JPH04295856A - Toner for developing electrostatic charge image - Google Patents

Abstract

PURPOSE:To obtain a toner giving a developer having superior durability, environmental stability and satisfactory cleanability and capable of forming an image free from ground stain and having high image density and high resolving power. CONSTITUTION:Resin particles produced by dispersion polymn. are dispersed in an org. solvent not dissolving the particles and a dye is dissolved in the solvent before or after the dispersion. The particles are colored by allowing the dye to penetrate into the particles, the solvent is removed and hard fine particles surface-treated with a fluorine-contg. silane compd. are incorporated into the colored particles to obtain a toner. The relation between the solubility (D1) of the dye to the solvent and the solubility (D2) to the resin of the particles is represented by D1/D2 <=0.5.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention is applicable to electrophotography, electrostatic recording,
The present invention relates to a dry toner for developing electrostatic images in electrostatic printing and the like.

0002

[Prior Art] As means for developing an electrostatic latent image formed on an electrophotographic photoreceptor or an electrostatic recording medium, there are two methods: a method using a liquid developer (wet development method), and a method using a liquid developer (wet development method). dye,
A method using a toner in which colorants such as pigments and a charge control agent are dispersed as necessary, or a one-component or two-component dry developer in which this toner is mixed with a solid carrier (dry development method). is generally adopted. and,
Although each of these methods has its own advantages and disadvantages, the dry developing method is currently in most use.

Incidentally, in order to provide high image quality and high durability, toner particles are required to have small particle size, sharp particle size distribution, sufficient coloring power, and uniform charging control. That is, reducing the particle size improves qualities such as resolution, sharpness, halftone reproducibility, and photographic reproducibility. Further, a sharp particle size distribution improves particularly halftone reproducibility and photographic reproducibility. Furthermore, the particle size distribution of the toner in the developer does not change even when used for a long time, resulting in stable image quality and a longer lifespan of the developer.

[0004] Toner manufactured by the conventional general manufacturing method of toner, that is, a method in which resin, dye/pigment, and charge control agent are melt-kneaded, and then crushed and classified using a mechanical or air collision type crusher. In particular, when attempting to obtain particles with a small particle size and narrow particle size distribution, there are the following drawbacks. That is, (1) The smaller the particle size, the worse the toner charging characteristics due to non-uniform dispersion of the charge control agent, and the more likely it is to cause scumming and toner scattering. (2) Furthermore, the surface of the small particle size toner obtained by pulverization has many protrusions, which tends to cause filming on the carrier, triboelectric charging member, or photoreceptor. (3) When the particle size is reduced, the coloring power of each toner becomes weaker. (4) It is difficult to clean small particle size toner remaining on the photoreceptor. (5) Production capacity and yield will decrease, especially when trying to obtain toner with a narrow distribution, production capacity and yield will decrease significantly;
The cost will be high. Moreover, even if classification is repeated, there is a limit to the particle size distribution that can be obtained.

[0005] Therefore, many proposals have been made regarding toners that provide high image quality and high durability and methods for producing the toners. For example, core particles containing colored pigments and charge control agents may be formed by a suspension polymerization method (Japanese Patent Publication No.
14895, Japanese Patent Publication No. 47-51830), this method uses a dispersion stabilizer that adheres to the surface,
It is difficult to remove surfactants, etc., easily causes electrostatic deterioration, and is also susceptible to environmental fluctuations. Furthermore, with this method, it is difficult to stably produce particles with a small particle size and a narrow particle size distribution.

On the other hand, as a method for easily obtaining toner with a small particle size and a narrow particle size distribution, Japanese Patent Application Laid-Open No. 58-106554
No. 61-18965 and No. 61-275766, attempts are made to produce toners with a so-called core-shell structure by attaching and coating colorants and toner characteristic imparting substances onto particles with a narrow particle size distribution. However, toners having such a structure have the disadvantage of poor electrical properties and durability due to the presence of coloring substances and other substances on the surface.

[0007] Furthermore, as another toner manufacturing method, a method has been proposed in which resin particles are immersed in a dye solution and dyed (Japanese Patent Application Laid-Open Nos. 50-46333 and 1999-10363).
No. 1, JP-A-56-154738, JP-A No. 61-2284
No. 58, No. 63-106667, No. 64-90454
Publications, etc.). Although these methods are preferable because they require fewer manufacturing steps, none of them have been sufficiently tested, and it is unclear whether the dye is uniformly colored within the particles, and furthermore, the above-mentioned literature does not Knowledge of the content alone was not enough to put it into practical use. In addition, JP-A-61-22
Publication No. 8458 describes an attempt to color particles by adding dye to particles produced by dispersion polymerization, but according to this method, the polarity of the toner can be controlled by a dispersion stabilizer permanently attached to the particle surface. Therefore, the triboelectric charging property is unstable due to environmental changes, and the stability over time is also poor.

Furthermore, in the proposed toner,
In both cases, there is the problem of poor cleaning due to smaller particle sizes.In other words, due to smaller particle sizes, the contact area between toners or between toners and the photoreceptor increases, resulting in increased adhesion force, which worsens cleaning performance with a blade. No active measures were taken against this. Especially in the case of spherical toner,
Since the toner packing density increases and the contact area increases, the adhesion force becomes considerably large and cleaning performance becomes extremely poor. In response to this, there have been attempts to improve the cleaning performance by externally adding additives to take advantage of the steric hindrance effect between toners or between toner and photoreceptor.
It has been difficult to satisfy charging stability and cleanability at the same time with conventional mixing or implantation treatments using additives.

[0009]

[Problems to be Solved by the Invention] In other words, a toner with a small particle size and narrow particle size distribution that has sufficiently stable triboelectric charging properties and good cleaning properties has not yet been found. This is the current situation.

[0010] Therefore, an object of the present invention is to provide a small-grain toner with a narrow particle size distribution that solves the above problems, and more specifically, has excellent resolution, sharpness, halftone reproducibility, and photographic reproducibility. Another object of the present invention is to provide a toner that is highly colored, has little change in charge amount due to environment, has stable chargeability over time, and has good cleaning properties.

[0011]

[Means for Solving the Problems] As a result of intensive studies, the present inventors have found that a toner containing hard fine powder that adopts a specific manufacturing method and is surface-treated with a fluorine-containing silane compound is suitable for the above purpose. This discovery led to the completion of the present invention.

