JP4603802B2 - Color toner - Google Patents

Description

  The present invention relates to a toner used in an electrophotographic method, an electrostatic recording method, an electrostatic printing method, and a toner jet recording method (magnetic recording method).

  Conventionally, many methods are known as electrophotographic methods (see, for example, Patent Document 1, Patent Document 2, and Patent Document 3). In general, a photoconductive substance is used to form an electric latent image on a photoconductor by various means, and then the latent image is developed with toner to form a visible image. After the toner is transferred to the recording material (transfer material), the toner image is fixed on the recording material by heat and pressure to obtain a copy. Toner that is not transferred and remains on the photoreceptor is cleaned by various methods, and the above-described steps are repeated.

  In recent years, with such high demands from users, such copying machines have been improved in the direction of higher image quality, smaller size, lighter weight, higher speed and higher reliability, and the performance of products has been strictly pursued. . It has been used for a long time since it has been used not only as a copier for business processing for copying original documents, but also for copying high-definition images of digital printers or graphic designs as computer output. Furthermore, in recent years, there has been an increasing demand for high-definition printers for outputting photographs taken with the explosive spread of digital cameras. On the other hand, consideration for the environment and energy saving is becoming increasingly necessary.

  A development process is mentioned as a difficult process in the electrophotographic image formation process in order to achieve the high image quality, high definition, and high stability of the image which is a user's request.

  In the electrophotographic method, the step of developing the electrostatic charge image is to form an image on the electrostatic charge image by utilizing electrostatic interaction between the charged toner particles and the electrostatic charge image. Among developers that develop electrostatic images using toner, a magnetic one-component developer using magnetic toner in which a magnetic material is dispersed in a resin, and a non-magnetic toner are charged by a charging member such as an elastic blade. There are a non-magnetic one-component developer to be developed and a two-component developer in which a non-magnetic toner is mixed with a magnetic carrier.

  With the development of technology that exposes a photoconductor using a small-diameter laser beam, etc., the electrostatic latent image has become finer, so that the electrostatic latent image can be developed faithfully and higher quality output can be obtained. In any of the development methods described above, both the toner particles and the carrier particles have been reduced in diameter. In particular, it is often performed to improve the image quality by reducing the average particle diameter of the toner.

  Reducing the average particle diameter of the toner is an effective means for improving the graininess and character reproducibility, particularly among the image quality characteristics. There are problems to be improved in fusing, toner scattering, and the like.

This is because the external additive added to the toner particles is deteriorated by long-term use, and the chargeability of the sleeve and carrier and the coatability of the toner on the sleeve are a predetermined amount. This is because the charge amount of the toner decreases as a result of two points that the regulating member for maintaining the toner is contaminated by the toner and the external additive, that is, the spent occurs. This phenomenon is likely to occur when the diameter of the toner is reduced. More specifically, friction charging is performed by a physical external force such as contact / collision between a toner and a sleeve in a one-component developer and contact / collision between a toner and a carrier in a two-component developer. This will damage all of the sleeve carrier and the regulating member. For example, in a toner, an external additive added to the surface of the toner is embedded in the toner, or a toner component is dropped off. In the charge imparting member and the regulating member, the toner component including the external additive is contaminated, and the coating component coated on the charge imparting member in order to properly stabilize the charge is worn or destroyed. These damages cause the initial characteristics of the developer to not be maintained as the number of copying increases, causing fogging, in-machine contamination, and fluctuations in image density. This phenomenon becomes more conspicuous especially as the pixel unit of the electrostatic latent image becomes finer.

  Second, when using a document with a high image area ratio, if a large amount of toner is supplied onto the charging member, it takes time until the toner is uniformly charged when supplied, and it is uncharged. The above-mentioned problem is caused by the toner contributing to the development. This phenomenon remarkably occurs when the diameter of the toner is reduced and the fluidity is lowered. Such an image defect is likely to be a problem when forming a full-color multicolor superimposed image, and particularly needs improvement. As countermeasures against this problem, studies on the charging series and resistance of the charge imparting member are mainly performed. Further, as a toner, studies have been made to quickly charge the toner by improving various charge control agents.

  As a magnetic carrier used for a two-component developer, an iron powder carrier, a ferrite carrier, or a resin-coated carrier in which magnetic fine particles are dispersed in a binder resin is known. Among them, a developer using a resin-coated carrier in which the surface of a carrier core material is coated with a resin can optimize resistance, has excellent charge controllability, and is relatively easy to improve environment dependency and stability over time. Therefore, it is preferably used.

  In order to solve the insufficiency of charging with respect to the toner having a small particle diameter as described above, it is also a preferable means to reduce the particle diameter of the carrier, particularly in the case of a two-component developer, but it increases the specific surface area of the carrier. Accordingly, it becomes easy to cause deterioration of spent resistance.

  Regarding these problems, although the amount of carrier to be used is increased, it is contrary to the miniaturization of a copying machine or a printer main body and is not practical.

  On the other hand, the fixing process is one of the most important and technically difficult processes for satisfying the user's needs.

  Various methods and apparatuses have been developed for the fixing process, but the most common method at present is a pressure heating method using a heated roller, film or belt.

  The pressure heating method is fixed by passing the toner image surface of the fixing sheet under pressure while passing through the surface of a heated body formed of a material having a releasability with respect to the toner (silicone rubber or fluororesin). Is to do. In this method, since the surface of the heating body and the toner image of the fixing sheet are in contact with each other under pressure, the thermal efficiency when fusing the toner image on the fixing sheet is extremely good, and the fixing is performed quickly. This is very effective in a high-speed electrophotographic copying machine. However, in the above method, since the surface of the heating body and the toner image are in pressure contact in a molten state, a part of the toner image may adhere to and transfer to the surface of the heating body, so that the next fixing sheet is stained (so-called so-called). "Offset phenomenon"). Therefore, it is an essential condition to prevent the toner from adhering to the heating body.

  For this reason, for the purpose of preventing offset, there is also a method for supplying an oil such as silicone oil to the fixing body and uniformly covering the fixing body as a color machine.

