• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A toner for electrostatic charge image developing containing carbon black dispersed in a well-dispersed state as well as a mixed charge control agent system containing a specific azo iron metal compound and an oxycarboxylic acid metal compound represented by the following formula (1) Lt; / RTI > The mixed charge control agent system exhibits an effect of synergistically improving the chargeability of spherical polymerized toner particles. The azo iron metal compound improves the dispersibility of carbon black in the toner particles. In the above formula, the definitions of R 1 to R 6 , n, n 'and A + are omitted.
    公开号:KR19980081071A
    申请号:KR1019980011797
    申请日:1998-04-03
    公开日:1998-11-25
    发明作者:도시유끼 우가이；가즈미 요시자끼
    申请人:미따라이후지오；캐논가부시끼가이샤；
    IPC主号:
    专利说明:

    Toner for developing an electrostatic latent image and method for manufacturing the same
    The present invention relates to a toner for developing an electrostatic latent image used in electrophotography and the like, and a method for producing such a toner.
    Until now, a lot of electronic photography is known. In such a method, generally, after the electrostatic latent image is formed on the image bearing member (photosensitive member) containing the photosensitive material by various means, the latent image is developed and visualized by the toner, Transferred onto a transfer (receiving) member, and then fixed by heating and / or compression as necessary to obtain a copy or printed matter.
    As printing apparatuses, LED printers and LBP printers are mainly used in accordance with the market demand, and these printers are required to have higher resolutions, that is, 400, 600 and 1200 dpi, compared with the conventional level of 240 to 300 dpi. Accordingly, there is a need for a development plan for achieving higher resolution. In addition, higher performance is required in copying apparatuses, and this demand is predominantly toward a digital image forming technology. The digital image forming method mainly involves using a laser for electrostatic charge image development for high resolution. Therefore, a development plan having high resolution and high definition as in the case of a printer is required. In accordance with this demand, the use of toners having smaller particle sizes has become common, and for example, Japanese Unexamined Patent Publication Nos. 1-112253, 1-191156, 2-214156, 2-294158 , JP-A-3-181952 and JP-A-4-162048 propose toners having a small particle size and a specific particle size distribution.
    The toner image formed on the photosensitive member in the developing step is transferred onto the transfer material in the transferring step, and the transfer residual toner remaining on the photosensitive member is cleaned in the cleaning step and is recovered in the waste toner container. In the cleaning step, a blade cleaner, a fur brush cleaner, a roller cleaner, and the like are generally used. In view of the size of the apparatus, the size of the entire image developing apparatus is inevitably increased due to the inclusion of the above-described cleaning apparatus, which hinders reduction of the overall apparatus size. Further, in view of environmental hygiene and effective toner utilization, it is preferable that the image forming system has a low waste toner and that the toner exhibits a good transfer efficiency.
    For this reason, various attempts have been made to improve the transferability of the toner. As an example of such an attempt, there has been attempted to reduce the frictional force acting between the photosensitive member and the cleaning member by increasing the sphericity and surface smoothness of the toner and prolonging the life of the photosensitive member. As a result of these factors, attempts have been made to increase the transfer efficiency by reducing the contact area between the toner and the photosensitive member and reducing the adhesive force of the toner acting on the photosensitive member.
    As a method for producing such a spherical and smooth surface toner, a polymerization method can be mentioned. When conventional toner particles are produced through a pulverization method, the toner composition melt-kneaded under heating is cooled and then pulverized. The toner particles obtained by the pulverization step cause irregular shapes and uneven surfaces. On the contrary, in the toner production through the polymerization method proposed in Japanese Patent Publication No. 36-10231, since toner particles are directly produced by suspension polymerization, it is possible to obtain spherical and smooth surface toner particles.
    However, such spherical smooth toner particles have a small contact area with the charging member due to sphere formation and smoothness, so that the chargeability is likely to be very low in a high humidity environment. In order to alleviate this difficulty, there is a need to provide a toner material excellent in chargeability than conventional toner.
    By using the triboelectric charging property of the resin as the toner component, it is possible to provide a toner having a charge, but since the chargeability obtained by this method is small, the toner tends to cause a hazy and unclear image. Therefore, the addition of the chargeability imparting dye or pigment, and also the charge control agent, was performed to provide the toner having the desired triboelectric charging property.
    The toner containing the charge control agent tends to contaminate the toner carrying member such as the developing sleeve, so that the triboelectric charge provided to the toner is liable to decrease as the number of times of image formation increases, thereby lowering the image density. In addition, the charge control agent of a specific type is insufficient in the effect of imparting triboelectrification property, and therefore, is susceptible to temperature or humidity, thereby easily causing fluctuations in image density due to changes in environmental conditions. In addition, since the charge control agent of a specific type is poor in dispersibility with respect to the resin, the obtained toner tends to have non-uniform triboelectric charge among the individual toner particles, thereby causing a faint image. Further, since the charge control agent has a poor storage stability, the obtained toner tends to lower the triboelectric chargeability during long-term storage.
    Examples of currently known negative charge imparting charge control agents include metal complex salts of monoazo dyes; Metal complexes of salicylic acid, naphthonic acid and dicarboxylic acid; Copper phthalocyanine pigments and resins containing acid components. On the other hand, examples of positive charge-imparting agents include nigrosine dyes, azine dyes, triphenylmethane dyes, quaternary ammonium salts and quaternary ammonium salts branched resins.
    Specifically, Japanese Patent Publication Nos. 43-17955, 55-42752, 61-155464, 63-1994 and 8-272146 disclose a negative charge control agent Various metal complexes have been proposed. Such metal complexes exhibit substantially good charging performance, but are insufficient for spherical smooth toner particles as described above, and thus there is room for improvement.
    On the other hand, the poor dispersibility of carbon black is a problem, and this problem is more serious in manufacturing toners according to the polymerization method, and thus this also needs to be improved.
    SUMMARY OF THE INVENTION An object of the present invention is to provide a toner for electrostatic latent image development in which the above-mentioned problems are solved.
    A more specific object of the present invention is to provide a toner for developing electrostatic images having excellent transferability.
    It is still another object of the present invention to provide a toner for electrostatic latent image development that exhibits good chargeability in various environments including a high temperature / high humidity environment and a low temperature / low humidity environment.
    It is still another object of the present invention to provide an electrostatic latent image toner which can continuously provide a high quality image for a long period of time.
    It is still another object of the present invention to provide a method for appropriately manufacturing such a toner.
    BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a diagram schematically showing a relationship between a transfer efficiency and a shape coefficient of a toner. Fig.
    2 is a diagram schematically showing a relationship between a friction load (reciprocal of the degree of lubrication exhibited by the toner) applied to the photosensitive drum and a shape coefficient of the toner.
    Fig. 3 schematically shows an example of an image forming apparatus to which the toner of the present invention is suitably applicable. Fig.
    DESCRIPTION OF THE REFERENCE NUMERALS
    1: photosensitive drum (image bearing member)
    2: drum charger
    3: developing unit
    3a - 3d: developing device
    4: Warrior Charger
    5: Cleaning device
    6: Recording material
    7: Fixing device
    8: recording material carrying member
    9: Exposure lamp
    10: Cassette
    11: Fixing roller
    12: Pressure roller
    13: Polygon mirror
    According to the present invention, there is provided a process for producing a polymerizable monomer composition comprising a polymerizable monomer, carbon black, an azo iron compound represented by the following formula (1) and an oxycarboxylic acid metal compound,
    Dispersing the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition, and
    A binder resin, carbon black, an azo iron compound represented by the following formula (1) and an oxycarboxylic acid metal compound represented by the following formula (1), which are prepared by polymerizing a polymerizable monomer in the form of particles to form toner particles containing a polymerized monomer as a binder resin: There is provided an electrostatic latent image developing toner comprising toner particles containing a compound.
