JP3435463B2 - Toner for developing electrostatic images - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a toner for developing an electrostatic charge image formed by electrophotography, electrostatic recording, electrostatic printing or the like.

[0002]

2. Description of the Related Art Generally, in an electrophotographic system or an electrostatic recording system, in order to develop an electrostatic latent image (electrostatic charge image) formed on a latent image carrier such as a photoconductive photoconductor or a dielectric. Then, the electrostatic charge image is supplied with the toner which is thinned and appropriately charged by a blade on a toner supply roller such as a developing sleeve, and after development, the toner image is transferred to a transfer material such as paper as necessary. Then, this is fixed by heating pressure, solvent vapor or the like to obtain a copy.

The developing methods applied in these systems are roughly classified into a dry developing method and a wet developing method. In the development, the latter wet development method is not often used because a copy is obtained in a wet or semi-dry state. The former dry development method is further divided into a method using a two-component developer and a method using a one-component developer. The two-component developing method includes a magnet brush method using an iron powder carrier, a cascade method using a bead carrier, and a fur brush method using a fur, depending on the type of carrier that carries the toner. The one-component developing method (which does not require a carrier) includes a powder cloud method in which toner particles are used in a mist state, and a contact method in which toner particles are brought into direct contact with an electrostatic latent image surface for development. A developing method (contact developing method), a jumping developing method in which toner particles are not brought into contact with the electrostatic latent image surface, but the toner particles are charged and fly toward the latent image surface by an electric field generated by the electrostatic latent image,
There is a magnet dry method in which a magnetic conductive toner is brought into contact with the electrostatic latent image surface to develop the toner.

As the toner applied to these various developing methods, fine powder in which a coloring material such as carbon black is dispersed in a binder resin made of natural resin or synthetic resin is used. For example, particles in which a colorant is dispersed in a binder resin such as polystyrene and finely pulverized to about 1 to 30 μm are used as toners. Also,
These components containing a magnetic material such as magnetite are used as a magnetic toner.

As described above, the toner used in various developing methods has a positive or negative charge depending on the polarity of the electrostatic image to be developed. To retain the charge in the toner, the triboelectric chargeability of the resin, which is a component of the toner, can be used. However, since the amount of charge of the toner is small in this method, the image obtained by development is fogged or aged. In many cases, a satisfactory image cannot be obtained due to various charging deteriorations. Therefore, in general, in order to impart a desired triboelectric charge to the toner, a dye, a pigment or other charge control agent that imparts a charging property is added.

Conventionally, as negative charge control agents, metal complex salts of monoazo dyes, nitrohumic acid and its salts, metal complexes of salicylic acid, naphthoic acid, dicarboxylic acids such as Co, Cr and Fe, sulfonated copper phthalocyanine pigments, nitro. A styrene oligomer in which a group or a halogen is introduced,
Chlorinated paraffins, melamine resins and the like are available, but these dyes and pigments and other charge control agents have a complicated structure, inconsistent properties, and poor stability. Also, due to decomposition during heat kneading, mechanical shock, friction, changes in temperature and humidity conditions,
It is easily decomposed or deteriorated, and a phenomenon that charge controllability is deteriorated is likely to occur. Also, in many cases, the charging property changes depending on the environment. Further, when the conventional toner containing the charge control agent is used for a long time, there is a problem that filming occurs on the photoconductor due to poor charging.

Further, the dye / pigment or other charge control agent added to these toners must be exposed to some extent on the toner surface in order to impart chargeability. Therefore, due to friction between the toner particles, collision between the toner particles and the carrier particles, friction between the toner particles and the electrostatic latent image holding member, these additives (charge control agents) may drop off from the toner surface, resulting in contamination of carrier particles or static electricity. Contamination of the electrostatic latent image carrier, such as the photosensitive belt or drum, occurs. As a result, the charging property is deteriorated, the deterioration progresses as the number of times of use increases, the image density decreases, and fine line reproducibility and fog properties become practical problems.

Therefore, it has been attempted to improve the above problems by improving the affinity and dispersibility of the binder resin of the toner and the dye / pigment or other charge control agent for imparting the charging property. For example, there is a method of performing surface treatment in order to increase the affinity of the additive added for the purpose of controlling the charge, but the surface treatment often lowers the chargeability. There is also a method of finely dispersing by improving mechanical shearing force to improve dispersibility, but the proportion of the additive for the charge control agent appearing on the toner surface is decreased, and the chargeability tends not to be sufficiently imparted. There is.

As can be seen from the above, the additives (dyes and pigments or other charge control agents) that can stably impart sufficient chargeability to the toner for a long period of time are very limited and have been put to practical use. Are few. Further, in order to obtain not only a black and white image but also a color image, it is preferable that the one added to the toner is colorless, but most of the conventionally used dyes and pigments or other charge control agents are colored, Therefore, at present, there are few that have been put to practical use.