  However, this method is extremely effective in preventing toner offset, but has a problem that the fixing device becomes complicated because a device for supplying the liquid for preventing offset is required. This is an impediment to designing inexpensive and inexpensive systems. Furthermore, a transparency film (OHP film) that uses an overhead projector for presentations has a low oil absorption capability unlike paper, and thus the stickiness of the surface of the OHP film after fixing becomes a problem. In the case of paper, there is also a problem that writing with water-based ink or the like cannot be performed due to absorbed oil. Under such circumstances, there is a strong demand for a full-color toner that can be fixed with a system that is oil-less or has a small amount of oil applied.

  Under such circumstances, even in color toners, oil-less fixing or oil small amount application fixing is realized by including a release agent in the toner.

  It is known to include a release agent in the toner particles (see, for example, Patent Document 4, Patent Document 5, and Patent Document 6).

  Further, a large number of toner release particles are disclosed (for example, Patent Document 7, Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14). , Patent Document 15 and Patent Document 16).

  The release agent is used for improving the offset resistance at the time of low-temperature fixing or high-temperature fixing of the toner and for improving the fixing property at the time of low-temperature fixing. On the other hand, the developing property is reduced by reducing the blocking resistance of the toner, the developing property of the toner is lowered by the temperature rise in the machine, or the release agent oozes out on the toner particle surface when the toner is left for a long period of time. Or drop.

  Further, an application has been filed that enables oil-less fixing by defining the elastic modulus of the release agent-containing toner. The gazettes have certainly invented an invention in which both transparency of OHP and high-temperature offset resistance are achieved by specifying viscoelasticity in the vicinity of fixing set temperatures of 150 ° C. and 170 ° C. (Patent Document 17, (See Patent Document 18). However, in the case of high-speed fixing in which the temperature of the heating element drops drastically during continuous paper feeding, fixing problems at low temperatures, the so-called low-temperature offset phenomenon, fixing such as paper discharge / stacking defects, and long-term stable developability There is a problem with respect to the point of providing.

The paper discharge / stacking failure will be described. As a problem in the case of oilless or oil small amount application fixing, the transfer paper is discharged in a form in which the front end of the transfer paper is pulled toward the fixing body after passing through the fixing nip. This is a phenomenon caused by insufficient releasability between the toner melting surface and the fixing member. In this case, a problem of poor stacking of a large number of discharged papers arises. In addition, when the level of the above phenomenon is bad, the transfer paper is wound around the fixing member, causing a discharge failure. In order to prevent this paper discharge failure, a member such as a separation claw is brought into contact with the fixing roller in contact or non-contact. However, in the case of contact, the offset toner staying on the separation claw, etc., increases the contact pressure to the fixing roller, damages the surface of the fixing body, and reduces the fixing property of that part, thereby reducing the gloss with other parts. A difference is produced, and the quality of the fixed image is different only in that portion. Furthermore, the toner staying in the separation claw part is peeled off at a certain timing and transferred to the pressurizing body, and so-called back dirt is generated that stains the back surface of the output image. In order to reduce this phenomenon, attempts have been made to contact a web impregnated with silicone oil or the like , but this is contrary to the downsizing and cost reduction of the fixing device as described above. This sticking phenomenon occurs as the affinity between the toner and the fixing member increases, and the fixing structure tends to deteriorate as the fixing speed increases and the fixing temperature decreases.

As a further requirement in the fixing process, there is a toner that can be fixed at a low temperature to cope with power saving and high speed of a printer and a copying machine main body. In particular, the formation of a full-color image is performed by using three color toners of yellow, magenta, and cyan, which are the three primary colors of the color material, or four color toners with black toner added thereto. Is fixed on paper and fixed on an overhead projector sheet (OHT) to satisfy color reproduction / transparency. Therefore, the technical difficulty is high.

  In order to solve these problems, it is preferable to use a resin having a sharp melt property, and in particular, a polyester resin is contained in the toner.

  Polyester resins are excellent in low-temperature fixability, but because of their acid value and hydroxyl value, it is difficult to control the charge amount in the case of toner. In particular, this phenomenon occurs remarkably when the molecular weight distribution of the resin is broad. Specifically, the difficulty in controlling the amount of charge is the degree of environmental characteristics such as overcharging under low humidity (so-called charge-up) and insufficient amount of charge under high humidity, and the slow rise of the charge amount. . Further, when the molecular weight of the polyester resin is reduced in order to improve the low-temperature fixability, the oligomer component increases, and the frequency of occurrence of toner contamination on the photosensitive member and the charging member increases.

  As a general polymerization catalyst for producing a polyester resin for toner, an organotin catalyst such as dibutyltin oxide and monobutyltin oxide and an antimony system such as antimony trioxide have been used. However, these technologies satisfy the color reproducibility such as low-temperature fixability and high-temperature offset resistance, color mixing and transparency required for full color toners that satisfy the above-mentioned high user requirements, and the charge amount. There are problems in terms of stably controlling the rising characteristics, the charge amount of the toner, and further suppressing the contamination of the member on the photoreceptor.

  In view of this, an invention using a titanate ester of diol as a polymerization catalyst has been made (see Patent Document 19). In addition, an invention using a solid titanium compound as a polymerization catalyst has been made (see Patent Document 20). In these inventions, although the charge-up phenomenon of the toner is suppressed by using the titanium compound as a polymerization catalyst, the rising characteristics of charging have not been sufficiently satisfied.

  In general, when a sharp melt resin is used, when the toner is melted in the heat and pressure fixing step, the self-cohesion force of the binder resin is low, and thus a problem with high temperature offset resistance is likely to occur. Therefore, in order to improve the high temperature offset resistance at the time of fixing, a relatively high crystalline wax represented by polyethylene wax or polypropylene wax is used as a release agent.

  However, in full-color image toner, due to the high crystallinity of the release agent itself and the difference in refractive index from the material of the OHP sheet, transparency is hindered when projected with OHP, and the projected image is colored. Degree and brightness may be low.