    Formula 1
    Wherein R 1 and R 3 are independently selected from the group consisting of hydrogen, C 1-18 alkyl, C 2-18 alkenyl, sulfonamido, mesyl, sulfonic acid group, hydroxy, C 1-18 alkoxy, acetylamino, benzoylamino , A halogen atom or -O CO R 7 wherein R 7 is alkyl or aryl, n and n 'are an integer of 1 to 3,
    R 2 and R 4 independently represent hydrogen or nitro,
    R 5 and R 6 are independently hydrogen, halogen, nitro, carboxy, C 1-18 alkyl, C 2-18 alkenyl, C 7-18 aralkyl, C 1-18 alkoxy, C 6-18 aryl, -O · CO · R 7 wherein R 7 is C 1-18 alkyl or C 6-18 aryl, or (Wherein m is an integer of 1 to 3, and X represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen)
    A + is H +, Na +, K + , NH 4 + , or represents a mixture of these ions.
    According to still another aspect of the present invention, there is provided a process for producing a polymerizable monomer composition, comprising the steps of: (i) preparing a polymerizable monomer composition containing a polymerizable monomer, carbon black, an azo iron compound represented by the above formula (1) and an oxycarboxylic acid metal compound,
    (ii) dispersing the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition, and
    (iii) polymerizing the polymerizable monomer in the form of particles to form toner particles containing a polymerized monomer as a binder resin.
    These and other objects, features and advantages of the present invention will become more apparent upon consideration of the following description of preferred embodiments of the present invention with reference to the accompanying drawings.
    As described above, spherical toner particles having a smooth surface are liable to exhibit low chargeability in a high humidity environment, and accordingly, it is easy to provide an image involving toner scattering or fogging. On the other hand, if the chargeability is increased to solve this problem, the obtained toner is liable to be excessively charged in a low humidity environment, resulting in a low image density and a reduction in transfer efficiency.
    The present inventors have solved the problem by using a special azo iron compound and an oxycarboxylic acid metal compound together.
    A developer containing an organic acid metal compound widely used as a charge control agent may exhibit relatively high chargeability in some cases, but may easily exhibit a decrease in chargeability in a high humidity environment and a decrease in a charge speed in a low humidity environment.
    As one of the causes of the phenomenon, adsorption and desorption of moisture to a region close to a metal can be considered. More specifically, in a high humidity environment, the moisture adsorbed on the metal compound is increased to lower the chargeability, and in a low-humidity environment, the adsorbed moisture decreases and the resistivity becomes higher, which leads to a decrease in the charging speed.
    On the other hand, when a developer containing an oxycarboxylic acid which is considered to have a low negative charge density to carboxyl group oxygen in the organic acid is used, high charging performance can be obtained. This is probably because the electron density of the metal bound to the carboxyl group oxygen is not so increased when the negative charge density is low, so that the metal compound can exhibit a high magnetostatic property.
    Aromatic oxycarboxylic acids have been found to exhibit particularly high efficacy. The reason for this is not clear yet, but the aromatic oxycarboxylic acid has a resonance structure to provide a lower negative charge density to the carboxyl oxygen and to a sterically large structure suitable for blocking water molecules from bound metal atoms .
    Incidentally, it is also possible to use a salicylic acid chromium compound of Japanese Patent Publication No. 55-42752, a zinc salicylate compound of Japanese Patent Publication Nos. 63-2074 and 63-33755, Japanese Patent Publications No. 63-208865, 63-237065, A number of developers containing an oxycarboxylic acid metal compound have been proposed including aluminum salicylate compounds of U.S. Pat.
    However, according to the studies of the present inventors, in the case of using the spherical smooth surface toner sketched in the present invention, the oxycarboxylic acid metal compound alone exhibits a large difference in charge amount in the initial stage of continuous image formation and in the steady state A toner having a slow charging speed and a reduced image density can be obtained.
    As a result of a subsequent study to solve this problem, the present inventors have found that by using an azo iron compound in combination, it is possible to prevent the lowering of the charging speed in a low-humidity environment and further to provide an improved charging property in a high humidity environment .
    On the other hand, when the azo iron compound is used alone as the charge control agent, it is possible to obtain a satisfactory charge speed without difficulty due to a low charge amount at the time of start-up, but the chargeability in a normal state is low, It is liable to cause scattering and fogging.
    However, as a result of research conducted by the inventors of the present invention, it has been found that when a specific azo iron compound and an oxycarboxylic acid metal compound are used together, a greater effect than the sum of the effects obtained by using the individual compounds alone is obtained, It can be done.
    Although the reason for the above improvement is not yet clear, it is presumed that the co-dispersion of the individual compounds may be better in combination with the above compounds, leading to more effective performance and better environmental characteristics.
    The toner composition of the present invention shows a great effect on a spherical smooth surface toner containing carbon black as a coloring agent formed through a polymerization process and makes it possible to exhibit remarkably improved chargeability in such a high humidity environment.
    The reason for this improvement is not clear yet, but may be due to the dispersibility of the carbon black, which is remarkably improved by the combination of the azo iron compound with the polymerizable monomer composition. As a result, in the obtained toner particles, formation of a conduction path due to insufficient dispersion of the conductive carbon black is suppressed, exposure of the carbon black to the surface of the toner particles is suppressed, and charge leakage is suppressed and the electrification property is increased.
    As a result of further studies by the present inventors, it has been found that it is preferable to add the azo iron compound and the oxycarboxylic acid metal compound in an amount of A part by weight and B part by weight, respectively, satisfying the condition of 0.1 ≦ A / B ≦ 20. This condition is preferable in order to ensure the effect of the above-mentioned combination. Outside this range, a poor charging speed at the time of starting in a low-humidity environment considered to be caused by a change in the dispersion state of the individual compound and a decrease in charging property in a high-humidity environment are caused, I can not.
    The structure of the azo iron compound used in the present invention is represented by the following formula (1).
    Formula 1
    Wherein R 1 and R 3 are independently selected from the group consisting of hydrogen, C 1-18 alkyl, C 2-18 alkenyl, sulfonamido, mesyl, sulfonic acid group, hydroxy, C 1-18 alkoxy, acetylamino, benzoylamino , A halogen atom or -O CO R 7 , wherein R 7 is C 1-18 alkyl or C 6-18 aryl, n and n 'are an integer of 1 to 3,
    R 2 and R 4 independently represent hydrogen or nitro,
    R 5 and R 6 are independently hydrogen, halogen, nitro, carboxy, C 1-18 alkyl, C 2-18 alkenyl, C 7-18 aralkyl, C 1-18 alkoxy, C 6-18 aryl, -O · CO · R 7 wherein R 7 is alkyl or aryl having up to 18 carbon atoms each, or (Wherein m is an integer of 1 to 3, and X represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen)
    A + is H +, Na +, K + , NH 4 + , or represents a mixture of these ions.
    Here, lower alkyl and lower alkoxy mean an alkyl group and an alkoxy group, respectively, having not more than 5 carbon atoms (i.e., C 1 -C 5 ).
    A preferred class of the azo iron compounds used in the present invention may have a structure represented by the following formula (2).
    As can be seen from the comparison of formulas (1) and (2), formula (2) is obtained by replacing the R 5 and R 6 groups of formula (1)
    And
    X 1 and X 2 independently represent hydrogen, lower alkyl, lower alkoxy, nitro or halogen, and m and m 'are an integer of 1 to 3.
    In formula (2), R 1 to R 4 , n, n 'and A + are as shown in formula (1).
    Specific examples of the azo iron compounds preferably used in the present invention include the following azo iron compounds (1) to (6).
    The azo iron compound (1)
    The azo iron compound (2)
    Azo iron compound (3):
    The azo iron compound (4)
    Azo iron compound (5):
    The azo iron compound (6):
    The azo iron compound used in the present invention can be generally formed by coupling reaction of diazo-substituted aminophenol and substituted naphthol, and reacting the coupling product with a salt of iron such as iron sulfide.