That is, according to the present invention, a polymer dispersant that is soluble in the organic liquid is added to a hydrophilic organic liquid, and a polymer that is formed is dissolved in the organic liquid. Resin particles produced by adding and polymerizing at least one type of vinyl monomer that swells or is mostly insoluble are dispersed in an organic solvent that does not dissolve the resin particles. After dissolving the dye in the resin particles, the dye is infiltrated into the resin particles to color them,
A toner obtained by a method of subsequently removing the solvent, wherein the solubility of the dye in the solvent [D1]
and the solubility of the dye in the resin of the resin particles [D
An electrostatic charge image characterized in that it uses a dye in which the relationship [D1]/[D2]≦0.5 and contains hard fine powder surface-treated with a fluorine-containing silane compound. A developing toner is provided.

The toner of the present invention has high resolution, sharpness,
Excellent halftone reproducibility and photographic reproducibility are achieved by adopting a specific manufacturing method and using dyes with specific physical properties, which ensure uniform dyeing from the surface to the inside of the toner, resulting in high coloring power. This is because the toner of the present invention has a narrow particle size distribution and small particle size, and the charge amount of the toner of the present invention is stable against changes in the environment and over time. This is thought to be due to the fact that by mixing hard fine powder treated with a compound with the toner or fixing it on the toner surface, the toner surface becomes extremely hydrophobic and at the same time has a strong negative polarity.

Furthermore, although the toner of the present invention has small particle diameter, it has good cleaning properties. The mechanism is not necessarily clear, but by treating the surface of the hard fine powder with a fluorine-containing silane compound,
This is thought to be because the friction coefficient and adhesion force of the hard fine powder were reduced, and as a result, the toners moved more easily between each other and between the toners and the photoconductor, making cleaning with the blade easier.

The hard fine powder treated with the above-mentioned fluorine-containing silane compound is either externally mixed into the toner or strongly adhered with mechanical energy so that it is substantially fixed on the toner surface. Good too.

[0016] As a method for treating the hard fine powder with a fluorine-containing silane compound, the fluorine-containing silane compound can be directly mixed and stirred or spray coated on the hard fine powder, or mixed in a solvent and then spray coated, dip coated, or the like. can be used. As the solvent in this case, water, methyl alcohol, ethyl alcohol, n-butanol, isopropyl alcohol, ethylene glycol, methyl acetate, ethyl acetate, butyl cellosolve, toluene, etc. can be used. The processing amount (amount used) of the fluorine-containing silane compound is
It is sufficient to cover the entire surface of the hard fine powder, but it is more preferably 0.1 to 20.0% by weight based on the hard fine powder. Further, after the treatment, it may be dried by heating if necessary.

In the present invention, the fluorine-containing silane compound for surface treating the hard fine powder is represented by the following general formula (I
) to (VII) are preferred.

[0018]

[Formula 1] (wherein R is an alkyl group or an alkoxy group having 1 to 5 carbon atoms, X is a hydrogen atom or a fluorine atom, and m is 0 or 1 to 10
n represents an integer of 3 to 10. )

[chemical 2
] (wherein, R1 is an alkyl group having 1 to 13 carbon atoms containing a fluorine atom, R2 to R8 are an alkyl group or alkoxyl group having 1 to 5 carbon atoms, and R2 to R8 are may be the same or different),

[Formula 3] (where n is 0 or an integer from 1 to 13,
is a hydrogen atom or a fluorine atom, R1 to R3 are an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and R1 to R3 may be the same or different. )

embedded image (where n is 0 or 1, m is 0, 1, 2 or 3, X is an alkyl group having 1 to 13 carbon atoms containing a fluorine atom, and Y is It is a phenylene group or an SO3 group, R is a hydrogen atom or an alkyl group or an alkoxy group having 1 to 5 carbon atoms, and when m is 2 or 3, each R may be the same or different. )

[Formula 5] (wherein, n is an integer of 7 or more, n is 0 or an integer of 1 to 5, and X is a hydrogen atom or a fluorine atom, and each X may be the same or different. , R1 to R3 are 1
It is an alkyl group or an alkoxy group having ~5 carbon atoms, and R1 to R3 may be the same or different. )

[Formula 6] (wherein, n is an integer of 7 or more, m is 0 or an integer of 1 to 5, and X is a hydrogen atom or a fluorine atom, and each X may be the same or different. , R1 to R3 are 1
It is an alkyl group or an alkoxy group having ~5 carbon atoms, and R1 to R3 may be the same or different. )

[Formula 7] (where m is 0 or an integer of 1 to 13, n is 0 or 1 to 5
is an integer, X is a hydrogen atom or a fluorine atom, each X may be the same or different, and Y is S or N
H, R1 to R3 are alkyl groups or alkoxy groups having 1 to 5 carbon atoms, and R1 to R3 may be the same or different. )

In the present invention, specific examples of the fluorine-containing silane compound used for surface treating the hard fine powder include the following.

[Fluorine-containing silane compound represented by general formula (I)]

[Table 1-(1)]

[Table 1-(2)]

[Fluorine-containing silane compound represented by general formula (II)]

[Table 2-(1)]

[Table 2-(2)]

[Fluorine-containing silane compound represented by general formula (III)]

[Table 3-(1)]

[Table 3-(2)]

[Fluorine-containing silane compound represented by general formula (IV)]

[Table 4-(1)]

[Table 4-(2)]

[Table 4-(3)]

[Fluorine-containing silane compound represented by general formula (V)]

[Table 5]

[Fluorine-containing silane compound represented by general formula (VI)]

[Table 6]

[Fluorine-containing silane compound represented by general formula (VII)]

[Table 7-(1)]

[Table 7-(2)]

[Table 7-(3)]

Examples of the hard fine powder used in the present invention include oxides such as cerium oxide, chromium oxide, aluminum oxide, magnesium oxide, silicon oxide, tin oxide, zirconium oxide, iron oxide, titanium oxide, and zinc oxide; Sulfates such as calcium sulfate, barium sulfate, and aluminum sulfate; silicates such as calcium silicate and magnesium silicate; nitrides such as boron nitride and titanium nitride; silicon carbide, titanium carbide, boron carbide, tungsten carbide, zirconium carbide, etc. Carbides; Examples include borides such as zirconium boride and titanium boride.

Examples of commercially available hard fine powders include the following. AEROSIL manufactured by Nippon Aerosil Co., Ltd.
90,AEROSIL130,AEROSIL200,

AEROSIL300,AEROSIL380,A
EROSIL OX50,
AEROSIL MOX
80,AEROSIL MOX170,
AEROS
IL R972,AEROSIL R974,AERO
SIL R202,
AEROSIL R805,A
EROSIL R812
aluminum oxide C

Titanium oxide particles P25 WACKER-CH
EMIE GMBH HDK N20, HD
K V15, HDK N20E, HDK T30, HD
K T40 CABOT Co.
Cab-O-Sil M-5, Cab-O-Sil
MS-7,
Cab-O-Sil MS-75, Ca
b-O-Sil HS-5,
Cab-O-Sil
EH-5 Silicon carbide manufactured by Fujimi Abrasive Industry Co., Ltd. GC3000, GC4000, GC6000, G
C8000 Manufactured by Uemura Kogyo Co., Ltd.
Aluminum oxide Mechanox UB-10
Silica manufactured by Tokuyama Soda Co., Ltd.
Tokusil U, Tokusil UR, Toku
sil NR,
Tokusil
GU-N, Tokusil GU

The particle size of the hard fine powder used is 1 μm to 5 μm.
The thickness is preferably about μm. Moreover, two or more of these hard fine powders can be used simultaneously if necessary.

