JP3071518B2 - Dry electrophotographic toner - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a dry electrophotographic toner, and more particularly to a dry electrophotographic toner suitable for high image quality and high resolution.

[0002]

2. Description of the Related Art In a dry electrophotographic method, an electrostatic latent image is formed on a photoreceptor by a conventional method, and after development with a dry toner, a toner image is transferred onto copy paper, and then heat-fixed (normally, heat roller fixing). I have 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 if necessary, contains additives such as a charge control agent and an anti-offset agent. As a method for producing a dry toner, a kneading and pulverizing method is generally used. This involves mixing toner raw materials such as a binder resin and a dye / pigment with a mixer or the like, performing hot-melt kneading with a two-roll, three-roll, kneader, or the like, and then rolling and cooling the kneaded material, and mixing the resulting mixture with a mixer. Coarsely crushed with a pulverizer, hammer mill, etc.
Further, it is finely pulverized by an air jet mill or the like, and further subjected to air classification to obtain toner fine particles. The above method is the most general method, but its disadvantage is that the process is long and complicated. There are also problems such as dispersibility of the binder resin and the dye / pigment in the kneading, the charge controlling agent, the release agent, and the like, and also a problem such as a change in physical properties of the binder resin due to heat history, shearing force, and the like. This has a significant effect on manufacturability, toner properties, and the like. The particle size distribution of the toner obtained by the kneading and pulverizing method is broad, and coarse and fine powders have a large effect on image quality. In order to sharpen the particle size distribution, surplus particle size particles must be classified and removed, resulting in a decrease in yield and an increase in cost. In recent years, there has been a movement to reduce the toner particle size in response to higher image quality.
In the kneading and pulverizing method, it is necessary to repeat the pulverizing step, and at present, it is inevitable that the yield is reduced and the cost is increased.

Therefore, as a method for producing a toner which does not require a pulverizing step, for example, Japanese Patent Publication Nos. 47-51830 and 51-14895.
No., JP-A-53-17735, JP-A-53-17736, and JP-A-53-177
As described in Japanese Patent Publication No. 37 and the like, a method based on a polymerization method has been devised. 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 and polymerized by high-speed shear stirring with a homomixer or the like. is there. The toner produced by this method has a spherical particle shape and excellent fluidity as compared with the toner obtained by the pulverization method. In addition, the manufacturing process is simple and can be manufactured at low cost. However, the state of suspension of the toner monomer composition in water becomes a problem in the manufacturing process. Due to differences in the dispersion state and the stirring state of the colorant and the additives, the physical properties of the toner such as the particle size distribution and the charging are greatly changed, and it is difficult to control the production conditions. In particular, a pigment (carbon or the like) has a function of inhibiting polymerization, and a method of performing polymerization by performing a surface treatment or the like has been devised. However, the cost is increased and dispersibility is a major problem. Although the particle size distribution is sharper than that of the toner obtained by the pulverization method, it does not always have a uniform particle size. At present, it greatly changes depending on the dispersion state, manufacturing conditions, and the like.

[0004] To solve the above-mentioned drawbacks of the polymerization method, Japanese Patent Application Laid-Open Nos. 56-154738, 59-61844, 61-22
As described in JP-A-8458 and JP-A-63-106667, a method has been devised in which resin spherical particles are synthesized without containing a coloring agent and the like, and then colored particles are obtained. In this method, post-treatment of the obtained resin spherical particles becomes important. That is, there are a method for obtaining appropriate colored particles, a method for obtaining particles having appropriate charging, and a method for obtaining particles having appropriate cleaning performance. Among them, regarding charging control, this is extremely important as a toner characteristic, and various ideas have been devised.

Japanese Patent Application Laid-Open No. Sho 62-209541 discloses a method in which a charge control agent is fixed to the outside of particles by mechanical energy on the surface of the fine particles. It is difficult to stick to
Further, if the thermal characteristics of the charge controlling agent and the fine particles are different, the fixing characteristics of the fine particles are impaired.

Japanese Patent Application Laid-Open No. 63-198070 discloses a method in which resin fine particles and a charge control agent are fixed to the outside of the particles by mechanical energy on the surface of the fine particles. Is difficult to fix uniformly, and it is difficult to control charging.

[0007]

SUMMARY OF THE INVENTION A first object of the present invention is to provide a toner having a uniform particle size and a small particle size. A second object of the present invention is to provide a toner with uniform charging and stable charging performance. A third object of the present invention is to provide a low-cost toner with a simple manufacturing process.

[0008]

The present inventors have conducted various studies to obtain a toner having a uniform and small particle size, a uniform and stable charge, a simple manufacturing process and a low cost. As a result, they have found that the above-mentioned object can be achieved by adsorbing or dyeing a dye-based charge control agent having charge controllability into polymer particles of uniform particle size obtained by dispersion precipitation polymerization. That is, the toner of the present invention is a polymer having a uniform particle diameter, which is dispersed and polymerized by a polymer dispersant dissolved in the hydrophilic organic liquid in the hydrophilic organic liquid, and is represented by the following general formula (1). At least one of a quaternary ammonium salt compound and a fluorinated iminium compound represented by the general formula (2) is adsorbed or dyed in the polymer particles in a hydrophilic organic liquid, In addition, in a polymer particle having a uniform particle diameter dispersed and precipitated by a polymer dispersant dissolved in the hydrophilic organic liquid in the hydrophilic organic liquid, a fluorine-containing polymer represented by the following general formula (1):
At least one of a quaternary ammonium salt compound and a fluorinated iminium compound represented by the general formula (2) is dissolved in a hydrophilic organic liquid and adsorbed on the surface of the polymer particles, and the polymer particles are subjected to mechanical shock to be adsorbed. Wherein the compound of the following general formula is fixed to the surface of the polymer particles.