    The azo iron compound may be used in an amount of 0.1 to 8 parts by weight, preferably 0.1 to 6 parts by weight, per 100 parts by weight of the binder resin. If the amount is less than 0.1 part by weight, the above-mentioned effect is hardly exhibited. If the amount is more than 8 parts by weight, the charging member tends to be contaminated.
    Examples of the oxycarboxylic acid constituting the oxycarboxylic acid metal compound used in the present invention include malic acid, dimethylolbutanoic acid, tartaric acid, citric acid, salicylic acid and naphthoic acid. Of these, alkylsalicylic acids and dialkylsalicylic acids containing an alkyl group having 5 or fewer carbon atoms are preferred, with 3,5-dialkylsalicylic acid being particularly preferred. As the alkyl group, t-butyl group is most preferable.
    Specific examples of the oxycarboxylic acid include 2-hydroxy-3-naphthoic acid, alkyl-2-hydroxy-3-naphthoic acid having an alkyl group of 5 or less carbon atoms, 2-hydroxy-3-naphthoic acid.
    On the other hand, examples of the metal species constituting the oxycarboxylic acid metal compound include aluminum, zinc, chromium, cobalt, nickel, copper, iron and zirconium. Among them, aluminum and zinc compounds are particularly preferable when they are used together with an azo iron compound.
    Preferable examples of the oxycarboxylic acid metal compound include those represented by the following structural formula (A + represents hydrogen, an alkali metal or an alkaline earth metal ion).
    The oxycarboxylic acid metal compound may be used in an amount of 0.1 to 10 parts by weight, preferably 1 to 6 parts by weight, per 100 parts by weight of the binder resin. As with the case of the azo iron compound, if the amount is less than 0.1 parts by weight, the above effect is hardly exhibited. If the amount is more than 10 parts by weight, contamination of the charging member tends to occur.
    The toner particles of the present invention preferably have a shape factor SF-1 of 100 to 140 and a SF-2 of 100 to 120.
    The shape factors SF-1 and SF-2 referred to herein are based on values measured in the following manner. Sample particles were observed through a field emission scanning electron microscope (FE-SEM S-800, available from Hitachi Seisakusho KK) at a magnification of 1000 times, and 100 images of toner particles having a particle size (diameter) of 2 탆 or more were randomly Collect. The image data is input to an image analyzer (Luzex 3, available from Nireco K.K.) to obtain an average of shape coefficients SF-1 and SF-2 according to the following equations (1) and (2).
    SF-1 = [(MXLNG) 2 / AREA] x ( / 4) x 100
    SF-2 = [(PERI) 2 / AREA] x (1/4 ) X 100
    In the above equation, MXLNG represents the maximum length of the sample particles, PERI represents the periphery of the sample particles, and AREA represents the projected area of the sample particles.
    The shape factor SF-1 indicates the roundness of the toner particles, and when the shape factor SF-1 is greater than 140, it means that the shape of the toner particles deviates from the spherical shape and becomes amorphous. The shape factor SF-2 indicates the roughness of the toner particles, and the shape factor SF-2 greater than 120 indicates the remarkable surface roughness of the toner particles.
    Adjusting the shape coefficient of the toner to a small value as described above is advantageous in the following aspects. First, the toner can be transferred with high efficiency as the toner has a smaller contact area with the photosensitive member and shows a lower adhesion force.
    FIG. 2 is a graph showing the relationship between the transfer efficiency and the shape coefficient. As shown in the figure, when the shape coefficient is small, a high transfer efficiency is obtained. As a result, the amount of transfer residual toner recovered in the cleaning apparatus can be reduced, thereby reducing the size of the cleaning apparatus.
    The second advantage is that if the surface is smooth and uniform spherical toner particles are used, the charge of the toner after being transferred onto the transfer material becomes uniform, so that the transferred toner image again becomes an image It is possible to prevent the re-transfer phenomenon that the once transferred toner image is peeled off and attached to the photosensitive drum. As a result, the toner image on the transfer material is not disturbed, and a high-quality image is obtained.
    Thirdly, the use of a photosensitive drum with a smaller diameter becomes possible. More specifically, by using spherical smooth surface toner particles represented by small shape coefficients, it is possible to reduce the frictional force acting between the photosensitive drum and the cleaning member, thereby preventing the wear of the photosensitive drum.
    Fig. 2 is a graph showing the relationship between the load (which is applied by the cleaning member as the inverse of the lubrication degree of the toner particles) and the shape coefficient of the toner particles. 2 is based on measurement of a friction load (minimum traction force) against movement when the toner particles are applied to a glass sheet and then placed on a urethane rubber sheet having a load of 300 g and pulled in a horizontal direction parallel to the glass sheet . As shown in Fig. 2, the toner particles having a small shape coefficient exhibit a high degree of lubrication (low load). This was confirmed by the significantly reduced wear and extended life of the photosensitive drum.
    However, the use of such a spherical smooth surface toner, which is represented by a small shape factor, is disadvantageous in terms of chargeability because of the reduction of the contact point between the toner surface and the charging member as compared with the above amorphous toner, And fog.
    However, in the present invention, as described above, by mixing a special azoiron compound and an oxycarboxylic acid metal compound, it is possible to secure a good chargeability level even though the toner particles exhibit a small shape factor, thereby achieving high transfer efficiency, Allows the use of diameter drums.
    The toner particles according to the present invention having such a low shape factor can be obtained by a suspension polymerization method for direct toner production as described in Japanese Patent Publication No. 36-10231, Japanese Patent Laid-Open Nos. 59-53856 and 59-61842, The polymer which is soluble but which is produced is represented by a dispersion polymerization method for direct toner production using an insoluble aqueous organic solvent and a soap-free polymerization method in which the toner is directly produced by polymerization in the presence of a water-soluble polar polymerization initiator And may be produced through a polymerization method such as an emulsion polymerization method.
    In the present invention, suspension polymerization under normal pressure or elevated pressure, in which fine toner particles having a diameter of 3 to 10 mu m are relatively easily provided with a sharp particle size distribution and whose shape factor SF-1 can be easily adjusted to 100 to 140 and SF- It is particularly desirable to adopt the law. The adjustment of the average particle size and particle size distribution can be effected by controlling the type and amount of the dispersing agent which functions as the poorly soluble inorganic salt or protective colloid and the mechanical conditions including the stirring conditions or the container shape such as the rotor circumferential speed, the number of passes and the stirring blade shape, Can be achieved by changing the solid content concentration of the medium.
    The toner according to the present invention can be made of conventional toner-constituting resins including styrene polymers, styrene-acrylic copolymers and styrene-methacrylic copolymers.
    Corresponding monomers can be used in the direct preparation of toner particles through polymerization. Specific examples thereof include styrene monomers such as styrene, o- (m-, p-) methylstyrene and m- (p-) ethylstyrene; Acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl Acrylate monomers such as behenyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate; Butadiene, isoprene, cyclohexene, (meth) acrylonitrile and acrylamide. These monomers may be used alone or in admixture as described in Polymer Handbook 2, III, pp. 139-192 (John Wiley Son)], the glass transition temperature (Tg) is in the range of 40 to 75 ° C. In theory, when the glass transition temperature is lower than 40 占 폚, the storage stability or continuous image-forming ability of the resultant toner or developer tends to be inferior. On the other hand, if the temperature exceeds 75 캜, the fixing temperature of the resulting toner tends to rise, and in particular, the color mixing property is insufficient, resulting in a poor color reproducibility in the case of a toner for color image formation. In addition, the transparency of the OHP image can be remarkably lowered and high quality can not be expected.