  In order to solve these problems, a method using a wax having a low crystallinity has been proposed (see, for example, Patent Document 21 and Patent Document 22). There is a Montan wax as a wax having a relatively high transparency and a low melting point, and many uses of the wax have been proposed (see, for example, Patent Document 23, Patent Document 24, Patent Document 25, Patent Document 26, and Patent Document 27). . However, these waxes have some problems in order to sufficiently satisfy all of transparency with OHP, low-temperature fixability at the time of heat and pressure fixing, and high-temperature offset resistance.

In any of the toner which contains the above-mentioned release agent, good development properties due to the presence of the release agent on the toner surface, it does not exist that provide particularly stable rising characteristics of the charge for a long time.

  As described above, there has not yet been provided a toner that can achieve both low-cost, small-size, and high-speed machine fixing ability and developability that can satisfy image quality for a long time.

US Pat. No. 2,297,691 Japanese Patent Publication No.42-23910 Japanese Patent Publication No.43-24748 Japanese Patent Publication No.52-3304 Japanese Patent Publication No.52-3305 Japanese Unexamined Patent Publication No. 57-52574 Japanese Patent Laid-Open No. 3-50559 Japanese Patent Laid-Open No. 2-79860 JP-A-1-109359 Japanese Patent Laid-Open No. Sho 62-14166 JP-A-61-273554 JP 61-94062 A JP-A-61-138259 JP-A-60-252361 JP-A-60-252360 JP-A-60-217366 JP-A-6-59502 Japanese Patent Laid-Open No. 8-54750 JP 2002-148867 A JP 2001-64378 A Japanese Patent Laid-Open No. 4-301853 JP-A-5-61238 JP-A-1-185660 JP-A-1-185661 Japanese Patent Laid-Open No. 1-185662 JP-A-1-185663 JP-A-1-238672

  An object of the present invention is to solve the above-described problems, and to provide a toner that is excellent in low-temperature fixability and high-temperature offset resistance and can stably achieve a high-quality image for a long time in any environment.

  Another object of the present invention is to provide a toner having excellent color reproducibility such as color mixing and transparency in a color toner.

  Another object of the present invention is to provide an excellent toner that suppresses toner contamination on a charging member or the like of a photoreceptor or a developer.

  As a result of intensive studies, the present inventors have found that the above requirements can be satisfied by using a polar resin synthesized with a specific polymerization catalyst, and have reached the present invention. That is, the present invention is as follows.

(1) A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a charge control agent and a release agent is dispersed in an aqueous medium, granulated, and a polymerizable monomer and the color toner particles obtained by suspending polymerization using a body a polymerization initiator, a color toner containing an inorganic fine powder,
The color toner particles contain at least the colorant, the release agent, the charge control agent, and the polar resin,
The polar resin is a polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, isophthalic acid, anhydrous , using a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst. Containing at least a polyester resin having an acid value of 3 to 35 mg KOH / g obtained by polymerizing a monomer containing at least trimellitic acid ,
The release agent is an ester wax, the release agent has a weight average molecular weight (Mw) of 300 to 1,500, and a weight average molecular weight / number average molecular weight ratio (Mw / Mn) of 1.5 or less. Yes, the penetration is 15 degrees or less,
The charge control agent is an aluminum salicylate compound, a zinc salicylate compound, or a zirconium salicylate compound;
In the endothermic curve in differential scanning calorimetry (DSC) measurement of the color toner, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is 50 to 120 ° C., and the half width of the maximum endothermic peak is 15 ° C. or less. ,
In the water / methanol wettability test for the color toner particles, TA which is methanol mass% at the time when the transmittance becomes 50% of the initial value is 7 to 71,
In the water / methanol wettability test for the color toner, TB which is methanol mass% when the transmittance reaches 50% of the initial value is 20 to 69,
Color toner weight average particle diameter of the color toner is characterized 4~10μm der Rukoto.
(2) The color toner according to (1), wherein a tin compound of an alkyl carboxylic acid having 7 to 12 carbon atoms is used as the catalyst.
(3) The color toner according to (1) or (2), wherein the acid value of the polar resin is 7 to 15 (mgKOH / g).
(4) The color toner according to any one of (1) to (3) , wherein the toner has a weight average particle diameter of 6 to 7.5 μm.
(5) A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a charge control agent and a release agent is dispersed in an aqueous medium, granulated, and a polymerizable monomer body suspension polymerization to using a polymerization initiator to produce a color toner particles, a manufacturing method of a color toner externally added inorganic fine powder in the color toner particles,
The color toner particles contain at least the colorant, the release agent, the charge control agent, and the polar resin,
The polar resin is a polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, isophthalic acid, anhydrous , using a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst. Containing at least a polyester resin having an acid value of 3 to 35 mg KOH / g obtained by polymerizing a monomer containing at least trimellitic acid ,
The release agent is an ester wax, the release agent has a weight average molecular weight (Mw) of 300 to 1,500, and a weight average molecular weight / number average molecular weight ratio (Mw / Mn) of 1.5 or less. Yes, the penetration is 15 degrees or less,
The charge control agent is an aluminum salicylate compound, a zinc salicylate compound, or a zirconium salicylate compound;
In the endothermic curve in differential scanning calorimetry (DSC) measurement of the color toner, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is 50 to 120 ° C., and the half width of the maximum endothermic peak is 15 ° C. or less. ,
In the water / methanol wettability test for the color toner particles, TA which is methanol mass% at the time when the transmittance becomes 50% of the initial value is 7 to 71,
In the water / methanol wettability test for the color toner, TB which is methanol mass% when the transmittance reaches 50% of the initial value is 20 to 69,
Method for producing a color toner having a weight average particle diameter of the color toner is characterized 4~10μm der Rukoto.

In the toner of the present invention, a polyester resin that is polymerized using a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst, and particularly a toner containing a polyester resin having an appropriate acid value is used. As a result, the rising speed of charging is fast, and even when a large number of sheets are continuously printed, an image having a stable image density and excellent durability and stability without fogging can be obtained. Further, a toner having a wide fixing region can be provided without causing deterioration in developability due to the interaction between the polar resin comprising the polyester resin and the release agent. Therefore, according to the present invention, it is possible to provide a stable image over a long period of time.