[0009]

Embedded image [In the formula (1), R _{1 to} R ₄ represent a hydrogen atom or an organic group, and at least one of the groups R _{1 to} R ₄ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R ₇ —
1 carbon atom which may have a C (O) —OR ₈ group
Is a linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group having 3 to 66 fluorine atoms, wherein R ₅ , R ₆ , R ₇ and R ₈ have 1 to 30 carbon atoms. Up to three of the radicals R _{1 to} R ₄ , independently of one another, are a hydrogen atom, a linear or branched alkyl radical having 1 to 30 carbon atoms, an aryl or arylalkyl radical, an alkenyl radical. , An aryl group and an arylalkyl group are alkyl groups having 1 to 30 carbon atoms, and have 1 to 30 carbon atoms.
May be substituted with an alkoxy group, a hydroxyl group, or a halogen atom, and two of the groups R _{1 to} R ₄ may be bonded to each other, interrupted by 1 to 4 heteroatoms, and 0 to 6 A fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group Forming a substituted mononuclear or polynuclear ring system of 4 to 12 carbon atoms;
^- means an organic or inorganic anion, in particular C
l ^-, Br ^-, I -, BF ₆ ^-, sulfate, cyanate, thiocyanate, phosphate, BF _4, B (aryl) ₄ ^-, for example, tetraphenyl borate, p- chloro tetraphenylborate, p- methyl tetraphenyl Borates, phenolates, nitrophenolates, zinc tetracyanates, zinc tetrathiocyanates, saturated aliphatic or unsaturated aliphatic or aromatic carboxylates or sulfonates, perfluorinated saturated aliphatics or perfluorinated unsaturated aliphatics Or perfluorinated aromatic carboxylate or sulfonate. ]

[0010]

Embedded image [In the formula (2), R _{9 to} R ₁₂ represent a hydrogen atom or an organic group, and at least one of the groups R _{9 to} R ₁₂ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or a sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R
₇ -C (O) linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group -O-R have _eight by fluorine atoms also a good carbon atoms 1-69 3-66 Wherein R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 30 carbon atoms, and at most three of the groups R _{9 to} R ₁₂ independently of one another are a hydrogen atom, a carbon atom 1 A linear or branched alkyl group, an aryl group or an arylalkyl group, or an alkenyl group having up to 30 carbon atoms, wherein the aryl group and the arylalkyl group are an alkyl group having 1 to 30 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms. And two of the radicals R _{1 to} R ₄ may be linked to each other, interrupted by 1 to 4 heteroatoms and 0 to 6 It may contain a heavy bond and may contain a fluorine atom, a chlorine atom, A mononuclear or polynuclear ring system having 4 to 12 carbon atoms, which is substituted by an atom or iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group And X
^- means an organic or inorganic anion, in particular C
l ^-, Br ^-, I -, BF ₆ ^-, sulfate, cyanate, thiocyanate, phosphate, BF _4, B (aryl) ₄ ^-, for example, tetraphenyl borate, p- chloro tetraphenylborate, p- methyl tetraphenyl Borates, phenolates, nitrophenolates, zinc tetracyanates, zinc tetrathiocyanates, saturated aliphatic or unsaturated aliphatic or aromatic carboxylates or sulfonates, perfluorinated saturated aliphatics or perfluorinated unsaturated aliphatics Or perfluorinated aromatic carboxylate or sulfonate. ]

The dispersion-precipitated polymer particles used in the present invention are parent particles.
A polymer dispersant that dissolves in an aqueous organic liquid is added, and
Although soluble in hydrophilic organic liquids, the resulting polymer is
Swells or hardly dissolves in aqueous organic liquids 1
Add seed or two or more vinyl monomers to polymerize seed particles
After or during the step, the hydrophilic organic liquid is added to the seed particle dispersion.
Vinyl monomer diluted with the same or another hydrophilic organic liquid
Particle size distribution consisting of the process of growing seed particles by adding bodies
Are narrow polymer particles. (I) Production of Seed Particles Seed particles are synthesized in advance in a hydrophilic organic liquid. this
When the polymer dispersant dissolved in the hydrophilic organic liquid 0.1 ~
10% by weight, vinyl monomer is 50 times or more of polymer dispersant
Below, use an amount of 50% by weight or less based on the hydrophilic organic liquid.
And giving polymer particles having a narrow distribution of 0.1 to 10 μm
The particle size desired by the pan, the polymer dispersion stabilizer used,
Above depending on the type of vinyl monomer or hydrophilic organic liquid
May be performed outside the range. (Ii) Growth reaction In the present invention, once the above-mentioned polymerization has an average particle diameter of 10 μm or less,
Synthesize polymer particles with narrow particle size distribution (seed particle shape
). Further radical polymerization of vinyl monomer occurs in the system.
Once added under conditions that prevent coalescence of particles
The formed seed particles can be grown while maintaining their distribution.
Can be. Vinyl monomer during nuclear particle growth reaction
The formation of core particles in vinyl monomer solution?
It is desirable to add when the polymerization rate becomes 10% or more.
Preferably, the polymerization reaction of the core particles is completely completed.
Then, the second-stage growth reaction may be started. Further nuclear particle weight
Purify the combined reaction solution, unreacted vinyl monomer, and coarse particles
The growth reaction may be performed after removing particles and fine particles.
Therefore, the polymerization rate of the core particles in the present invention is 10% or more.
Means that the nuclear particle polymerization reaction is ongoing
Not only includes the purification at the end of the nuclear particle polymerization reaction
It is. Growth reactions are suitable for preventing coalescence of particles.
Appropriate conditions are selected. The growing polymer depends on the type of polymer
Most of vinyl monomers used for growth reaction regardless of
It is dissolved or swelled and has tackiness and adhesiveness. This
These particles collide due to the action of stirring, Brownian motion, etc.
If it exceeds the upper limit stabilized by the polymer dispersant,
I. Agglomeration causes particle enlargement and particle size distribution
Nagasu. Therefore, the particle size distribution of the seed particles is almost maintained.
In order for polymerization to proceed as it is, the collision frequency between particles must be
Seed particles before adding vinyl monomer to reduce
It is necessary to adjust the temperature to 15% by weight or less based on the aqueous organic liquid.
It is necessary. However, if the seed particle concentration is too low,
Coalescence is suppressed, but the amount of new particles
2-10 weight (although it can be separated later)
% Is preferred. Here it grows while keeping the particle diameter almost
Means the volume average particle size of the polymer particles obtained
And the ratio of the expected growth volume average diameter is 1.10 or less.
means. Expected growth volume average particle size is defined as follows
I do. Seed particle volume average particle diameter x [[(Effectively used for growth reaction
Vinyl monomer weight) / (total weight of seed particles)] + 1]
¹/³  Here, the weight of the vinyl monomer effectively used for the growth reaction and
Is unreacted and grows from the added vinyl monomer weight
Remove those that did not participate in the reaction (newly generated particles)
Weight. The amount of unreacted vinyl monomer is gas chromatography
Newly generated from the graph or the weight of collected particles
Particle weight grows by gravity sedimentation or centrifugal sedimentation in liquid
It can be determined separately from the particles.

