JP5268504B2 - Toner and image forming method - Google Patents

Abstract

A toner which has i) toner base particles containing at least a binder resin and a colorant and ii) a fatty acid metal salt composition as an external additive. The fatty acid metal salt composition contains a nonionic surface-active agent and a fatty acid metal salt. This toner and an image forming process making use of the toner can keep the toner from adhering to a toner carrying member throughout running, promise a stable chargeability of the toner and can keep any deterioration of halftone image quality from being caused by excess charging of the toner and any image fog from being caused by insufficient charging of the toner.

Description

  The present invention relates to a toner used in an image forming method using an electrophotographic method or an electrostatic recording method. Specifically, the present invention relates to an image forming method using a toner composed of toner particles having a binder resin, a colorant, and a release agent, and an external additive powder.

  The developing method used in an electrophotographic apparatus is such that toner is attached to an electrostatic latent image formed on an electrostatic latent image carrier to visualize the electrostatic latent image, which is transferred to a recording medium and fixed. A toner image is obtained through the steps.

  Developers used for electrophotography are classified into two-component developers and one-component developers. In addition, the toner is classified as magnetic or non-magnetic.

  The toner of the present invention can be used in both developers.

  In recent years, a one-component development method has been widely adopted in electrophotography. In this method, the toner is charged by rubbing between the toner carrier and the toner regulating member. By adopting such a method for imparting charge to toner, it has become easier to achieve a reduction in price and size of a printer. In addition, with the recent demand for colorization, a non-magnetic one-component system that is advantageous for cost reduction and size reduction has been widely adopted.

  In addition, a two-component developer is advantageous in terms of stabilizing toner charging. Therefore, in electrophotography, both one-component and two-component toners and development methods are employed.

  On the other hand, as the price of printers is reduced and the size is reduced, it is also required to reduce the total power consumption. In particular, it is required to reduce energy consumption in the fixing process. To that end, it is necessary to develop a toner that can be fixed at a lower temperature.

  As the toner is fixed at a low temperature, the resistance of the toner to mechanical stress tends to deteriorate. This is considered to be due to the fact that the toner's property to mechanical stress deteriorates in the normal use temperature range by giving priority to toner fixability in order to adapt to low temperature fixing.

  Furthermore, there is a high demand for high-speed printers on the market. The problem in printing at high speed is that the above-mentioned low-temperature fixing performance is required, and that the stress resistance is much higher. Generally, in a high-speed machine, mechanical movement in the apparatus becomes faster. For this reason, heat is likely to be generated at the shaft of the roller or the frictional part. In particular, in the one-component development method in which the toner is charged by rubbing between the toner carrier and the toner regulating member, there is a technical requirement level for maintaining a balance between the demand for the toner and the durability accompanying the increase in speed. high.

  In order to satisfy these requirements at a high level, toner particles prepared by polymerization, toner obtained by spheroidizing pulverized toner with heat, toner obtained by agglomerating emulsified particles, and the like have been proposed.

  Many of such toners have been devised to increase mechanical strength compared to conventional melt-kneaded pulverized toners. For example, the core / shell structure is provided by changing the composition of the resin that composes the toner particle surface and the toner particle interior. There has been proposed a toner having such a structure that uses a material having high mechanical strength for the shell portion and a material effective for fixing the core portion (see, for example, Patent Document 1).

  However, even with such a toner, in a non-magnetic one-component image forming apparatus with a high process speed, a toner conveyance defect occurs due to a phenomenon that the surface of the toner conveyance member is contaminated with toner (toner fusion to the toner carrier). Cheap.

  As a result of investigating the toner fusion to the toner carrier, it is considered that the particles having a small particle size (fine powder component) in the toner are accumulated on the surface of the toner carrier without being developed and concentrated through durability. In order to reduce the selection of such durable toner particles, it is important to improve the releasability of the toner from the surface of the toner carrier and to stabilize the chargeability of the toner.

  In addition, such toner is liable to cause problems such as image fogging and streak image phenomenon (development streak) caused by regulation due to toners adhering to the toner regulating member.

  Although it is preferable to use the above-described toner with increased mechanical strength in such a non-magnetic one-component image forming apparatus having a high process speed, a toner satisfying the demand for further reduction in energy and speed has been obtained. Absent.

  On the other hand, various surface treatment agents (external additives) have been proposed for improving the durability of the toner.

  Among these proposals, inventions have been made in which fatty acid metal salts are used as toner external additives.

  For example, a toner composed of a negatively chargeable toner and a fatty acid metal salt is disclosed (for example, see Patent Documents 2 and 3).

  Further, a toner containing a fatty acid metal salt having a specific volume average particle size is disclosed (for example, see Patent Documents 4 and 5).

  In addition, a toner is disclosed in which the circularity of the toner containing the fatty acid metal salt and the particle diameter ratio of the fatty acid metal salt are defined (see, for example, Patent Document 6).

  Toners using these external additives are effective in improving the blade cleaning characteristics, improving the blade turnability, and suppressing the surface of the electrostatic latent image carrier. Further, uniform charging properties and the effect of suppressing drum filming can be obtained.

  However, although such toner has excellent lubricity on the surface of the electrostatic latent image carrier, the fatty acid metal salt is easily consumed selectively during the endurance, and such an effect is reduced in the second half of the endurance. In addition, in order to obtain the above effects, it is necessary to add a sufficient amount of the fatty acid metal salt, but problems such as charged partial contamination are likely to occur due to the influence of the excess fatty acid metal salt. Furthermore, since such a problem tends to become a significant problem in color toners used in high-speed image forming apparatuses, an appropriate amount of a material having a sufficient effect is used when applied to a high-speed apparatus. We have to go.

  Further, inventions have been made that pay attention to the relationship between the number average particle diameter of the toner, the ratio of 3.17 μm or less, and the number particle diameter of the fatty acid metal salt.

  According to this invention, there is obtained a toner with little friction of the photoconductor, no image fogging and no image blur even when printed at high temperature and high humidity, a uniform halftone and a small amount of toner scattering of fine dots (for example, (See Patent Document 7).

  Furthermore, a toner is disclosed in which the relationship between the toner particle diameter and the fatty acid metal salt particle diameter is defined by a one-component developer including toner particles having a melt viscosity in a certain range, a fluidity improver and a fatty acid metal salt. . According to this, a toner having a high density and less fog and excellent sharpness can be obtained (see, for example, Patent Document 8).

  However, although the toner as described above has less fog and can output a fine image, further improvement is necessary in application to a non-magnetic one-component image forming apparatus having a high process speed, and these inventions are sufficient. Performance has not been expressed.

  Therefore, the conventional techniques as described above have some problems with the high demands currently required.

  On the other hand, as a typical method for producing a fatty acid metal salt, a method of reacting a solution of an inorganic metal compound dropwise with a solution of an alkali metal salt of a fatty acid (metathesis method), or a fatty acid and an inorganic metal Examples include a method (melting method) in which a compound is kneaded at a high temperature to react.

  Further, various studies have been made on the refinement of fatty acid metal salts.

  For example, an invention has been made about a production method for forming a fatty acid metal salt into fine particles and a toner using the same (for example, see Patent Document 9).

Such toner is refined by controlling the solvent concentration and temperature during synthesis when the fatty acid metal salt is produced by a wet method. The toner containing such a fatty acid metal salt sufficiently exhibits the performance as a lubricant and provides a high effect as a cleaning aid.
Japanese Patent No. 3055119 Japanese Patent Laid-Open No. 08-129304 Japanese Patent Laid-Open No. 2002-14488 JP 2004-163807 A JP 2002-296829 A JP 2006-17934 A Japanese Patent No. 0347966 Japanese Patent Application Laid-Open No. 09-311499 Japanese Patent No. 0390580

  Conventional fatty acid metal salts are not sufficiently effective in preventing toner adhesion to the surface of the toner carrying member, and there is still room for improvement. In addition, in the toner containing a fatty acid metal salt, an image having a high density and a low fog and an excellent sharpness can be obtained, but it has a problem with a high demand for a high-speed color machine having a high process speed. is there.

  As a result of intensive studies, the present inventor has found that the above-described problems can be overcome by adding a fatty acid metal salt containing a specific compound as an external additive to the toner.

  SUMMARY OF THE INVENTION A first object of the present invention is to provide a toner and an image forming method capable of suppressing fusion to a toner carrier through durability.

  A second object of the present invention is a toner and an image forming method in which the chargeability of the toner is within an appropriate range through durability, the halftone image quality is deteriorated due to overcharging of the toner, and the image fog is extremely small due to insufficient charging of the toner. It is to provide.

  A third object of the present invention is to provide a toner and an image forming method with little primary charging member contamination caused by a transfer residual toner on an electrostatic latent image carrier through durability.

  The above-described problems can be achieved by the present invention described below.

That is, the present invention relates to a toner comprising toner particles having a binder resin and a colorant, and a fatty acid metal salt composition as an external additive, the fatty acid metal salt composition comprising a nonionic surfactant and a fatty acid. containing a metal salt, the content of nonionic surfactant of the fatty acid metal salt composition is a toner according to claim 5ppm to 510ppm der Rukoto.

  By using the toner of the present invention, it is possible to improve the releasability of the toner from the surface of the toner carrier, and it is possible to minimize the occurrence of problems such as fine powder concentration on the surface of the toner carrier. As a result, a stable toner particle size can be maintained throughout the durability, and toner fusion (toner filming) to the toner carrier can be suppressed.

  Further, by using the toner of the present invention, it becomes possible to maintain the charging property of the toner within an appropriate range throughout the durability. As a result, it is possible to form an image with very little halftone unevenness due to toner overcharging and extremely low image fogging due to insufficient toner charging.

  Further, by using the toner of the present invention, it is possible to suppress the charging member contamination caused by the external additive in the transfer residual toner on the electrostatic latent image carrier. As a result, the occurrence of primary charging failure and halftone unevenness during the endurance of the electrostatic latent image carrier is extremely reduced, and stable image formation is possible through the endurance.

  By adding a fatty acid metal salt composition containing a nonionic surfactant as an external additive to the toner, the releasability of the toner can be improved, and the toner can be fused to the toner carrier (toner filming). ) Can be suppressed. In addition, since the releasability is excellent, the fine powder having a relatively small particle size is suppressed from staying on the surface of the toner carrying member, and a stable particle size distribution can be maintained throughout the durability.

  Furthermore, by adding a fatty acid metal salt composition containing a nonionic surfactant as an external additive to the toner, the charge stability of the toner can be enhanced, and the charge amount can be maintained within an appropriate range throughout the durability. It becomes possible to do. For this reason, generation | occurrence | production of a halftone unevenness and image fog can be suppressed favorably.

  In the configuration of the present invention, contamination of the charging member due to the external additive in the transfer residual toner on the electrostatic latent image carrier can be suppressed. The occurrence of defects and halftone unevenness is extremely reduced, and stable image formation is possible through durability.

  The fatty acid metal salt composition containing a nonionic surfactant that is preferably used in the present invention will be described.

  First, the example of a nonionic surfactant is demonstrated concretely below.

  The nonionic surfactant is a general term for substances belonging to nonionic (nonionic) surfactants classified according to the miscellaneous goods industrial quality labeling regulations by the Ministry of Economy, Trade and Industry.

  In addition, there are anions (anions), cations (cations), amphoteric surfactants, etc., but fatty acid metal salt compositions containing ionic surfactants are all subject to environmental fluctuations in charging characteristics. It tends to be intense. Such a material having a large environmental fluctuation in the charging characteristics tends to hinder the charging characteristics of the toner and cause problems such as fogging and toner leakage in a high humidity environment. Moreover, the reason why such an environmental change in charging characteristics occurs is that moisture is easily adsorbed on the fatty acid polarization portion of the fatty acid metal salt composition, and the charge cannot be partially retained due to the adsorbed water. It is estimated that there is. As a result of studying cationic and anionic surfactants, it was found that a fatty acid metal salt composition having a preferable particle size and charging characteristics could not be stably formed and was not suitable for use in a fatty acid metal salt composition. It was.