    The molecular weight and distribution of the binder resin can be calculated through GPC (gel permeation chromatography) measurement. For the specific GPC measurement, the toner sample is extracted with a toluene solvent for 20 hours using a Soxhlet extractor, and toluene is then distilled off from the extract using a rotary evaporator. Then, an organic solvent which can dissolve the ester wax like chloroform but does not dissolve the binder resin is added, and the remaining extract is thoroughly washed and dissolved in THF (tetrahydrofuran). The resulting THF solution is filtered through a solvent-resistant membrane filter having a pore diameter of 0.3 [mu] m. The GPC device (GPC-150C, available from Waters Co.) is then used with a combination of A-801, 802, 803, 804, 805, 806 and 807 columns available from Showa Denko KK , And the molecular weight distribution can be obtained by referring to a calibration curve obtained using a standard polystyrene resin sample. As a result of such GPC measurement, the binder resin constituting the toner according to the present invention has a number average molecular weight (Mn) of 5,000 to 10 5 , and a ratio (Mw / Mn) of a weight average molecular weight (Mw) 2 < / RTI >
    The toner particles may contain a polar polymer or a copolymer as a result of adding the polar polymer or copolymer to the polymerizable monomer composition.
    Examples of such polar or polar copolymers include polymers of nitrogen-containing monomers such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate, and copolymers of such nitrogen-containing monomers with styrene monomers; Styrene-unsaturated carboxylic acid ester copolymers; Halogen-containing monomers such as vinyl chloride, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, polymers of monomers including unsaturated dicarboxylic acids, unsaturated dicarboxylic acid anhydrides and nitro group-containing monomers, and monomers containing styrene monomers such as Copolymer; Polyester resins, polycarbonate resins, and epoxy resins.
    In the toner according to the present invention, carbon black is used as a colorant. (BET specific surface area (S BET ) of not more than 100 m 2 / g, a pH of not less than 2.0, a volatile content of not more than 2 wt%, and DBP (dibutyl phthalate) absorption It is particularly preferable to use carbon black having a viscosity of 50-200 ml / 100 g.
    The carbon black may have an average primary particle size of 10 to 70 nm, more preferably 20 to 60 nm, still more preferably 25 to 45 nm. When the average major particle size of the carbon black is less than 10 nm, the polymerizable monomer composition containing the carbon black and the specific azo iron compound tends to have an excessively large viscosity, and it becomes difficult to form fine particles without aggregation. Also, it is difficult to disperse the carbon black into the polymerizable monomer composition because of the main particle size being too small. On the other hand, if the average major particle size of the carbon black exceeds 70 nm, only a low coloring ability can be obtained even if the carbon black is well dispersed, and if the carbon black is used in a large amount to increase the coloring ability, .
    The pH of the carbon black is preferably 2.0 or more, more preferably 4.0 or more. If the pH of the carbon black is less than 2.0, carbon black has a lot of functional groups, and they are liable to inhibit polymerization.
    The specific surface area (S BET ) of the carbon black is preferably 100 m 2 / g or less, more preferably 30 to 90 m 2 / g, and still more preferably 40 to 90 m 2 / g. The volatile matter content of the carbon black is preferably 2% by weight or less, more preferably 0.1 to 1.8% by weight, further preferably 0.1 to 1.7% by weight. If the specific surface area exceeds 100 m 2 / g, the polymerization tends to be suppressed. The volatile water content exceeding 2% by weight means that a large amount of polymerization inhibitor is not suitable for providing the polymerized toner according to the present invention.
    The DBP absorption of the carbon black is preferably 50 to 200 ml / 100 g, more preferably 110 to 200 ml / 100 g, and still more preferably 120 to 160 ml / 100 g. If the DBP absorption is less than 50 ml / 100 g, the carbon black can not be sufficiently dispersed in the toner particles, so that it tends to exhibit a low coloring ability. If it exceeds 200 ml / 100 g, the produced toner particles have excessively high conductivity, resulting in low electrification property in a particularly high humidity environment.
    The carbon black may be added in an amount of 1 to 20 parts by weight per 100 parts by weight of the binder resin. In order to exhibit good dispersibility, it is more preferred that 3 C / A 50 is satisfied with respect to A part by weight of the azo iron compound. More preferably 3 parts by weight C / A 38.
    When the amount of the azo iron compound is relatively low (C / A 50) as compared with that of carbon black, the viscosity of the polymerizable monomer composition is not sufficiently raised, and it is difficult to stably disperse the carbon black. In this case, since the carbon black is gradually deposited over time, the resulting toner tends to fail to exhibit sufficient coloring ability.
    If the amount of the azo iron compound is excessively large (C / A 3) relative to that of the carbon black, the azo iron compound tends to cause secondary aggregation, which tends to exhibit low dispersibility in the polymerizable monomer. Secondary aggregates inhibit polymerization, Can be easily made to be recovered as toner particles.
    The effect of addition of the azo iron compound for improving the dispersibility of carbon black was confirmed, for example, by the following test. A polymerizable mixture consisting of 60 parts by weight of styrene, 1 part by weight of an azo iron compound and 10 parts by weight of carbon black was stirred for 180 minutes at 200 rpm using a stirrer. On the other hand, another polymerizable mixture was prepared similarly except that the addition of the azo iron compound was omitted. The two mixtures were tested as stationary for evaluation of dispersion stability. As a result, the mixture containing no azo iron compound precipitated after 3 days, while the mixture containing the azo iron compound was not precipitated even after 30 days of standing.
    The above mentioned values for various properties of carbon black are based on the values measured according to the following method.
    (1) DBP absorption degree
    DBP (dibutyl phthalate) was spotted on a carbon black dried sample (according to Japanese Industrial Standard K6221, method A).
    (2) Specific surface area (S BET ) based on nitrogen adsorption method
    Measured according to ASTM D3037.
    (3) Volatile water content
    Calculated by measuring the weight of the carbon black sample before and after heating (according to Japanese Industrial Standard K6221).
    (4) Average main particle size
    The number average major particle size was determined using a transmission electron microscope (according to ASTM D3849-89) at a magnification of 30,000 times for 100 randomly selected particles.
    (5) pH
    The carbon black sample is mixed with 10 ml of water per 1 g of carbon black, boiled together, cooled, and the supernatant is removed to leave a turbid sample, and the pH value is measured (according to Japanese Industrial Standard K6221).
    The toner according to the present invention is constituted by a black toner containing carbon black, but can also be used for forming a color image by using it in combination with yellow toner, magenta toner and cyan toner separately provided in addition to monochromatic use.
    Further, the toner according to the present invention can be made into either a non-magnetic toner or a magnetic toner. In the magnetic toner, 40 to 150 parts by weight of the powdery magnetic material per 100 parts by weight of the binder resin may be added.
    The toner particles used in the present invention include, for example, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobisisobutyronitrile, 1,1'-azobis Azo-1-carbonitrile), azo or diazo polymerization initiators such as 2,2'-azobis-4-methoxy-2,4-dimethylvaleronitrile and azobisisobutyronitrile, and benzoyl peroxide, Polymerization of a polymerizable monomer composition containing a peroxide type polymerization initiator such as methyl ethyl ketone peroxide, diisopropyl peroxycarbonate, cumene hydroperoxide, 2,4-dichlorobenzoyl peroxide and lauroyl peroxide Or by polymerization of the polymerizable monomer composition in the presence of the polymerization initiator.
    The amount of the polymerization initiator to be added may vary depending on the desired degree of polymerization of the binder resin, but may generally be in the range of 0.5 to 20% by weight of the polymerizable monomer. The specific polymerization initiator used may be somewhat different depending on the polymerization method, but the above-mentioned one or more polymerization initiators can be selected according to its 10-hour half-life temperature.
    In order to control the degree of polymerization, crosslinking agents, chain transfer agents, polymerization inhibitors, and the like known in the art may be further added.