By the way, when the resin particles are produced by the dispersion polymerization method, a polymer dispersant is generally used. Therefore, the polymer dispersant remains on the surface of the resin particles, and when the dispersion-polymerized particles are made into toner, the charging property is controlled by the polymer dispersant remaining on the surface. When the surface on which the polymer dispersant remains is negatively charged, negative charge is obtained, but it is not sufficiently satisfied. Therefore, even if an attempt is made to impart more negative electrification by attaching a negative electrification compound to the negative electrification surface, strong negative electrification cannot be imparted due to the large ionic repulsion. On the other hand, a positively chargeable ammonium salt, for example, has a good adhesion to the negatively chargeable surface, but has a weak chargeability, and it is substantially impossible to control the charge. The suspension polymerization toner and the kneaded and pulverized toner have the same problem as the mechanism.

[0011]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide toner particles with stable and appropriate chargeability for a long period of time, and to provide a permanently good copy image. To provide a toner for developing a charge image.

[0012]

The toner for developing an electrostatic charge image of the present invention comprises a LUMO (Lowest Unoccupaid Molecular Orb).
ital; the lowest unoccupied orbital) is 0.1L from the midpoint M of the long molecular axis L
It is characterized by containing a compound distributed in the above three-dimensional space. Here, “a compound in which LUMO is distributed in a three-dimensional space of 0.1 L or more from the center M of the long axis of the molecule”
The term “transferred“ toner material for electrostatic image development ”is sometimes used) refers to a binder resin (including resin particles obtained by dispersion polymerization or suspension polymerization), a colorant and other additives for controlling charge. The present invention also proposes a kneaded and pulverized toner, a dispersion polymerization toner, or a suspension polymerization toner containing the above compound (toner pigment for developing an electrostatic image).

The "molecular long axis L" of the compound is defined as the interatomic distance that passes through the center of the compound molecule and is most distant from the compound molecule. Further, the "0.1 L three-dimensional space" means a sphere having a radius of 0.1 L centered on the midpoint M. Since the LUMO is an electron-accepting orbit, if the LUMO is more outside in the compound, it is possible to easily receive an electron from an electron donor such as a carrier existing in the surroundings, and therefore, the compound and the toner containing the compound. Can charge quickly. Since LUMO is mainly composed of π electrons, n (Non-bonding, lawn pair) electrons, and relatively high-energy σ electrons, the intramolecular position of LUMO can be qualitatively predicted as described above. It can be easily visualized by using the trajectory method and graphic.

Specific compounds used as a toner material for electrostatic image development which can be used in the present invention include those represented by the following formula (1).

[Chemical 2] Hereinafter, the dispersion polymerization toner and the suspension polymerization toner will be described. It should be noted that the kneading toner has been sufficiently described in many documents in the related art, and will not be described here.

(Dispersion Polymerized Toner) First, the description will be given starting with the “dispersion polymerized toner” of the present invention. [Resin Particle A] The resin particle A in the present invention is as follows. That is, the resin particles A have a volume average particle diameter (D
v) and the number average particle size (Dp) are 1.00 ≦ (Dv
/Dp)≦1.20 and Dv is 1 to 10 μm
Particles. The resin particles A are added to a hydrophilic organic liquid with a polymer dispersant that is soluble in the hydrophilic organic liquid, and the polymer particles are dissolved in the hydrophilic liquid, but the resulting polymer swells in the hydrophilic liquid. Or produced by adding and polymerizing one or more vinyl monomers which hardly dissolve. It also includes a reaction in which polymer particles having a particle size smaller than the target particle size and having a narrow particle size distribution are used to grow in the above 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.

[Hydrophilic Organic Liquid] The hydrophilic organic liquid as a diluent for the monomer used during the formation of the seed particles and the reaction for growing the seed particles is methyl alcohol, ethyl alcohol, denatured ethyl alcohol, isopropyl. Alcohol, n-butyl alcohol, isobutyl alcohol, t-butyl alcohol, s-butyl alcohol, t
Alcohols such as amyl alcohol, 3-pentanol, octyl alcohol, benzyl alcohol, cyclohexanol, furfuryl alcohol, tetrahydrofurfuryl alcohol, ethylene glycol, glycerin, and diethylene glycol, methyl cellosolve, cellosolve, isopropyl cellosolve, butyl cellosolve, ethylene glycol Representative examples include ether alcohols such as monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether.

These organic liquids can be used alone or as a mixture of two or more kinds. The organic liquid other than alcohols and ether alcohols is used in combination with the above-mentioned alcohols and ether alcohols, under the condition that the organic liquid does not have solubility in the produced polymer particles. It is possible to suppress the size of particles to be generated, the coalescence of seed particles and the generation of new particles by performing the polymerization while changing the SP value of. In this case, the organic liquid used in combination includes hydrocarbons such as hexane, octane, petroleum ether, cyclohexane, benzene, toluene and xylene, halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene and tetrabromoethane, and ethyl ether. , Ethers such as dimethyl glycol, silioxane and tetrahydrofuran, acetals such as methylal and diethyl acetal, 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, propionic acid, nitropropene, nitrobenzene, dimethylamine, monoethanolamine, pyridine, dimethylsulfoxide, dimethylforma Sulfur, such as de, nitrogen-containing organic compounds, other water is also included.

In the solvent containing the hydrophilic organic liquid as a main component,
The polymerization may be carried out in the presence of the following ions.