  Hereinafter, the present invention will be described in detail.

  The toner of the present invention has toner particles containing at least a colorant, a release agent, and a polar resin and an inorganic fine powder, and the polar resin is a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst. The toner particles are obtained by granulating in an aqueous medium.

  As a result of intensive studies, the present inventors have found the following. It has been found that a preferable toner can be obtained by including in the toner a polar resin having at least a polyester resin obtained by polymerization using a tin compound of an alkylcarboxylic acid having 5 to 15 carbon atoms as a catalyst. Is one of the features.

The tin compound of the alkyl carboxylic acid is a suitable catalyst in the esterification reaction and transesterification reaction, and can easily adjust the softening point and physical properties of the resin. For example, although the condensation time is longer, the low molecular weight component can be reduced. Therefore, when this catalyst is used, an oligomer component (number average molecular weight in GPC measurement: a component of about 500 or less)
Thus, it is possible to provide a polyester resin having a so-called sharp molecular weight in which a low molecular weight is reduced without containing a large amount of.

  When a polyester resin obtained by using this specific catalyst is contained in the toner, a toner showing good results as described below can be obtained.

  For example, the dispersibility of the polyester resin and the colorant and the adhesion between the polyester resin and the colorant during toner production can be improved.

  When a polyester resin or colorant is dissolved in a monomer or solvent using a suspension polymerization method or a suspension granulation method, the polyester resin has an appropriate viscosity with the oligomer component excluded as much as possible. The viscosity can be stabilized and the colorant is uniformly dispersed. In addition, when using an emulsion aggregation method to disperse and aggregate a polyester resin or a colorant in emulsion particles, as described above, if the polyester resin has an appropriate viscosity with the oligomer component excluded as much as possible, the colorant is , As well as uniformly distributed. Further, the presence of the inorganic tin compound in the polyester resin reduces the reaggregation property of the colorant. That is, the fine dispersion stabilization of the colorant is increased, and the color toner has excellent color reproducibility such as color mixing and transparency. In addition, since the inorganic tin compound also has a releasing effect, it suppresses the chemical adhesion between the toner and the photoreceptor or charge imparting member, and the photoreceptor filming, fogging, toner scattering, streak image, etc. The image defect is not developed.

  Further, by using a polyester resin that does not contain a large amount of the oligomer component, a toner having high thermal stability and high blocking resistance can be obtained. Further, the effect of low-temperature fixability is enhanced by the sharply distributed polyester resin having a large amount of low molecular weight polymer components.

In addition, the toner of the configuration of the present invention is characterized in that the average circularity value can be increased and the circularity standard deviation value can be reduced as compared with the conventional pulverized toner. Specifically, with the configuration of the present invention, when the toner of the present invention is measured by a flow type particle image measuring device, the number-based average circularity value is 0.96 or more, more preferably 0.8. The value of 97 or more and the circularity standard deviation can be 0.04 or less, more preferably 0.035 or less.
That is, the toner of the present invention more preferably has an average circularity of 0.960 to 0.995 and a circularity standard deviation in a number-based equivalent circle diameter-circularity scattergram measured by a flow particle image measuring device. The toner has an average circularity of 0.970 to 0.990 and a circularity standard deviation of 0.02 to 0.035.

  Further, the toner having the constitution of the present invention can be added with a large amount of a release agent described in detail below without impairing the developability. Specifically, it is possible to add a release agent in a total amount of 10 parts by mass or more in 100 parts by mass of the toner.

  Furthermore, in order for the effect of the present invention to be exhibited well, the polyester resin may have an appropriate acid value. By defining the acid value of the catalyst and polar resin used in obtaining the polar resin, the mutual action works well, the charging speed and saturation charge amount of the toner can be increased, and the charge-up is suppressed. It is also possible. Further, since the polyester resin and the release agent have an appropriate affinity, the low-temperature fixability and the high-temperature offset resistance can be satisfied, and a wide fixing area can be secured. That is, the release agent compatible with the polar resin functions plastically and can improve the low-temperature fixability. On the other hand, a release agent that is incompatible with the polar resin can sufficiently exhibit the release effect inherent in the release agent. This effect becomes more prominent when the toner is produced using a suspension polymerization method in which a polar resin can exist on the toner surface. Further, when the toner of the present invention is a toner having a small particle diameter of 4 to 10 μm, the toner can provide a high-quality image.

  Furthermore, when the toner of the present invention is a color toner, it is preferable to contain a low crystalline toner as a release agent. In particular, it is more preferable from the viewpoint of compatibility with the polyester resin that at least an ester-based wax is contained as a release agent. Thereby, the color mixing property and transparency of the color toner can be improved. Furthermore, since the release agent can be present in the vicinity of the toner surface at a level that does not impair the developability, the above-described paper discharge / stacking failure can be solved.

  The carbon number of the alkyl carboxylic acid in the tin compound of the alkyl carboxylic acid used in the present invention is preferably 5 or more and 15 or less, and more preferably 7 or more and 12 or less.

  When the alkyl carboxylic acid has less than 5 carbon atoms, it is difficult to obtain a dispersion / stabilizing effect of the colorant, and there are problems in color reproducibility such as color mixing and transparency in the case of a color toner. On the other hand, when the number of carbon atoms of the alkyl carboxylic acid is greater than 15, the catalytic effect of the esterification reaction starts to deteriorate, it becomes difficult to adjust the molecular weight, and a polyester resin having a broad molecular weight distribution can be obtained.

  In the present invention, the tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms is not particularly limited, but is preferably a compound represented by the general formula (I).

（式中、ｎは５〜１５の整数を示す。）

(In the formula, n represents an integer of 5 to 15.)