In the present invention, the hard fine powder whose surface has been treated with a fluorine-containing silane compound is either externally mixed into the toner as described above or treated with mechanical energy so as to be immobilized on the toner surface. However, in this case, the amount of hard fine powder treated with a fluorine-containing silane compound added to the toner is 0.01% by weight to 10% by weight.
is preferred.

[0031] As for the mixing method, a general mixing device such as a V-blender, Henschel mixer, speed kneader, etc. can be used. Methods of applying mechanical energy include applying impact to the mixture using a blade rotating at high speed, accelerating the particles by injecting the mixture into a high-speed air stream, and causing the particles to collide with each other or the mixed particles against a suitable collision plate. There is. Specific equipment includes Ong Mill (Hosokawa Micron) and I-type mill (Nippon Pneumatic Industries) with lower air pressure for grinding than normal grinding, a hybridization system (Nara Kikai Seisakusho), Henschel mixer, automatic Examples include mortar.

In the present invention, a polymer dispersant that is soluble in the organic liquid is added to the hydrophilic organic liquid, and the resulting polymer is swollen in the organic liquid. Resin particles (hereinafter referred to as resin particles A) produced by adding and polymerizing at least one type of vinyl monomer that is generally insoluble or mostly insoluble are used as core particles. Resin particles A usually have a ratio of volume average particle diameter (Dv) to number average particle diameter (Dp) of 1.00≦
(Dv/Dp)≦1.20, and Dv is 1 to 1
It is 0 μm.

[0033] The method for producing the resin particles A includes a reaction in which a polymer having a narrow particle size distribution, which is smaller than the target particle size, is used in advance and grown in the above-mentioned system. The monomer utilized in the growth reaction may be the same monomer that produced the seed particles or a different monomer, but the polymer must not be soluble in the hydrophilic organic liquid.

Examples of the hydrophilic organic liquid used as a monomer diluent during seed particle formation and seed particle growth reaction in the present invention include 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,
Alcohols such as diethylene glycol; ether alcohols such as methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether; These organic liquids can be used alone or in a mixture of two or more.

[0035] Organic liquids other than alcohols and ether alcohols can be used in combination with the above-mentioned alcohols and ether alcohols under various conditions that do not provide solubility to the polymer particles produced in the organic liquid. By changing the SP value and changing the polymerization conditions, it is possible to suppress the size of the particles produced, the coalescence of seed particles, and the generation of new particles. In this case, organic liquids used in combination include hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene, and xylene; halogenated hydrocarbons such as carbon tetrachloride, trichlorethylene, and tetrabromoethane; ethyl ether; , dimethyl glycol, trioxane, tetrahydrofuran, and other ethers; methylal, diethyl acetal, and other acetals;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and 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, and dimethylamine , sulfur- and nitrogen-containing organic compounds such as monoethanolamine, pyridine, dimethyl sulfoxide, and dimethyl formamide;
Also includes water.

[0036] In the above-mentioned solvent mainly composed of a hydrophilic organic liquid, SO4 ions (-2 valence), NO2 ions (-1 valence), P
O4 ion (-3 valence), Cl ion (-1 valence), Na ion (+1 valence), K ion (+1 valence), Mg ion (+
Polymerization may be carried out in the presence of Ca ions (+2 valence), Ca ions (+2 valence), and other inorganic ions. Furthermore, by changing the type and composition of the mixed solvent at the start of polymerization, during polymerization, and at the end of polymerization, it is possible to adjust the average particle size, particle size distribution, drying conditions, etc. of the resulting polymer particles.

In the present invention, suitable examples of the polymeric dispersant used during the production of seed particles or growth particles include acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid, Acids such as itaconic acid, crotonic acid, fumaric acid, maleic acid or maleic anhydride; acrylic monomers containing hydroxyl groups, such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-hydroxypropyl acrylate , β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylate, Diethylene glycol monomethacrylate, glycerin monoacrylate, glycerin monomethacrylate, N-methylolacrylamide, N-methylolmethacrylamide, etc.; vinyl alcohol or ethers with vinyl alcohol, such as vinyl methyl ether,
Vinyl ethyl ether, vinyl propyl ether, etc.; Esters of vinyl alcohol and compounds containing a carboxy group, such as vinyl acetate, vinyl propionate, vinyl butyrate, etc.; Acrylamide, methacrylamide, diacetone acrylamide, or methylol compounds thereof; Acrylic acid Acid chlorides such as chloride and methacrylic acid chloride; vinylpyridine, vinylpyrrolidone,
Homopolymers or copolymers containing nitrogen atoms or their heterocycles such as vinylimidazole and ethyleneimine; polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, polyoxypropylene alkylamine, polyoxyethylene alkyl amide , polyoxypropylene alkylamide, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ether, polyoxyethylene nonylphenyl ether; and methylcellulose, hydroxyethylcellulose, hydroxypropyl Examples include celluloses such as cellulose.

[0038] Furthermore, the above hydrophilic monomer and styrene, α
- Those having a benzene nucleus such as methylstyrene and vinyltoluene, derivatives thereof, or copolymers such as acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide; Furthermore, crosslinking monomers such as ethylene glycol dimethacrylate, Copolymers with diethylene glycol dimethacrylate, allyl methacrylate, divinylbenzene, etc. can also be used.

These polymeric dispersants are appropriately selected depending on the hydrophilic organic liquid used, the desired species of polymer particles, and the production of seed particles or grown particles. In order to mainly sterically prevent this, a material is selected that has high affinity and adsorption to the polymer particle surface, and high affinity and solubility to hydrophilic organic liquids. In addition, in order to enhance the repulsion between particles sterically, those with molecular chains of a certain length, preferably those with a molecular weight of 10,000 or more, are selected. However, if the molecular weight is too high, the viscosity of the liquid will increase significantly, resulting in poor operability and stirring performance, and the probability of precipitation of the produced polymer on the particle surface will vary, so care must be taken. In addition, some of the monomers of the polymer dispersant mentioned above,
It is also effective for stabilization to coexist with the monomers constituting the target polymer particles.