Embedded image SO ₄ ²⁻ , NO ₂ ⁻ , PO ₄ ³⁻ , Cl ⁻ , Na ⁺ , K ⁺ , Mg ²⁺ , Ca ^{2+ are} also used as a mixed solvent at the start of polymerization, during the polymerization and at the end of the polymerization. The type and composition can be changed to adjust the average particle size, particle size distribution, drying conditions, etc. of the resulting polymer particles.

[Dispersion Stabilizer] Suitable examples of the polymer dispersant used in the production of seed particles or the production of grown particles include, for example, acrylic acid, methacrylic acid, α-cyanoacrylic acid, α-cyanomethacrylic acid. Acids, itaconic acid, crotonic acid, fumaric acid, maleic acid, maleic anhydride, or other acids, or a hydroxyl group-containing acrylic monomer such as β-hydroxyethyl acrylate, β-hydroxyethyl methacrylate, β-acrylic acid. -Hydroxypropyl, β-hydroxypropyl methacrylate, γ-hydroxypropyl acrylate, γ-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 3-chloro-2-hydroxypropyl methacrylate, diethylene glycol monoacrylic Acid ester, diethylene glycol Lumonomethacrylate,
Glycerin monoacrylic acid ester, glycerin monomethacrylic acid ester, N-methylol acrylamide,
N-methylol methacrylamide, etc., vinyl alcohol or ethers with vinyl alcohol, eg vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, etc., or esters of vinyl alcohol and compounds containing carboxyl groups, eg vinyl acetate, propion Vinyl chloride, vinyl butyrate, acrylamide, methacrylamide, diacetone acrylamide or methylol compounds thereof, acid chlorides such as acrylic acid chloride and methacrylic acid chloride, nitrogen atom such as vinylpyridine, vinylpyrrolidone, vinylimidazole, ethyleneimine or the like. Homopolymers or copolymers such as those having a heterocycle, polyoxyethylene, polyoxypropylene, polyoxyethylene alkylamine, Polyoxyethylene type such as oxypropylene alkylamine, polyoxyethylene alkylamide, polyoxypropylene alkylamide, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl phenyl ether, polyoxyethylene stearyl phenyl ester, polyoxyethylene nonyl phenyl ester , And methylcellulose,
Cellulose such as hydroxyethyl cellulose and hydroxypropyl cellulose, or those having a benzene nucleus such as styrene, α-methylstyrene, vinyltoluene and the above hydrophilic monomer, or a derivative thereof, or acrylic acid such as acrylonitrile, methacrylonitrile and acrylamide, or A copolymer with a methacrylic acid derivative and a copolymer with a crosslinkable monomer such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, allyl methacrylate and divinylbenzene can also be used.

These polymer dispersants are appropriately selected depending on the hydrophilic organic liquid to be used, the seed of the intended polymer particles, and the production of seed particles or grown particles. In order to prevent the unification of the polymer mainly in three dimensions, a polymer having a high affinity for the polymer particle surface and an adsorptive property and a high affinity for a hydrophilic organic liquid and a high solubility is selected. Also,
In order to increase the repulsion between the particles in a three-dimensional manner, a molecular chain having a certain length, preferably a molecular weight of 10,000 or more is selected. However, when the molecular weight is too high, the viscosity of the liquid is remarkably increased, the operability and the stirring property are deteriorated, and the precipitation probability of the produced polymer on the surface of the particles is varied, so that caution is required. In addition, some of the monomers of the above-mentioned polymer dispersant,
It is also effective for stabilization to make the target polymer particles coexist in the monomer constituting the particles.

Further, together with these polymer dispersants, metals such as cobalt, iron, nickel, aluminum, copper, tin, lead and magnesium or alloys thereof (particularly preferably having a particle size of 1 μm or less), iron oxide, copper oxide, Fine powder of inorganic compounds of oxides of nickel oxide, zinc oxide, titanium oxide, silicon oxide, etc., higher alcohol sulfuric acid ester salts, alkylbenzene sulfonates, α-olefin sulfonates, anionic surfactants such as phosphoric acid esters, alkyl Amine salts, amino alcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt types such as imidazoline, and alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, alkyl dimethyl benzyl ammonium salts, pyridinium salts, alkyl isoquinolinium salts, benzethonium chloride, etc. Nonionic surfactants such as quaternary ammonium salt type cationic surfactants, fatty acid amide derivatives, and polyhydric alcohol derivatives, for example, alanine type "for example, dodecyldi (aminoethyl) glycine, di (octylaminoethyl) glycine", etc. The use of the amino acid type and betaine type amphoteric surfactants in combination can further improve the stability and particle size distribution of the produced polymer particles.

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

[Monomer] Further, the above-mentioned vinyl monomer is one that can be dissolved in a hydrophilic organic liquid.
Styrene, o-methylstyrene, m-methylstyrene,
p-methylstyrene, α-methylstyrene, p-ethylethylene, 2,4-dimethylstyrene, pn-butylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-
Nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p-phenylstyrene, p-chlorostyrene, 3,4-dichlorostyrene, and other styrenes, methyl acrylate, acrylic acid Ethyl, n-butyl acrylate, isobutyl acrylate, propyl acrylate, n-octyl acrylate, dodecyl acrylate, lauryl acrylate, acrylic acid 2
-Ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, methyl α-chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-methacrylate. Α such as octyl, dodecyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate
-Methyl fatty acid monocarboxylic acid esters, acrylic acid such as acrylonitrile, methacrylonitrile, acrylamide, or a methacrylic acid derivative, vinyl chloride,
Meaning of vinylidene chloride, vinyl bromide, vinyl fluoride, and other vinyl halides, alone or as a mixture with each other, and with a monomer containing 50% by weight or more of these and copolymerizable with them. To do.