  Nonionic (nonionic) surfactants are further classified into fatty acid-based, higher alcohol-based, and alkylphenol-based surfactants. A preferable group as the surfactant contained in the fatty acid metal salt composition is a higher alcohol type or alkylphenol type surfactant.

The nonionic surfactant contained in the fatty acid metal salt composition is preferably an ether type, specifically, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene polyoxyethylene stearyl ether, polyoxyethylene alkyl ethers such as polyoxyethylene oleyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene octylphenyl ether; polyoxyalkylene alkyl ether.

  Among these, lauryl alcohol ethylene oxide addition ether, oleyl alcohol ethylene oxide addition ether, McCall alcohol ethylene oxide addition ether, and nonylphenol alcohol ethylene oxide addition ether are preferable.

  The content of the preferred nonionic surfactant in the fatty acid metal salt composition is 10 ppm to 500 ppm, more preferably 10 ppm to 400 ppm, more preferably 15 ppm to 350 ppm in the fatty acid metal salt composition.

  When the content of the nonionic surfactant is 15 ppm or more, the fatty acid metal salt composition is appropriately charged, the developer is more evenly consumed, and the roughness is suppressed in the second half of the durability. A halftone image can be obtained. Further, since the consumption proceeds promptly, the occurrence of fusion to the surface of the toner carrier is suppressed, and the occurrence of image fogging and streak images is also suppressed.

In addition, when the content of the nonionic surfactant is 500 ppm or less, good charging characteristics can be maintained even in a high humidity environment, and image fogging can occur even when durable or left standing . Generation can be suppressed satisfactorily.

  Fatty acids in the fatty acid metal salt composition include monovalent saturated fatty acids such as butyric acid, valeric acid, lauric acid, myristic acid, palmitic acid, stearic acid and montanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacin Examples thereof include polyvalent saturated fatty acids such as acids, monovalent unsaturated fatty acids such as crotonic acid and oleic acid, and polyvalent unsaturated fatty acids such as maleic acid and citraconic acid.

  Saturated or unsaturated fatty acids having 8 to 35 carbon atoms are preferred. Among them, an acid mainly composed of stearic acid is preferable.

  Many fatty acids existing in nature exist as a mixture of acid components having different carbon numbers. Taking stearic acid obtained as a natural product as an example, stearic acid having 18 carbon atoms as a main component and further containing a trace amount of fatty acid components such as 14 carbon atoms, 16 carbon atoms, 20 carbon atoms and 22 carbon atoms. Usually, a product obtained by increasing the purity of the fatty acid component through a purification process to some extent is commercially available. Furthermore, as a high-purity product, there are Japanese Pharmacopoeia grade products and the like, but it is preferable to use these to obtain the effect. When stearic acid is used as the fatty acid, the purity of stearic acid is preferably 90.0% by mass or more, more preferably 95.0% by mass or more of the whole.

  When the purity of stearic acid is 90.0% by mass or more, the heat resistance of the stearic acid metal salt particles is particularly good, which is preferable from the viewpoint of ease of production and easy handling.

  Here, the purity of the fatty acid is the purity of the stearic acid component, and fatty acids having carbon numbers other than 18 and other organic and inorganic substances are considered as impurities.

  As the main metal species forming the salt, lithium, sodium, potassium, copper, rubinium, silver, zinc, magnesium, calcium, strontium, aluminum, iron, cobalt, nickel and the like can be used. Further, it is preferable to use zinc or calcium in order to keep the charging property of the toner within an appropriate range throughout the durability.

  In addition to the main metal species, other metal species can be included. At this time, the element ratio of the other metal species group (the ratio of the other metal species in the whole) is preferably less than 30%.

  Most preferred fatty acid metal salts are zinc stearate and calcium stearate.

  The preferred physical properties of the fatty acid metal salt composition will be specifically described below.

  In order for the fatty acid metal salt composition to appropriately express the effects of the present application, the median diameter (D50s) on a volume basis is preferably 0.15 μm or more and 1.05 μm or less, more preferably 0.15 μm or more, It is 0.65 μm or less, more preferably 0.30 μm or more and 0.60 μm or less.

  When the median diameter (D50s) on the volume basis of the fatty acid metal salt composition used for the toner is 0.15 μm or more, it works well as a lubricant and sufficiently obtains the effect of suppressing toner fusion to the toner conveying member. It is done. On the other hand, when the median diameter (D50s) on the volume basis of the fatty acid metal salt composition is 1.05 μm or less, the effect of the present application is particularly remarkable. This is considered to be because the particle diameter of the fatty acid metal salt composition is an appropriate size for adhering to the toner particles, and adhesion to the toner particles is enhanced. In addition, when the median diameter (D50s) on the volume basis of the fatty acid metal salt composition is 0.15 μm or more and 0.65 μm or less, the balance between the adhesion to the toner particles and the action as a lubricant by the fatty acid metal salt is particularly high. By being good, the effect of the present application is exhibited very well. It seems that the nonionic surfactant existing on the surface of the fatty acid metal salt composition also contributes to the effect of suppressing overcharge.

  As the thermal characteristics of the fatty acid metal salt composition, the melting point is preferably 122.0 ° C. or higher and 130.0 ° C. or lower when the endothermic peak temperature by differential scanning calorimetry is defined as the melting point.

  When the melting point of the fatty acid metal salt composition is within the above range, it is possible to balance the suppression of aggregation due to heat and the suppression of toner fusion, and to further improve the storage stability as a toner.

  In addition, the method for incorporating a nonionic surfactant into the fatty acid metal salt composition is not particularly limited, but as described later, the synthesis of the fatty acid metal salt is performed in water, and the dispersion stabilizer is not used in the water. A method in which an ionic surfactant is present and incorporated in a fatty acid metal salt is easy and suitable. However, as described above, the method is not limited, and a nonionic surfactant may be contained by treatment after the production of the fatty acid metal salt.

  Next, the suitable manufacturing method of a fatty-acid metal salt composition is demonstrated concretely.

  Examples of a typical method for producing a fatty acid metal salt composition currently used include a method in which an inorganic metal compound solution is dropped into a solution of an alkali metal salt of a fatty acid (reaction method), or a fatty acid. And a method in which an inorganic metal compound is kneaded and reacted at a high temperature (melting method).

  The fatty acid metal salt composition used in the present invention contains a nonionic surfactant. A preferred production method is a wet method for containing a surfactant with little variation among particles of the fatty acid metal salt composition, and among them, a metathesis method is preferred.

  The manufacturing process includes a step of dropping the solution of the inorganic metal compound into the solution of the alkali metal salt of the fatty acid to replace the alkali metal of the fatty acid with the metal of the inorganic metal compound.

  However, synthesis by a general metathesis method tends to be a fatty acid metal salt composition having an average particle size of more than 7.0 μm and a particle size of 10 μm or more but a content of about 20% by mass or more. There is.

  If you want to produce finely divided fatty acid metal salts, add a substance that has a dispersion stabilizing effect to the aqueous system during synthesis in the aqueous medium, and change the interfacial energy between the resulting fatty acid metal salt composition and the dispersion medium. It is good to let them. Examples of the means for changing the interfacial energy include a method using a surfactant.

  It is particularly preferable to use a nonionic surfactant as the surfactant capable of obtaining such an action. As the nonionic surfactant, those described above are used.

  As for the surfactant, an HLB value obtained by quantifying the hydrophilic / hydrophobic balance is proposed and widely used in various fields.

  Therefore, various surfactants were examined for the surfactants used in the synthesis of the fatty acid metal salt composition. As a result, there are groups of surfactant species and HLB values that can effectively produce the fatty acid metal salt composition. I found out.

  A suitable HLB value for dispersing and stabilizing the fatty acid metal salt composition is 5.0 to 15.0.

A nonionic surfactant satisfying a preferred HLB value can be achieved by controlling the alcohol component and the ethylene oxide addition component in the surfactant. More specifically, the following compounds are mentioned.
Lauryl alcohol ethylene oxide addition ether:
Ethylene oxide 5 mol adduct HLB value 10.8
Ethylene oxide 10 mol adduct HLB value 14.1
Ethylene oxide 23 mol adduct HLB value 16.9
Oleyl alcohol ethylene oxide addition ether:
Ethylene oxide 10 mol adduct HLB value 12.4
Ethylene oxide 20 mol adduct HLB value 15.3
McCall alcohol ethylene oxide addition ether:
Ethylene oxide 5 mol adduct HLB value 9.3
Ethylene oxide 7 mol adduct HLB value 10.8
Ethylene oxide 11 mol adduct HLB value 13.2
Ethylene oxide 14 mol adduct HLB value 14.2
Nonylphenol alcohol ethylene oxide addition ether:
Ethylene oxide 4 mol adduct HLB value 8.9
Ethylene oxide 6 mol adduct HLB value 10.9
Ethylene oxide 7 mol adduct HLB value 11.7
Ethylene oxide 10 mol adduct HLB value 13.3
Ethylene oxide 12 mol adduct HLB value 14.1
Ethylene oxide 14 mol adduct HLB value 14.8

In addition, as a formula for calculating the HLB of the surfactant component used in the present invention, the following HLB value-number system by Griffin is used.
(1) In the case of polyhydric alcohol fatty acid ester, HLB value = 20 (1-S / A)
S: ester saponification value, A: neutralization value of fatty acid (2) in the case of tall oil, pine resin, beeswax, lauric polyhydric alcohol derivative HLB value = (E + P) / 5
E: Ethylene oxide content (% by mass) in the constituent molecules
P: Polyhydric alcohol content (% by mass) in the constituent molecules
(3) When the hydrophilic group is ethylene oxide HLB value = E / 5
E: Ethylene oxide content (% by mass) in the constituent molecules
As the production apparatus, for example, the continuous reaction apparatus shown in FIG. 1 can be preferably used.

  Reference numerals 001 and 002 in the figure are tanks for holding an aqueous solution, one of which holds (a) a fatty acid salt aqueous solution (component (a)) containing a surfactant, and the other is (b) An inorganic metal salt aqueous solution or dispersion (component (b)) containing a surfactant is retained. It is a tank that holds Reference numeral 003 is a reaction apparatus, reference numeral 007 is a crushing apparatus, and reference numeral 008 is a slurry tank of a fatty acid metal salt composition.

  The reactor 003 is preferably one that can separately feed and mix the components (a) and (b) into the mixer, and in particular, the components (a) and (b) can be separately fed into the mixer as fast as possible. It is preferred that they can be fed and mixed. For example, it is preferable that each raw material solution (or dispersion liquid) is injected into the mixed layer from different directions and mixed with each solution (or dispersion liquid), and at the same time, the mixture can be discharged out of the system from the mixing tank. It is preferable that the component (a) and the component (b) can be mixed efficiently. Moreover, it is preferable that (a) component and (b) component react with the temperature controlled at 70 to 90 degreeC.

  As these apparatuses, it is preferable to use a flow jet mixer, a line homogenizer, a line mill such as a sand mill, or the like.

  In addition, when the alkali metal salt or ammonium salt of the unreacted fatty acid remains after the reaction between the component (a) and the component (b), the reaction is performed as follows. After the (a) component and the (b) component are discharged from the mixing tank, the alkali of unreacted fatty acid is mixed by mixing an aqueous solution or dispersion containing 0.001 to 15.0% by mass of an inorganic metal salt. Metal salts or ammonium salts can be reacted to the fatty acid metal salt composition.

  The slurry containing the fatty acid metal salt composition that has undergone the reaction is held in the tank 008 as a reaction slurry via the crusher 007, and then sent to the next step (which may be followed by a classification step). In addition, it is good also as a circulation system which once returns the reaction slurry to the crusher 007, and crushes again.

  Although the apparatus which can be used as a crusher here is not specifically limited, For example, Milder L series (made by Taiheiyo Kiko), a pro shear mixer (made by Taiheiyo Kiko) etc. can be used. Preferably, a milder L series generator modified into a tooth shape can be used.