In order to prevent coalescence due to the stickiness of the seed particles during the reaction, the temperature of the vinyl monomer also has an appropriate range. During the growth reaction, the vinyl monomer accounts for 25% by weight of the hydrophilic organic liquid.
The following is preferred. If the vinyl monomer concentration is too low, coalescence of the particles can be suppressed, but the growth rate of the particles cannot be high and productivity is poor, and the polymerization rate is slow, so that the polymerization is preferably carried out in the range of 8 to 20% by weight. Is good. In order to prevent the concentration of the vinyl monomer to be added to the entire system from being excessively lowered or excessively increased, a means for appropriately adjusting the addition rate in accordance with 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 rather diluted with a hydrophilic organic liquid to some extent. The added vinyl monomer diffuses into the system, but the diffusion rate is not considered to be particularly high compared to the time required for the particles to aggregate and coalesce. Therefore, it is preferable to use a pre-diluted vinyl monomer in order to maintain the particle size distribution, and it is better to add the vinyl monomer so as to be 50% by weight or less based on the hydrophilic organic liquid.

The vinyl monomer to be added may be the same vinyl monomer as that used for producing the seed particles, or may be another vinyl monomer. The growth reaction can be performed 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 at all limited to being the same as that used for producing the seed particles. Rather, in order to prevent the seed particles from being combined with each other, it may be preferable to select a material that is farther away from the hydrophilic organic liquid from which the seed particles have been produced than the SP value of the seed particle polymer. However, if the distance is too far, attention must be paid to the fact that the number of newly generated particles extremely increases and the frequency of aggregation of the particles increases.

[0015] A polymer dispersion stabilizer can also be added to the dispersion or the vinyl monomer to which the seed particles are added at the time of the growth reaction, thereby enhancing the stabilizing effect of the particles and preventing aggregation.
It is a major feature of the present invention that particles can be grown while maintaining a sharper particle size distribution by repeating the process of growing core particles several times rather than once.

According to the above-mentioned method of the present invention, polymer particles having a volume-average particle size ratio of 1.15 or less and a volume-average particle size of 1 to 100 μm can be obtained. .

In the present invention, the hydrophilic organic liquid used as a diluent for the vinyl monomer used at the time of forming the seed particles and during the growth reaction of the seed particles includes methyl alcohol, ethyl alcohol, denatured ethyl alcohol, isopropyl alcohol, n- Butyl alcohol, isobutyl alcohol, tert-butyl alcohol, sec-butyl alcohol, tert-amyl alcohol, 3-pentanol, octyl alcohol, benzyl alcohol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerin, diethylene glycol Alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol Bruno ethyl ether, diethylene glycol monomethyl ether, and ether alcohols such as diethylene glycol monoethyl ether. One or a mixture of two or more of these organic liquids can be used. In addition, alcohols,
And by using together with the above-mentioned alcohols and ether alcohols in organic liquids other than ether alcohols, various SP values are changed under conditions that do not impart solubility to the produced polymer particles of the organic liquid, By changing the polymerization conditions, coalescence of seed particles and generation of new particles can be suppressed. These organic liquids used in combination include hexane, octane, petroleum ether, cyclohexane, benzene, toluene, hydrocarbons such as xylene, carbon tetrachloride,
Trichloroethylene, halogenated hydrocarbons such as tetrabromoethane, ethyl ether, dimethyl glycol,
Trioxane, ethers such as tetrahydrofuran, methylal, acetal such as diethyl acetal, acetone, methyl ethyl ketone, methyl isobutyl ketone,
Ketones such as cyclohexane, esters such as butyl formate, butyl acetate, ethyl propionate and cellosolve acetate, acids such as formic acid, acetic acid and propionic acid, nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine and dimethylsulfoxide , Dimethylformamide, and other sulfur- and nitrogen-containing organic compounds, and other water.

The polymerization may be carried out in a state where the following ions are present in the above-mentioned solvent mainly composed of a hydrophilic organic liquid.

Embedded image

The average particle size and the particle size distribution of the polymer particles produced can be adjusted by changing the type and composition of the mixed solvent at the start of polymerization, during the polymerization, and at the end of the polymerization.

Suitable examples of the dispersion stabilizer at the time of producing seed particles or producing growing particles include, for example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, itaconic acid, crotonic acid, fumaric acid Acids, such as maleic acid or maleic anhydride, or acrylic monomers containing a hydroxyl group, for example, β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate, β-hydroxy methacrylate Propyl, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, Guri Serine monoacrylate, glycerin monomethacrylate, N-methylol acrylamide, N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or vinyl Esters of alcohol and compounds containing a carboxyl group, such as vinyl acetate, vinyl propionate, vinyl butyrate,
Acrylamide, methacrylamide, diacetone acrylamide or a methylol compound thereof, acid chlorides such as acrylic acid chloride, methacrylic acid chloride, those having a nitrogen atom such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine, or a heterocyclic ring thereof Homopolymers or copolymers such as polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, poly Polyoxyethylene such as oxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester and polyoxyethylene nonyl phenyl ester Len, methylcellulose, hydroxyethylcellulose, celluloses such as hydroxypropylcellulose, or the hydrophilic monomer and styrene, α-methylstyrene, those having a benzene nucleus such as vinyltoluene or derivatives thereof, or acrylonitrile, methacrylonitrile, Copolymers with acrylic acid or methacrylic acid derivatives such as acrylamide, and copolymers with crosslinkable monomers such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene and the like can also be used.