Further, the above-mentioned polymer in the present invention may be polymerized in the presence of a so-called cross-linking agent having two or more polymerizable double bonds in order to enhance offset resistance. The cross-linking agent preferably used is an aromatic divinyl compound which is divinylbenzene, divinylnaphthalene or a derivative thereof, other ethylene glycol dimethacrylate, diethylene glycol methacrylate, triethylene glycol methacrylate, trimethylolpropane triacrylate, allyl methacrylate, tert-butyl. Aminoethyl methacrylate, tetraethylene glycol dimethacrylate, 1,
Examples include diethylenic carboxylic acid esters such as 3-butanediol dimethacrylate, all divinyl compounds such as N, N-divinylaniline, divinyl ether, divinyl sulfide, divinyl sulfone, and compounds having three or more vinyl groups. Are used alone or as a mixture.

When the growth polymerization reaction is subsequently carried out using the thus crosslinked seed particles, the inside of the growing polymer particles is crosslinked. On the other hand, when the vinyl monomer solution used for the growth reaction contains the above-mentioned cross-linking agent, a polymer whose particle surface is hardened is obtained.

[Chain Transfer Agent] Further, for the purpose of adjusting the average molecular weight, a compound having a large chain transfer constant in the presence of polymerization may be used, for example, a low molecular compound having a mercapto group, carbon tetrachloride, or tetrachloride. Carbon bromide may be mentioned.

[Polymerization Initiator] As the polymerization initiator of the above-mentioned monomer, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc. Azo polymerization initiators, lauryl peroxide, benzoyl peroxide, peroxide polymerization initiators such as t-butyl peroctoate, persulfate polymerization initiators such as potassium persulfate, sodium thiosulfate, A system in which an amine is used in combination is used. The concentration of the polymerization initiator is 0.1 with respect to 100 parts by weight of the vinyl monomer.
10 to 10 parts by weight is desirable.

[Polymerization Conditions] The polymerization conditions for obtaining the seed particles are: a polymer dispersant in a hydrophilic organic liquid; The concentration and blending ratio are determined. Generally, if the average particle size of the particles is reduced, the concentration of the polymer dispersant is set high, and if the average particle size 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, and if the distribution is relatively wide, the vinyl monomer concentration is set high.

The particles are prepared by completely dissolving the polymer dispersion stabilizer in the hydrophilic organic liquid, and then using one or more vinyl monomers, a polymerization initiator, and other inorganic fine powders and surface active agents if necessary. 30 to 30 by adding agents, dyes, pigments, etc.
Decomposition of the initiator used with normal stirring at 0 rpm, preferably at a speed as low as possible, while using a stirring blade of a turbine type rather than a paddle type while stirring at a speed such that the flow in the tank becomes uniform. Polymerization is carried out by heating at a temperature corresponding to the speed. Since the temperature at the initial stage of polymerization has a great influence on the type of particles produced, it is desirable to raise the temperature to the polymerization temperature after adding the monomer, and dissolve the initiator in a small amount of solvent before charging. At the time of polymerization, it is necessary to sufficiently expel oxygen in the air in the reaction vessel with an inert gas such as nitrogen gas or argon gas. If the oxygen purge is insufficient, fine particles are likely to be generated. It takes 5 to 40 hours to carry out the polymerization in a high polymerization rate region, but the polymerization may be stopped in a state of a desired particle size and particle size distribution,
Further, the polymerization rate can be increased by sequentially adding the polymerization initiator or by carrying out the reaction under high pressure.

After completion of the polymerization, it may be used in the dyeing step as it is, or after removing unnecessary fine particles, residual monomer, polymer dispersion stabilizer and the like by operations such as sedimentation, centrifugation and decantation, The dye may be collected by collecting it as a polymer slurry, but if the dispersion stabilizer is not removed, the stability of the dyeing system is high and unnecessary aggregation is suppressed.

[Dyeing Step] Dyeing in the present invention is as follows. That is, the resin particles A are dispersed in an organic solvent that does not dissolve the resin particles A, the dye is dissolved in the solvent before or after this, and the dye is permeated into the resin particles A to be colored, In the method of producing a dyed toner by removing the solvent, the relationship between the liquid solubility of the dye in the organic solvent (D ₁ ) and the solubility of the dye in the resin of the resin particles A (D ₂ ) is (D ₁ ) / (D
₂ ) Select and use a dye satisfying ≦ 0.5. This allows
It is possible to efficiently manufacture the toner in which the dye penetrates (diffuses) to the deep part of the resin particle A. Solubility in this specification is defined as measured at a temperature of 25 ° C. The solubility of the dye in the resin has 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 observation of the dissolved state or the deposited state of the dye can be easily performed by using a microscope. In order to know the solubility of the dye in the resin, an indirect observation method may be used instead of the above direct observation method. This method may use a liquid having 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 may be determined as the solubility in the resin.