  The reaction slurry thus obtained is separated into a fatty acid metal salt composition cake and a filtrate using a commonly used filtration apparatus. The fatty acid metal salt composition cake is sufficiently washed with warm water or the like in order to reduce the amount of impurities. As the washing water at this time, ion-exchanged water adjusted to 50 μSiemens / m or less can be preferably used.

  The washed fatty acid metal salt composition cake is dried in the next step to obtain a fatty acid metal salt composition. In the drying process, the fatty acid metal salt composition cake can be spread in a thin layer in a tray-like container and dried in a drying oven set at a predetermined temperature. A fluidized bed dryer (manufactured by Okawara Seisakusho Co., Ltd.) that performs drying therein is preferably used. The specific drying temperature varies depending on the type of the fatty acid metal salt composition to be obtained. For example, in the case of zinc stearate, it is 40 ° C. or higher and 90 ° C. or lower. When the drying treatment is performed at a temperature higher than 90 ° C., the fine particles are aggregated and the average particle size may be increased. In addition, a drying temperature of 40 ° C. or lower is not preferable because it takes time to dry the moisture in the fatty acid metal salt composition. The drying treatment of the fatty acid metal salt composition cake may be performed at normal pressure, but in order to dry efficiently, the drying may be performed under reduced pressure or vacuum drying, or the fatty acid metal may be dried with a low boiling point solvent or the like. After washing the salt composition cake, the obtained fatty acid metal salt composition cake may be dried. As the low boiling point solvent used at this time, those capable of efficiently removing water from the fatty acid metal salt composition are preferable, and examples thereof include methanol, ethanol, acetone and methylene chloride.

  Next, the raw material used when manufacturing a fatty acid metal salt composition is demonstrated.

  As raw material components, an aqueous solution or dispersion of (a) a fatty acid salt solution having a surfactant and (b) an inorganic metal salt having a surfactant is used.

  As the fatty acid salt used in the preparation of the fatty acid salt aqueous solution of the component (a), the above-mentioned preferred fatty acids or fatty acid salts (for example, alkali metal salts and ammonium salts) can be used. Moreover, it is preferable to use a C4-C30 fatty acid or its salt from a viewpoint on manufacture. The fatty acid having the carbon number in the above range has a moderate solubility in water, and high production efficiency can be obtained.

  The content of the fatty acid salt in the fatty acid salt aqueous solution as the component (a) is preferably in the range of 0.001 to 20% by mass. Within this range, it is possible to satisfactorily balance production efficiency with adjustment of the particle size of the resulting fatty acid metal salt composition. Considering the amount of the fatty acid metal salt composition obtained and the particle size thereof, the more preferable content of the alkali metal salt or ammonium salt of the fatty acid in the aqueous solution is in the range of 0.5 to 15% by mass.

  Further, a nonionic surfactant is added to the aqueous system of component (a). As the surfactant at this time, one type or a plurality of types selected from the nonionic surfactants exemplified above are used.

  The amount of the nonionic surfactant to be used is 0.1% by mass to 10.0% by mass with respect to the aqueous system of component (a). If the addition amount of the nonionic surfactant is less than 0.1% by mass, it is difficult to lower the central particle size, and a particle size distribution effective for electrophotographic characteristics cannot be formed. In addition, when the content is 10.0% by mass or more, the charging property of the obtained fatty acid metal salt composition is deteriorated, and the load on wastewater treatment is increased, which is not economical.

  Examples of the inorganic metal salt used for the preparation of the aqueous solution or dispersion of the inorganic metal salt (b) include chlorides, sulfates, carbonates, nitrates or phosphoric acids of alkaline earth metals such as calcium, barium and magnesium. Salts, etc., or chlorides, sulfates, carbonates, nitrates or phosphates of metals such as titanium, zinc, copper, manganese, cadmium, mercury, zirconium, lead, iron, aluminum, cobalt, nickel and silver I can do things. These substances may be used alone or in combination of two or more.

  It is preferable that content of the said inorganic metal salt in the aqueous solution or dispersion liquid of the inorganic metal salt which is (b) component is the range of 0.001-20 mass%. Within this range, it is possible to satisfactorily balance production efficiency with adjustment of the particle size of the fatty acid metal salt composition obtained. Considering the amount of the fatty acid metal salt composition to be obtained and the particle size thereof, the preferable content of the inorganic metal salt in the aqueous solution or dispersion is in the range of 0.01 to 10% by mass.

  Also for the component (b), it is preferable to use a surfactant in the same manner as the component (a). In addition, about the kind and quantity of surfactant, although content with respect to the water in said (a) component may be equivalent, you may change a kind and may use several surfactant. It is also preferable to adjust the amount of the component (b) with the same surfactant as the component (a).

  As the water used for the preparation of the component (a) and the component (b), those commonly used may be used, such as metal ions such as ion-exchanged water, purified water, or distilled water. Those having less impurities are preferred.

  In addition, the reaction ratio of (a) component at the time of fatty-acid metal salt composition manufacture, and (b) component can be changed arbitrarily. In particular, with respect to the molar amount of the carboxylic acid contained in the fatty acid salt of the component (a), the charge characteristic of the fatty acid metal salt composition is set to be equal to or more than the theoretically required molar equivalent as a cation atom in the component (b). It is preferable in terms of stabilization and improvement of toner carrier fusion. More preferably, the component (b) is 1.1 times the molar equivalent of the component (a).

  As described above, a fatty acid metal salt composition containing a surfactant is obtained by mixing and reacting two components.

  The content of the fatty acid metal salt composition is preferably 0.02 parts by mass to 1.00 parts by mass with respect to 100 parts by mass of the toner particles, and 0.05 parts by mass or more and 0.50 parts by mass. Is more preferable.

  If the amount of the fatty acid metal salt composition is within the above range, the effect of preventing toner filming on the toner conveying member can be obtained satisfactorily, and toner dropping can be suppressed in both.

  The fatty acid metal salt composition is used as an external additive, but is more preferably used in combination with other external additives described later.

  A known method can be used as the external addition method for the toner particles. For example, a mixer such as a Henschel mixer (manufactured by Mitsui Miike) or a hybridizer (manufactured by Nara Machinery Co., Ltd.) can be used as the apparatus.

Next, a preferable form of toner particles will be described.
The toner production method is not particularly limited as long as the characteristics can be achieved, and a known production method can be used.
That is, a melt-kneading pulverization method, a suspension polymerization method, an emulsion polymerization method, a suspension granulation method, or the like can be used.

  Among these, a suspension polymerization method, an emulsion polymerization method, and a suspension granulation method including a step of producing a toner in an aqueous medium are preferable, and among them, a suspension polymerization method and a suspension in an aqueous medium are preferable. A granulation method is more preferred. Further, as the composition of the toner particles, it is preferable to use a production method capable of forming a toner having a core / shell structure exhibiting stress resistance.

  Examples of the toner production method by polymerization include a direct polymerization method, a suspension polymerization method, an emulsion polymerization method, an emulsion association polymerization method, and a seed polymerization method. Among these, the balance between the particle size and the particle shape is balanced. In view of easiness, it is particularly preferable to produce by suspension polymerization. In this suspension polymerization method, a monomer composition is prepared by uniformly dissolving or dispersing a colorant (and, if necessary, a polymerization initiator, a crosslinking agent, a charge control agent, and other additives) in the polymerizable monomer. Then, the monomer composition is dispersed in a continuous layer containing a dispersion stabilizer (for example, an aqueous phase) using an appropriate stirrer, and a polymerization reaction is performed to obtain a desired particle size. The toner which has is obtained.

  When toners are produced by this suspension polymerization method, individual toner particle shapes are almost spherical, making it easy to obtain toners with a high degree of circularity. Therefore, it has high transferability.

  Furthermore, a toner having a core / shell structure in which a surface layer is provided by adding a polymerizable monomer and a polymerization initiator to the fine particles obtained by suspension polymerization can be designed as necessary. .

  The toner contains a colorant as an essential component in order to impart coloring power. Examples of the organic pigment or dye preferably used in the present invention include the following.

  As an organic pigment or organic dye that can be used as a cyan colorant, a copper phthalocyanine compound and a derivative thereof, an anthraquinone compound, a basic dye lake compound, or the like can be used. Specifically, C.I. I. Pigment blue 1, C.I. I. Pigment blue 7, C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 60, C.I. I. Pigment blue 62, C.I. I. And CI Pigment Blue 66.

  Organic pigments or organic dyes that can be used as magenta colorants include condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, perylene compounds Is used. Specifically, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment violet 19, C.I. I. Pigment red 23, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 122, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 150, C.I. I. Pigment red 166, C.I. I. Pigment red 169, C.I. I. Pigment red 177, C.I. I. Pigment red 184, C.I. I. Pigment red 185, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. And CI Pigment Red 254.

  As the organic pigment or organic dye that can be used as the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complexes, methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 62, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 94, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 147, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 176, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 181, C.I. I. Pigment yellow 191, C.I. I. And CI Pigment Yellow 194.

  These colorants can be used alone or mixed and further used in the form of a solid solution. The colorant used for the toner is selected from the viewpoints of hue angle, saturation, brightness, light resistance, OHP transparency, and dispersibility in the toner.

  The colorant is added in an amount of 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  As the black colorant, carbon black, a magnetic material, and a color toned to black using the yellow / magenta / cyan colorant are used.

  The toner preferably has a release agent of 0.5 to 50 parts by mass with respect to 100 parts by mass of the binder resin in order to obtain a good fixed image. Examples of the release agent include various waxes.

  Examples of the release agent usable in the toner include petroleum waxes such as paraffin wax, microcrystalline wax, petrolactam and derivatives thereof, montan wax and derivatives thereof, hydrocarbon waxes and derivatives thereof by Fischer-Tropsch method, and polyethylene. Polyolefin waxes and derivatives thereof, natural waxes such as carnauba wax and candelilla wax, and derivatives thereof.

  These derivatives include oxides, block copolymers with vinyl monomers, and graft modified products. Furthermore, higher fatty alcohols, fatty acids such as stearic acid and palmitic acid, or compounds thereof, acid amide waxes, ester waxes, ketones, hydrogenated castor oil and derivatives thereof, plant waxes, animal waxes and the like can be mentioned. Among these waxes, those having a maximum endothermic peak temperature in differential scanning calorimetry of 40 ° C. to 110 ° C. are preferable, and those of 45 ° C. to 90 ° C. are more preferable. More preferred are paraffin wax and Fischer-Tropsch wax whose maximum endothermic peak temperature measured by DSC is 70 ° C to 85 ° C.

  The maximum endothermic peak temperature of the release agent component is measured according to “ASTM D 3418-82”. For the measurement, for example, DSC-7 manufactured by PerkinElmer is used. The temperature correction of the device detection unit uses the melting points of indium and zinc, and the correction of heat uses the heat of fusion of indium. An aluminum pan is used as a measurement sample, an empty pan is set as a control, and measurement is performed at a heating rate of 10 ° C./min.

  As content when using a mold release agent, the range of 0.5 thru | or 50 mass parts is preferable with respect to 100 mass parts of binder resin. If the content is less than 0.5 parts by mass, the effect of suppressing the low temperature offset is poor, and if it exceeds 50 parts by mass, the long-term storage stability is deteriorated and the dispersibility of other toner materials is deteriorated, and the toner fluidity is deteriorated. Leading to a decrease in image quality and image characteristics.

  Further, it is preferable to use a charge control agent for the toner.

  As the charge control agent, for example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic hydroxycarboxylic acids, and aromatic dicarboxylic acid based metal compounds. Other examples include aromatic hydroxycarboxylic acids, aromatic mono- and polycarboxylic acids and metal salts thereof, anhydrides, esters, and phenol derivatives such as bisphenol. Moreover, a styrene-acrylic acid copolymer, a styrene-methacrylic acid copolymer, a styrene-acrylic-sulfonic acid copolymer, a nonmetal carboxylic acid compound, and the like can be given.

