtained toner is improved. In this case, a mechanical impact force is applied to the particle surface to immobilize the adsorbed organic compound on the particle surface, for example, a ball mill pot, a Henschel mixer,
Mixer such as V blender, I-type mill, vibration mill, crusher such as kryptron, ong mill, hybridization system, mechanofusion system,
Surface treatment equipment such as surfing system is raised. Temperature conditions are important in both methods,
It is necessary to set conditions so that the organic compound on the surface is fixed and embedded at a temperature at which the particles are slightly swollen or dissolved and aggregation of the particles does not occur.

[0050]

EXAMPLES The present invention will be described in more detail with reference to examples, but the present invention is not limited thereto. All parts here are based on weight.

(Production of Resin Particles) Synthesis Example 1 A four-necked flask equipped with an agitator blade of an angled fan turbine (four blades), a cooler, and a gas introduction tube was charged with 100 parts of methanol dried with a molecular sieve 5A. Put, polyvinylpyrrolidone (average molecular weight Mn = 40,000)
3.0 parts was added little by little with stirring to completely dissolve it. Further, 20 parts of styrene and 0.13 part of 2,2'-azobisisobutyronitrile were added and completely dissolved to obtain a transparent solution. The inside of the flask was purged with dry argon gas while stirring, and left for 1 hour while flowing a small amount.
Polymerization was started in a constant temperature water bath of 60.0 ± 0.1 ° C. while stirring at a stirring speed of 50 rpm. The liquid began to turn cloudy 15 minutes after heating. It was confirmed by gas chromatography using ethylbenzene as an internal standard that the polymerization rate reached 55% 6 hours after the initiation of the polymerization. Further, a small amount of the liquid at this time was sampled, residual monomers and polyvinylpyrrolidone were removed by centrifugal sedimentation, and the particle size and particle size distribution were analyzed by a Coulter counter. The volume average particle size Dv = 4.8 μm, number average particle size Dp
= 4.6 μm. At this time, while maintaining the internal temperature at 60 ° C., a mixed solution of 25 parts of styrene, 0.25 parts of 2,2′-azobisisobutyronitrile and 60 parts of methanol was filled over 3 hours. Although the white turbidity of the solution became thin after the addition, it was uniformly maintained as a dispersion, and the polymerization was carried out for 30 hours as it was. It was confirmed by gas chromatography that the polymerization rate reached 95%. When the obtained dispersion was cooled and treated with a centrifuge at 1000 rpm for 10 minutes, the polymer particles were completely settled and the upper liquid was slightly clouded. Remove the supernatant and add 10 more methanol.
0 part was added and the mixture was washed with stirring for 1 hour. The procedure of centrifuging and washing with methanol was repeated once more, and finally, washing with water and filtration with a 1 μm microfilter were performed. It was confirmed that the filtrate was transparent and there were no particles of 1 μm or smaller.

(Production of Colored Resin Particles) Coloring Example 1 300 parts of methanol and 2 parts of Oil Black HBB (manufactured by Orient Chemical Co., Ltd.) were added to a separable flask equipped with a stirring blade and a cooling tube, and heated and stirred at 60 ° C. for 1 hour. .. This solution was filtered with a 1 μm filter to obtain a saturated solution. Next, 300 parts of the obtained saturated solution was put in the same apparatus, 50 parts of the resin particles obtained in Synthesis Example 1 was added thereto, and the mixture was heated and stirred at 50 ° C. for 1 hour. Then cool to room temperature, filter,
The particles were dried under reduced pressure to obtain black uniform spherical particles.

Coloring Example 2 300 parts of methanol and 2 parts of Oil Black HBB (manufactured by Orient Chemical Co.) were added to a separable flask equipped with a stirring blade and a cooling tube, and heated and stirred at 60 ° C. for 1 hour. This solution was filtered with a 1 μm filter to obtain a saturated solution. Next, 300 parts of the obtained saturated solution was put in the same apparatus, 50 parts of the resin particles obtained in Synthesis Example 1 was added thereto, and the mixture was heated and stirred at 50 ° C. for 1 hour. After that, it was cooled to room temperature, and this solution was filtered to obtain a state of a methanol-containing cake of black uniform spherical particles.