    During the suspension polymerization to prepare the toner according to the invention, inorganic and / or organic dispersion stabilizers can be used in the aqueous dispersion medium. Examples of inorganic dispersion stabilizers include calcium phosphate, magnesium phosphate, aluminum phosphate, zinc phosphate, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, calcium metasilicate, calcium sulfate, barium sulfate, bentonite, silica and alumina . Examples of the organic dispersion stabilizer include polyvinyl alcohol, gelatin, methylcellulose, methylhydroxypropylcellulose, ethylcellulose, carboxymethylcellulose sodium salt and starch. These dispersion stabilizers are preferably used in an aqueous dispersion medium in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the polymerizable monomer.
    When an inorganic dispersion stabilizer is used, a commercially available product can be used as such, but in order to obtain fine particles of the stabilizer, a stabilizer may be formed in the dispersion medium. In the case of tricalcium phosphate, it is suitable to mix, for example, an aqueous solution of sodium phosphate and an aqueous solution of calcium chloride under strong stirring to produce tricalcium phosphate particles in an aqueous medium suitable for suspension polymerization. In order to finely disperse the dispersion stabilizer well, it is also effective to promote the predetermined function of the stabilizer by using 0.001 to 0.1% by weight of the surfactant in combination. Examples of the surfactant include sodium dodecylbenzenesulfonate, sodium tetradecyl sulfate, sodium pentadecyl sulfate, sodium octyl sulfate, sodium oleate, sodium laurate, potassium stearate and calcium oleate.
    When the toner according to the present invention is produced through direct polymerization, the toner particles can be directly produced in the following manner. After the addition of carbon black, a charge control agent, a polymerization initiator and other additives to the polymerizable monomer and uniformly dissolving or dispersing the mixture in a homogenizer or an ultrasonic disperser to form a polymerizable monomer composition, By controlling the agitation time, the droplets of the polymerizable monomer composition can be dispersed by a usual stirrer, homomixer or homogenizer under the condition that the desired particle size of the produced toner particles can be obtained, . Subsequently, stirring can be continued to such an extent as to keep the particles of the polymerizable monomer composition formed and to suppress sedimentation of the particles. The polymerization may be carried out at a temperature of 40 DEG C or higher, generally 50 to 90 DEG C. This temperature can be raised in the latter stage of the polymerization. It is also possible to distill a part of the aqueous system in a later stage of polymerization or after polymerization to remove part of the unpolymerized polymerizable monomer and the by-product which may generate an offensive odor in the toner fixing step. The color toner particles produced after the reaction are washed, filtered and dried. In suspension polymerization, it is generally preferred to use from 300 to 3,000 parts by weight of water per 100 parts by weight of the monomer composition as the dispersing medium.
    As a preferable method for more uniformly dispersing the carbon black, a masterbatch manufacturing process can be employed. Therefore, only carbon black and the azo iron compound are added to a part of the polymerizable monomer and mixed before carbon black, charge control agent, polymerization initiator and other additives are added to the polymerizable monomer. As a result, the carbon black is mixed at a higher concentration in the dispersion liquid and dispersed at a higher concentration, so that a high shear force is applied to the carbon black to improve the dispersion imparted by the addition of the azo iron compound and to improve the dispersibility of the carbon black have.
    The weight average particle size (D4) of the toner according to the present invention may be 3.0 to 10.0 mu m, preferably 3.0 to 8.0 mu m.
    Good high reproducibility can be obtained when the weight average particle size of the toner is 10.0 占 퐉 or less and a charge-up phenomenon or a reduction in image density in a particularly low humidity environment is less likely when the toner has a weight average particle size of 10.0 占 퐉 or less .
    The particle size distribution of the toner can be measured using a Coulter counter model TA-II or a Coulter multisizer (each manufactured by Electronics Inc.).
    In the measurement, a 1% NaCl aqueous solution can be prepared using reagent grade sodium chloride as an electrolytic solution. It is also possible to use ISOTON R-II (product of Scientific Japan K.K.). 0.1 to 5 ml of a surfactant, preferably an alkylbenzenesulfonate, is added as a dispersion medium to 100 to 150 ml of the electrolytic solution, and 2 to 20 mg of a sample is added. In order to obtain a volume-based distribution and a water-based distribution after dispersing the sample dispersion in the electrolytic solution produced by using the ultrasonic dispersing machine for about 1 to 3 minutes, the particle size distribution in an area of 2 탆 or more . The weight-average particle size (D4) and the number-average particle size (D1) can be obtained from the volume-based distribution and the number-based distribution using the median as a representative value for each channel, respectively.
    The toner according to the present invention can constitute a one-component developer or a two-component developer. In the case of providing a two-component developer for a magnetic brush developing method, the toner may be mixed with a carrier which may include ferrite, magnetite or iron powder optionally coated with an acrylic resin, a silicone resin, a fluorine-containing resin or the like. The toner according to the present invention may also constitute a one-component developer in the form of a magnetic toner or a non-magnetic toner.
    Fig. 3 shows an example of an image forming apparatus in which the toner of the present invention formulated with a two-component developer can be suitably used.
    3, the apparatus includes one photosensitive drum (image bearing member) 1 having a drum charger 2, an exposure lamp 9 and a polygonal mirror 13 for image light scanning arranged therearound And an image forming section provided. The laser light emitted from the light source (not shown) is scanned by the rotation of the polygonal mirror 13, deflected by the reflection mirror, focused by the f-theta lens to form focused scanning laser light, And forms an electrostatic latent image corresponding to the provided image signal.
    Subsequently, the latent image on the photosensitive drum 1 is developed with the developer in the developing apparatus 3a (or 3b - 3d) of the developing unit 3 to form a visible image (toner image) on the photosensitive drum 1. The recording material 6 as a transfer (storage) material stored in the cassette 10 is electrostatically transported by the transfer material transporting member 8 rotating simultaneously with the photosensitive drum 1 and transferred to the transfer site, Here, the toner image on the photosensitive drum 1 is transferred onto the recording material 6 by the action of the transfer charger 4.
    The above operation can be repeated in succession over a plurality of cycles to form a superimposed toner layer on one recording material 6 to be matched with each other. After the cycle is completed, the recording material 6 is separated from the recording material carrying member 8 by the action of a separation ring or the like, and is conveyed to the fixing device 7 by the conveying belt, The recording material 6 passing between the fixing roller 11 and the pressure roller 12 under the application of heat and pressure to provide a toner image fixed on the recording material by one fixing operation. The remaining toner particles remaining on the photosensitive drum 1 without being transferred onto the recording material are removed from the photosensitive drum 1 by the cleaning device 5. [
    Hereinafter, the present invention will be described more specifically based on examples and comparative examples, and parts used in the formulations are parts by weight unless otherwise specified.
    Production Example 1 of aluminum compound
    0.2 mol of di-t-butylsalicylic acid was added to 1 liter of a 0.25 mol / l NaOH aqueous solution and dissolved by heating. The solution was recovered by heating, and 0.05 mol / l of Al 2 (SO 4) 3 aqueous solution under stirring, and the mixture was filtered product was introduced into 1 liter under a neutral to slightly alkaline conditions. The recovered product was washed until the washings became neutral and then dried to recover the target di-t-butylsalicylic acid aluminum compound.
    In addition, the analysis of FE (Field Dispersion) mass spectrum of the product revealed that the product consisted mainly of a compound of oxycarboxylic acid and aluminum bonded at a molar ratio of 3: 2.
    Production example 2 of aluminum compound
    Hydroxynaphthalene-3-carboxylic acid aluminum compound was obtained through almost the same procedure as in Preparation Example 1, except that 2-hydroxynaphthalene-3-carboxylic acid was used instead of di-t-butylsalicylic acid. Of purity.
    Production Example 3 of zinc compound
    A zinc di-t-butylsalicylate compound was prepared by a synthetic method similar to Preparation Example 1, except that an aqueous solution of ZnSO 4 was used instead of the aqueous solution of Al 2 (SO 4 ) 3 .