Furthermore, in combination with these polymer dispersants, cobalt, iron, nickel, aluminium, copper, tin, lead,
Metals such as magnesium or their alloys (particularly preferred are particles with a particle size of 1 μm or less); fine inorganic compound powders of oxides such as iron oxide, copper oxide, nickel oxide, zinc oxide, titanium oxide, and silicon oxide; higher alcohol sulfuric esters Anionic surfactants such as salts, alkylbenzene sulfonates, α-olefin sulfonates, and phosphoric acid esters; amine salt types such as alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, imidazolines, alkyltrimethylammonium salts, Quaternary ammonium salt-type cationic surfactants such as dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, pyridium salts, alkylisoquinolinium salts, and benzethonium chloride; nonionic surfactants such as fatty acid amide derivatives and polyhydric alcohol derivatives. Activator: For example, even if an amino acid type surfactant such as alanine type [e.g. dodecyldi(aminoethyl)glycine, di(octylaminoethyl)glycine] or betaine type amphoteric surfactant is used in combination, the stability of the produced polymer particles and The improvement in particle size distribution can be further enhanced.

In general, the amount of polymer dispersant used during the production of seed particles varies depending on the type of polymerizable monomer for forming the desired polymer particles, but it is usually 0.
．． It is 1 to 10% by weight, preferably 1 to 5% by weight. When the concentration of the polymer dispersant is low, the resulting polymer particles have a relatively large particle size, and when the concentration is high, the polymer particles have a small particle size. Even if it is used in excess, there is little effect on reducing the particle size.

[0042] The above-mentioned polymeric dispersants and inorganic fine powders, pigments, and surfactants added as necessary are not only necessary during the production of seed particles, but also during the growth reaction. In order to prevent particles from coalescing, they may be present in the vinyl monomer solution or seed particle dispersion to be added for polymerization.

The initially formed particles are stabilized by a polymeric dispersant distributed in a balanced manner in the hydrophilic organic liquid and on the surface of the polymer particles, but the unreacted vinyl monomer is stabilized by the hydrophilic organic If it is present in a large amount in the liquid, it will have a somewhat swollen viscosity and will overcome the steric repulsion of the polymeric dispersant and coagulate. Furthermore, if the amount of monomer is extremely large relative to the hydrophilic organic liquid, the resulting polymer will be completely dissolved and will not precipitate until the polymerization has progressed to a certain extent. In this case, the state of precipitation is such that highly sticky lumps are formed. Therefore, the amount of monomer to hydrophilic organic liquid when producing particles is naturally limited, and although it varies somewhat depending on the type of hydrophilic organic liquid, the monomer/hydrophilic organic liquid ratio is approximately 1 or less,
Preferably, 1/2 or less is appropriate.

The vinyl monomer in the present invention is one that can be dissolved in a hydrophilic organic liquid, such as styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2
, 4-dimethylstyrene, p-n-butylstyrene, p
-tert-butylstyrene, p-n-hexylstyrene, p-n-octylstyrene, p-n-nonylstyrene, p-n-decylstyrene, p-n-dodecylstyrene, p-methoxystyrene, p-phenylstyrene , p
- Styrenes such as chlorostyrene and 3,4-dichlorostyrene; methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, acrylic acid Lauryl, 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, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and other α-methyl fatty acid monocarboxylic acid esters Acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, and acrylamide; Vinyl chloride, vinylidene chloride, vinyl bromide, vinyl fluoride, and other vinyl halides alone or in mixtures thereof, and 50% by weight of these; It means a mutual mixture of monomers containing the above and copolymerizable with these.

The polymer of the present invention may be polymerized in the presence of a so-called crosslinking agent having two or more polymerizable double bonds in order to improve offset resistance. Preferably used crosslinking agents include divinylbenzene, divinylnaphthalene, and aromatic divinyl compounds that are derivatives thereof, as well as ethylene glycol dimethacrylate, diethylene glycol methacrylate,
triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate,
Diethylene carboxylic acid esters such as tert-butylaminoethyl methacrylate, tetraethylene glycol methacrylate, and 1,3-butanediol dimethacrylate; all divinyl compounds such as N,N-divinylaniline, divinyl ether, divinyl sulfide, and divinyl sulfone; Compounds having two or more vinyl groups can be mentioned, and these can be used alone or as a mixture.

[0046] When a growth polymerization reaction is successively carried out using the seed particles crosslinked in this manner, the interior of the growing polymer particles becomes crosslinked. On the other hand, when the vinyl monomer solution used in the growth reaction contains the above-mentioned crosslinking agent, a polymer having a hardened particle surface can be obtained.

In the present invention, polymerization may be carried out in the presence of a compound having a large chain transfer constant for the purpose of controlling the average molecular weight. Examples include low molecular weight compounds having a mercapto group, carbon tetrachloride, carbon tetrabromide, and the like.

[0048] Furthermore, as the polymerization initiator for the monomer,
For example, 2,2'-azobisisobutyronitrile, 2,2
Azo polymerization initiators such as '-azobis(2,4-dimethylvaleronitrile), peroxide polymerization initiators such as lauryl peroxide, benzoyl peroxide, tert-butyl peroctoate, potassium persulfate, etc. A persulfide-based initiator or a system in which it is combined with sodium thiosulfate, an amine, etc. is used. The concentration of the polymerization initiator is 0.1 to 1 with respect to 100 parts by weight of vinyl monomer.
0 parts by weight is preferred.

The polymerization conditions for obtaining resin particles A include the concentration and blending of the polymer dispersant and vinyl monomer in the hydrophilic organic liquid in accordance with the target average particle size and target particle size distribution of the polymer particles. The ratio is determined. Generally, if the average particle size of the particles is to be made small, the concentration of the polymeric dispersant is set high, and if the average particle size is to be made large, the concentration of the polymeric dispersant is set to be low. On the other hand, if you want to make the particle size distribution very sharp, you need to lower the vinyl monomer concentration and
If a relatively wide distribution is acceptable, the vinyl monomer concentration is set high.

The resin particles A are manufactured by completely dissolving the polymer dispersant in a hydrophilic organic liquid, and then adding one or more vinyl monomers, a polymerization initiator, and other inorganic fine powders as necessary. Adding surfactants, dyes, pigments, etc., 30 to 300
With normal stirring at rpm, preferably at the lowest possible speed,
Moreover, by using turbine-type stirring blades rather than paddle-type stirring blades at a speed that makes the flow uniform in the tank, and heating at a temperature corresponding to the decomposition rate of the initiator used, polymerization is carried out. It is done. Note that since the temperature at the initial stage of polymerization has a large effect on the particle size produced, it is desirable to raise the temperature to the polymerization temperature after adding the monomers and to dissolve the initiator in a small amount of solvent before adding it. During polymerization, it is necessary to sufficiently expel oxygen in the air in the reaction vessel using an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles are likely to be generated.