[Dye] As the dye used for coloring, the ratio of the dye to the resin constituting the resin particles (D ₁ ) / D is determined from the solubility (D ₁ ) of the dye in the organic solvent used as described above. (D ₂ ) needs to be 0.5 or less. Further, (D ₁ ) / (D ₂ ) is preferably 0.2 or less. The dye is not particularly limited as long as it satisfies the above-mentioned solubility characteristics, but a water-soluble dye such as a cationic dye or an anionic dye may have a large environmental change, and the electric resistance of the toner becomes low, which lowers the transfer rate. Because there is a risk
It is preferable to use vat dyes, disperse dyes, oil-soluble dyes,
Oil-soluble dyes are particularly preferable. Further, several kinds 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 is arbitrarily selected according to the degree of coloring, but usually 1 part by weight of the resin particles and 1 part of the dye are used.
It is preferably used in a proportion of ˜50 parts by weight. For example, when alcohols such as methanol and ethanol having a high SP value are used as the dyeing solvent and a styrene-acrylic resin having an SP value of about 9 is used as the resin particles, dyes that can be used include, for example, Dyes such as. CI SOLVENT YELLOW (6,9,17,31,35,1,102,103,105) CI SOLVENT ORANGE (2,7,13,14,66) CI SOLVENT RED (5,16,17,18,19,22,23,143,145,146,1
49,150,151,157,158) CI SOLVENT VIOLET (31,32,33,37) CI SOLVENT BLUE (22,63,78,83 ~ 86,91,94,95,104) CI SOLVENT GREEN (24,25) CI SOLVENT BROWN (3,9) Such.

Among commercially available dyes, for example, Aizen SOT dyes Yellow-1.3,4, Oran manufactured by Hodogaya Chemical Co., Ltd.
ge-1.2,3, Scarlet-1, Red-1,
2.3, Brown-2, Blue-1, 2, Viol
et-1, Green-1, 2, 3, Black-1,
4,6,8 and BASF Sudan dye, Yell
ow-140, 150, Orange-220, Red
-290, 380, 460, Blue-670 and Mitsubishi Kasei's dialresin, Yellow-3G, F, H2
G, HG, HC, HL, Orange-HS, G, Re
d-GG, S, HS, A, K, H5B, Violet-
D, Blue-J, G, N, K, P, H3G, 4G, G
reen-C, Brown-A and oil colors manufactured by Orient Chemical Co., Yellow-3G, GG-S, # 10.
5, Orange-PS, PR, # 201, Scarl
et- # 308, Red-5B, Brown-GR, #
416, Green-BG, # 502, Blue-BO
S, HN, Black-HBB, # 803, EE, E
X, Sumiplast made by Sumitomo Chemical Co., Ltd., Blue GP, O
R, red FB, 3B, yellow FL7G, GC, Nippon Kayaku's Kayaron, polyester black EX-SH
3. Blue A-2R of Kayaset Red-B or the like can be used. Of course, the dye is not limited to the above examples because it is appropriately selected depending on the combination of the resin particles and the solvent used for dyeing.

[Organic Solvent for Dyeing] The organic solvent used for dyeing the resin particles with the dye is one in which the resin particles to be used are insoluble or causes some swelling, specifically, a solubility parameter ( The difference in SP value) is 1.0 or more, preferably 2.0 or more. For example, for styrene-acrylic resin particles, alcohols such as methanol, ethanol and n-propanol having a high SP value, or n- having a low SP value.
Hexane, n-heptane, etc. are used. If the difference in SP value is too large, the wetting of the resin particles becomes poor, and good dispersion of the resin particles cannot be obtained.
The difference in P value is preferably 2-5.

[Dyeing Step] After the resin particles are dispersed in the organic solvent in which the dye is dissolved, it is preferable to keep the liquid temperature below the glass transition temperature of the resin particles and stir. This makes it possible to dye the resin particles while preventing them from aggregating. The stirring method may be carried out using a commercially available stirrer such as a homomixer or a magnetic stirrer. Further, the dye may be directly added to the slurry obtained at the end of the polymerization by dispersion polymerization, that is, the dispersion liquid in which the polymerized resin particles are dispersed in the organic solvent, and the mixture may be heated and stirred under the above conditions. If the heating temperature exceeds the glass transition temperature, fusion of the resin particles will occur. The method for drying the slurry after dyeing is not particularly limited,
After filtration, it may be dried under reduced pressure or directly dried under reduced pressure without filtering. In the present invention, the colored particles obtained by filtering and then air-drying or drying under reduced pressure have almost no aggregation, and are reproduced without substantially impairing the particle size distribution of the introduced resin particles.