Example 1 Methanol 3 was placed in a separable flask equipped with a stirring blade and a cooling tube.
00 parts, Oil Black HBB (manufactured by Orient Chemical Co.)
Two parts were added, and the mixture was heated with stirring at 60 ° C. for 1 hour. This is 1μ
A saturated solution (Solution A) was obtained by filtration through an m filter. Next, 300 parts of methanol and 6 parts of Compound Example 1 were added to the same apparatus, and the mixture was heated and stirred and filtered in the same manner to obtain a saturated solution (solution B). 150 parts of Solution A and 150 parts of Solution B were put in the same apparatus, and 50 parts of the polymer particles of Synthesis Example 1 were added thereto, and the temperature was 50 ° C.
The mixture was heated and stirred for 1 hour. Then cool to room temperature and filter,
The particles were dried under reduced pressure to obtain black uniform spherical particles. 2.5 parts of the obtained particles were mixed with 97.5 parts of a ferrite carrier to obtain a two-component developer. The charge amount of the obtained developer was measured by a blow-off device to find that it was −22.3 μC / g.
Met. When this developer was set on a commercially available electrophotographic copying machine (IMAGIO MF530 manufactured by Ricoh Co., Ltd.) to form an image,
The fine line reproducibility was good, and a clear halftone vivid image was obtained.

Example 2 The apparatus of Example 1 was charged with 260 parts of methanol and 40 parts of toluene.
Parts, and 5 parts of Compound Example 2 were added, and the mixture was heated and stirred and filtered in the same manner as in Example 1 to obtain a saturated solution (solution C). Solution A1
50 parts, solution C 150 parts and polymer particles 50 parts were used in Example 1.
The mixture was placed in the same apparatus as in Example 1, and heated and stirred, filtered by cooling, and dried under reduced pressure in the same manner as in Example 1 to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The obtained developer had a charge amount of −25.1 μC / g, and when an image was formed with this developer, a clear image was obtained.

Example 3 To the apparatus of Example 1, 250 parts of methanol, 50 parts of 2-ethylhexyl alcohol, and 5 parts of Compound Example 4 were added, and heated and stirred for filtration as in Example 1 to obtain a saturated solution (solution D).
Got 150 parts of solution A, 150 parts of solution D and 50 parts of polymer particles were placed in the same apparatus as in Example 1, and heated and stirred in the same manner.
It was filtered by cooling and dried under reduced pressure to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The obtained developer had a charge amount of −23.9 μC / g, and when an image was formed with this developer, a clear image was obtained.

Example 4 600 parts of methanol and 0.7 parts of Compound Example 1 were placed in an Erlenmeyer flask, ultrasonically dispersed at room temperature, stirred with a magnetic stirrer, and completely dissolved. To this solution, 50 parts of the black uniform spherical particles obtained in Coloring Example 1 were added, further ultrasonically dispersed at room temperature, and sufficiently stirred with a magnetic stirrer. Pour all of this dispersion into a stainless steel vat,
This was left in a vacuum desiccator to evaporate and dry the solvent.
The completely dried particles were crushed with a mesh to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The charge amount of the obtained developer is −27.6 μC / g.
Met. When an image was formed with this developer, a clear image was obtained.

Example 5 In an Erlenmeyer flask, 500 parts of methanol, 100 parts of 2-ethylhexyl alcohol and 0.6 parts of Compound Example 3 were taken and dissolved in the same manner as in Example 4 to disperse 50 parts of black uniform spherical particles. This dispersion was put in an evaporator to evaporate the solvent. The completely dried particles were crushed with a mesh to obtain black uniform spherical particles. Example 1 of the obtained particles
Similarly to the above, a developer was used. The charge amount of the obtained developer is -2.
It was 9.2 μC / g. When an image was formed with this developer, a clear image was obtained.