  Furthermore, among these, a monoazo metal complex, a metal complex of an aromatic hydroxycarboxylic acid, a metal complex of an aromatic dicarboxylic acid, and a metal salt thereof are preferable, and further, the central metal is Fe, Al, Cr, Mono-azo metal complex of Ni, aromatic hydroxycarboxylic acid metal complex whose central metal is Fe, Al, aromatic dicarboxylic acid metal complex whose central metal is Fe, Al, and metal salts thereof, styrene-acrylic acid ester-sulfonic acid A copolymer of a group-containing monomer is more preferable.

  In particular, when toner particles are produced by polymerization in an aqueous medium, an aromatic hydroxycarboxylic acid metal complex whose central metal is Fe or Al, or styrene-- from the viewpoint that the layer structure can be controlled during the polymerization reaction. An acrylic ester-sulfonic acid group-containing monomer copolymer is preferred.

  The weight average particle diameter (D4) of the toner is preferably 3.0 to 15.0 μm, more preferably 5.0 to 10.0 μm from the viewpoint of durability. Toner particles of less than 3 μm are likely to adhere to the surface layer of the toner carrier during development, and the chargeability is likely to be hindered. In particular, when a halftone image is output immediately after a pattern having a different image printing rate is output, a development ghost is likely to occur when toner containing a large amount of toner particles of less than 3 μm is used. Further, since the toner having such a small particle diameter is easily fused on the toner carrier, the toner carrier tends to be contaminated during the durability.

  The toner particle size distribution is preferably 1.05 or more and less than 1.90, preferably 1.05 or more and less than 1.50, in the D4 / D1 ratio obtained by dividing the weight average particle size (D4) by the number average particle size (D1). Is more preferable, and more preferably 1.10 or more and less than 1.30. When this range is satisfied, the image quality of the halftone image can be maintained satisfactorily through durability.

  Further, the shape of the toner is preferably controlled for the purpose of improving charging stability, developability, transferability, and fluidity.

  As a preferable range of shape control in the toner, the average circularity of the toner is 0.920 to 0.995 in the equivalent circle diameter-circularity scattergram based on the number of toners measured by the flow type particle image measuring apparatus. The circularity standard deviation is preferably 0.040 or less, more preferably the average circularity is 0.950 to 0.990, and the circularity standard deviation is 0.035 or less.

  If the average circularity and the standard deviation of the circularity of the toner are within the above ranges, it is possible to better achieve both the charging property and the cleaning property, and to suppress the occurrence of fusion to the toner carrier surface. Can do.

  The toner needs to contain a fatty acid metal salt composition, but in addition to that, external additives other than the fatty acid metal salt composition are added to the toner for the purpose of improving charging stability, developability, fluidity, and durability. It is preferable to externally add to the particles.

  Specific examples of the external additive include silica fine powder, hydrophobized silica fine powder, titanium oxide, surface hydrophobized titanium oxide, various resin particles, and the like, and these are preferably used alone or in combination. .

  Among these, hydrophobized silica fine powder and titanium oxide are more preferable. Furthermore, other types of external additives may be combined.

As the hydrophobized silica fine powder suitably used in the present invention, known silica fine powder can be used, but preferably the specific surface area by nitrogen adsorption measured by the BET method is 20 m ² / g or more, more preferably The thing in the range of 40-400 m < ² > / g can be used.

  Specific examples of the hydrophobizing agent in the hydrophobized silica fine powder include silicone varnish, various modified silicone varnishes, silicone oil, various modified silicone oils, silane coupling agents, silane coupling agents having a functional group, and other organic materials. A silicon compound is mentioned. These treatment agents may be used alone or in combination.

  The amount of the hydrophobized silica fine powder used is not particularly defined, but is 0.2 to 5.0 parts by mass, preferably 0.7 to 3.0 parts by mass with respect to 100 parts by mass of toner particles. Good to use part.

  Next, image formation using toner will be described.

  The image forming method to which the toner can be applied can be used without being limited to either the two-component developing method or the one-component developing method. Further, the present invention is not limited to the classification of toner magnetic or non-magnetic, and both toners can be used.

  The conditions for the developing step in the image forming method may be that the toner carrier and the surface of the photosensitive member as the electrostatic latent image carrier are in contact or non-contact. Here, the case of contact will be described with reference to FIG.

  The developing container 104 contains toner 108 and includes a toner carrier 105 that rotates in the direction of the arrow in contact with the electrostatic latent image carrier (photoconductor). Further, a developing blade 117 for regulating the amount of toner and charging, and a coating roller that rotates in the direction of the arrow in order to attach the toner 108 to the toner carrier 105 and to charge the toner by friction with the toner carrier 105 116 is provided. A developing bias power source is connected to the toner carrier 105. A bias power source (not shown) is also connected to the application roller 116, and when negatively charged toner is used, the voltage is more negative than the developing bias. When positively charged toner is used, the voltage is more positive than the developing bias. Is set.

  Here, the length in the rotation direction at the contact portion between the photosensitive member and the toner carrier 105, that is, the so-called development nip width is preferably 0.2 to 8.0 mm. If the thickness is less than 0.2 mm, the development amount is insufficient, and it is difficult to obtain a satisfactory image density, and the transfer residual toner tends to be insufficiently collected. If it exceeds 8.0 mm, the toner supply amount becomes excessive, fogging is likely to occur, and wear of the photoconductor tends to be remarkable.

  The toner coat amount is controlled by the developing blade 117, and the developing blade 117 is in contact with the toner carrier 6 through the toner layer. The contact pressure at this time is preferably in the range of 4.9 to 49 N / m (5 to 50 gf / cm). If it is less than 4.9 N / m, in addition to controlling the toner coating amount, uniform frictional charging becomes difficult, causing fogging. On the other hand, if it exceeds 49 N / m, the toner particles are subjected to an excessive load, so that the deformation of the particles and the fusion of the toner to the developing blade or the toner carrier are likely to occur.

  The free end portion of the regulating member may have any shape as long as it has a preferable NE length (the length from the contact portion of the developing blade to the toner carrier to the free end). Various cross-sectional shapes can be used, and in addition to a linear shape, an L-shape bent near the tip, a shape swelled in a spherical shape near the tip, and the like are preferably used.

  As the toner coat amount regulating member, a rigid metal blade or the like may be used in addition to the elastic blade for press-fitting toner.

  As the elastic regulating member, it is preferable to select a material of a triboelectric charge series suitable for charging the toner to a desired polarity. For example, rubber elastic bodies such as silicone rubber, urethane rubber and NBR, synthetic resin elastic bodies such as polyethylene terephthalate, and metal elastic bodies such as stainless steel, steel and phosphor bronze can be used. Moreover, those composites may be sufficient.

  Further, when durability is required for the elastic regulating member and the toner carrier, it is preferable that the metal elastic body is bonded or coated with a resin or rubber so as to contact the sleeve contact portion.

  Furthermore, an organic substance or an inorganic substance may be added to the elastic regulating member, and it may be melt-mixed or dispersed.

  For example, the chargeability of the toner can be controlled by adding a metal oxide, metal powder, ceramics, carbon allotrope, whisker, inorganic fiber, dye, pigment, surfactant or the like. In particular, when the elastic body is a molded body such as rubber or resin, fine metal oxide powders such as silica, alumina, titania, tin oxide, zirconia, and zinc oxide, carbon black, a charge control agent generally used for toners, etc. It is also preferable to contain.

  Furthermore, application of a DC electric field and / or an AC electric field to the regulating member also improves the uniform thin-layer coating property and uniform charging property due to the loosening action on the toner, achieving a sufficient image density and high quality. Images can be obtained.

  As the charging member, there are a non-contact type corona charger and a contact type charging member using a roller or the like, and any of them is used. For efficient uniform charging, simplification, and low ozone generation, a contact type is preferably used.

  In FIG. 2, a contact-type charging member is used.

  The primary charging member 12 used in FIG. 2 is a charging roller that basically includes a central core 12b and a conductive elastic layer 12a that forms the outer periphery thereof. The charging roller 12 is brought into contact with the entire surface of the electrostatic latent image carrier with a pressing force, and is driven to rotate as the electrostatic latent image carrier 6 rotates.

  As a preferable process condition when the charging roller is used, the contact pressure of the roller is 4.9 to 490 N / m (5 to 500 gf / cm), and a DC voltage superimposed on an AC voltage is used as an applied voltage. Sometimes AC voltage = 0.5-5 kVpp, AC frequency = 50 Hz-5 kHz, DC voltage = ± 0.2- ± 1.5 kV, and when DC voltage is used, DC voltage = ± 0.2- ± 5 kV It is. In addition, since the amount of scraping of the drum can be suppressed, it is more preferable to use only a DC voltage as the applied voltage. Other contact charging means include a method using a charging blade and a method using a conductive brush. These contact charging means are superior to non-contact corona charging in that a high voltage is unnecessary and generation of ozone is reduced. The material of the charging roller and charging blade as the contact charging means is preferably conductive rubber, and a release coating may be provided on the surface thereof. As the releasable coating, nylon resin, PVDF (polyvinylidene fluoride), PVDC (polyvinylidene chloride), and the like are applicable.

  As the description of the image forming apparatus illustrated in FIG. 2, the contact charging unit has been described. However, in the case of using the contact charging unit in the image forming apparatus having other configurations, the same apparatus and conditions can be used. .

  As the toner carrying member, an elastic roller can be used, and a method can be used in which toner is coated on the surface of the elastic roller and the like and developed by bringing it into contact with the surface of the photosensitive member. As the elastic roller, one having an elastic layer having an ASKER-C hardness of 30 to 60 degrees is preferably used. When development is performed by bringing the toner carrying member into contact with the surface of the photoreceptor, the development is performed by an electric field acting between the photoreceptor and the elastic roller facing the surface of the photoreceptor via the toner. Therefore, the surface of the elastic roller or the vicinity of the surface has a potential, and it is necessary to have an electric field in a narrow gap between the photoreceptor surface and the toner carrying surface. Therefore, the elastic rubber of the elastic roller is resistance-controlled in the middle resistance region, and the electric field is maintained while preventing conduction with the surface of the photoreceptor, or a thin insulating layer is provided on the surface layer of the conductive roller. Can also be used.

The toner coat amount on the toner carrier is preferably 0.1 to 1.5 mg / cm ² . If the amount is less than 0.1 mg / cm ^2, it is difficult to obtain a sufficient image density. If the amount is more than 1.5 mg / cm ^2, it becomes difficult to uniformly charge all of the individual toner particles, causing fogging. Become. Furthermore, 0.2 to 0.9 mg / cm ² is more preferable.

  In the image forming method, the toner carrier may be rotated in the same direction at the portion facing the photoconductor, or may be rotated in the opposite direction. When both rotations are in the same direction, it is preferable to set the peripheral speed of the toner carrier to be 1.05 to 2.0 times the peripheral speed of the photosensitive member.

As the photoreceptor, a photosensitive drum or a photosensitive belt having a photoconductive insulating material layer such as a-Se, CdS, ZnO ₂ , OPC, or a-Si is preferably used.

  The photosensitive layer in the OPC photoreceptor may be a single layer type having a charge generation material and a material having charge transport performance in the same layer, or a function-separated type photosensitive layer having the charge transport layer and the charge generation layer as components. May be. A laminated photosensitive layer having a structure in which a charge generation layer and then a charge transport layer are laminated in this order on a conductive substrate is one preferred example. In addition, the binder resin of the organic photosensitive layer is not particularly limited, but polycarbonate resin, polyester resin, and acrylic resin are particularly excellent in transferability, and the toner can be fused to the photosensitive member and external additives. It is preferable because filming is difficult to occur.

  Next, image formation using toner will be described below with reference to FIG.

  In FIG. 3, 1 is a photosensitive member, P is a transfer target such as paper, 16 is an electrostatic conveyance belt that conveys a transfer member, 17 is a transfer member, 15 is a fixing unit, and 2 is in direct contact with the photosensitive member 5. 1 shows a primary charging member that performs charging.