[0051] In order to carry out polymerization in a high polymerization rate range, 5 to 40
Although several hours of polymerization time is required, the polymerization rate can be accelerated by stopping the polymerization when the desired particle size and particle size distribution are achieved, by sequentially adding a polymerization initiator, or by conducting the reaction under high pressure. be able to. After polymerization, the polymer slurry can be used as it is for the dyeing process, or it can be used as a polymer slurry after removing unnecessary fine particles, residual monomers, polymer dispersants, etc. through operations such as sedimentation, centrifugation, and decantation. It may be collected as a dye and dyed. However, if the polymer dispersant is not removed, the dyeing system will be more stable and unnecessary aggregation will be suppressed.

In the present invention, the resin particles A obtained as described above are subsequently dyed, and the dyeing is carried out as follows. That is, the resin particles A are dispersed in an organic solvent that does not dissolve the resin particles A, and before and after dissolving the dye in the solvent, the dye is permeated into the resin particles A to color them, and then the solvent In the method of obtaining a dyed toner by removing the dye, the relationship between the solubility of the dye in the organic solvent [D1] and the solubility of the dye in the resin of the resin particles A [D2] is [D1]/[
D2]≦0.5, and this allows the dye to penetrate deep into the resin particles A (
This makes it possible to efficiently produce toner that has been dispersed.

[0053] In the present invention, the solubility is 25°C.
Defined as measured at a temperature of The solubility of the dye in the resin has exactly the same definition as the solubility of the dye in the solvent, and means the maximum amount of the dye that can be contained in the resin in a compatible state. The state of dissolution or the state of precipitation of the dye can be easily observed using a microscope. Note that in order to know the solubility of the dye in the resin, an indirect observation method may be used instead of the above-mentioned direct observation method. This method uses a liquid with a solubility coefficient similar to that of the resin, that is, a solvent that dissolves the resin well, and the solubility of the dye in this solvent is determined as the solubility in the resin.

In the present invention, the dye used for dyeing is determined by the solubility of the dye in the organic solvent used [D1] and the solubility of the dye in the resin constituting the resin particles A [D2].
The ratio [D1]/[D2] must be 0.5 or less. In particular, it is preferable that [D1]/[D2] be 0.2 or less.

There are no particular restrictions on the dye as long as it satisfies the above-mentioned solubility characteristics, but water-soluble dyes such as cationic dyes and anionic dyes may be subject to large environmental fluctuations, and the resistance of the toner may be low, making transfer difficult. Since there is a risk that the rate may deteriorate,
Preferably, vat dyes, disperse dyes, and oil-soluble dyes are used.
Particularly preferred are oil-soluble dyes. Moreover, several types of dyes can be used in combination depending on the desired color tone. The ratio (weight) of the dye to be dyed and the resin particles A is arbitrarily selected depending on the degree of coloring, but usually for 100 parts by weight of the resin particles,
1 to 50 parts by weight of dye is preferred.

For example, alcohols such as methanol and ethanol with a high SP value are used as the dyeing solvent, and the resin particles A
When a styrene/acrylic resin with an SP value of about 9 is used, examples of dyes that can be used include the following dyes. C. I. SOLVENT YELLOW(6,9,1
7, 31, 35, 100, 102, 103, 105)C
．． I. SOLVENT Orange (2, 7, 13
, 14, 66) C. I. SOLVENT RED (5
,16,17,18,19,22,23,143,14
5,146,149,150,151,157,158
)C. I. SOLVENT VIOLET(31,3
2,33,37)C. I. SOLVENT BLUE
(22, 63, 78, 83-86, 91, 94, 95,
104)C. I. SOLDENT GREEN (24
, 25) C. I. SOLDENT Brown (3,
9) etc.

Commercially available dyes include, for example, vertical dye SOT dye Yellow-1, 3, 4 and Orange from Hodogaya Chemical Industry Co., Ltd.
e-1, 2, 3, Scarlet-1, Red-1, 2
,3,Brown-2,Blue-1,2,Viole
t-1, Green-1, 2, 3, Black-1, 4
, 6, 8 and BASF's sudan dye, Yellow
-140,150, Orange-220, Red-2
90, 380, 460, Blue-670, Mitsubishi Kasei Diaresin, Yellow-3G, F, H2G, H
G, HC, HL, Orange-HS, G, Red-G
G, S, HS, A, K, H5B, Violet-D, B
lue-J, G, N, K, P, H3G, 4G, Green
n-C, Brown-A, orient chemical oil color, Yellow-3G, GG-S, #105, Or
ange-PS, PR, #201, Scarlet-#
308, Red-5B, Brown-GR, #416,
Green-BG, #502, Blue-BOS, II
N, Black-HBB, #803, EE, EX, Sumitomo Chemical Co., Ltd. Sumiplast, Blue GP, OR, Red FB, 3B, Yellow FL7G, GC, Nippon Kayaku Co., Ltd. Kayalon, Polyester Black EX-SF300, Kayaset Red -B Blue A-2R, etc. can be used. Of course, the dye is not limited to the above example, since it is appropriately selected depending on the combination of the resin particles A and the solvent used during dyeing.

The organic solvent used for dyeing the resin particles A with the dye is one that does not dissolve the resin particles A, or one that causes some swelling. Specifically, the solubility parameter of the organic solvent [SP value] and the [SP value] of the resin particles used is 1.0 or more, preferably 2.0 or more.
0 or more are used. For example, for styrene/acrylic resin, alcohols such as methanol, ethanol, n-propanol, etc., which have a high [SP value], or n-hexane, n-heptane, etc., which have a low [SP value], are used. Of course, if the difference in [SP value] is too large, wetting to the resin particles will be poor and good dispersion of the resin particles will not be obtained, so the difference in [SP value] is preferably 2 to 5.

As a dyeing method, it is preferable to disperse the resin particles A in an organic solvent in which a dye is dissolved, and then maintain the liquid temperature at a temperature below the glass transition temperature of the resin particles A and stir the mixture. Thereby, the rate of penetration of the dye into the resin particles A can be accelerated, and it becomes possible to obtain sufficiently colored resin particles A in about 30 minutes to 1 hour. Stirring may be carried out using a commercially available stirrer, such as a homomixer or a magnetic stirrer.

Alternatively, the dye is directly added to the slurry obtained at the end of the polymerization by dispersion polymerization, that is, a solution in which the polymerized resin particles A are dispersed in an organic solvent, and the mixture is heated and stirred under the above conditions. Good too. If the heating temperature exceeds the glass transition temperature, resin particles will fuse together.