(Suspension Polymerization Toner) Next, the “suspension polymerization toner” of the present invention will be described. [Monomer] The polymerizable monomer used for suspension polymerization is a monomer having a vinyl group, and specific examples thereof include the following monomers. That is, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene,
Examples thereof include styrene such as 2,4-dimethylstyrene, butylstyrene, and octylstyrene, and derivatives thereof, and among them, a styrene monomer is most preferable. Other vinyl monomers include ethylenically unsaturated monoolefins such as propylene, butylene, isobutylene, vinyl chloride, vinylidene chloride, vinyl bromide, vinyl halides such as vinyl fluoride, vinyl acetate, vinyl propionate. Vinyl esters such as vinyl benzoate and vinyl butyrate, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, propyl acrylate, -n-octyl acrylate, dodecyl acrylate, acrylic acid-2 -Ethylhexyl, stearyl acrylate, 2-chloroethyl acrylate, phenyl acrylate, α
-Methyl chloroacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isopropyl methacrylate, n-octyl methacrylate, dodecyl methacrylate, methacrylic acid 2
-Α-methylene aliphatic monocarboxylic acid esters such as ethylhexyl, stearyl methacrylate, phenyl methacrylate, diethylaminoethyl methacrylate, acrylonitrile, methacrylonitrile, acrylic acid or methacrylic acid derivatives such as acrylamide, vinyl methyl ether, vinyl isobutyl ether Such as vinyl ethers, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone and other vinyl ketones, N-vinyl pyrrole, N-vinyl carbazole, N
-N- such as vinylindole and N-vinylpyrrolidone
Examples thereof include vinyl compounds and vinylnaphthalene, and these monomers can be used alone or in combination.

[Crosslinking Agent] In order to form a crosslinked polymer in the monomer composition, suspension polymerization may be carried out in the presence of the following crosslinking agent. As the cross-linking agent, divinylbenzene, divinylnaphthalene, polyethylene glycol diacrylate, diethylene glycol diacrylate,
Triethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexane glycol dimethacrylate, neopentyl glycol diacrylate, dipropylene glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,
2'-bis (4-methacryloxydiethoxyphenyl) propane, 2,2'-bis (4-acryloxydiethoxyphenyl) propane, trimethylolpropane trimethacrylate, trimethylolmethane tetraacrylate, dibromoneopentyl glycol di Examples thereof include methacrylate and diallyl phthalate. If the amount of cross-linking agent used is too large, the toner will not easily melt due to heat,
The heat fixing property and the heat pressure fixing property are inferior. If the amount of the cross-linking agent used is too small, properties such as blocking resistance and durability required as a toner are deteriorated, and in the heat roll fixing, a part of the toner is not completely adhered to the paper and is adhered to the roll surface. Cold offset occurs in which the toner adheres and is transferred to the next paper. Therefore, the amount of the crosslinking agent used is 0.001-1 with respect to 100 parts by weight of the polymerizable monomer.
It is 5 parts by weight, preferably 0.1 to 10 parts by weight.

[Release Agent] In order to prevent offset of the resulting toner, the polymerization composition may contain a release agent. As a release agent, low molecular weight polyethylene,
Polyolefins such as polypropylene are preferred. This low molecular weight olefin polymer is preferably dispersed in a polymerizable monomer together with a colorant. The releasing agent is preferably used in an amount of 1 to 15 parts by weight based on 100 parts by weight of the polymerizable monomer. When the amount of the release agent used is less than 1 part by weight, the obtained toner does not have a sufficient release effect and is easily offset on the roller. On the other hand, if the amount used exceeds 15 parts by weight, the release agent will be spent from the toner on the frictional charge imparting member, and the fluidity of the toner will be extremely deteriorated.

[Colorant] As the colorant contained in the monomer, there are known dyes and pigments such as carbon black and grafted carbon black obtained by coating the surface of carbon black with a resin. It can be used. Other colorants include lamp black, iron black,
Ultramarine blue, nigrosine dye, aniline blue, phthalocyanine green, Hansa yellow G, rhodamine 6G, lake, chalco oil blue, chrome yellow, quinacridone, benzidine yellow, rose bengal, triallylmethane dye, monoazo dye, disazo dye, etc. There are dyes and pigments. In addition, these coloring agents can be used in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the polymerizable monomer.

[Dispersion Stabilizer] As the dispersion stabilizer, the following can be used. That is, polyvinyl alcohol, starch, methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, sodium polyacrylate, water-soluble polymer such as sodium polymethacrylate, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, talc, clay , Diatomaceous earth, metal oxide powder, etc. are used. These are preferably used in the range of 0.1 to 10% by weight with respect to water.

[Polymerization Initiator] In the present invention, the polymerization initiator may be added to the dispersion liquid containing the monomer composition after granulation, but it is uniformly polymerized into individual monomer composition particles. From the viewpoint of adding an initiator, it is desirable to include the initiator in the monomer composition before granulation. As such a polymerization initiator,
2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,
Azo- or diazo-type polymerization initiators such as 1'-azobis- (cyclohexane-1-carbonitrile), 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisbutyronitrile, benzoyl Examples thereof include peroxide type polymerization initiators such as peroxide, methyl ethyl ketone peroxide, isopropyl peroxide, 2,4-dichlorolylbenzoyl peroxide and lauryl peroxide.