These polymer compound dispersants may be appropriately selected depending on the hydrophilic organic liquid to be used, the seeds of the desired polymer particles, and the production of the seed particles or the growth particles.
In particular, those having high affinity and adsorptivity to the polymer particle surface and high affinity to the hydrophilic organic liquid and high solubility are selected in order to mainly prevent steric coalescence of the polymer particles. Further, in order to increase the repulsion of the particles three-dimensionally, those having a certain length of the molecular chain, preferably those having a molecular weight of 10,000 or more are selected. However, if the molecular weight is too high, the viscosity of the solution will increase significantly, the operability and the stirring property will be deteriorated, and the resulting polymer will have a variation in the probability of precipitation on the particle surface, so care must be taken. In addition, coexistence of a monomer of the above-mentioned polymer compound dispersant with a monomer constituting part of the intended polymer particles is also effective in stabilizing the particles.

In general, the amount of the polymer dispersant used for producing the seed particles varies depending on the kind of the polymerizable monomer for forming the desired polymer particles, but it is 0.1% by weight based on the hydrophilic organic liquid.
It is preferably from 10 to 10% by weight, more preferably from 1 to 5% by weight. When the concentration of the polymer dispersion stabilizer is low, the polymer particles formed have a relatively large diameter, and when the concentration is high, small particles are obtained. The effect of reducing the diameter is small.

The above-mentioned polymer dispersion stabilizer is, of course, necessary for the production of seed particles, but is added to the vinyl monomer solution for the purpose of preventing coalescence of the particles during the growth reaction. Alternatively, the polymerization may be performed in the presence of a seed particle dispersion.

The seed particles formed at the beginning are stabilized by the polymer dispersion stabilizer distributed in the hydrophilic organic liquid and on the surface of the polymer particles in an equilibrium state. When significantly present in organic liquids, they are somewhat swollen and sticky, and agglomerate over the steric repulsion of the polymeric dispersion stabilizer.

Further, when the amount of the vinyl monomer is extremely large relative to the hydrophilic organic liquid, the produced polymer is completely dissolved, and does not precipitate unless polymerization proceeds to some extent. The state of precipitation in this case takes the form of forming a highly sticky mass. Therefore, the amount of the vinyl monomer with respect to the hydrophilic organic liquid at the time of producing the seed particles is naturally limited, and slightly varies depending on the type of the hydrophilic organic liquid, but is about 50% by weight or less, preferably 30% by weight or less.
% By weight or less is appropriate.

In the present invention, the vinyl monomer is a compound which can be dissolved in a hydrophilic organic liquid and includes, for example, styrene,
o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene,
2,4-dimethylstyrene, pn-butylstyrene,
p-tert-butylstyrene, pn-hexylstyrene, p-n-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenyl styrene,
Styrenes such as p-chlorostyrene and 3,4-dichlorostyrene, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic Lauryl acrylate, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α-methyl methyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, methacrylic acid Isobutyl, n-octyl methacrylate, dodecyl methacrylate, lauryl methacrylate, 2-methacrylic acid
Ethylhexyl, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc., α-methyl fatty acid monocarboxylic acid esters, acrylonitrile, methacrylonitrile, acrylic acid such as acrylamide, or methacrylic acid derivative, chloride Vinyl, vinylidene chloride, vinyl bromide, vinyl fluoride and other vinyl halides, etc., alone or in a mixture of each other; Means a mixture.

The polymer in the present invention may be crosslinked by polymerization in the presence of a so-called crosslinking agent having two or more polymerizable double bonds. As a preferably used crosslinking agent, divinylbenzene, divinylnaphthalene and aromatic divinyl compounds which are derivatives thereof, other ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trityl propane triacrylate, allyl methacrylate, tert-butyl All divinyl compounds such as diethylenic carboxylic esters such as aminoethyl methacrylate, tetraethylene glycol dimethacrylate, l, 3-butadiol dimethacrylate, N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and Compounds having three or more vinyl groups are used alone or in a mixture. When the growth polymerization reaction is subsequently performed using the seed particles thus cross-linked, the inside of the polymer particles to be formed is cross-linked. On the other hand, when the above-mentioned crosslinking agent is contained in the vinyl monomer solution used for the growth reaction, a polymer having a cured particle surface is obtained.

Examples of the monomer used as a polymerization initiator include 2,2'-azobisisobutyronitrile,
Azo polymerization initiators such as 2,2′-azobis (2,4-dimethylvaleronitrile), lauryl peroxide,
A peroxide-based polymerization initiator such as benzoyl peroxide and tert-butyl peroctoate, a persulfide-based initiator such as potassium persulfate, or a system in which sodium thiosulfate and an amine are used in combination are used. . The polymerization initiator concentration was 0.1 to 100 parts by weight of the vinyl monomer.
10 parts by weight are preferred.

The concentration of the polymer dispersant and the vinyl monomer in the hydrophilic organic liquid and the mixing ratio are determined in accordance with the target, average particle size, and target particle size distribution of the polymer particles. Is done. In general, if the average particle diameter of the seed particles is to be reduced, the concentration of the polymer dispersant is set high, and if the average particle diameter is increased, the concentration of the polymer dispersant is set low. On the other hand, if the particle size distribution is to be made extremely sharp, the vinyl monomer concentration is set low if the vinyl monomer concentration is low or a relatively wide distribution is acceptable. 5 for the amount of stabilizer used
When used in an amount exceeding 0 times, it is difficult to obtain particles having a particle diameter within an average particle diameter of ± 25% and a distribution of 90% or more by weight, and thus are not suitable as seed particles.