Example 6 In an Erlenmeyer flask, 425 parts of methanol, 100 parts of 2-ethylhexyl alcohol, and 0.7 parts of Compound Example 2 were placed, and ultrasonic dispersion was carried out at room temperature in the same manner as in Example 4 and magnetic stirring was carried out completely. Dissolved. 125 parts of a methanol-containing cake was added to this solution, and ultrasonic dispersion and stirring were performed. This dispersion was opened in a stainless vat, and the solvent was evaporated and dried in a vacuum desiccator. The completely dried particles were crushed with a mesh to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The charge amount of the obtained developer was −26.9 μC / g. When an image was formed with this developer, a clear image was obtained.

Example 7 600 parts of methanol and 0.7 parts of the compound example 1 were placed in an Erlenmeyer flask, ultrasonically dispersed at room temperature, and stirred magnetically to completely dissolve them. To this solution was added 50 parts of the black uniform spherical particles obtained in Polymerized Particle Coloring Example 1,
Further, the mixture was ultrasonically dispersed at room temperature and sufficiently stirred with a magnetic stirrer. The whole amount of this dispersion was put into a stainless steel vat, and this was left in a vacuum desiccator to evaporate and dry the solvent. The completely dried particles were disintegrated with a mesh and treated with a hybridization system (NHS-1, manufactured by Nara Machinery Co., Ltd.) at 7500 rpm for 3 minutes to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The obtained developer has a charge amount of -30.1.
It was μC / g. When an image was formed with this developer, a clear image was obtained. In addition, when a durability test was performed up to 50,000 sheets, background stains, dust, insufficient image density,
No abnormal image such as reduced resolution was observed, and the 50,000th image was also clear. Also, the charge amount of the 50,000th sheet is -2
It was 8.8 μC / g and the charge was stable.

Example 8 In an Erlenmeyer flask, 425 parts of methanol, 100 parts of 2-ethylhexyl alcohol, and 0.6 parts of Compound Example 3 were taken and dissolved in the same manner as in Example 7. 125 parts of the methanol-containing cake was added and ultrasonically dispersed and stirred. The dispersion was put in an evaporator and the solvent was evaporated and dried. The completely dried particles were disintegrated with a mesh and treated with a hybridization system in the same manner as in Example 7 to obtain black uniform spherical particles. The obtained particles were used as a developer in the same manner as in Example 1. The charge amount of the obtained developer was −32.6 μC / g. When an image was formed with this developer, a clear image was obtained. No abnormal image was found in the durability test up to 50,000 sheets, and the 50,000th image was also clear, and the charge amount was −
It was stable at 30.9 μC / g.

Comparative Example 300 parts of the solution A prepared in Example 1 and 50 parts by weight of polymer particles were placed in the same apparatus as in Example 1, and heated and stirred in the same manner as in Example 1, cooled, filtered and dried to obtain black uniform spherical particles. Obtained. The obtained particles were used as a developer in the same manner as in Example 1,
The charge amount was as high as 82.1 μC / g, and good charge control could not be achieved only with the coloring dye.

[0063]

According to the invention of claim 1, since the toner has a narrow particle size distribution and a small particle size, a clear image can be obtained. According to the second aspect of the invention, the toner charge amount is stable, and a large number of good quality images can be obtained. According to the third aspect of the invention, it is possible to obtain a higher quality image.

Claims (3)

[Claims] 1. A toner for developing an electrostatic charge image, which comprises resin particles adsorbing or permeating an organic compound represented by the following general formula. [Chemical 1] 2. An organic compound represented by the following general formula is adsorbed or permeated into a resin particle in a hydrophilic organic liquid,
A toner for developing an electrostatic charge image, which is obtained by applying a mechanical shock to this to fix the organic compound on the surface of the resin particle. [Chemical 1] 3. The toner for developing an electrostatic charge image according to claim 1, wherein the resin particles are dispersed and precipitation-polymerized in a hydrophilic organic liquid by a polymer dispersant which is soluble in the organic liquid.