    Preparation of polymerized toner Example A
    450 parts by weight of 0.1 M Na 3 PO 4 was added to 710 parts by weight of deionized water and the mixture was heated to 60 ° C and stirred at 12,000 rpm by a TK homomixer (manufactured by Tokushu Kika Kogyo KK) after, the addition of the CaCl 2 aqueous solution 68 parts by weight of an aqueous solution of 1.0 M to obtain an aqueous medium containing Ca 3 (PO 4) 2.
    Styrene 80 parts by weight
    20 parts by weight of n-butyl acrylate
    10 parts by weight of carbon black
    (D 1 (main) = 40 nm, S BET = 50 m 2 / g, pH = 7.0, DBP absorption = 137 ml / 100 g)
    Di-t-butylsalicylic acid Al compound 1 part by weight
    1 part by weight of the azo iron compound (1)
    Saturated polyester resin 5 parts by weight
    (P MW (peak molecular weight = 7600; AV (acid value) = 8 mgKOH / g)
    Ester wax (T mp = 75 캜) 15 parts by weight
    The above components were heated to 60 DEG C and stirred at 12,000 rpm by a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) for uniform dissolution and dispersion, and 2,2'-azobis (2,4-dimethylvalero Nitrile) was dissolved to form a polymerizable monomer composition.
    Separately, the same composition was prepared except that no polymerization initiator was added, and the mixture was allowed to stand for evaluation of dispersion stability. As a result, no precipitation was observed even after 30 days of standing.
    The polymerizable monomer composition was added to the aqueous medium prepared above and stirred at 10,000 rpm in a N 2 atmosphere at 60 ° C for 10 minutes by means of a TK homomixer to form particles of the polymerizable monomer composition. The reaction system was then agitated using a paddle stirring blade and heated to 80 DEG C for 10 hours of the reaction. After the polymerization reaction, the residual monomer was distilled off under reduced pressure, and after cooling, hydrochloric acid was added to the reaction system to dissolve calcium phosphate. The polymerized particles were then filtered, washed and dried to obtain polymerized toner particles A having a weight average particle size of about 7.5 μm and a sharp particle size distribution. The properties of the toner particle A are shown in Tables 3 and 4 together with the characteristics of the toner particles prepared in the other production examples described below.
    98.5 parts by weight of the toner particles A thus prepared were mixed with 1.5 parts of hydrophobic silica having a BET specific surface area (S BET ) of 200 m 2 / g to obtain a toner A (polymerized toner), and 5 parts of the toner were mixed with an acrylic resin- coated magnetic ferrite carrier 95 To obtain a developer A (two-component developer).
    As a result of measuring the shape factor, toner A showed SF-1 = 111 and SF-2 = 109.
    Preparation Example B-S for Polymerized Toner
    Toner particles B-S were prepared in a similar manner to Production Example A, except that the types and amounts of the azo iron compounds and oxycarboxylic acid metal compounds shown in Tables 1 and 2 were changed. Subsequently, the toner particles B-S were further mixed with the acrylic resin-coated magnetic ferrite carrier with toner B-S by the external addition of hydrophobic silica similarly to Production Example A to form a developer B-S.
    Separately, the same polymerizable monomer composition was prepared except that no polymerization initiator was added in Production Example L for providing a polymerization toner L containing no azo iron compound, and the resulting dispersion was allowed to stand for evaluation of dispersion stability. As a result, During the day, the carbon black settled.
    Production Example of Polymerized Toner T
    Styrene 60 parts
    Carbon black 10 parts
    Azo iron compound (1) 1 part
    To disperse the above components, a masterbatch dispersion was formed by stirring for 3 hours in a friction stirrer (Attritor 1S, manufactured by Mtrsui Kozan K.K.).
    71 parts of the master batch dispersion prepared above
    Styrene 20 parts
    20 parts of n-butyl acrylate
    Di-t-butylsalicylic acid Al compound 1 part
    Saturated polyester resin 5 parts
    Ester wax 15 parts
    The components were heated to 60 DEG C and stirred at 12,000 rpm with a TK homomixer to homogeneously dissolve and disperse 5 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) to obtain a polymerizable monomer composition .
    Toner particles T were prepared using the polymerizable monomer composition in the same manner as in Production Example 1. Toner T and Developer T (two-component system) were prepared from Toner Particle T in a manner similar to Production A.
    Examples 1 to 17 and Comparative Examples 1 to 3
    After each of the toner AS (developer AS) prepared above was modified to provide a variable developing contrast for a black type image formation test, a commercially available color copying machine (CLC-500, Black type image forming test was carried out using a commercially available product of Kikai Kaisha.
    (HT / HH = 30 ° C / 80% RH) and / or high temperature / low humidity (NT / LH = 23 ° C / 5% RH) RH), 400 volts for NT / LH, 320 volts for NT / NH, and 250 volts for HT / HH under the following methods and evaluation standards: transfer efficiency, onset chargeability, charge stability, , Fog and image density of each toner were evaluated.
    (1) Transfer efficiency
    In the environment of N.T./L.H., a solid black image was formed on the photosensitive drum and recovered by adhesion with a transparent adhesive tape. The image density D1 of the toner image recovered by a color reflection density meter (X-RITE-404A, manufactured by X-Rite Co.) was measured. Subsequently, the solid black image was formed on the photosensitive drum again, transferred to the recording material, and the solid black image on the recording material was recovered by bonding with the same transparent adhesive tape. The image density (D2) of the recovered image was measured and the transfer efficiency was determined from the measured image densities (D1 and D2) according to the following equation (3).
    Transfer efficiency (%) = (D 2 / D 1) x 100
    (2) Starting charging property
    Each toner was idle for 3 minutes in an NT / LH environment, and then continuous copying test was performed on 1000 sheets. Charge (TC 0 ) in the initial stage of image formation and charge (TC 1000 ) And the developer on the developing sleeve in the developing device was measured. The starting charging performance was evaluated according to the following standard based on the turn-off value determined according to the following equation (4).
    Get off (%) = | (TC 1000 -TC 0 ) / TC 1000 | x 100
    A: 0 to 10%
    B: 11 to 20%
    C: 21 to 30%
    D: 31 to 40%
    E: 41 to 50%
    F: ≥ 51%
    (3) Stability of competition
    Each toner was subjected to a continuous radiation test for 50,000 sheets in the HT / HH environment and the toner charge (TC 1000 and TC 50000 ) for the 1000th paper and 50,000th paper was measured for the developers in the developing sleeve . Stability of Daejeon is getting off (%) = | (TC 50,000 -TC 1000 ) / TC 50,000 | x < RTI ID = 0.0 > 100 < / RTI >
    A: 0 to 10%
    B: 11 to 20%
    C: 21 to 30%
    D: 31 to 40%
    E: 41 to 50%
    F: ≥ 51%
    (4) Toner scattering
    For each toner, N.T./N.H. Continuous image formation for 50,000 sheets was performed in the environment. Then, the developing device was collected from the image forming apparatus and installed in the idle rotating apparatus. The A4 paper was placed directly underneath the developing sleeve of the developing unit and the sleeve was idled for 10 minutes to measure the weight of the toner that fell on the A4 paper. Toner scattering was evaluated based on toner weight (rounded value) according to the following standard.
    A: ≤ 3 mg
    B: 4 to 6 mg
    C: 7 to 9 mg
    D: 10 to 12 mg
    E: 13 to 15 mg
    F: ≥ 16 mg
    (5) Fog
    H.T./H.H. And the reflection density of the white background portion of the white paper after image formation was measured by a reflection density meter (TC6MC, manufactured by Y.K. Tokyo Denshoku Gijutsu Center). The increase in the measured image density with respect to the reflection image density of the blank paper before image formation was defined as the increase rate (%) with respect to the blank image density. The fog was evaluated on the basis of the increase rate (rounded value) according to the following standard.