  A bias power source (not shown) is connected to the primary charging member 2 so as to uniformly charge the surface of the photoreceptor 1.

A transfer bias power source 32 having a polarity opposite to that of the photosensitive member 1 is connected to the transfer member 17.

  The toner images formed and supported on the electrostatic latent image carrier (photoconductor) 1 are sequentially transferred onto the transfer material P.

A transfer bias for sequentially superimposing and transferring the first to fourth color toner images from the photosensitive member 1 to the transfer material P has a polarity opposite to that of the toner and is applied from a bias power source (not shown).

  Thereafter, the unfixed multicolor toner image on the transfer material P enters the fixing device 15 and is fixed by heating and pressing to obtain an image.

After completion image transfer to the transfer material P, the cleaning member 18 in the electrostatic transport belt 16 is brought into contact, the toner remaining on the electrostatic transport belt 16 without being transferred onto the transfer material P (transfer residual toner) Recover.

  The electrostatic conveyance belt 16 includes a belt-shaped base layer and a surface treatment layer provided on the base layer. The surface treatment layer may be composed of a plurality of layers. Rubber, elastomer, or resin can be used for the base layer and the surface treatment layer.

  Examples of the rubber and elastomer include natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, and chlorinated polyethylene. Further, acrylonitrile butadiene rubber, urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, polysulfide rubber, polynorbornene rubber, and hydrogenated nitrile rubber can also be used. Furthermore, one type or two or more types selected from the group consisting of thermoplastic elastomers (for example, polystyrene-based, polyolefin-based, polyvinyl chloride-based, polyurethane-based, polyamide-based, polyester-based, and fluororesin-based) can be used. . However, it is not limited to the said material.

  As the resin, a resin such as a polyolefin resin, a silicone resin, a fluorine resin, or a polycarbonate can be used. A copolymer or a mixture of these resins may be used.

  As the base layer, one obtained by coating, dipping, or spraying the above-described rubber, elastomer, or resin on one side or both sides of a core layer having a woven fabric shape, a nonwoven fabric shape, a thread shape, or a film shape may be used.

  The material constituting the core layer is not particularly limited. For example, natural fibers such as cotton, silk, hemp and wool, polyester fibers, nylon fibers, acrylic fibers, polyolefin fibers, polyvinyl chloride fibers, polyvinyl chloride fibers, and the like. Vinylidene fibers, polyurethane fibers, polyalkyl paraoxybenzoate fibers and the like can be used. Further, one or two kinds selected from the group consisting of synthetic fibers such as polyacetal fiber, aramid fiber, polyfluoroethylene fiber and phenol fiber; inorganic fibers such as carbon fiber and glass fiber; metal fibers such as iron fiber and copper fiber The above can be used.

  Further, a conductive agent may be added to the base layer and the surface treatment layer in order to adjust the resistance value of the transfer belt. Although it does not specifically limit as a electrically conductive agent, For example, metal powder, such as carbon, aluminum, and nickel, metal oxides, such as a titanium oxide, and quaternary ammonium salt containing polymethyl methacrylate, polydiacetylene, polyethyleneimine, etc. 1 type (s) or 2 or more types selected from the group consisting of these conductive polymer compounds can be used.

  The toner can also be used in an image forming apparatus that collectively transfers multiple toner images onto a recording material using an intermediate transfer belt. A configuration example of an image forming apparatus having an intermediate transfer belt will be described below using the image forming apparatus shown in FIG.

  The toner image formed and supported on the electrostatic latent image bearing member (photosensitive member) 1 is applied from the primary transfer roller 6 to the intermediate transfer belt 5 in the process of passing through the nip portion between the photosensitive member 1 and the intermediate transfer belt 5. The primary transfer is sequentially performed on the outer peripheral surface of the intermediate transfer belt 5 by the electric field formed by the primary transfer bias.

  A primary transfer bias for sequentially superimposing and transferring the first to fourth color toner images from the photoreceptor 1 to the intermediate transfer belt 5 has a polarity opposite to that of the toner and is applied from a bias power source (not shown).

  In the primary transfer process of the first to third color toner images from the photoreceptor 1 to the intermediate transfer belt 5, the secondary transfer roller 8 and the cleaning charging member 18 can be separated from the intermediate transfer belt 5.

  Reference numeral 7 denotes a secondary transfer roller, which is supported in parallel with the secondary transfer counter roller 6 and arranged in a state in which it can be separated from the lower surface of the intermediate transfer belt 5.

  The transfer of the multi-color toner image transferred onto the intermediate transfer belt 5 onto the transfer material P is performed by bringing the secondary transfer roller 7 into contact with the intermediate transfer belt 5 and the intermediate transfer belt 5 and the secondary transfer roller 7. The transfer material P is fed to the contact nip with a predetermined timing, and a secondary transfer bias is applied from the bias power source 31 to the secondary transfer roller 7. The multi-color toner image is secondarily transferred from the intermediate transfer belt 5 to the transfer material P by the secondary transfer bias.

  Thereafter, the unfixed multicolor toner image on the transfer material P enters the fixing device 15 and is fixed by heating and pressing to obtain an image.

  After the image transfer to the transfer material P is completed, a cleaning member 18 is brought into contact with the intermediate transfer belt 5 to collect toner (transfer residual toner) remaining on the intermediate transfer belt 5 without being transferred to the transfer material P. To do.

  The intermediate transfer belt includes a belt-shaped base layer and a surface treatment layer provided on the base layer. The surface treatment layer may be composed of a plurality of layers. Rubber, elastomer, or resin can be used for the base layer and the surface treatment layer.

  For example, as rubber and elastomer, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, ethylene-propylene terpolymer, chloroprene rubber, chlorosulfonated polyethylene, chlorinated polyethylene, acrylonitrile butadiene rubber, Urethane rubber, syndiotactic 1,2-polybutadiene, epichlorohydrin rubber, acrylic rubber, silicone rubber, fluorine rubber, polysulfurized rubber, polynorbornene rubber, hydrogenated nitrile rubber and thermoplastic elastomer (for example, polystyrene, polyolefin, 1 type or 2 types or more selected from the group consisting of polyvinyl chloride, polyurethane, polyamide, polyester, fluororesin, etc. can be used.However, it is not limited to the said material.

  As the resin, a resin such as a polyolefin resin, a silicone resin, a fluorine resin, or a polycarbonate can be used. A copolymer or a mixture of these resins may be used.

  As the base layer, one obtained by coating, dipping, or spraying the above-described rubber, elastomer, or resin on one side or both sides of a core layer having a woven fabric shape, a nonwoven fabric shape, a thread shape, or a film shape may be used.

  The material constituting the core layer is not particularly limited. For example, natural fibers such as cotton, silk, hemp and wool; regenerated fibers such as chitin fiber, alginic acid fiber and regenerated cellulose fiber; and half fibers such as acetate fiber Synthetic fiber: polyester fiber, nylon fiber, acrylic fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinyl chloride fiber, polyvinylidene chloride fiber, polyurethane fiber, polyalkyl paraoxybenzoate fiber, polyacetal fiber, aramid fiber, polyfluoroethylene fiber and phenol Synthetic fibers such as fibers; inorganic fibers such as carbon fibers, glass fibers, and boron fibers; one or more selected from the group consisting of metal fibers such as iron fibers and copper fibers can be used.

  Further, a conductive agent may be added to the base layer and the surface treatment layer in order to adjust the resistance value of the intermediate transfer belt. Although it does not specifically limit as a electrically conductive agent, For example, metal powder, such as carbon, aluminum, and nickel, metal oxides, such as a titanium oxide, and quaternary ammonium salt containing polymethyl methacrylate, polyvinyl aniline, polyvinyl pyrrole, One kind or two or more kinds selected from the group consisting of polydiacetylene, polyethyleneimine, boron-containing polymer compounds, conductive polymer compounds such as polypyrrole, and the like can be used.

  Below, the measuring method of each physical property which concerns on this invention is described collectively.

<Quantification method of nonionic surfactant>
The content of the nonionic surfactant in the fatty acid metal salt composition can be quantified by the following method.

  Specifically, it can be performed by analyzing an organic volatile substance to be thermally desorbed obtained by heating a fatty acid metal salt composition, using a gas chromatography equipped with a mass spectrometer. As a preferable measuring apparatus, for example, a combination of TRACE2000GC / MS (manufactured by ThermoQuest) and a headspace sampler can be used.

The following was used as conditions.
Extraction condition 120.0 ℃
Sample amount 1.0g
Column 0.32 mm Capillary column A method for identifying an unknown substance from a chart can be performed by searching a library from a mass spectrum chart for a substance having a peak. When the substance could be identified, the peak derived from the nonionic surfactant among the substances was defined as the surfactant peak. For the quantification, a calibration curve was prepared with the surfactant used at the time of synthesis and a standard reagent of the substance qualitatively determined from the mass spectrum chart, and the analyte was quantified based on the calibration curve. Note that peaks that could not be identified were defined as unknown peaks and excluded from the quantitative operation.

  Since the analysis is performed by the above method, only the components that can be volatilized are involved in the measurement. Therefore, not all nonionic surfactants in fatty acid metal salts have been quantified, but because the correspondence between the measurement results of this method and the performance can be obtained, this method is used in this application. did.

<Measuring method of particle size and particle size distribution of fatty acid metal salt composition>
The particle size and particle size distribution of the fatty acid metal salt composition were measured using a laser diffraction / scattering particle size distribution analyzer LA-920 (manufactured by HORIBA). The attached dedicated software is used for setting the measurement conditions and analyzing the measurement data. As a specific measurement method, first, an electrolyte solution (a solution obtained by dissolving special grade sodium chloride in ion-exchanged water to a concentration of about 1% by mass, for example, “ISOTON II” Beckman Coulter, Inc.) The batch type cell containing “manufactured” is set in a laser diffraction / scattering particle size distribution measuring apparatus LA-920 (manufactured by HORIBA) to adjust the optical axis and the background.

  Next, about 1 mg of a fatty acid metal salt composition in a glass 30 cc sample bottle and about 0.2 ml and 20 ml of an aqueous electrolytic solution of a dilution obtained by diluting “Contaminone N” as a dispersant with ion exchange water about 3 times by mass Add A dispersion for measurement is obtained by subjecting the sample bottle to ultrasonic dispersion for 60 seconds using an ultrasonic disperser. “Contaminone N” here is a 10% by weight aqueous solution of a neutral detergent for pH 7 precision measuring instrument cleaning, made of nonionic surfactant, anionic surfactant, and organic builder, manufactured by Wako Pure Chemical Industries, Ltd. However, it can be substituted if the same effect can be obtained. The measurement was performed within 1 minute after ultrasonic irradiation for the purpose of suppressing reaggregation after dispersion.

  The ultrasonic disperser used was a UH-50 type (manufactured by SMT) with a titanium alloy chip having a diameter of 5 mm as a vibrator. The ultrasonic dispersion was performed while cooling in the aqueous layer so that the temperature of the dispersion did not exceed 40 ° C.

  The obtained fatty acid metal salt composition dispersion was added to a batch cell until the transmittance of the tungsten lamp reached 95% to 90%, and the particle size distribution was measured.

<Measuring method of melting point>
The melting point was measured using a differential scanning calorimeter (DSC-7 (manufactured by Perkin Elmer)) according to ASTM D3418-82.

  The measurement was performed by raising the temperature from room temperature to 150.0 ° C. under a temperature raising condition of 1.0 ° C./min (no modulation).

  The melting point of the fatty acid metal salt composition was defined as the maximum endothermic peak temperature of the obtained measurement result.

<Method for measuring particle size distribution of toner>
The weight average particle diameter (D4) and number average particle diameter (D1) of the toner are measured by a fine particle size distribution measuring apparatus “Coulter Counter Multisizer 3” (registered trademark, Beckman Measured using a Coulter Co.).