Examples thereof include tin compounds such as pentanoic acid, hexanoic acid, 2,2-dimethylpropanoic acid, 2-ethylhexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, tetradecanoic acid, and dodecanoic acid. Of these, tin 2-ethylhexanoate is particularly preferably used. Moreover, in this invention, you may use the tin compound of 2 or more types of alkyl carboxylic acids.

  The addition amount of the tin compound of the alkyl carboxylic acid having 5 to 15 carbon atoms is 0.01% by mass to 2% by mass, preferably 0.05% by mass to 1% by mass, with respect to the total amount of the polyester unit component. More preferably, 0.1 mass%-0.7 mass% is good. When the content is less than 0.01% by mass, the reaction time during the polymerization of the polyester becomes long, and the effect of improving the dispersion and stability of the colorant is hardly obtained. Further, the molecular weight distribution of the polyester resin becomes broad, and the resulting toner is less likely to exhibit good fixability. On the other hand, if it exceeds 2% by mass, the charging characteristics of the toner will be affected, and the charge amount will vary greatly depending on the environment, which is not preferable.

  The polar resin contained in the toner of the present invention only needs to have at least a polyester resin obtained by using the above-mentioned specific catalyst, and may contain other resins generally used as a toner. It is. The polyester resin component contained in the total resin is preferably 3% by mass or more in order to exhibit the effects of the present invention. When it is less than 3% by mass, it is difficult to obtain particularly good charging characteristics among the effects of the present invention.

  By making the acid value (mgKOH / g) of the polar resin used in the present invention 3 or more and 35 or less, the effect of the present invention can be exhibited. The acid value is preferably 5 or more and 30 or less, more preferably 7 or more and 15 or less.

  If the acid value is less than 3, the toner charge rises slowly and causes image defects such as fogging and scattering before the charge rises. On the other hand, when the acid value is larger than 35, the charge-up is particularly remarkable in a low humidity environment, and there are problems such as a decrease in image density and scattering of characters.

  The toner particles of the present invention are produced by granulating in an aqueous system using a method such as suspension polymerization, emulsion polymerization or suspension granulation from the viewpoint of sufficiently exerting the effects of the present invention. There should be. In the case of a general pulverized toner, it is very technically difficult to add a large amount of a release agent to toner particles in terms of developability. By granulating toner particles in an aqueous system, it is possible to take a technique that does not exist on the toner surface even when a large amount of a release agent is used. Among these, the suspension polymerization method is the most preferable aspect from the viewpoint of production cost such that the release agent is incorporated in the toner and no solvent is used.

  The weight average particle diameter of the toner of the present invention is preferably 4 to 10 μm from the viewpoint of sufficiently exhibiting the effects of the present invention. More preferably, it is 5-9 micrometers, More preferably, it is 6-7.5 micrometers.

  When the weight average particle diameter of the toner is less than 4 μm, it becomes easy to cause charge-up, thereby causing bad effects such as fogging, scattering, and low image density. In addition, the charging member is easily contaminated during long-term image output, making it difficult to provide a stable high-quality image. Furthermore, not only is it difficult to clean the transfer residual toner remaining on the photosensitive member, but also fusion or the like is likely to occur.

  On the other hand, if it is larger than 10 μm, the fine line reproducibility of minute characters and the like, and the image scattering are deteriorated, and a recently desired high-quality image cannot be provided.

  In the water / methanol wettability test for the toner particles of the present invention, the methanol mass% (TA) until the transmittance reaches 50% of the initial value is preferably from 10 to 70, more preferably from 15 to 60, and even more preferably. Is preferably 20 or more and 50 or less.

  Similarly, in the water / methanol wettability test for the toner of the present invention, the methanol mass% (TB) until the transmittance reaches the initial 50% is preferably 30 to 90, more preferably 35 to 80, Preferably 40 or more and 70 or less are good.

  When TA is less than 10 or TB is less than 30, it indicates that the affinity with water is high, and the chargeability in a high humidity environment is lowered. In particular, this phenomenon appears as deterioration of image printing in the second half of the durability.

  On the other hand, when TA exceeds 70 due to toner surface exposure or modification of the release agent, or when TB exceeds 90 due to the use of a highly hydrophobic inorganic fine powder and its addition, the water repellency is too high. Therefore, particularly in a low-humidity environment, the developing sleeve coat uniformity is deteriorated due to the charge-up phenomenon, the image density is low, and the toner adheres to the charging member and the photoreceptor. Addition of a large amount of inorganic fine powder is not preferable because it deteriorates the fixing performance, contaminates the photosensitive member, the charging member of the photosensitive member, the toner charging member in the developing process, and the like.

Further, the difference (TB−TA) in the methanol mass% in the water / methanol wettability test between the toner particles and the toner is preferably 60 or less , more preferably 5 or more and 45 or less, and still more preferably 10 or more and 30 or less.

  When the toner particles are easily wetted with water, it is important to adjust the toner wettability to be suppressed by the type and amount of additives such as inorganic fine powder. However, if (TB-TA) is larger than 60, even if an image having no problem is obtained initially, durability stability is lacking. Specifically, it causes adverse effects such as fogging and scattering in the second half of the durability. Further, the change in developability becomes large, and it becomes difficult to control the amount of toner applied on the paper. In particular, in the case of a color image, a problem that the initial image when the same image is output and the color tone of the image during continuous paper passage are likely to occur.

  The toner of the present invention has toner particles containing at least a colorant, a release agent, and a polar resin, and inorganic fine particles. In an endothermic curve in differential thermal analysis (DSC) measurement, the toner is in a temperature range of 30 to 200 ° C. The peak temperature of the maximum endothermic peak is preferably in the range of 50 to 120 ° C, more preferably in the range of 55 to 100 ° C, and further preferably in the range of 60 to 75 ° C.

  This maximum endothermic peak can be adjusted depending on the type of release agent in the toner. When the peak value is in the above range, both the fixability and the developability can be achieved. The use of two or more release agents is also a method suitably used to achieve the present invention, but it is important that the maximum peak temperature range is the above range.

  When the maximum peak temperature is less than 50 ° C., the storage stability of the toner and the developability such as fogging and scattering are deteriorated.