    A: 0 ≤ 5%
    B: 0.6 to 1.0%
    C: 1.1 to 1.5%
    D: 1.6 to 2.0%
    E: 2.1 to 4.0%
    F: ≥4.1%
    (6) Image density
    After solid black images were formed in the initial stage and continuous images were formed for 30,000 sheets, the image density of each solid black image was measured with a Macbeth density meter.
    The evaluation results of the respective toners are shown in Table 5.
    The polymerizable monomer composition (each composition further contains 80 parts by weight of styrene (St), 20 parts by weight of n-butyl acrylate (n-BA), 5 parts by weight of saturated polyester and 15 parts by weight of ester wax) Toner particlesCarbon black (parts by weight)Oxycarboxylic acid metal compound (parts by weight)Azo iron compound (parts by weight) A101.01.0 B101.01.0 C101.01.0 D101.01.0 E100.21.0 F103.20.2 G107.51.0 H100.53.0 I102.50.1 J109.01.0 K102.012 L101.00 M1001.0 N101.01.0 O102.09.2 P101.01.0 Q105.03.0 R103.05.0 S101.01.0 T101.01.0
    The azo iron compound and oxycarboxylic acid metal compound used in each toner tonerAzo iron compoundOxycarboxylic acid metal compoundA / B KindsContent A (parts by weight)KindsContent B (parts by weight) A(One)OneDTBSAlOneOne B(One)One2HN3CAlOneOne C(2)OneDTBSAlOneOne D(One)OneDTBSZnOneOne E(One)0.2DTBSAlOne0.2 F(One)3.2DTBSAl0.216 G(One)7.5DTBSAlOne7.5 H(One)0.52HN3CAl30.17 I(One)2.5DTBSAl0.125 J(One)9DTBSZnOne9 K(One)2DTBSAl120.16 L(One)One--- M--DTBSAlOne- N(One)OneDTBSCoOneOne O(One)2DTBSAl9.20.22 P(7)OneDTBSAlOneOne Q(One)5DTBSAl31.7 R(One)3DTBSAl50.6 S(One)OneAcAcCoOneOne T(One)OneDTBSAlOneOne DTBSAl = di-t-butyl salicylic acid aluminum compound 2HN3CAl = 2-hydroxynaphthalene-3-carboxylic acid aluminum compound DTBSZn = di-t-butyl zinc salicylate compound DTBSCo = di-t-butyl salicylic acid cobalt compound AcAcCo = Cobalt compound
    Toner particle composition (for analysis) Toner particlesSt (parts by weight)n-BA (parts by weight)Carbon black (parts by weight)Oxycarboxylic acid metal (parts by weight)Azo iron (parts by weight)Saturated polyester (parts by weight)Ester wax (parts by weight) A60.415.27.60.80.83.811.4 B60.415.27.60.80.83.811.4 C60.415.27.60.80.83.811.4 D60.415.27.60.80.83.811.4 E61.015.27.60.20.83.811.4 F60.015.07.52.40.13.811.2 G57.814.57.25.40.73.610.8 H59.915.07.50.42.33.711.2 I60.315.17.61.90.13.711.3 J57.114.37.26.40.73.610.7 K55.613.96.91.48.33.510.4 L61.015.37.60.803.811.5 M61.015.37.600.83.811.5 N60.415.27.60.80.83.811.4 O56.714.27.11.46.53.510.6 P60.415.27.60.80.83.811.4 Q58.014.57.23.62.23.610.9 R58.014.57.22.23.63.610.9 S60.415.27.60.80.83.811.4 T60.415.27.60.80.83.811.4
    Shape coefficient and size of toner particles Toner particlesSF-1SF-2Weight average particle size D4 (占 퐉) A1101096.5 B1111106.6 C1101106.4 D1121116.6 E1121116.6 F1101136.9 G1111136.8 H1151146.8 I1121106.6 J1151166.9 K1121137.0 L1091096.6 M1141136.9 N1121106.6 O1121147.0 P1141136.6 Q1121106.7 R1131116.8 S1111136.4 T1111106.5
    Toner evaluation resulttonerTransfer efficiency (%)Initially charged (N.T./L.H.)H.T./H.H. Stability of competitionToner scatteringFogImage density EarlyAfter 30000 sheets Example 1A98AAAA1.501.48 2B97AAAA1.491.47 3C98AAAA1.511.49 4D98AAAA1.501.48 5E98ABAA1.491.46 6F97BAAA1.501.48 7G98BBAA1.501.47 8H98BBAA1.511.48 9I97BCCC1.491.44 10J96BBBB1.491.46 11K98CCBB1.491.44 12N97CCCC1.491.44 13O97CBAA1.501.47 14P96BCCC1.511.46 15Q98AAAA1.501.48 16R97AAAA1.501.48 17T98AAAA1.501.49 Comparative Example 1L97CFFF1.491.39 2M97FDDD1.481.41 3S96CEFF1.491.41
    According to the present invention, an electrostatic latent image developing toner containing carbon black in a well dispersed state as well as a mixed charge control agent system containing a specific azo ferrous metal compound and an oxycarboxylic acid metal compound can be obtained by polymerization reaction in an aqueous system . The mixed charge control agent system exhibits an effect of synergistically improving the chargeability of spherical polymerized toner particles. The azo iron metal compound improves the dispersibility of carbon black in the toner particles.
    权利要求:
    Claims (38)
    [1" claim-type="Currently amended] A process for producing a polymerizable monomer composition comprising a polymerizable monomer, carbon black, an azo iron compound represented by the following formula (1) and an oxycarboxylic acid metal compound,
    Dispersing the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition, and
    A binder resin, carbon black, an azo iron compound represented by the following formula (1) and an oxycarboxylic acid metal compound represented by the following formula (1), which are prepared by polymerizing a polymerizable monomer in the form of particles to form toner particles containing a polymerized monomer as a binder resin: A toner for developing electrostatic images comprising toner particles containing a compound.
    Formula 1

    Wherein R 1 and R 3 are independently selected from the group consisting of hydrogen, C 1-18 alkyl, C 2-18 alkenyl, sulfonamido, mesyl, sulfonic acid group, hydroxy, C 1-18 alkoxy, acetylamino, benzoylamino , A halogen atom or -O CO R 7 wherein R 7 is alkyl or aryl, n and n 'are an integer of 1 to 3,
    R 2 and R 4 independently represent hydrogen or nitro,
    R 5 and R 6 are independently hydrogen, halogen, nitro, carboxy, C 1-18 alkyl, C 2-18 alkenyl, C 7-18 aralkyl, C 1-18 alkoxy, C 6-18 aryl, -O · CO · R 7 wherein R 7 is C 1-18 alkyl or C 6-18 aryl, or (Wherein m is an integer of 1 to 3, and X represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen)
    A + is H +, Na +, K + , NH 4 + , or represents a mixture of these ions.
    [2" claim-type="Currently amended] The toner according to claim 1, wherein the azo iron compound is represented by the following formula (2).
    (2)

    In the formula, R 1 to R 4, n, n 'and A + are the same as in formula 1, X 1 and X 2 are, each independently represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen, m and m 'Is an integer of 1 to 3.
    [3" claim-type="Currently amended] The toner according to claim 1, wherein the oxycarboxylic acid metal compound is an aromatic oxycarboxylic acid metal compound.
    [4" claim-type="Currently amended] The toner according to claim 1, wherein the oxycarboxylic acid metal compound contains aluminum or zinc as a metal.
    [5" claim-type="Currently amended] The method according to claim 1, wherein the oxycarboxylic acid metal compound is selected from the group consisting of an alkyl salicylic acid aluminum compound, an alkyl salicylic acid zinc compound, a dialkylsalicylic acid aluminum compound and a dialkylsalicylic acid zinc compound (wherein each alkyl represents an alkyl group having 5 or fewer carbon atoms) ≪ / RTI >
    [6" claim-type="Currently amended] The toner according to claim 1, wherein the oxycarboxylic acid metal compound is a 3,5-ditetrabutylsalicylic acid aluminum compound or a 3,5-ditetrabutylsalicylic acid zinc compound.