[Magnetic Material] The toner of the present invention may be a magnetic toner containing a magnetic material. To obtain a magnetic toner, magnetic particles may be added to the monomer composition. Examples of the magnetic material that can be used in the present invention include powders of ferromagnetic metals such as iron, cobalt and nickel, and powders of alloys and compounds such as magnetite, hematite and ferrite. The magnetic particles have a particle size of 0.0
5 to 5 μm, preferably 0.1 to 1 μm is used, but when a small particle size toner is produced, the particle size is 0.8
It is desirable to use magnetic particles of μm or less. The magnetic particles are preferably contained in 10 to 60 parts by weight in 100 parts by weight of the monomer composition. Further, these magnetic particles may be treated with a surface treating agent such as a silane coupling agent or a titanium coupling agent, or an appropriate reactive resin. In this case, depending on the surface area of the magnetic particles or the density of hydroxyl groups present on the surface, the surface treatment agent is usually used in an amount of 5 parts by weight or less, preferably 0.1 to 3 parts by weight, based on 100 parts by weight of the magnetic particles. Thus, sufficient dispersibility in the polymerizable monomer is obtained, and the physical properties of the toner are not adversely affected.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

Example 1 In a 500 ml four-necked flask equipped with a stirring blade and a condenser, 3.5 parts by weight of methyl vinyl ether-maleic anhydride copolymer (molecular weight 40,000, manufactured by GAF) and 100 parts by weight of methanol were placed. And stir at 60 ° C. for 2 hours,
A methyl vinyl ether-maleic anhydride copolymer was completely dissolved to prepare a dispersion stabilizer. Then, the mixture was cooled to room temperature and charged with the following. Styrene 60 parts by weight Methyl methacrylate 40 parts by weight t-dodecyl mercaptan 0.06 parts by weight 1,3-butanediol dimethacrylate 0.5 parts by weight While stirring these, the inside of the flask was purged with nitrogen gas, The stirring was continued gently (100 rpm) for about 1 hour until the residual oxygen concentration became 0.1%. Then, after raising the temperature of the constant temperature water bath to 60 ° C., 0.2 parts by weight of 2,2′-azobisisobutyronitoyl was used as an initiator,
Polymerization was continued for 24 hours. After 15 minutes of heating, the liquid began to turn cloudy and remained a cloudy and stable dispersion after 24 hours of polymerization. Partial sampling and gas chromatography,
As a result of measurement by the internal standard method, the polymerization rate is 95%.
It was confirmed that When the obtained dispersion was cooled and centrifuged at 2000 rpm with a centrifuge, the polymer particles were completely settled and the upper liquid was transparent. The supernatant was removed, 200 g of methanol was newly added, and the mixture was washed with stirring for 1 hour. The procedure of centrifugation and washing with methanol was repeatedly filtered. The material separated by filtration was dried under reduced pressure at 50 ° C. for 24 hours to obtain resin particles of white powder with a yield of 90%. The obtained particles had a volume average particle diameter Dv = 5.44 μm. The Tg (glass transition point) was 63 ° C. Hereinafter, the polymer particles are referred to as (B).

Next, 2 parts by weight of Oil Black 860 (manufactured by Orient Chemical Co., Ltd.) was dissolved by heating in 100 parts by weight of methanol, cooled, and filtered by a filter of about 1 μm to prepare a dye solution. Next, 3 times the polymer particles (B) were added to the filtrate.
0 part by weight was added and dispersed, and the mixture was heated with stirring at 50 ° C for 1 hour. Then, the dispersion liquid was cooled to room temperature and filtered to obtain a colored resin fine particle dispersion liquid. Then, as a charge control agent, H ₄ N
(CH ₂ ) ₂ (CF ₂ ) ₇ CF ₃ in water / methanol (1 /
1) It was dissolved in a mixed solvent, and 2 parts by weight was added to 100 parts by weight of the colored resin particles. After stirring for 1 hour, the mixture was filtered and dried to obtain a toner. LUMO position of charge control agent: H ₄ N (CH ₂ ) ₂ CF ₂ C
LUMO of _{F 2 CF 2 CF 2 C'F 2} C'F 2 CF '2 C'F 3
Is composed of the 2p orbital of C '(three-dimensional space of 0.1 L or more from the midpoint M of the molecular long axis L)

After sufficiently mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method.
The charge amount was −41 μC / g. The charge amount after 1 minute was -35 μC / g, and the rise of charge was very good. In addition, a running test of 30,000 sheets was performed using a commercially available electrophotographic copying machine (Imagio 420, manufactured by Ricoh Co., Ltd.) using this toner. As a result, an image with good reproducibility of fine lines without image fog and background stain was obtained.

Example 2 A toner was obtained in the same manner as in Example 1 except that 4 parts by weight of t-butylacrylamide sulfonic acid was further added to the charged monomer of Example 1. After sufficiently mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method. The charge amount was -49 μC / g. Also, 1
The amount of charge after minute was -41 μC / g, and the rise of charge was very good. Using this toner, a running test was performed on 30,000 sheets of IMAGEO 420 (manufactured by Ricoh Co., Ltd.), and as a result, an image having good fine line reproducibility without image fog and background stain was obtained.