  On the other hand, when the maximum peak temperature is higher than 120 ° C., the plastic effect given to the toner is small and the low-temperature fixability is slightly inferior. In addition, when the temperature control of the fixing device is lowered during continuous paper passing, the release agent cannot be satisfactorily interposed between the fixing body and the toner, and the transfer paper is likely to stick to the fixing body (so-called fixing sticking) phenomenon. Become.

  The half-value width of the endothermic peak is preferably 15 ° C. or less, and more preferably 7 ° C. or less.

  When the half width exceeds 15 ° C., since the crystallinity of the release agent is not high, the hardness of the release agent is soft and may promote contamination of the photosensitive member and the charging member.

  The total amount of the release agent contained in the toner is preferably 2.5 to 25 parts by mass, more preferably 4 to 20 parts by mass, and more preferably 6 to 18 parts by mass in 100 parts by mass of the toner. More preferably, it is contained.

  If the total amount of release agent is less than 2.5 parts by mass, the release effect at the time of fixing cannot be fully exerted, and the transfer paper can be discharged and loaded when the fixing body becomes low temperature. Not only is it difficult to do this, but also the transfer paper tends to wrap around. On the other hand, when the amount is larger than 25 parts by mass, the charge imparting member and the photosensitive member are significantly contaminated by the release agent, causing problems such as fog and fusion.

  The toner of the present invention preferably has a number average molecular weight (Mn) of 2000 to 50,000, more preferably 5000 to 40,000, and still more preferably 10,000 to 25,000. If the number average molecular weight (Mn) is smaller than 2000, the elasticity of the toner particles themselves is too low, and high temperature offset tends to occur. On the other hand, if the number average molecular weight (Mn) is larger than 50,000, the elasticity of the toner particles tends to be high, and it becomes impossible to exude the release agent to the fixing surface at the time of fixing. Paper wrapping is likely to occur.

  The toner of the present invention preferably has a weight average molecular weight (Mw) of 10,000 to 1,500,000, more preferably 50,000 to 1,000,000, and even more preferably 100,000 to 750,000. If the weight average molecular weight (Mw) is less than 10,000, the toner base itself has too low elasticity and tends to cause high temperature offset. On the other hand, if the weight average molecular weight (Mw) is larger than 1,500,000, the elasticity of the toner base itself tends to be high, and it becomes impossible to allow the release agent to ooze out well on the fixing surface at the time of fixing. Paper wrapping is likely to occur. In addition, the fixing gloss is extremely low.

  In order to obtain a toner having the desired physical properties, the reaction temperature at the time of producing the resin or polymerized toner and the kind and amount of the polymerization initiator, crosslinking agent, chain transfer agent, or release agent used in the production are appropriately determined. Adjust it.

  In order to achieve an appropriate medium gloss image, the toner of the present invention preferably has a melt index (MI) value at 125 ° C. of 1 to 50, more preferably 3 to 40. When the MI value is less than 1, the gloss is too low, and when the MI value is greater than 50, a high gloss image with glare is obtained.

  The glass transition temperature (Tg) of the toner of the present invention is preferably 50 to 75 ° C, more preferably 52 to 70 ° C, and further preferably 54 to 65 ° C. When the Tg is less than 50 ° C., the storage stability of the toner is deteriorated. On the other hand, when it is higher than 75 ° C., the low-temperature fixing performance is deteriorated.

  Examples of the release agent used in the toner of the present invention include polymethylene waxes such as paraffin wax, polyolefin wax, microcrystalline wax, and Fischer tropish wax, amide wax, higher fatty acid, long chain alcohol, ketone wax, ester wax, and the like. Derivatives such as these graft compounds and block compounds may be mentioned, and distillation may be performed as necessary.

  Among the above waxes, ester waxes represented by the following general formulas (A) to (C) are more preferable.

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ_１及びＲ_２は炭素数が１〜４０の有機基であり、且つＲ_１とＲ_２との炭素数差が３以上である基を示し、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

(In the formula, a and b represent integers of 0 to 4, a + b is 4, R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and the number of carbon atoms of R ₁ and R _2. (The difference is 3 or more, n and m are integers from 0 to 40, and n and m are not 0 at the same time.)

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ_１は炭素数が１〜４０の有機基を示し、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

(In the formula, a and b represent an integer of 0 to 4, a + b represents 4, R ₁ represents an organic group having 1 to 40 carbon atoms, n and m represent an integer of 0 to 40, and n And m are never 0 at the same time.)

（式中、ａ及びｂは０〜３の整数を示し、ａ＋ｂは３以下であり、Ｒ_１及びＲ_２は炭素数が１〜４０の有機基であり、且つＲ_１とＲ_２との炭素数差が３以上である基を示し、Ｒ_３は炭素数が１以上の有機基を示し、ｋは１〜３の整数であり、ｎ及びｍは０〜４０の整数を示し、ｎとｍが同時に０になることはない。）

(In the formula, a and b represent integers of 0 to 3, a + b is 3 or less, R ₁ and R ₂ are organic groups having 1 to 40 carbon atoms, and carbons of R ₁ and R _2. a group is the number difference is 3 or more, R ₃ represents one or more organic groups having a carbon number, k is an integer from 1 to 3, n and m represents an integer of 0 to 40, n and m Are never 0 at the same time.)

  As a molecular weight of a mold release agent, it is preferable that a weight average molecular weight (Mw) is 300-1,500, and it is more preferable that it is 400-1250. When the weight average molecular weight is less than 300, the release agent is likely to be exposed on the surface of the toner particles, the photoreceptor, the charging roller, and the charging member are easily contaminated, and image defects such as fogging and fusion are likely to occur. On the other hand, when the weight average molecular weight exceeds 1500, adverse effects such as deterioration in fixing wrapping property, deterioration in low-temperature fixing property, and deterioration in OHT transparency occur.

  Further, when the weight average molecular weight / number average molecular weight ratio (Mw / Mn) of the release agent is 1.5 or less, the maximum peak of the DSC endothermic curve of the release agent becomes sharper, and the toner particles at room temperature. This is preferable because the mechanical strength of the toner is improved and a sharp melting characteristic is exhibited at the time of fixing.