The method of drying the slurry after dyeing is not particularly limited, but it may be air-dried after filtration, drying under reduced pressure after filtration, or direct drying under reduced pressure without filtration. In the present invention, the colored particles obtained by air drying or vacuum drying after filtration have almost no agglomeration, and reproduce the particle size distribution of the introduced resin particles with almost no damage.

In the present invention, in order to improve the triboelectric charging properties of the toner particles produced through the dyeing process, it is possible to incorporate a charge control agent into the toner particles. be. (1) In the process of dyeing resin particles, by dissolving the charge control agent together with the dye in an organic solvent, the charge control agent remains on the surface of the resin particles after the organic solvent is removed after dyeing. Make it adhere. (2) Charge control agent particles are mechanically implanted onto the surface of the dried resin particles after dyeing. Note that supplementary heating may be applied during driving. In this case, by setting the size of the charge control agent particles to 1 μm or less, the charge control agent particles are firmly implanted into the surface of the resin particles, particularly to the extent that they do not easily separate in the developer.

Furthermore, the ratio of the charge control agent to the colored resin particles can be arbitrarily selected since the amount of charge required of the toner varies depending on the developing means. Usually, the amount is preferably 0.1 to 50 parts by weight per 100 parts by weight of the colored resin particles. If it is less than 0.1 part by weight, the effect of charge control will be too small, and if it exceeds 50 parts by weight, it will adversely affect fixing properties.

As for the method of implanting the charge control agent, the colored resin particles and the charge control agent are mixed in advance, and then mechanical energy is applied. Mixing method: ball mill, V
Any blender, Henschel, etc. will do. Methods of applying mechanical energy include applying impact force to the mixture using blades rotating at high speed, accelerating the particles by introducing the mixture into high-speed airflow, and causing the particles to collide with each other or against a suitable collision plate. There is. Specific equipment includes an Ong Mill (Hosokawa Micron Corporation), an I-type mill (Japan Pneumatic Industries) with lower air pressure for grinding than normal grinding, a hybridization system (Nara Kikai Seisakusho), Examples include automatic mortar.

Specific examples of charge control agents include the following. nigrosine, azine dye containing an alkyl group having 2 to 16 carbon atoms (Japanese Patent Publication No. 1627/1983),
Basic dyes [for example, C.I. I. Basic Yellow
w 2 (C.I.41000), C.I. I. Basic
Yellow 3, C. I. Basic Red 1 (
C. I. 45160), C. I. Basic Red
9 (C.I.42500), C.I. I. Basic Vi
olet1 (C.I.42535), C. I. Basi
c Violet 3 (C.I.42555), C.I. I
．． BasicViolet 10 (C.I.45170
), C. I. BasicViolet 14 (C.I.
．． 42510), C. I. Basic Blue 1 (
C. I. 42025), C. I. Basic Blue
e 3 (C.I.51005), C. I. Basic
Blue 5 (C.I.42140), C.I. I. Bas
ic Blue 7 (C.I.42595), C.I. I.
Basic Blue 9 (C.I.52015), C
．． I. Basic Blue24 (C.I.52030
), C. I. Basic Blue25 (C.I.52
025), C. I. Basic Blue 26 (C.
I. 44045), C. I. Basic Green
1 (C.I.42040), C.I. I. Basic Group
een4 (C.I. 42000), etc.], lake pigments of these basic dyes (lake-forming agents include phosphotungstic acid, phosphomolybdic acid, phosphotungsten-molybdic acid, tannic acid, lauric acid, gallic acid, ferric acid, C.I. I. Sovent
Black 3 (C.I.26150), Hansa Yellow G (C.I.11680), C.I. I. Mordl
ant Black 11,C. I. Pigment
Black1, benzolmethyl-hexadecyl ammonium chloride, decyl-trimethylammonium chloride, or dialkyltin compounds such as dibutyl or dioctyl, dialkyltin borate compounds, guanidine derivatives, vinyl polymers containing amino groups,
Polyamine resins such as condensation polymers containing amino groups, Japanese Patent Publication Nos. 41-20153 and 43-27596,
Metal complex salts of monoazo dyes described in No. 44-6397 and No. 45-26478. Tokuko Sho 55-4275
No. 2, Special Publication No. 58-41508, Special Publication No. 58-738
Metal complexes of salicylic acid, dialkyl salicylic acid, naphthoic acid, dicarboxylic acid such as Zn, Al, Co, Cr, Fe, etc., and sulfonated copper phthalocyanine pigments, etc., described in Japanese Patent Publication No. 59-7385.

[0066] It is also possible to implant the following fine particles that have been atomized by means such as recrystallization, pulverization, and emulsification. Fine particles with relatively high Tg, such as submicron fine particles of PMMA (polymethyl methacrylate), PTFE (polytetrafluoroethylene), and PVDF (polyvinylidene fluoride).

Furthermore, polyolefin, fatty acid ester,
A release agent such as a fatty acid metal salt, higher alcohol, or paraffin wax can also be applied to the surface of the toner. When performing implantation treatment, it may be performed simultaneously with implantation of the charge control agent, or it may be performed separately before and after implantation.

[0068]

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto. Note that all parts and percentages shown below are based on weight.

Production Example (Production of Base Particles) 320 parts of methanol was placed in a three-necked flask equipped with a stirring blade and a condenser, and 6.4 parts of polyvinylpyrrolidone (average molecular weight 40,000) was added little by little while stirring. and completely dissolved. Furthermore, the following composition was added and completely dissolved. styrene
25.6 copies
n-butyl methacrylate
6.4 parts 2,2'-azobisisobutyronitrile 0.2 parts

[
While stirring these, the inside of the flask was purged with nitrogen gas and left for 1 hour. Polymerization was started in a constant temperature water bath at 60° C.±0.1° C. while stirring at a stirring speed of 200 rpm. 15 minutes after heating, the liquid begins to become cloudy and 2
Even after 0 hours of polymerization, the dispersion remained cloudy and stable. As a result of measuring a portion of the sample using gas chromatography using an internal standard method, it was confirmed that the polymerization rate was 93%.

When the obtained dispersion was cooled and centrifuged at 2000 rpm using a centrifuge, the polymer particles were completely settled and the upper liquid was transparent. The supernatant liquid was removed, 200 parts of methanol was newly added, and the mixture was stirred and washed for 1 hour. Repeat centrifugation and washing with methanol 5 times.
Filtered. The filtered product was dried under reduced pressure at 50° C. for 24 hours to obtain white powder styrene/n-butyl methacrylate copolymer particles with a yield of 95%. The obtained particles had a volume average particle diameter Dv=7.40 μm, Dv/Dp=1.07
(number average particle diameter 6.92 μm). Moreover, Tg was 65°C.