The seed particles are produced by completely dissolving a polymer dispersion stabilizer in a hydrophilic organic liquid, and then adding one or more vinyl monomers, a polymerization initiator, and, if necessary, an inorganic fine powder. Add surfactants, dyes, pigments, etc., and add 30 to 300
With normal stirring at rpm, preferably at very low speed,
Moreover, polymerization is carried out by using a turbine type stirring blade rather than a paddle type while heating at a temperature corresponding to the decomposition rate of the initiator used while stirring at a speed such that the flow in the tank becomes uniform. Since the initial polymerization temperature has a large effect on the seed particle diameter to be generated, it is preferable to dissolve the initiator in a small amount of the solvent after adding the vinyl monomer and raise the temperature to the polymerization temperature, and then feed the initiator. . At the time of polymerization, it is necessary to sufficiently purge 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. To carry out the polymerization in the high polymerization rate region, the polymerization time of 5 to 40 hours is necessary, but the desired particle diameter, or stop the polymerization in the state of the particle diameter distribution, or also sequentially add a polymerization initiator, The polymerization rate can be increased.

After completion of the polymerization, unnecessary fine particles, residual monomers, polymer stabilizers, etc. are removed by operations such as sedimentation, centrifugation, and decantation, and then the polymer slurry is recovered, washed and washed to obtain a spherical particle diameter. Polymer particles (in a solvent) can be obtained. Here, if an operation such as filtration and spray drying is performed after washing, a polymer particle powder having a uniform spherical particle diameter can be obtained. Further, by repeating the growth reaction, more uniform large-diameter particles can be obtained.

The uniform spherical polymer particles obtained in the polymerization step are colored with a saturated solution of a dye. As the solvent for preparing the saturated dye solution, the hydrophilic organic liquid used in the polymerization step is used. For this reason, it is possible to dye in the state of a polymer slurry without drying the polymer particles in the above step. In the dyeing, the polymer particles are dispersed in a saturated dye solution of a hydrophilic organic liquid, and heated and stirred.
Thus, it is considered that the polymer particles swell in the heated organic liquid, and the dye molecules dissolved in the liquid are adsorbed in the particles. The dyes used here are disperse dyes, pad dyes, metal-containing dyes, oil-soluble dyes, and the like, and include the following.

C. I. No. Acid Yellow-1118820 "-135-"-161-Acid Orange-113091 "-715510" -1914690 "-202014600" -28 16240 "-74 18745" -122-Acid Red-614680 "-8 14900, "-51 45430" -52 45100 "-80 68215" -87 45380 "-92 45410 Acid Bio Red-78 12205"-82-"-93-Acid Bull--9 42090" -102 50320 "-104424735 "-117 17055" -120 26400 "-229-"-234-Acid Green-342085 "-742055" -942100 "-1213425" -1644 25 "-1920440" -44 61590 "-75-〃-76-Acid Brown -13 10410〃-46-〃-231-〃-232- −-294-〃-295-〃-296-Acid Black- 112-〃-118-〃-119-〃-121- −-154-〃-155-Basic Yellow -149505〃-241000〃-1148055〃-14-〃-36-Basic Orange-1546045 ２１-21 48035 Basic Red-2 250240 〃-9 42500 〃-12 48070 “-37-Basic Violet-1 42535 〃-3 42555 〃-10 45170 〃-14 42510 Basic Blue-1 42025 〃-3 51004 〃 -5 42140 -7-4595 -9 -52015 -24 52030 -25 52025 〃-26 44045 Direct Yellow -12 24895 〃-24 22010 〃 -26 25300 Direct Orange -6 23375 〃 -8 22130 〃 -26 29150 Direct Red-1 22310 〃 -4 29165 ｌ -28 22120 Direct Green ｌ 30280 Direct Brown -2 22311 〃 -44 35005 〃 -58 22340 〃 -59 22345 〃 -106 36200 Disperse Yellow -3 11855 〃 -31 48000 Disperse Orange -1 11080 〃 -3 1105 １１ -11 60700 〃 -45-Disperse Red -11110 〃 〃 46 755 〃-5 11215 〃-7 11150 〃1111 2015 〃-12-− -13 11115 “-1560710 〃-17 111210 Disperse Blue −1 64500 〃-361505 −-662050 〃−762500 〃−43 -〃 -44-〃 -52-〃 -68-Solvent Yellow-16 12700 〃 -21 18690 〃 -56 1102 〃 〃 -61-Solvent Orange -1 11920 −２-2 12100 〃 -5 18745: 1 〃 -6 18736: 1 １４ -14 26020 〃 -37-〃 -40-〃 -45 11700 Solvent Red -1112150 〃-8 12715 〃-23 26100 〃-30 27291 〃-49 45170: 1 〃 -81 -〃 -82-〃- 83 -〃 -84-１００ -100 12716 Solvent Levioret-8 42535: 1 ２１ -21-Solvent Blue -24 563: 1 １２ -12 62100 〃 -55-〃 -73-Solvent Brown -20- One type may be used, or two or more types may be used together.

The fluorinated quaternary ammonium salt compound and the fluorinated iminium compound used in the present invention have the structures of the above-mentioned general formulas (1) and (2). The compound is raised.

[0035]

[Table 1] Table 1

The method of dyeing these compounds on the polymer particles is the same as the above-mentioned coloring method, and may be carried out simultaneously with the coloring of the polymer particles or after the coloring. It is desirable to carry out the coloring at the same time in order to simplify the process.

The method of adsorbing these compounds on the surface of the polymer particles is carried out by dissolving the compound in a hydrophilic organic liquid, stirring and immersing the polymer particles in the solution, and drying the hydrophilic organic liquid as a solvent. The compound is adsorbed on the particle surface. By dissolving the charge control agent in the hydrophilic organic liquid, it is possible to uniformly adsorb the charge control agent on the surface of the polymer particles. Water is considered to be the most common solvent for dissolving the charge control agent. However, most of the charge control agents effective in the present invention are insoluble in water and cannot be used with water alone. On the other hand, since the surface-treated polymer particles are polymerized in the hydrophilic organic liquid, that the present invention can be carried out in a slurry state of the polymer particles, and that the hydrophilic organic liquid is effective to dryness, etc. And a hydrophilic organic liquid.