The penetration of the release agent is preferably 15 degrees or less, and preferably 8 degrees or less. When the penetration exceeds 15 degrees, the half-width of the endothermic peak of the release agent exceeds 15 degrees, which easily contaminates the photoconductor, the charging member, and the charging member, such as fogging or fusion. It is easy to cause image defects.

  Specifically, the component constituting the polyester resin used in the present invention is a divalent or higher valent alcohol monomer component, a divalent or higher carboxylic acid, a divalent or higher carboxylic acid anhydride, or a divalent or higher carboxylic acid. It can be obtained by polycondensation with an acid monomer component such as an ester.

  Specific examples of the dihydric or higher alcohol monomer component include polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (3. 3) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (2.0) -polyoxyethylene (2.0) -2,2-bis (4-hydroxyphenyl) propane, polyoxypropylene (6) -2,2-bis (4-hydroxyphenyl) propane and other alkylene oxide adducts of bisphenol A, ethylene glycol , Diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-pro Lenglycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, dipropylene glycol, polyethylene glycol, Examples include polypropylene glycol, polytetramethylene glycol, bisphenol A, hydrogenated bisphenol A, and the like.

  Examples of the trivalent or higher alcohol monomer component include sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1,2,4-butanetriol. 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, trimethylolethane, trimethylolpropane, 1,3,5-trihydroxymethylbenzene, etc. Is mentioned.

  The divalent or higher carboxylic acid monomer component includes aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid or their anhydrides; alkyl dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, or their anhydrides. Succinic acid substituted with an alkyl group or alkenyl group having 6 to 18 carbon atoms or an anhydride thereof; unsaturated dicarboxylic acids such as fumaric acid, maleic acid and citraconic acid or the anhydride thereof; In particular, isophthalic acid is preferably used because of its high reactivity.

  Other monomers include glycerin, sorbit, sorbitan, and polyhydric alcohols such as oxyalkylene ethers of novolak-type phenolic resins; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, and anhydrides thereof. And polyvalent carboxylic acids.

  Among these, in particular, a bisphenol derivative represented by the following general formula (1) is a dihydric alcohol monomer component, and a carboxylic acid component comprising a divalent or higher carboxylic acid or an acid anhydride thereof, or a lower alkyl ester thereof ( For example, fumaric acid, maleic acid, maleic anhydride, phthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc.) are used as acid monomer components, and polyester resins obtained by condensation polymerization of these components have good charging characteristics. This is preferable.

（式中、Ｒはエチレン又はプロピレン基を示し、ｘ，ｙはそれぞれ１以上の整数であり、かつｘ＋ｙの平均値は２〜１０である。）

(In the formula, R represents an ethylene or propylene group, x and y are each an integer of 1 or more, and the average value of x + y is 2 to 10.)

  In addition, the polar resin contained in the toner particles of the present invention is preferably contained in the toner particles in a total amount of 1% by mass or more.

As the binder resin to be contained in the toner of the present invention, other resins can be contained in addition to the polar resin made of the polyester resin. Examples of the binder resin contained in the toner of the present invention include the following binder resins in addition to the polar resin composed of the polyester resin.
Polystyrene; Homopolymers of styrene-substituted products such as poly-p-chlorostyrene and polyvinyltoluene; styrene-p-chlorostyrene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-acrylic Acid ester copolymer, styrene-methacrylic acid ester copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl ethyl ether copolymer Styrene copolymers such as polymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; acrylic resins; methacrylic resins; polyvinyl acetate ;Silicone resin Polyester resins; polyamide resin; furan resins, epoxy resins, and the like xylene resin and the like. These resins are used alone or in combination.

  The binder resin used in the present invention has at least a polyester resin as a main component. From the viewpoint of developability and fixability, the polyester resin and / or a styrene copolymer that is a copolymer of styrene and another vinyl monomer is used. A polymer may also be contained.

  As a comonomer for the styrene monomer of the styrenic copolymer, acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, dodecyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, methacrylic acid, Monocarboxylic acid having a double bond such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, octyl methacrylate, acrylonitrile, methacrylonitrile, acrylamide or a substituted product thereof; maleic acid, butyl maleate, methyl maleate, Dicarboxylic acids having a double bond such as dimethyl maleate and substituted products thereof; vinyl esters such as vinyl chloride, vinyl acetate and vinyl benzoate; ethylene-based olefins such as ethylene, propylene and butylene Vinyl methyl ketone, vinyl ketones such as vinyl hexyl ketone, vinyl methyl ether, vinyl ethyl ether, vinyl ethers such as vinyl isobutyl ether. These vinyl monomers are used alone or in combination of two or more.

  The styrenic copolymer is preferably cross-linked with a cross-linking agent such as divinylbenzene in order to widen the fixing temperature range of the toner and improve the offset resistance.

The toner particles of the present invention are preferably obtained by granulation in an aqueous medium. In particular, a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a release agent and a polymerization initiator is dispersed in an aqueous medium, granulated, and the polymerizable monomer. It is good that it is obtained by polymerizing.

  The method for producing toner particles by the polymerization method will be described by exemplifying the suspension polymerization most preferably used among the toner particles produced in the aqueous system of the present invention.

  A polymerizable monomer, a colorant, a polar resin, a release agent, and other additives as necessary are uniformly dissolved or dispersed by a disperser such as a homogenizer, a ball mill, a colloid mill, or an ultrasonic disperser. The monomer system thus obtained is suspended in an aqueous medium containing a dispersion stabilizer. The polymerization initiator may be added simultaneously with the addition of other additives to the polymerizable monomer, or may be mixed immediately before being suspended in the aqueous medium. Also, a polymerization initiator dissolved in a polymerizable monomer or solvent can be added immediately after granulation and before starting the polymerization reaction. Then, the polymerizable monomer composition is granulated, and the polymerizable monomer is polymerized to obtain toner particles.