Next, 1.0 part of Oil Black 803 (Orient Chemical Co., Ltd.) was heated and dissolved in 200 parts of methanol, cooled, and filtered through a 1 μm filter to prepare a dye solution. Subsequently, 24 parts of the above-mentioned copolymer particles were added to the filtrate to disperse it, and the mixture was heated and stirred at 50° C. for 1 hour. Thereafter, the dispersion was cooled to room temperature and filtered, and then heated to 50°C for 24 hours.
It was dried under reduced pressure for hours to obtain colored resin particles. (Hereafter, these will be referred to as colored resin particles B.)

Example 1 To 100 parts of AEROSIL 130 (silica particles; manufactured by Nippon Aerosil Co., Ltd.), 5 parts of the above-mentioned exemplified compound (a)-1 as a fluorine-containing silane compound was added, and the mixture was mixed at 2500 rpm using a closed Henschel mixer. The mixture was mixed and stirred intermittently for 30 minutes. The obtained fine powder was dried at 150° C. for 2 hours to obtain a fine silica powder treated with a fluorine-containing silane compound.

Next, colored resin particles B1 obtained in the production example
To 00 parts, 0.7 parts of the silica fine particles treated with the above-mentioned fluorine-containing silane compound were added and stirred for 20 minutes at 1500 rpm using a Henschel mixer to obtain toner (a). 3 parts of this toner (a) and 97 parts of a ferrite carrier coated with silicone resin to a thickness of 1 μm and having an average particle size of 100 μm are mixed in a ball mill,
A developer was obtained.

Next, images were produced using a digital copier Imageo 420 manufactured by Ricoh under environments of low temperature and low humidity (10°C, 15%) and high temperature and high humidity (30°C, 85%). , the image density is high in both environments.
A high-resolution image without background stains was obtained. The amount of charge in both environments is low temperature and low humidity (-26.2μC/g), high temperature and high humidity (-26.2μC/g)
23.2 μC/g), and there was almost no change. These results are shown in Table 8.

[0076] Furthermore, when we conducted a copy test of 30,000 copies at room temperature and humidity (20°C, 65%), the same high image quality as the initial one was maintained even after 30,000 copies, and there was almost no change in the amount of charge. There wasn't. Table 9 shows the results regarding durability.

Example 2 A toner was prepared in the same manner as in Example 1, except that [Exemplary Compound (A)-7] was used instead of the fluorine-containing silane compound [Exemplary Compound (A)-1] in Example 1. (b) was created.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Comparative Example 1 AEROSIL 130 (silica particles; manufactured by Nippon Aerosil Co., Ltd.) was heated to 250 ml using a closed Henschel mixer.
The mixture was mixed and stirred by driving intermittently for 30 minutes at 0 rpm. Thereafter, heat treatment was performed at 150° C. for 2 hours to obtain fine silica powder.

A toner (c) was obtained in the same manner as in Example 1, except that the silica fine powder treated with the fluorine-containing silane compound in Example 1 was replaced with the above-mentioned fine silica powder, and a developer was also prepared.

Next, using Imagio 420, low temperature and low humidity (
Images were produced in environments of high temperature (10℃, 15%) and high temperature and high humidity (30℃, 85%).In low temperature and low humidity, images with high image density, no background smear, and high resolution were obtained. However, under high temperature and high humidity conditions, background smearing occurred and the resolution was also poor. In addition, significant cleaning defects were observed under high temperature and high humidity conditions. The amount of charge in both environments was low temperature and low humidity (-23.8 μC/g) and high temperature and high humidity (-8.2 μC/g), and the charge amount in high temperature and high humidity was small. These results are shown in Table 8.

[0082] In addition, when a 30,000-sheet copy test was conducted at room temperature and normal humidity (20°C, 65%), background smear appeared after 10,000 copies, and toner scattering was severe after 30,000 copies.
In addition, cleaning defects also occurred. Table 9 shows the results regarding durability.

Comparative Example 2 Silane coupling agent CH3 (
5 parts of CH2)2Si(OC2H5)3 were added and mixed and stirred using a closed Henschel mixer by driving intermittently for 30 minutes at 2500 rpm. The obtained fine powder was dried at 150° C. for 2 hours to obtain a fine silica powder treated with a silane coupling agent.

Toner (d) was obtained in the same manner as in Example 1, except that the fine silica powder treated with the silane coupling agent was used in place of the fine silica powder treated with a fluorine-containing silane compound in Example 1, and then developed. A drug was created.

Next, in the same manner as in Example 1, Imagio 4
When an environmental test and a continuous copy test were conducted using No. 20, as shown in Tables 8 and 9, the environmental fluctuation was large and the durability was not good.

Comparative Example 3 0.0 parts of the charge control agent 3,5-di-t-butylsalicylic acid zinc salt was added to 100 parts of the colored resin particles B obtained in the production example.
After adding 5 parts of the mixture and stirring with an Ooster blender for 10 minutes, the mixture was treated with a hybridization system (Nara Kikai Seisakusho) at a rotational speed of 7000 rpm for 10 minutes to obtain colored resin particles C.

Next, 0.7 parts of the silica fine powder treated with a silane coupling agent prepared in Comparative Example 2 was added to 100 parts of the colored resin particles C, and the mixture was mixed with a Henschel mixer at 1500 rpm for 20 minutes. The mixture was stirred for a minute to prepare toner (e).

Hereinafter, a developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. At low temperature and low humidity, the image density was high, there was no background smudge, and the image quality was high. Although a high-resolution image was obtained, under high temperature and high humidity conditions, background smearing occurred and the resolution was not good. In addition, significant cleaning defects were observed under high temperature and high humidity conditions. The amount of charge in both environments is low temperature and low humidity (-33.8μC/g) and high temperature and high humidity (-13.9μC/g).
C/g), and the amount of charge at high temperature and high humidity was small. The results are shown in Tables 8 and 9.

Example 3 Toner (f) was prepared in the same manner as in Example 1, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used instead of AEROSIL130 in Example 1.
It was created.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Comparative Example 4 Silane coupling agent CH3 (C
Toner (g) was prepared in the same manner as in Example 3 except that H2)2Si(OC2H5)3 was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, these results showed large environmental fluctuations and poor durability.

Example 4 Instead of AEROSIL130 in Example 1, P
Toner (h) was prepared in the same manner as in Example 1, except that 25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 5 A toner was prepared in the same manner as in Example 4, except that [Exemplary Compound (A)-7] was used instead of the fluorine-containing silane compound [Exemplary Compound (A)-1] in Example 4. (i) was created.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Comparative Example 5 CH3(CH2)2Si(OC2
Toner (j) was prepared in the same manner as in Example 4 except that H5)3 was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, these results showed large environmental fluctuations and poor durability.

Example 6 A toner was prepared in the same manner as in Example 1, except that [Exemplified Compound (B)-2] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (k) was created.