The solubility of the compound used in the present invention in a hydrophilic organic liquid varies depending on its structure. Therefore, in order to improve the solubility of these compounds, two or more kinds of hydrophilic organic liquids can be mixed and used at the time of adsorption or dyeing. As the solvent to be mixed, acetone, methyl ethyl ketone, isopropyl alcohol, butyl alcohol, isobutyl alcohol, n-heptanol, 2-ethyl-1-butanol, n-octanol, 2-ethylhexyl alcohol, n-decanol,
And dioctyl alcohol. The mixing ratio of these solvents may be such that the polymer particles do not dissolve or agglomerate, but swell or dissolve the most part, and desirably 5 to 30 parts by weight to 95 to 70 parts by weight of methanol.

When adsorbing on the surface of the polymer particles, the hydrophilic organic liquid used as a solvent may be dried to dryness by evaporating to dryness, freeze-drying, heating to dryness using a hot plate or the like, or heating under reduced pressure using an evaporator or the like. Drying is possible. In any of the methods, it is necessary to completely evaporate the solvent, and pressure reduction, heating, and the like may be performed as necessary. However, the heating temperature should not cause the particles to agglomerate, and is preferably a temperature not higher than Tg. As a method of further fixing the charge control agent adsorbed on the particle surface to the particle surface, a method of applying a mechanical impact force to the particle surface is used. For example, a mixing machine such as a ball mill pot, a Henschel mixer, a V blender, a type I, Pulverizers such as mills, vibratory mills, and cryptotrons; and further, surface treatment devices such as ong mills and hybridization systems. In any method, the temperature condition is important, and it is necessary to set conditions so that the charge control agent on the surface is fixed and embedded at a temperature at which the particles slightly swell or dissolve, and aggregation of the particles does not occur. .

Hereinafter, the present invention will be described specifically with reference to Examples, but the present invention is not limited thereto. (Example of polymer particle synthesis) Angled fan turbine (4 blades)
Methanol dried with a molecular sieve 5A into a four-necked flask equipped with a stirring blade and a condenser gas inlet tube.
0 parts by weight, and polyvinylpyrrolidone (average molecular weight M
(n: 40,000) 3.0 parts by weight were added little by little while stirring, and completely dissolved. Furthermore, 20 parts by weight of styrene,
0.13 parts by weight of 2,2'-azobisisobutyronitrile was added and completely dissolved to obtain a transparent solution. The flask was purged with dry argon gas while stirring, and left for 1 hour while flowing a small amount. The polymerization was started while stirring at a stirring speed of 50 rpm in a constant temperature water bath at 60.0 ± 0.1 ° C. After 15 minutes from heating, the solution began to become cloudy. Six hours after the start of the polymerization, it was confirmed by gas chromatography using ethylbenzene as an internal standard that the conversion had reached 55%. Further, a small amount of the liquid at this time was sampled, and the residual monomer and polyvinylpyrrolidone were removed by centrifugal sedimentation. The particle size and the particle size distribution were analyzed using a Coulter counter, and the volume average particle size Dv = 4.
8 μm, and the number average particle diameter Dp was 4.6 μm. At this time, while maintaining the internal temperature at 60 ° C., a mixed solution of 25 parts by weight of styrene, 0.25 parts by weight of 2,2′-azobisisobutyronitrile and 60 parts by weight of methanol was filled over 3 hours. After the addition, the turbidity of the liquid became thin, but the liquid was kept uniformly as a dispersion, and polymerization was carried out for 30 hours as it was. It was confirmed by gas chromatography that the polymerization rate had reached 95%. When the resulting dispersion was cooled and centrifuged at 1000 rpm for 10 minutes in a centrifuge, the polymer particles were completely settled and the upper liquid was slightly cloudy. The supernatant was removed, and 100 parts by weight of methanol was newly added, followed by stirring and washing for 1 hour. The operation of centrifugation and washing with methanol was repeated once, and finally, washing with water was performed and filtration was performed with a microfilter of 1 μm or less. The filtrate is clear,
It was confirmed that there were no particles of 1 μm or less.

(Coloring Example 1 of Polymer Particles) In a separable flask equipped with a stirring blade and a condenser, methanol 30 was added.
0 parts by weight and 2 parts by weight of oil black HBB (manufactured by Orient Chemical Co., Ltd.) were added, and the mixture was heated and stirred at 60 ° C. for 1 hour. This solution was filtered through a 1 μm filter to obtain a saturated solution. Next, 300 parts by weight of the obtained saturated solution was added to the same apparatus, and 50 parts by weight of the polymer particles obtained in the above Synthesis Example were added thereto.
The mixture was heated and stirred at 50 ° C. for 1 hour. Thereafter, the mixture was cooled to room temperature, filtered, and dried under reduced pressure to obtain black uniform spherical particles.

(Polymerized Particle Coloring Example 2) Methanol 30 was placed in a separable flask equipped with a stirring blade and a condenser.
0 parts by weight and 2 parts by weight of oil black HBB (manufactured by Orient Chemical Co., Ltd.) were added, and the mixture was heated and stirred at 60 ° C. for 1 hour. The solution was filtered through a 1 μm filter to obtain a saturated solution. Next, 300 parts by weight of the obtained saturated solution was placed in the same apparatus, and 50 parts by weight of the polymer particles obtained in the above Synthesis Example were added thereto.
The mixture was heated and stirred at ℃ for 1 hour. Thereafter, the solution was cooled to room temperature, and the solution was filtered to obtain a state of a methanol-containing cake of black uniform spherical particles.