  In addition, attached dedicated software “Beckman Coulter Multisizer 3 Version 3.51” (manufactured by Beckman Coulter, Inc.) for setting measurement conditions and analyzing measurement data was used. The data was analyzed based on data measured with 25,000 effective measurement channels, and the weight average particle diameter (D4) and number average particle diameter (D1) of the toner were calculated.

  As the electrolytic aqueous solution used for the measurement, special grade sodium chloride is dissolved in ion-exchanged water so as to have a concentration of about 1% by mass, for example, “ISOTON II” (manufactured by Beckman Coulter, Inc.) can be used.

  Prior to measurement and analysis, dedicated software was set up as follows.

  In the “Standard Measurement Method (SOM) Change Screen” of the dedicated software, set the total count in the control mode to 50000 particles, set the number of measurements once, and set the Kd value to “standard particles 10.0 μm” (Beckman Coulter, Inc.) Set the value obtained using The threshold and noise level are automatically set by pressing the threshold / noise level measurement button. Also, the current is set to 1600 μA, the gain is set to 2, the electrolyte is set to ISOTON II, and the aperture tube flash after measurement is checked.

  In the “pulse to particle size conversion setting screen” of the dedicated software, the bin interval is set to logarithmic particle size, the particle size bin is set to 256 particle size bin, and the particle size range is set to 2 μm to 60 μm.

The specific measurement method is as follows.
(1) About 200 ml of the electrolytic aqueous solution is put in a glass 250 ml round bottom beaker exclusively for Multisizer 3, set on a sample stand, and the stirrer rod is stirred counterclockwise at 24 rotations / second. Then, dirt and bubbles in the aperture tube are removed by the “aperture flush” function of the analysis software.
(2) About 30 ml of the electrolytic aqueous solution is put in a glass 100 ml flat bottom beaker, and about 0.3 ml of a diluted solution obtained by diluting “Contaminone N” with ion-exchanged water 3 times as a dispersant is added thereto. “Contaminone N” is a 10% by weight aqueous solution of a neutral detergent for cleaning a precision measuring instrument having a pH of 7 consisting of a nonionic surfactant, an anionic surfactant and an organic builder, manufactured by Wako Pure Chemical Industries.
(3) An ultrasonic disperser “Ultrasonic Dissipation System Tetora 150” (manufactured by Nikkaki Bios Co., Ltd.) having an electrical output of 120 W, in which two oscillators with an oscillation frequency of 50 kHz are incorporated with the phase shifted by 180 degrees, was prepared. A predetermined amount of ion-exchanged water is put into this water tank, and about 2 ml of the above-mentioned Contaminone N is added to this water tank.
(4) The beaker of (2) is set in the beaker fixing hole of the ultrasonic disperser, and the ultrasonic disperser is operated. And the height position of a beaker is adjusted so that the resonance state of the electrolyte solution surface in a beaker may become the maximum.
(5) In a state where the electrolytic aqueous solution in the beaker of (4) is irradiated with ultrasonic waves, about 10 mg of toner is added to the electrolytic aqueous solution little by little and dispersed. Then, the ultrasonic dispersion process is continued for another 60 seconds. In the ultrasonic dispersion, the temperature of the water tank is appropriately adjusted so as to be 10 ° C. or higher and 40 ° C. or lower.
(6) To the round bottom beaker of (1) installed in the sample stand, the electrolyte solution of (5) in which the toner is dispersed is dropped using a pipette, and the measurement concentration is adjusted to about 5%. . The measurement is performed until the number of measured particles reaches 50,000.
(7) The measurement data is analyzed with the dedicated software attached to the apparatus, and the weight average particle diameter (D4) and the number average particle diameter (D1) are calculated. When the graph / volume% is set with the dedicated software, the “average diameter” on the analysis / volume statistics (arithmetic average) screen is the weight average particle size (D4), and the graph / number% is set with the dedicated software. The “average diameter” on the analysis / number statistic (arithmetic average) screen is the number average particle diameter (D1).

<Toner shape measurement method>
The equivalent circle diameter, circularity, and frequency distribution of the toner are used as a simple method for quantitatively expressing the shape of the toner particles. Here, the equivalent circle diameter, circularity, and frequency distribution of the toner were measured using a flow type particle image measuring device FPIA-3000 (manufactured by Toa Medical Electronics Co., Ltd.), and calculated using the following formula.
Equivalent circle diameter = (particle projected area / π) ^1/2 × 2
Circularity = (perimeter of a circle having the same area as the particle projection area) / (perimeter of the particle projection image)
Here, the “particle projected area” is the area of the binarized toner particle image, and the “peripheral length of the particle projected image” is the length of the contour line obtained by connecting the edge points of the toner particle image. Define.

  The circularity is an index indicating the degree of unevenness of the toner particles, and is 1.00 when the toner particles are perfectly spherical. The more complicated the surface shape, the smaller the circularity.

  The circle equivalent number average diameter and the particle diameter standard deviation SDd, which mean the average value in the number-based particle size frequency distribution of the toner, are di and the frequency is the particle size (center value) at the dividing point i of the particle size distribution. Calculated from the following equation.

  Further, the average circularity and the circularity standard deviation SDc, which mean the average value of the circularity frequency distribution, are calculated from the following equations, where the circularity (center value) at the division point i of the particle size distribution is ci and the frequency is fci. Is done.

  As a specific measuring method, 10 ml of ion-exchanged water from which impure solids have been removed in advance is prepared in a container, and a surfactant, preferably an alkylbenzene sulfonate, is added as a dispersant therein, followed by further measurement. Add about 0.02 g of sample and disperse uniformly. As a means for dispersion, an ultrasonic disperser UH-50 type (manufactured by SMT Corporation) equipped with a titanium alloy chip having a diameter of 5 mm as a vibrator is used, and a dispersion for measurement is made using a dispersion treatment for 5 minutes. In this case, the dispersion is appropriately cooled so that the temperature of the dispersion does not exceed 40 ° C.

  To measure the shape of the toner particles, the flow type particle image measuring device is used, the concentration of the dispersion is readjusted so that the toner particle concentration at the time of measurement is 8000 / μl, and 1000 or more toner particles are measured. . After the measurement, using this data, the equivalent circle diameter of the toner, the circularity frequency distribution, and the like are obtained.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the examples.

[Production Example of Fatty Acid Metal Salt Composition (1)]
In this production example, synthesis was performed by a method (metathesis method) in which a solution of an inorganic metal compound was dropped into a solution of an alkali metal salt of a fatty acid in the presence of a nonionic surfactant.

  A continuous reaction apparatus having a wet classifier was used (see FIG. 1). Prepare a flow jet mixer that can supply and mix components (a) and (b) separately with a metering pump, and a 10 L receiving vessel with a stirring device having a turbine blade with a diameter of 6 cm, and rotate the turbine blade at 400 rpm. I let you. The components (a) and (b) whose temperatures were adjusted to 80 ° C. in advance were adjusted with a metering pump so that the liquid flow rate was 3.0 L / min. did.

  The mixed solution discharged from the flow jet mixer was put into a container. The flow rate of each solution was adjusted with a metering pump so that the solutions were finished simultaneously. After the entire amount was charged, the reaction was terminated by aging for 10 minutes while maintaining the temperature at 80 ° C.

  Coarse particles were removed from the reaction slurry containing the fatty acid metal salt composition after completion of the reaction through a crusher 007 (milder L in which a generator was modified into a tooth shape). The reaction slurry containing the fatty acid metal salt composition after completion of the reaction is held in the tank 008 and sent to the next step.

  The following were used as said (a) component and (b) component.

The following components were mixed as the component (a) shown in Table 2 and mixed with a stirrer equipped with a disper blade until the powder in the liquid was uniformly dispersed.
Fatty acid A-1: Sodium stearate grade 1 (manufactured by Kishida Chemical Co., Ltd.) 2.0 parts by mass Nonionic surfactant: activator (1) 0.010 parts by mass Water 100 parts by mass This component (a) Was introduced into the holding tank for the component (a) containing the raw material A indicated by 001 in FIG.

Moreover, the following component was mixed as (b) component, and it mixed until the powder in a liquid was disperse | distributed uniformly with the stirring apparatus equipped with the disper blade.
Inorganic metal salt B-1: Zinc sulfate grade 1 (manufactured by Kishida Chemical Co., Ltd.) 2.2 parts by mass Nonionic surfactant: activator (1) 0.010 parts by mass Water 100 parts by mass (b) The component was introduced into a holding tank for component (b) containing raw material B indicated by 002 in FIG.
The total amount of component (a) was adjusted so that the fatty acid metal salt composition became 5 kg after drying. Further, each amount was controlled by a metering pump 004 so that the amounts of the components (a) and (b) introduced into the flow jet mixer were the same flow rate, and mixing and reaction were performed.

  Next, the fatty acid metal salt composition slurry thus obtained was filtered, and the obtained fatty acid metal salt composition cake was washed four times with ion-exchanged water adjusted to 20 μS / m or less. The obtained washed fatty acid metal salt composition cake was dried at 50 ° C. or lower in a fluidized bed dryer (Okawara Seisakusho) into which dry nitrogen was introduced. For the purpose of removing coarse particles in the obtained fatty acid metal salt composition, sieving was performed with a mesh having an opening of 35 μm to obtain a fatty acid metal salt composition SA-1.

  In addition, using a heat exchanger (not shown), the reaction slurry is adjusted to around 40 ° C., which is a temperature suitable for wet classification. In the wet classifier, the coarse powder component is returned again to the crusher 007 via the heat exchanger 006, and is crushed again together with the reaction slurry containing the fatty acid metal salt and circulated to the classification step.

  Next, the fatty acid metal salt slurry thus obtained was filtered, and the obtained fatty acid metal salt cake was washed four times with ion-exchanged water adjusted to 20 μS / m or less. The obtained washed fatty acid metal salt cake was dried at 50 ° C. or lower in a fluidized bed dryer (Okawara Seisakusho) into which dry nitrogen was introduced. For the purpose of removing coarse particles in the obtained fatty acid metal salt, sieving was carried out with a net having an opening of 35 μm to obtain a fatty acid metal salt composition (SA-1). Table 4 shows the physical properties of the fatty acid metal salt composition obtained.

[Production Examples (2) to (18) of fatty acid metal salt composition]
The active agent shown in Table 1, and the raw material A and raw material B shown in Table 2 were adjusted with the combination shown in Table 3, and (a) component and (b) component were adjusted, respectively.

  Next, in the same manner as in Production Example (1), the amounts of the components (a) and (b) introduced into the flow jet mixer are controlled at the same flow rate by the metering pump 004 to perform mixing and reaction. The fatty acid metal salt compositions (SA-2) to (SA-18) were obtained.

  In addition, about manufacture example (4), manufacture example (5), and manufacture example (6), the frequency | count of the water washing of the fatty acid metal salt composition cake in a process was 10 times. Moreover, about manufacture example (14) and manufacture example (15), the fatty acid metal salt composition cake water washing frequency in a process was made into 2 times.

  Table 4 shows the physical properties of the fatty acid metal salt composition obtained.