Example 3 Carbon black MA1 was added to 40 parts by weight of styrene monomer.
00 (manufactured by Mitsubishi Kasei Co., Ltd.) and 0.5 parts by weight of 2,2'-azobisisobutyronitrile as a polymerization initiator are added, and a three-one motor driven stirring blade, a cooler, a gas introduction pipe and a thermometer are added. It was put in a 500 ml four-necked separable flask attached, and stirred at room temperature for 30 minutes under a nitrogen stream, and oxygen in the flask was replaced with nitrogen. Then, the mixture was stirred in a hot water bath at 70 ° C. for 6 hours at 60 rpm to obtain a graft carbon black. Next, styrene monomer 50 parts by weight n-butyl methacrylate 14.5 parts by weight 1,3-butanediol dimethacrylate 0.5 parts by weight t-butylacrylamide sulfonic acid 3 parts by weight Low molecular weight polyethylene 2 parts by weight (Mitsui Petrochemical Co., Ltd. Manufactured by Mitsui High Wax 210P) A mixture of 30 parts by weight of the above-mentioned graft carbon black was dispersed in a ball mill for 10 hours. After dissolving 1 part by weight of each of 2,2'-azobisisobutyronitrile and sodium nitrite in this dispersion, 250 parts of a 2% aqueous solution of polyvinyl alcohol was added to the TK homomixer (made by Tokushu Kika Co., Ltd.). ) By 6000
A suspension was obtained by stirring at rpm for 10 minutes. The above suspension was placed in a 500 ml four-neck separable flask equipped with a three-one motor-driven stirring blade, a condenser, a gas introduction tube, and a thermometer, and stirred at room temperature for 30 minutes under a nitrogen stream to remove oxygen in the flask. It was replaced with nitrogen. Then, the mixture was stirred in a hot water bath at 70 ° C. for 8 hours at 90 rpm to complete the polymerization, and suspension-polymerized particles were prepared. 100 parts by weight of the particles were redispersed in a mixed solution of water / methanol = 1/1 (weight ratio) so that the solid content was 30%, and H ₄ N (CH ₂ ) ₂ (CF ₂ ) was used as a charge control agent.
₇ CF ₃ of 3 parts by weight was added, and the mixture was stirred and then filtered and dried to obtain a toner.

After thoroughly mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method.
The charge amount was −26 μC / g. The charge amount after 1 minute was -21 μC / g, and the rise of charge was very good. Also, using this toner, IMAGIO 42
As a result of running a 30,000-sheet running test at 0, an image with good reproducibility of fine lines without image fog and background stain was obtained.

Example 4 2-ethylhexyl acrylate and carnauba wax were used instead of n-butyl methacrylate and low molecular weight polyethylene of Example 3, respectively, except that a suspension was prepared at 60 ° C. in a TK homomixer. A toner was obtained in the same manner as in Example 1. After sufficiently mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method. As a result, the charge amount was −33 μC / g. Also,
The charge amount after 1 minute was -26 μC / g, and the rise of charge was very good. Further, as a result of performing a running test on 30,000 sheets with IMAGEO 420 using this toner, a clear image without image fog was obtained.

Example 5 Binder resin (styrene-methyl acrylate copolymer) 100 parts by weight Colorant (carbon black # 44, manufactured by Mitsubishi Carbon Co.) 0.7 parts by weight Charge control agent (H ₄ N (CH ₂ ) ₂ (CF ₂ ) ₇ CF ₃ ) 3.0 parts by weight was kneaded and pulverized to obtain a toner. After sufficiently mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method. The charge amount was -20 μC /
It was g. In addition, the charge amount 1 minute after mixing was -15 μC / g, and the charging rate was significantly improved. Further, when an image was recorded by using this toner with Imagio 420 for 1 minute after the power was turned on, a clear image was obtained.

[0052] Comparative Example 1   Binder resin (styrene-methyl acrylate copolymer) 100 parts by weight   Colorant (Carbon Black # 44, Mitsubishi Carbon Co., Ltd.) 0.7 parts by weight   Charge control agent 3.0 parts by weight

[Chemical 4] Position of LUMO of charge control agent: LUMO is a toner obtained by kneading and pulverizing a mixture composed of 2p orbitals of two N atoms (a three-dimensional space from the midpoint M of the molecular long axis L to 0.1 L or more). Got After sufficiently mixing the toner and the carrier, the charge amount of the toner was measured by the blow-off method, and the charge amount was +35 μC / g. The charge amount after 1 minute was +3 μC / g. When an image was recorded using this toner for 1 minute after power was turned on with IMAGEO 420, an unclear image was obtained.

[0053]

According to the present invention, since the saturated charge amount is improved, an image with contrast can be obtained. Further, since the charge rising characteristic is improved, the warm-up time and the charging time required for toner replenishment can be shortened. Also, since the environment resistance is improved, a stable image can be obtained even under various environments. Furthermore, since each charging property can be stabilized for a long period of time, a more stable image can be obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-2-114269 (JP, A) JP-A-4-204663 (JP, A) JP-A-3-213877 (JP, A) JP-A-6- 230609 (JP, A) JP-A-57-101854 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) G03G 9/08 CA (STN) REGISTRY (STN)

Claims (4)

(57) [Claims] 1. A toner for developing an electrostatic charge image, comprising a compound represented by the following formula (1). [Chemical 1] 2. A kneaded and pulverized toner containing the compound according to claim 1. 3. A dispersion-polymerized toner containing the compound according to claim 1. 4. A suspension polymerization toner containing the compound according to claim 1.