Example 1 In a separable flask equipped with a stirring blade and a condenser, methanol 30 was added.
0 parts by weight and 2 parts by weight of oil black HBB (manufactured by Orient Chemical Co., Ltd.) were added, and the mixture was stirred at 60 ° C. for 1 hour. This was filtered through a 1 μm filter to obtain a saturated solution (hereinafter, solution A). Next, 300 parts by weight of methanol and 3 parts by weight of Compound Example 6 were added to the same apparatus, followed by heating, stirring and filtration to obtain a saturated solution (hereinafter, solution B). 150 parts by weight of the solution A and 150 parts by weight of the solution B were placed in the same apparatus, and the above synthesis example 1 was added thereto.
Was added, and the mixture was heated and stirred at 50 ° C. for 1 hour. Next, the mixture was cooled to room temperature, separated by filtration, and dried under reduced pressure to obtain black uniform spherical particles. 97.5 parts by weight of ferrite carrier was mixed with 2.5 parts by weight of the obtained particles to obtain a two-component developer. The charge amount of the obtained developer was measured by a blow-off device and found to be -15.1 μC / g. This developer is used in a commercially available electrophotographic copying machine (IMAGIO 42 manufactured by Ricoh Company).
When the image was set at 0), the reproducibility of fine lines was good, and a clear image of halftone was obtained.

Example 2 In the apparatus of Example 1, 270 parts by weight of methanol and 3 parts of toluene
0 parts by weight and 3 parts by weight of Compound Example 1 were added, and the mixture was similarly heated, stirred and filtered to obtain a saturated solution (solution C). Solution C15
0 parts by weight, 150 parts by weight of the solution A, and 50 parts by weight of the polymer particles were placed in the apparatus of Example 1 and heated and stirred in the same manner, followed by filtration by cooling 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 −18.6 μC / g. When an image was formed with this developer, a clear image was obtained.

Example 3 600 parts by weight of methanol and 0.5 part by weight of Compound Example 6 were placed in an Erlenmeyer flask, ultrasonically dispersed at room temperature, further stirred with a magnetic stirrer, and completely dissolved. To this solution, 50 parts by weight of the black uniform spherical particles obtained in Polymerized Particle Coloring Example 1 were added, and the mixture was further ultrasonically dispersed at room temperature and sufficiently stirred with a magnetic stirrer. The entire dispersion was poured into a stainless steel vat, left in a vacuum desiccator, and the solvent was evaporated to dryness. The completely dried particles were crushed by 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 −16.9.
μC / g. When an image was formed with this developer, a clear image was obtained.

Example 4 Into an Erlenmeyer flask, 525 parts by weight of methanol and 0.5 part by weight of Compound Example 6 were placed, ultrasonically dispersed at room temperature and stirred with a magnetic stirrer in the same manner as in Example 3, and completely dissolved. To this solution, 125 parts by weight of the methanol-containing cake obtained in Polymerized Particle Coloring Example 2 was added, followed by ultrasonic dispersion and stirring. The entire amount of the dispersion was placed in a stainless steel vat, and the solvent was evaporated and dried in a desiccator under reduced pressure. The completely dried particles were crushed by 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 −17.7 μC / g. When an image was formed with this developer, a clear image was obtained.

Example 5 600 parts by weight of methanol and 0.5 part by weight of Compound Example 6 were placed in an Erlenmeyer flask, ultrasonically dispersed at room temperature, further stirred with a magnetic stirrer, and completely dissolved. The black uniform spherical particles 50 obtained in Polymerized Particle Coloring Example 1 were added to this solution.
A part by weight was added, the mixture was further ultrasonically dispersed at room temperature, and sufficiently stirred with a magnetic stirrer. The entire amount of the dispersion was placed in a stainless steel vat, and left in a vacuum desiccator to evaporate and dry the solvent. Disintegrate the completely dried particles with a mesh,
The hybridization system (NHS-1,
(Nara Machinery Co., Ltd.) at 10,000 rpm for 5 minutes 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 −18.4 μC / g. When an image was formed with this developer, a clear image was obtained. Also, 5
When a durability test was performed on up to 10,000 sheets, no abnormal images such as background stain, dust, insufficient image density, and reduced resolution were not observed, and the image on the 50,000th sheet was also clear. The charge amount of the 50,000th sheet was −17.6 μC / g, and the charge was stable.

Example 6 In an Erlenmeyer flask, 525 parts by weight of methanol and 0.5 part by weight of Compound Example 6 were placed, and ultrasonically dispersed and stirred with a magnetic stirrer in the same manner as in Example 3, and completely dissolved. To this solution, 125 parts by weight of the methanol-containing cake obtained in Polymerized Particle Coloring Example 2 was added, followed by ultrasonic dispersion and stirring. The entire amount of the dispersion was placed in a stainless steel vat, and the solvent was evaporated and dried in a desiccator under reduced pressure. The completely dried particles were crushed with a mesh and subjected to hybridization treatment in the same manner as in Example 5 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 -19.1 μC / g. When an image was formed with this developer, a clear image was obtained. No abnormal image was observed even in the durability test up to 50,000 sheets, the image on the 50,000 sheet was clear, and the charge amount was −18.1 μC /
g.

Comparative Example 300 parts by weight of the solution A prepared in Example 1 and polymer particles 50
A part by weight was put into the apparatus of Example 1, and heated and stirred, cooled, filtered and dried 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, but the charge amount was 82.1 μC / g. On the other hand, when the undyed polymer particles were similarly used as a developer, the charge amount was 85.
It was as high as 5 μC / g, and good charge control could not be performed using only the coloring dye.

[0050]

As described above, the dry electrophotographic toner of the present invention has a good charge rise due to the presence of the charge control agent on the particle surface, and it is sufficient to use only the amount required for the generation of charge. There is no problem such as the dispersibility of the charge control agent and the charge control agent present inside the pulverized particles and not contributing to the generation of charge. Further, it is difficult to uniformly charge the surface of the particles with the method of mechanically directly charging the charge control agent as it is in the form of crystals, and the charging tends to be unstable. Since it is adsorbed and fixed on the surface, it is uniformly adsorbed on the surface and the generation of charge is stabilized.