In addition to the above synthetic products, the following samples were used from among the fatty acid metal salts available on the market. In addition, none of these contains a nonionic surfactant.
Fatty acid metal salt (SA-19)
: Nippon Oil & Fats Co., Ltd. Zinc stearate MZ-2
Fatty acid metal salt (SA-20)
: Zinc Chemical Industry Co., Ltd. 12 hydroxy zinc stearate SZ-120HF
Fatty acid metal salt (SA-21)
: Zinc Chemical Industry Co., Ltd. Zinc Stearyl Phosphate LBT-1830F

<Example of toner particle production>
[Toner particle production example (1)]
A sodium phosphate aqueous solution was added to a 2 liter four-necked flask equipped with a high-speed stirring device TK-homomixer, the rotation speed was adjusted to 9000 rpm, and the mixture was heated to 63 ° C. An aqueous calcium chloride solution was gradually added thereto to prepare an aqueous dispersion medium containing a minute hardly water-soluble dispersant.
on the other hand,
Styrene monomer 80 parts by mass 2-ethylhexyl acrylate monomer 20 parts by mass Divinylbenzene monomer 0.1 part by mass Saturated polyester resin 5 parts by mass (terephthalic acid-propylene oxide modified bisphenol A, acid value 15 mg KOH / G)
・ Carbon black (primary particle size 40 nm) 8 parts by mass ・ Mold release agent (behenyl behenate) 10 parts by mass ・ Aluminum benzylate compound 2.0 parts by mass

  The above materials were dispersed for 3 hours using a ball mill, and then the contents were separated from the ball mill. The contents were heated to 65 ° C. Next, 3 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator was added thereto. This polymerizable monomer composition was put into the aqueous dispersion medium and granulated while maintaining a rotation speed of 9000 rpm. Thereafter, the mixture was reacted at 65 ° C. for 4 hours while stirring with a paddle stirring blade, and then polymerized at 80 ° C. for 5 hours. Subsequently, vacuum distillation was performed at 80 ° C. and a pressure of 13.3 kPa (100 Torr) or less to remove residual monomers, and the reaction was completed.

  After completion of the reaction, the suspension is cooled, hydrochloric acid is added to dissolve the hardly water-soluble dispersant, filtered using a pressure filtration device, washed with ion-exchanged water, dried at a temperature of 45 ° C. or lower, and then air classification. To obtain a toner particle (1). The obtained toner particles were analyzed and found to contain 100 parts of a binder resin.

[Toner particle production example (2)]
In the toner particle production example (1), the concentration of the hardly water-soluble dispersant is adjusted so that the weight average diameter of the toner particles is about 5 μm, and the vacuum pressure is adjusted to 90 ° C. Toner particles (2) were obtained in the same manner as in Production Example (1).

[Toner particle production example (3)]
Toner particle (3) was prepared in the same manner as in toner particle production example (1) except that the concentration of the poorly water-soluble dispersant was adjusted so that the weight average diameter of the toner particles was around 10 μm in toner particle production example (1). Obtained.

[Toner particle production example (4)]
Toner particle (4) was prepared in the same manner as in toner particle production example (1) except that the concentration of the poorly water-soluble dispersant was adjusted so that the weight average diameter of the toner particles was about 11 μm in toner particle production example (1). Obtained.

[Toner particle production example (5)]
In the toner particle production example (1), the concentration of the hardly water-soluble dispersant is adjusted so that the weight average diameter of the toner particles is about 4.5 μm, and the vacuum degree is adjusted to 90 ° C. Toner particles (5) were obtained in the same manner as in Particle Production Example (1).

[Toner particle production example (6)]
In the toner particle production example (1), the concentration of the hardly water-soluble dispersant is adjusted so that the weight average diameter of the toner particles is about 7.5 μm, and the vacuum distillation temperature is adjusted to 90 ° C. Toner particles (6) were obtained in the same manner as in Toner Particle Production Example (1).

[Toner particle production example (7)]
In the toner particle production example (1), carbon black is C.I. I. Instead of Pigment Yellow 93, the concentration of the poorly water-soluble dispersant was adjusted so that the weight average diameter of the toner particles was about 7.5 μm. Further, toner particles (7) were obtained in the same manner as in the toner particle production example (1) except that the vacuum distillation temperature was 90 ° C. and the degree of vacuum was adjusted.

[Toner particle production example (8)]
In the toner particle production example (1), carbon black is C.I. I. Instead of Pigment Red 122, the concentration of the poorly water-soluble dispersant was adjusted so that the weight average diameter of the toner particles was about 7.5 μm. Further, toner particles (8) were obtained in the same manner as in the toner particle production example (1) except that the vacuum distillation temperature was 90 ° C. and the degree of vacuum was adjusted.

[Toner particle production example (9)]
In the toner particle production example (1), carbon black is C.I. I. Pigment Blue 15: 3 was used, and the concentration of the poorly water-soluble dispersant was adjusted so that the weight average diameter of the toner particles was about 7.5 μm. Furthermore, toner particles (9) were obtained in the same manner as in the toner particle production example (1) except that the vacuum distillation temperature was 90 ° C. and the degree of vacuum was adjusted.

[Toner particle production example (10)]
・ Styrene-n-butyl acrylate copolymer 100 parts ・ Carbon black (primary particle size 40 nm) 6 parts ・ 3,5-di-tert-butylsalicylic acid aluminum compound 4 parts ・ Ester wax 2 parts Premixing was performed. Next, the mixture was melt-kneaded with a twin-screw extruder, cooled and roughly pulverized to about 1 to 2 mm using a hammer mill, and then finely pulverized with an air jet type pulverizer. Further, the toner particles (10) were obtained by air classification to be about 6.5 μm.

[Toner particle production example (11)]
In the toner particle production example (10), carbon black was changed to C.I. I. Toner particles (11) were obtained in the same manner as in the toner particle production example (10) except that the pigment yellow 74 was used.

[Toner Particle Production Example (12)]
In the toner particle production example (10), carbon black was changed to C.I. I. Toner particles (12) were obtained in the same manner as in Toner Particle Production Example (10) except that the pigment red 84 was used.

[Toner particle production example (13)]
In the toner particle production example (10), carbon black was changed to C.I. I. Toner particles (13) were obtained in the same manner as in the toner particle production example (10) except that the pigment blue was changed to 15: 3.

<Example of toner production>
[Toner Production Example (1)]
Hydrophobic silica fine powder having a BET specific surface area of 200 m ² / g treated with 100 parts by mass of the toner particles (1), 0.1 part by mass of the fatty acid metal salt composition (SA-1), hexamethyldisilazane and dimethyl silicone oil. (S-1) 1.5 parts by mass were charged into a Henschel mixer (Mitsui Mining Co., Ltd.). A Henschel mixer having an internal volume of 10 liters was used, and the processing conditions in the Henschel mixer were set so that the baffle plate was 90 degrees and the rotation speed was 3000 rotations with respect to the circumferential direction of the stirring blade. Using this apparatus, the fatty acid metal salt composition (SA-1) and the external additive component (S-1) were added to the toner particles at the same timing and mixed for 10 minutes to obtain a toner (1).

[Toner Production Examples (2) to (5)]
Example of toner production except that the amount of the fatty acid metal salt composition (SA-1) and the kind and amount of the hydrophobic silica fine powder are changed as shown in Table 5 with respect to 100 parts by mass of the toner particles (1). Toners (2) to (5) were obtained in the same manner as (1).

[Toner Production Example (6)]
Toner production except that 0.05 part by weight of fatty acid metal salt composition (SA-1) and 0.05 part by weight of fatty acid metal salt composition (SA-7) are used per 100 parts by weight of toner particles (1). In the same manner as in Example (1), Toner (6) was obtained.

[Toner Production Example (7)]
A toner (7) was obtained in the same manner as in Toner Production Example (1) except that the fatty acid metal salt composition (SA-1) was replaced with the fatty acid metal salt composition (SA-3).

[Toner Production Example (8)]
BET after changing fatty acid metal salt composition (SA-1) to fatty acid metal salt composition (SA-4), changing the addition amount of S-1 to 1.4 parts by mass, and further treating with hexamethyldisilazane Toner (8) was obtained in the same manner as in Toner Production Example (1) except that 0.3 part by mass of anatase-type titanium oxide (T-1) having a specific surface area of 25 m ² / g was added. The fatty acid metal salt composition, the hydrophobic silica fine powder, and titanium oxide were added to the toner particles at the same timing.

[Toner Production Examples (9) and (10)]
The fatty acid metal salt composition (SA-1) is replaced with the fatty acid metal salt composition (SA-5) or the fatty acid metal salt composition (SA-6), and the titanium oxide T-1 is formulated in Table 5. Toners (9) and (10) were obtained in the same manner as in Toner Production Example (1) except that addition was performed. The fatty acid metal salt composition, the hydrophobic silica fine powder, and titanium oxide were added to the toner particles at the same timing.

[Toner Production Examples (11) to (13)]
Similar to Toner Production Example (8), except that toner particles (2) and fatty acid metal salt composition (SA-7) to fatty acid metal salt composition (SA-9) are used and formulated as shown in Table 5. Thus, toners (11) to (13) were obtained.

[Toner Production Example (14)]
Using 100 parts by mass of toner particles (3), 0.9 part by mass of fatty acid metal salt composition (SA-10), 1.7 parts by mass of hydrophobic silica fine powder (S-1), and stearic acid Toner (14) was obtained in the same manner as in Toner Production Example (1) except that 0.05 part by mass of hydrotalcite having a BET specific surface area of 8 m ² / g after the surface treatment was added. The fatty acid metal salt composition, the hydrophobic silica fine powder, and the hydrotalcite were added to the toner particles at the same timing.

[Toner Production Examples (15) to (22)]
Toners (15) to (22) were obtained in the same manner as in Toner Production Example (14) except that the formulations shown in Table 5 were used.

[Toner Production Examples (23) to (26)]
Toners (23) to (9) are prepared in the same manner as in Toner Production Example (1) except that toner particles (6) to (9) and a fatty acid metal salt composition (SA-1) are used. (26) was obtained. These are used in the examples described later as a full-color toner set including black toner, yellow toner, magenta toner, and cyan toner.

[Toner Production Examples (27) to (30)]
Toners (27) to (30) were obtained in the same manner as in Toner Production Example (1) except that the toner particles (10) to (13) were used and the formulations shown in Table 5 were used. These are used in the examples described later as a full-color toner set including black toner, yellow toner, magenta toner, and cyan toner.

[Toner Comparative Production Examples (1) to (3)]
Comparative toners (1) to (3) were prepared in the same manner as in Toner Production Example (1) except that the fatty acid metal salt composition (SA-1) was replaced with the fatty acid metal salt compositions (SA-19) to (SA-21). )

[Toner Comparative Production Examples (4) to (7)]
Comparative toner (4) in the same manner as in Toner Production Example (1) except that toner particles (10) to (13) and fatty acid metal salt composition (SA-19) are used and the respective formulations are listed in Table 5. To (7) was obtained.

  Table 5 summarizes the external additive formulation of the obtained toner and the physical properties of the toner.

In the table, S-1 to S-3 and T-1 to T-3 are the following external additives.
S-1: Silica having a BET specific surface area of 200 m ² / g hydrophobized with hexamethyldisilazane and dimethylsiloxane S-2: Silica S-3 having a BET specific surface area of 300 m ² / g hydrophobized with dimethylsiloxane : BET specific hydrophobized by hexamethyldisilazane and dimethylsiloxane surface area ^90m 2 / g of silica T-1: anatase-type titanium oxide hexamethyl dicyanamide Raza hydrophobized BET specific surface area of ^{25 m} 2 / g Te in emissions T-2: BET specific surface area of 26 m ² / g rutile type titanium oxide hydrophobized with hexamethyldisilazane T-3: higher fatty acid-treated hydrotalcite [Example (1)]
The image forming apparatus used in this embodiment will be described below.

  In Example 1, image evaluation was performed using an image forming apparatus as shown in FIG.

  FIG. 3 is a schematic view of a modified color laser beam printer (Canon: LBP-5500) using a non-magnetic one-component contact developing type electrophotographic process. The transfer material P is biased by the suction roller 63 and is sucked and transported to the transfer transport belt 16. Each color image formed on the photoconductor is sequentially transferred to the transfer material P adsorbed on the transfer conveyance belt by applying a bias having a polarity opposite to that of the toner from the transfer roller 17, and is superposed thereon. Heat fixing.

  In this evaluation machine, four development process cartridges having four color toners of cyan, yellow, magenta, and black are arranged, and an electrostatic latent image visualized using each toner is sequentially transferred onto a transfer material, Further, the image forming method fixes an unfixed image on a transfer material.

  Each process cartridge is a non-magnetic one-component contact developing type cartridge that performs development by pressing a one-component developing device as shown in FIG. 3 against an electrostatic latent image carrier. It is arranged.