[0100] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 7 A toner was prepared in the same manner as in Example 6, except that [Exemplified Compound (B)-7] was used instead of the fluorine-containing silane compound [Illustrated Compound (B)-2] in Example 6. (l) was created.

[0102] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 8 Toner (m
)It was created.

[0104] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 9 Instead of AEROSIL130 in Example 6, P
Toner (m) was prepared in the same manner as in Example 6, except that 25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 10 A toner was produced in the same manner as in Example 9, except that [Exemplified Compound (B)-7] was used instead of the fluorine-containing silane compound [Illustrated Compound (B)-2] in Example 9. (o) was created.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 11 A toner was prepared in the same manner as in Example 1, except that [Exemplified Compound (C)-2] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (p) was created.

[0110] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 12 Fluorine-containing silane compound in Example 11 [Exemplary compound (
Toner (q) was prepared in the same manner as in Example 11, except that [Exemplary Compound (c)-15] was used instead of [C)-2].

[0112] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 13 Instead of AEROSIL130 in Example 11,
Toner (r) was prepared in the same manner as in Example 11, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used.

[0114] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 14 Instead of AEROSIL130 in Example 11,
Toner (s) was prepared in the same manner as in Example 11, except that P25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 15 Fluorine-containing silane compound in Example 14 [Exemplary compound (
Toner (t) was prepared in the same manner as in Example 14, except that [Exemplified Compound (c)-15] was used instead of [C)-2].

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 16 A toner was produced in the same manner as in Example 1, except that [Exemplified Compound (d)-4] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (u) was created.

[0120] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 17 Fluorine-containing silane compound in Example 16 [Illustrative compound (
Toner (v) was prepared in the same manner as in Example 16, except that [Exemplary Compound (d)-36] was used instead of [d)-4].

[0122] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 18 Instead of AEROSIL130 in Example 16,
Toner (w) was prepared in the same manner as in Example 16, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used.

[0124] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 19 Instead of AEROSIL130 in Example 16,
Toner (x) was prepared in the same manner as in Example 16, except that P25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 20 Fluorine-containing silane compound in Example 19 [Illustrative compound (
Toner (y) was prepared in the same manner as in Example 19 except that [Exemplary Compound (d)-36] was used instead of [D)-4].

[0128] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 21 A toner was produced in the same manner as in Example 1, except that [Exemplified Compound (E)-1] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (z) was created.

[0130] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 22 Fluorine-containing silane compound in Example 21 [Illustrative compound (
Toner (α) was prepared in the same manner as in Example 21, except that [Exemplified Compound (e)-10] was used instead of [E)-1].

[0132] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 23 Instead of AEROSIL130 in Example 21,
A toner (β) was prepared in the same manner as in Example 21, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used.

[0134] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 24 Instead of AEROSIL130 in Example 21,
A toner (γ) was prepared in the same manner as in Example 21, except that P25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

[0136] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 25 Fluorine-containing silane compound in Example 24 [Illustrative compound (
Toner (δ) was prepared in the same manner as in Example 24, except that [Exemplified Compound (e)-10] was used instead of [e)-1].

[0138] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 26 A toner was prepared in the same manner as in Example 1, except that [Exemplified Compound (F)-2] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (ε) was created.

[0140] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 27 Fluorine-containing silane compound in Example 26 [Illustrative compound (
Toner (ζ) was prepared in the same manner as in Example 26, except that [Exemplary Compound (f)-11] was used instead of [F)-2].

[0142] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 28 Instead of AEROSIL130 in Example 26,
A toner (η) was prepared in the same manner as in Example 26, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used.

[0144] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 29 Instead of AEROSIL130 in Example 26,
A toner (θ) was prepared in the same manner as in Example 26, except that P25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

[0146] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 30 Fluorine-containing silane compound in Example 29 [Illustrative compound (
Toner (I) was prepared in the same manner as in Example 29, except that [Exemplified Compound (F)-11] was used instead of [F)-2].

[0148] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 31 A toner was produced in the same manner as in Example 1, except that [Exemplified Compound (I)-4] was used instead of the fluorine-containing silane compound [Illustrated Compound (I)-1] in Example 1. (κ) was created.

[0150] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 32 Fluorine-containing silane compound in Example 31 [Exemplary compound (
A toner (λ) was prepared in the same manner as in Example 31, except that [Exemplified Compound (g)-26] was used instead of [g)-4].

[0152] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 33 Instead of AEROSIL130 in Example 31,
A toner (μ) was prepared in the same manner as in Example 31, except that Mechanox UB-10 (aluminum oxide; manufactured by Uemura Kogyo Co., Ltd.) was used.

[0154] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 34 Instead of AEROSIL130 in Example 31,
A toner (v) was prepared in the same manner as in Example 31, except that P25 (titanium oxide particles; manufactured by Nippon Aerosil Co., Ltd.) was used.

[0156] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

Example 35 Fluorine-containing silane compound in Example 34 [Illustrative compound (
Toner (ξ) was prepared in the same manner as in Example 34, except that [Exemplary Compound (g)-26] was used instead of [G)-4].

[0158] A developer was prepared in the same manner as in Example 1, and an environmental test and a continuous copy test were conducted using Imageo 420. As shown in Tables 8 and 9, the results showed that both environmental stability and durability were very good.

[0159]

[Table 8-(1)]

[Table 8-(2)]

[Table 8-(3)]

[0160]

[Table 9-(1)]

[Table 9-(2)]

[Table 9-(3)]

[0161]

Effects of the Invention As mentioned above, the toner of the present invention is obtained by a specific manufacturing method using a dye with specific physical properties.
Furthermore, it contains hard fine powder that has been surface-treated with a fluorine-containing silane compound, and developers (one-component developers, two-component developers) using this toner have the following outstanding effects: play. (a) Images with high image density and high resolution can be obtained without background smudges. (b) Even when used for a long time, there is little change in image quality and physical properties of the developer, and the environmental stability is also good. (c) Cleanability is good.

Claims (1)

[Claims] Claim 1: Adding a polymer dispersant soluble in the organic liquid to a hydrophilic organic liquid, and further dissolving the polymer in the organic liquid, but the resulting polymer swells in the organic liquid. Dispersing resin particles produced by adding and polymerizing at least one type of vinyl monomer that is mostly insoluble in an organic solvent that does not dissolve the resin particles,
A toner obtained by a method in which a dye is dissolved in the solvent before and after this, the dye is infiltrated into the resin particles to color the resin particles, and the solvent is then removed, the toner having a solubility of the dye in the solvent. The relationship between [D1] and the solubility of the dye in the resin of the resin particles [D2] is [D1
]/[D2]≦0.5, and further contains hard fine powder surface-treated with a fluorine-containing silane compound.