    [7" claim-type="Currently amended] The non-cigarette toner according to claim 1,
    [8" claim-type="Currently amended] The toner of claim 1, wherein the binder resin comprises a resin selected from the group consisting of styrene polymers, styrene-acrylic copolymers, and styrene-methacrylic copolymers.
    [9" claim-type="Currently amended] The toner according to claim 1, wherein the toner particles further contain a polar resin.
    [10" claim-type="Currently amended] 10. The toner according to claim 9, wherein the polar resin comprises a polyester or a polycarbonate.
    [11" claim-type="Currently amended] The toner according to claim 1, having a shape providing a shape factor SF-1 of from 100 to 140 and SF-2 of from 100 to 120.
    [12" claim-type="Currently amended] The toner according to claim 1, wherein the toner has a weight average particle size of 3 to 10 탆.
    [13" claim-type="Currently amended] The toner according to claim 1, wherein the toner has a weight average particle size of 3 to 8 탆.
    [14" claim-type="Currently amended] The toner according to claim 1, wherein 0.1 to 8 parts by weight of the azo iron compound is added per 100 parts by weight of the binder resin.
    [15" claim-type="Currently amended] The toner according to claim 1, wherein 0.1 to 6 parts by weight of the azo iron compound is added per 100 parts by weight of the binder resin.
    [16" claim-type="Currently amended] The toner according to claim 1, wherein 0.1 to 10 parts by weight of the oxycarboxylic acid metal compound is added per 100 parts by weight of the binder resin.
    [17" claim-type="Currently amended] The toner according to claim 1, wherein 0.1 to 6 parts by weight of the oxycarboxylic acid metal compound is added per 100 parts by weight of the binder resin.
    [18" claim-type="Currently amended] The toner according to claim 1, wherein A / B satisfies 0.1 A / B 20 when A part by weight of an azo iron compound is added and B parts by weight of an oxycarboxylic acid metal compound is added.
    [19" claim-type="Currently amended] The toner according to claim 1, wherein 1 to 20 parts by weight of carbon black is added per 100 parts by weight of the binder resin.
    [20" claim-type="Currently amended] (i) a step of producing a polymerizable monomer composition containing a polymerizable monomer, carbon black, an azo iron compound represented by the following formula (1) and an oxycarboxylic acid metal compound,
    (ii) dispersing the polymerizable monomer composition in an aqueous medium to form particles of the polymerizable monomer composition, and
    (iii) polymerizing the polymerizable monomer in the form of particles to form toner particles containing the polymerized monomer as a binder resin.
    Formula 1

    Wherein R 1 and R 3 are independently selected from the group consisting of hydrogen, C 1-18 alkyl, C 2-18 alkenyl, sulfonamido, mesyl, sulfonic acid group, hydroxy, C 1-18 alkoxy, acetylamino, benzoylamino , A halogen atom or -O CO R 7 wherein R 7 is alkyl or aryl, n and n 'are an integer of 1 to 3,
    R 2 and R 4 independently represent hydrogen or nitro,
    R 5 and R 6 are independently hydrogen, halogen, nitro, carboxy, C 1-18 alkyl, C 2-18 alkenyl, C 7-18 aralkyl, C 1-18 alkoxy, C 6-18 aryl, -O · CO · R 7 wherein R 7 is C 1-18 alkyl or C 6-18 aryl, or (Wherein m is an integer of 1 to 3, and X represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen)
    A + is H +, Na +, K + , NH 4 + , or represents a mixture of these ions.
    [21" claim-type="Currently amended] The method according to claim 20, wherein the azo iron compound is represented by the following formula (2).
    (2)

    In the formula, R 1 to R 4, n, n 'and A + are the same as in formula 1, X 1 and X 2 are, each independently represents hydrogen, lower alkyl, lower alkoxy, nitro or halogen, m and m 'Is an integer of 1 to 3.
    [22" claim-type="Currently amended] 21. The method of claim 20, wherein the oxycarboxylic acid metal compound is an aromatic oxycarboxylic acid metal compound.
    [23" claim-type="Currently amended] 21. The method of claim 20, wherein the oxycarboxylic acid metal compound comprises aluminum or zinc as the metal.
    [24" claim-type="Currently amended] 21. The method according to claim 20, wherein the oxycarboxylic acid metal compound is an alkyl salicylic acid aluminum compound, an alkyl salicylic acid zinc compound, a dialkylsalicylic acid aluminum compound and a dialkylsalicylic acid zinc compound (wherein each alkyl represents an alkyl group having 5 or fewer carbon atoms) ≪ / RTI >
    [25" claim-type="Currently amended] The method according to claim 20, wherein the oxycarboxylic acid metal compound is a 3,5-ditetrabutylsalicylic acid aluminum compound or a 3,5-ditetrabutylsalicylic acid zinc compound.
    [26" claim-type="Currently amended] 21. The method of claim 20, wherein the toner is a non-magnetic toner.
    [27" claim-type="Currently amended] 21. The method of claim 20, wherein the polymerizable monomer comprises at least one monomer selected from the group consisting of styrene monomers, acrylate ester monomers and methacrylate ester monomers.
    [28" claim-type="Currently amended] 21. The method of claim 20, wherein the polymerizable monomer composition further comprises a polar resin.
    [29" claim-type="Currently amended] 29. The method of claim 28, wherein the polar resin comprises a polyester or polycarbonate.
    [30" claim-type="Currently amended] 21. The method of claim 20, wherein the toner has a shape providing a shape factor SF-1 of 100 to 140 and SF-2 of 100 to 120.
    [31" claim-type="Currently amended] 21. The method of claim 20, wherein the weight average particle size of the toner is from 3 to 10 mu m.
    [32" claim-type="Currently amended] 21. The method of claim 20, wherein the weight average particle size of the toner is from 3 to 8 占 퐉.
    [33" claim-type="Currently amended] The method according to claim 20, wherein 0.1 to 8 parts by weight of the azo iron compound is added per 100 parts by weight of the polymerizable monomer.
    [34" claim-type="Currently amended] The method according to claim 20, wherein 0.1 to 6 parts by weight of the azo iron compound is added per 100 parts by weight of the polymerizable monomer.
    [35" claim-type="Currently amended] The method according to claim 20, wherein 0.1 to 10 parts by weight of the oxycarboxylic acid metal compound is added per 100 parts by weight of the polymerizable monomer.
    [36" claim-type="Currently amended] The method according to claim 20, wherein 0.1 to 6 parts by weight of the oxycarboxylic acid metal compound is added per 100 parts by weight of the polymerizable monomer.
    [37" claim-type="Currently amended] The method according to claim 20, wherein A / B satisfies 0.1 A / B 20 when A parts by weight of an azo iron compound is added and B parts by weight of an oxycarboxylic acid metal compound is added.
    [38" claim-type="Currently amended] The method according to claim 20, wherein 1 to 20 parts by weight of carbon black is added per 100 parts by weight of the polymerizable monomer.
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    同族专利:
    公开号 | 公开日
    CN1155857C|2004-06-30|
    CN1197939A|1998-11-04|
    EP0869398B1|2001-06-20|
    DE69800949D1|2001-07-26|
    DE69800949T2|2001-10-31|
    US5856055A|1999-01-05|
    EP0869398A2|1998-10-07|
    EP0869398A3|1999-01-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1997-04-04|Priority to JP8616797
    1997-04-04|Priority to JP97-86167
    1998-04-03|Application filed by 미따라이후지오, 캐논가부시끼가이샤
    1998-11-25|Publication of KR19980081071A
    2001-02-01|Application granted
    2001-02-01|Publication of KR100280855B1
    优先权:
    申请号 | 申请日 | 专利标题
    JP8616797|1997-04-04|
    JP97-86167|1997-04-04|
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