In this example, an apparatus in which the following parts (a) to (f) were modified was used.
(A) The toner carrier was driven so that all the four colors were 150% in the forward direction with respect to the peripheral rotation speed of the photoreceptor.
(B) A phosphor bronze blade (thickness 0.4 mm) was used for controlling the coat layer of the toner on the toner carrier.
(C) The base layer side of the electrostatic latent image bearing member was grounded, and the applied voltage between the toner bearing member and the electrostatic latent image bearing member during development was fixed at -330V DC.
(D) A DC voltage of 200 V was applied between the toner carrier and the phosphor bronze blade so that the blade side was positive.
(E) The photoreceptor was adjusted so that the dark portion potential was −700 V and the light portion potential was −150 V.
(F) The transfer voltage at each station was set to DC 1770V.
(G) The drive system was modified and the process speed was controlled so that the output speed was 30 sheets / min with A4 vertical feed.
(H) A mono color mode (mono color mode) in which only a single color is driven.

  As Example 1, a cartridge developing unit 44 was prepared in which the above apparatus was used and the developing unit 104 having the structure shown in FIG. 2 was filled with the Bk toner (1) obtained in the toner production example (1). The other cartridge developing devices 41, 42 and 43 used the products as they were. These were arranged side by side in the image forming apparatus of FIG.

<Evaluation conditions>
The toner filling amount was 200 g.

  A horizontal line image adjusted so that the image printing ratio becomes 1.0% in a low temperature and low humidity environment (15 ° C., 10% RH) and a high temperature and high humidity environment (30 ° C., 70% RH) is passed intermittently. Made paper. The method of intermittent paper passing was performed by passing three sheets, taking a rest time of 5 seconds, and then passing paper again from a state where the process operation was completely stopped. The evaluation was performed by the method described later at the timing of the endurance early stage (10 to 50 sheets), the middle endurance stage (10000 sheets), and the last stage of endurance (20,000 sheets). The respective evaluation results are shown in Tables 6 and 7.

・ Change in durable particle size of toner At the initial stage of durability (50 sheets) and at the middle stage of durability (10000 sheets), a small amount of toner in the developing container is collected from the toner inlet, and the particle size is measured with Coulter Multisizer III (weight) Average particle size (D4), volume-based 10.1 μm or more, number-based 3.17 μm or less). Using the obtained results, the ratio was calculated by dividing [Results of Endurance Medium Toner] by [Results of Initial Toner], which was used as an index of particle size change.

-Toner fusion The toner on the surface of the toner carrier was removed by performing vacuum suction with a suction device with a narrowed tip for each durable sheet. Subsequently, a transparent tape (for example, a transparent cellophane tape manufactured by Nichiban Co., Ltd.) was adhered to the toner removal portion of the toner carrier surface, and the substance remaining on the toner carrier surface was collected. Next, this tape was attached to plain paper CLC paper for copying machines (80 g / m ² , manufactured by Canon Inc.). Further, an unused tape similar to that used for collecting the toner carrier surface was pasted on the same paper as a background. Subsequently, the density | concentration of the tape part was each measured using the Macbeth densitometer (made by RD924 Macbeth), the difference was computed, and the following reference | standard evaluated.
A: density less than 0.050 B: density 0.050 or more, less than 0.075 C: density 0.075 or more, less than 0.125 D: density 0.125 or more, less than 0.150 E : density 0 . 150 or more

-Stripe image Print density 15% and 25% halftone images were output, and the degree of development streaks on the image (dark streaks on continuous images) was visually evaluated.
A: Not generated.
B: Almost no occurrence.
C: Several weak streaks occur.
D: Many weak streaks are generated.
E: Remarkable streaks are generated.

-Halftone image quality A halftone image of 2 dots and 3 spaces was output at a resolution of 600 dpi, and the obtained image was visually evaluated for halftone image quality (development density unevenness).
A: No shading unevenness is felt. B: Shading unevenness is slightly observed, but is hardly noticeable.
C: Some shading unevenness is observed.
D: Light and shade unevenness can be confirmed.
E: Shading unevenness is very conspicuous.

-Fog For each durable sheet, a chart including a white background portion was output on plain paper CLC paper for copying machines (80 g / m ² , manufactured by Canon Inc.). Measure the whiteness of the white area of the printout image and the whiteness of the unused transfer paper using a “reflectometer” (manufactured by Tokyo Denshoku), and calculate the fog density (%) from the difference. Evaluated by criteria.
A: reflection density less than 0.3% B: reflection density 0.3% or more, less than 1.0% C: reflection density 1.0% or more, less than 2.0% D: reflection density 2.0% or more, 3 Less than 0% E: Reflection density 3.0% or more

-Charging contamination The primary charger was visually evaluated for its contamination status and the effect on the image caused by the contamination.
A: Almost no contamination and no image defects.
B: Some contamination can be confirmed, but there is no influence on the image.
C: Although there is contamination, there is a slight influence on the image.
D: There is contamination and the influence on the image is observed.
E: Contamination is significant and image defects are caused by primary charging failure.

[Example (2) to Example ( 19 )]
An image was formed in the same manner as in Example (1) except that the toner (2) to the toner ( 19 ) were used, and each toner was evaluated. The evaluation results are shown in Tables 6 and 7.

[Comparative Example (1) to Comparative Example (3)]
An image was formed in the same manner as in Example (1) except that comparative toner (1) to comparative toner (3) were used, and each toner was evaluated. The evaluation results are shown in Tables 6 and 7.

  From the above results, by using a toner containing a fatty acid metal salt composition containing a nonionic surfactant and a fatty acid metal salt as an external additive, the toner particle size change throughout the durability can be reduced, and the durability stability. It was found that can be improved. Further, the small change in particle size due to the durability of the toner means that the coat stability of the toner on the toner carrier and the developability of the toner from the toner carrier to the latent image carrier are excellent. Thus, it was found that the toner of the present invention is excellent in these respects.

  It is also clear that a toner containing a fatty acid metal salt composition containing a nonionic surfactant and a fatty acid metal salt as an external additive has excellent characteristics in toner fusion, streak image, and halftone image quality. became. This is presumably because the toner particles are prevented from being overcharged by the influence of the nonionic surfactant contained in the fatty acid metal salt, and appropriate charging characteristics are maintained even in a low humidity environment. Is done.

* In the table, OUT represents that the durability test was stopped due to toner exhaustion.

[Example (23)]
In this example (23), a full color image was formed using an image forming apparatus as shown in FIG. 4 and image evaluation was performed. The apparatus shown in FIG. 4 is a laser beam printer using a non-magnetic one-component contact development type electrophotographic process having an intermediate transfer belt. Specifically, it has a development process cartridge having four color toners of cyan, yellow, magenta, and black, and the electrostatic latent image is developed using each toner. Next, the developed toner image is sequentially transferred onto an intermediate transfer belt and an unfixed image is superimposed, and then secondarily transferred onto a transfer material using a secondary transfer device and further unfixed onto the transfer material. The image is fixed. As each developing process cartridge, a non-magnetic one-component contact developing type cartridge having the configuration shown in FIG. 2 was used, and toners (23) to (26) were used as toners.

Further, the process cartridge and the main body are set as follows.
(A) The toner carrier was driven so that all the four colors were 150% in the forward direction with respect to the peripheral rotation speed of the photoreceptor.
(B) A phosphor bronze blade (thickness 0.4 mm) was used for controlling the coat layer of the toner on the toner carrier.
(C) The base layer side of the electrostatic latent image carrier was grounded, and the applied voltage applied between the toner carrier and the electrostatic latent image carrier during development was fixed at -350V DC.
(D) A DC voltage of 200 V was applied between the toner carrier and the phosphor bronze blade so that the blade side would be positive.
(E) The photosensitive member had a dark part potential of −700 V and a light part potential of −150 V.
(F) The primary transfer voltage at each station was set to 1500V.
(G) The primary transfer voltage was 1500V and the secondary transfer voltage was 1750V.
(H) The drive system was modified and the process speed was controlled so that the output speed was 32 sheets / min with A4 vertical feed.

<Evaluation conditions>
A horizontal line image adjusted to have an image printing ratio of 1.0% in a low temperature and low humidity environment (15 ° C., 10% RH) and a high temperature and high humidity environment (30 ° C., 70% RH) was passed through intermittently. . The method of intermittent paper passing was performed by passing three sheets, taking a rest time of 5 seconds, and then passing paper again from a state where the process operation was completely stopped. Evaluation was performed at the initial stage of durability (10 to 50 sheets), the middle stage of durability (10000 sheets), and the last stage of durability (20000 sheets). The evaluation criteria for each item are in accordance with the evaluation criteria in Example 1.

  The evaluation results are shown in Table 8.

[Example (24)]
An image was formed in the same manner as in Example (23) except that the toners (27) to (30) were used, and each toner was evaluated. The evaluation results are shown in Table 8.

[Comparative Example (4)]
An image was formed in the same manner as in Example (23) except that the comparative toners (4) to (7) were used, and each toner was evaluated. The evaluation results are shown in Table 8.

* In the table, OUT represents that the durability test was stopped due to toner exhaustion.

It is the schematic of the continuous reaction apparatus which can be used for the synthesis | combination of a fatty-acid metal salt composition. 1 is a schematic view of a non-magnetic one-component developing device. 1 is a schematic view of a full-color image forming apparatus. 1 is a schematic view of a full-color image forming apparatus.

Explanation of symbols

001 Holding tank for raw material (a) 002 Holding tank for raw material (b) 003 Reactor 007 Crushing device 008 Slurry tank 92 Toner carrier 95 Toner supply roller 98 Toner 96 Regulating blade 3 Laser light 2 Charging device 13 Cleaning device 15 Fixing Device 17 Transfer roller 32 Transfer bias power supply P Paper 11 Paper feed roller 7 Secondary transfer roller

Claims (13)

A toner comprising toner particles having a binder resin and a colorant, and a fatty acid metal salt composition as an external additive,
The fatty acid metal salt composition contains a nonionic surfactant and a fatty acid metal salt ,
The toner content of the nonionic surfactant of the fatty acid metal salt composition is characterized 5ppm to 510ppm der Rukoto.   The toner according to claim 1, wherein the nonionic surfactant is an ether type surfactant.   The toner according to claim 1, wherein the nonionic surfactant has an HLB value in a range of 5.0 or more and 15.0 or less.   The toner according to claim 1, wherein the content of the nonionic surfactant in the fatty acid metal salt composition is 10 ppm to 500 ppm. The nonionic surfactant is polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, according to any one of claims 1 to 4, characterized in that selected from the group consisting of polyoxyethylene alkyl phenyl ether Toner. The toner according to any one of claims 1 to 5 metal species definitive in the fatty acid metal salt, characterized in that it is a zinc or calcium. The fatty acid metal salt, the toner according to any one of claims 1 to 6 zinc stearate or wherein the calcium der Rukoto stearate.   The toner according to any one of claims 1 to 7, wherein the fatty acid metal salt composition has a melting point of 122.0 ° C or higher and 130.0 ° C or lower.   2. The volume-based particle size distribution of the fatty acid metal salt composition measured by a laser diffraction / scattering particle size distribution analyzer has a volume-based median diameter (D50s) of 0.15 μm or more and 1.05 μm or less. The toner according to any one of 8 to 8.   The toner according to claim 9, wherein a median diameter (D50s) on a volume basis is 0.15 μm or more and 0.65 μm or less.   The toner according to claim 9, wherein a median diameter (D50s) on a volume basis is 0.30 μm or more and 0.60 μm or less.   The toner according to claim 1, wherein the fatty acid metal salt composition is contained in an amount of 0.02 to 1.00 parts by mass with respect to 100 parts by mass of the toner particles. A developing step for visualizing the supported toner using electrostatic latent image on the toner carrying member, a transfer step of transferring the visualized toner image by the toner on the recording material, and the toner image on the recording material an image forming method of have a fixing step of fixing the,
As the toner, an image forming method which comprises using a toner according to any of claims 1 to 12.

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