Continuation of the front page (56) References JP-A-3-168650 (JP, A) JP-A-3-80261 (JP, A) JP-A-63-23167 (JP, A) JP-A-3-213877 (JP) , A) (58) Field surveyed (Int.Cl. ⁷ , DB name) G03G 9/097 G03G 9/08

Claims (2)

(57) [Claims] 1. A quaternary fluorinated ammonium represented by the following general formula (1) in polymerized particles having a uniform particle diameter dispersed and precipitated by a polymer dispersant dissolved in a hydrophilic organic liquid in the hydrophilic organic liquid. At least one of a salt compound and a fluorinated iminium compound represented by the general formula (2):
A dry electrophotographic toner characterized by being adsorbed or dyed on said polymer particles in a hydrophilic organic liquid. [In the formula (1), R _{1 to} R ₄ represent a hydrogen atom or an organic group, and at least one of the groups R _{1 to} R ₄ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R ₇ —
1 carbon atom which may have a C (O) —OR ₈ group
Is a linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group having 3 to 66 fluorine atoms, wherein R ₅ , R ₆ , R ₇ and R ₈ have 1 to 30 carbon atoms. Up to three of the radicals R _{1 to} R ₄ , independently of one another, are a hydrogen atom, a linear or branched alkyl radical having 1 to 30 carbon atoms, an aryl or arylalkyl radical, an alkenyl radical. , An aryl group and an arylalkyl group are alkyl groups having 1 to 30 carbon atoms, and have 1 to 30 carbon atoms.
May be substituted with an alkoxy group, a hydroxyl group, or a halogen atom, and two of the groups R _{1 to} R ₄ may be bonded to each other, interrupted by 1 to 4 heteroatoms, and 0 to 6 A fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group Forming a substituted mononuclear or polynuclear ring system of 4 to 12 carbon atoms;
^- is an organic or inorganic anion. ] [In the formula (2), R _{9 to} R ₁₂ represent a hydrogen atom or an organic group, and at least one of the groups R _{9 to} R ₁₂ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or a sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R
₇ -C (O) linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group -O-R have _eight by fluorine atoms also a good carbon atoms 1-69 3-66 Wherein R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 30 carbon atoms, and at most three of the groups R _{9 to} R ₁₂ independently of one another are a hydrogen atom, a carbon atom 1 A linear or branched alkyl group, an aryl group or an arylalkyl group, or an alkenyl group having up to 30 carbon atoms, wherein the aryl group and the arylalkyl group are an alkyl group having 1 to 30 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms. Or two of the radicals R _{9 to} R ₁₂ may be linked to each other, interrupted by 1 to 4 heteroatoms and 0 to 6 It may contain a heavy bond and may be a fluorine atom, a chlorine atom, A mononuclear or polynuclear ring system having 4 to 12 carbon atoms, which is substituted by an atom or iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group Form, and
X ^- represents an organic or inorganic anion. ] 2. A quaternary fluorinated ammonium represented by the following general formula (1), wherein polymer particles having a uniform particle diameter are dispersed and polymerized by a polymer dispersant dissolved in the hydrophilic organic liquid in the hydrophilic organic liquid. At least one of a salt compound and a fluorinated iminium compound represented by the general formula (2):
The polymer particles are dissolved in a hydrophilic organic liquid and adsorbed on the surface of the polymer particles, and a mechanical shock is applied to the polymer particles so that the adsorbed fluorine-containing quaternary ammonium salt compound (1) or fluorine-containing iminium compound (2) is polymerized particles. A dry electrophotographic toner fixed on a surface. [In the formula (1), R _{1 to} R ₄ represent a hydrogen atom or an organic group, and at least one of the groups R _{1 to} R ₄ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R ₇ —
1 carbon atom which may have a C (O) —OR ₈ group
Is a linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group having 3 to 66 fluorine atoms, wherein R ₅ , R ₆ , R ₇ and R ₈ have 1 to 30 carbon atoms. An alkyl group and up to three of the radicals R _{9 to} R ₁₂ independently of one another are a hydrogen atom, a linear or branched alkyl group of 1 to 30 carbon atoms, an aryl or arylalkyl group,
An alkenyl group, an aryl group and an arylalkyl group are alkyl groups having 1 to 30 carbon atoms,
It may be substituted by 30 alkoxy groups or hydroxyl groups or halogen atoms, two of the groups R _{1 to} R ₄ may be linked to each other, interrupted by 1 to 4 heteroatoms and 0 to 6 Atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group Form a mononuclear or polynuclear ring system of 4 to 12 carbon atoms substituted with
^- is an organic or inorganic anion. ] [In the formula (2), R _{9 to} R ₁₂ represent a hydrogen atom or an organic group, and at least one of the groups R _{9 to} R ₁₂ is a hydroxyl group and a chloromethyl group and / or a carboxamide and / or a sulfonic acid. Amide and / or urethane group and / or amino group and / or R ₅ —O—R ₅ group and / or R
₇ -C (O) linear or branched fluorine-containing alkyl group or fluorine-containing alkenyl group -O-R have _eight by fluorine atoms also a good carbon atoms 1-69 3-66 Wherein R ₅ , R ₆ , R ₇ and R ₈ are alkyl groups having 1 to 30 carbon atoms, and at most three of the groups R _{9 to} R ₁₂ independently of one another are a hydrogen atom, a carbon atom 1 A linear or branched alkyl group, an aryl group or an arylalkyl group, or an alkenyl group having up to 30 carbon atoms, wherein the aryl group and the arylalkyl group are an alkyl group having 1 to 30 carbon atoms, and an alkoxy group having 1 to 30 carbon atoms. Or two of the radicals R _{9 to} R ₁₂ may be linked to each other, interrupted by 1 to 4 heteroatoms and 0 to 6 It may contain a heavy bond and may be a fluorine atom, a chlorine atom, A mononuclear or polynuclear ring system having 4 to 12 carbon atoms, which is substituted by an atom or iodine atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group or an amino group Form, and
X ^- represents an organic or inorganic anion. ]