  As the polymerizable monomer used when the toner of the present invention is produced by the polymerization method, a vinyl polymerizable monomer capable of radical polymerization is used. As the vinyl polymerizable monomer, a monofunctional polymerizable monomer or a polyfunctional polymerizable monomer can be used. Monofunctional polymerizable monomers include styrene; α-methylstyrene, β-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, pn-butyl. Styrene, p-tert-butyl styrene, pn-hexyl styrene, pn-octyl styrene, pn-nonyl styrene, pn-decyl styrene, pn-dodecyl styrene, p-methoxy styrene, p -Styrene derivatives such as phenylstyrene; methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, n-amyl acrylate, n-hexyl acrylate, 2 -Ethylhexyl acrylate, Acrylic polymerizable monomers such as n-octyl acrylate, n-nonyl acrylate, cyclohexyl acrylate, benzyl acrylate, dimethyl phosphate ethyl acrylate, diethyl phosphate ethyl acrylate, dibutyl phosphate ethyl acrylate, 2-benzoyloxyethyl acrylate; Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, iso-propyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, n-amyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, n-octyl methacrylate , N-nonyl methacrylate, diethyl phosphate ethyl methacrylate Methacrylic polymerizable monomers such as dibutyl phosphate ethyl methacrylate; methylene aliphatic monocarboxylic acid esters; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl formate; vinyl methyl ether, vinyl Examples include vinyl ethers such as ethyl ether and vinyl isobutyl ether; vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone, and vinyl isopropyl ketone.

As polyfunctional polymerizable monomers, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol Diacrylate, polypropylene glycol diacrylate, 2,2′-bis (4- (acryloxydiethoxy) phenyl) propane, trimethylolpropane triacrylate, tetramethylolmethane tetraacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol Dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol Dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, polypropylene glycol dimethacrylate, 2,2'-bis (4- (methacryloxy-diethoxy) phenyl) propane, Examples include 2,2′-bis (4- (methacryloxy / polyethoxy) phenyl) propane, trimethylolpropane trimethacrylate, tetramethylolmethane tetramethacrylate, divinylbenzene, divinylnaphthalene, and divinyl ether.

  In the present invention, the above monofunctional polymerizable monomers are used singly or in combination of two or more, or the above monofunctional polymerizable monomers and polyfunctional polymerizable monomers are combined. It is good to use. The polyfunctional polymerizable monomer can also be used as a crosslinking agent.

  As the polymerization initiator used in the polymerization of the polymerizable monomer described above, an oil-soluble initiator and / or a water-soluble initiator is used. For example, as the oil-soluble initiator, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) Azo compounds such as 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile; acetylcyclohexylsulfonyl peroxide, diisopropylperoxycarbonate, decanonyl peroxide, lauroyl peroxide, stearoyl peroxide, propionyl peroxide Oxide, acetyl peroxide, t-butylperoxy-2-ethylhexanoate, benzoyl peroxide, t-butylperoxyisobutyrate, cyclohexanone peroxide, methyl ethyl ketone peroxide, dicumyl peroxide Side, t- butyl hydroperoxide, di -t- butyl peroxide, peroxide initiators such as cumene peroxide.

  Water-soluble initiators include ammonium persulfate, potassium persulfate, 2,2′-azobis (N, N′-dimethyleneisobutyroamidine) hydrochloride, 2,2′-azobis (2-aminodinopropane) hydrochloric acid Salts, sodium azobis (isobutylamidine) hydrochloride, sodium 2,2′-azobisisobutyronitrile sulfonate, ferrous sulfate or hydrogen peroxide.

  In the present invention, in order to control the polymerization degree of the polymerizable monomer, a chain transfer agent, a polymerization inhibitor and the like can be further added and used.

  As the crosslinking agent used in the toner of the present invention, a compound having two or more polymerizable double bonds is used. For example, aromatic divinyl compounds such as divinylbenzene and divinylnaphthalene; carboxylic acid esters having two double bonds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, and 1,3-butanediol dimethacrylate; divinylaniline; And divinyl ether, divinyl sulfide, divinyl sulfone and other divinyl compounds; and compounds having three or more vinyl groups. These are used alone or as a mixture.

  As the colorant used in the toner of the present invention, the following yellow / magenta / cyan colorants can be used. As the black colorant, carbon black and a magnetic material can be used as the main colorant, and it is one of good modes to adjust the color and toner resistance by mixing the following color materials.

As the pigment system of the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used. Specifically, C.I. I. Pigment Yellow 3.7.10.12.12.14.15.17.233.24.60.62.7.74.75.5.83.93.95.99.9.100.101.104.108.109.110 111.117.123.128.129.138.139.147.148.150.155.166.168
. 169.177.179.180.181.183.185.191: 1.191.192.193.199 is preferably used. Examples of the dye system include C.I. I. solvent Yellow 33.567.79.93.112.162.163, C.I. I. disperse Yellow 42.64.2011.211 etc. are mentioned. By including such a yellow colorant in the toner, a yellow toner can be obtained.

  As the magenta colorant, condensed azo compounds, diketopyrrolopyrrole compounds, anthraquinones, quinacridone compounds, basic dye lake compounds, naphthol compounds, benzimidazolone compounds, thioindigo compounds, and perylene compounds are used. Specifically, C.I. I. Pigment Red 2, 3, 5, 6, 7, 23, 48; 2, 48; 3, 48; 4, 57; 1, 81; 1, 122, 146, 166, 169, 177, 184, 185, 202, 206, 220, 221, 238, 254, 269, C.I. I. Pigment Bio Red 19 and the like are particularly preferably used. By including such a magenta colorant in the toner, a magenta toner can be obtained.

  As the cyan colorant, phthalocyanine compounds and derivatives thereof, anthraquinone compounds, basic dye lake compounds, and the like are used. Specifically, C.I. I. Pigment Blue 1, 7, 15, 15: 1, 15: 2, 15: 3, 15: 4, 60, 62, 66 and the like are particularly preferably used. By incorporating such a cyan colorant into the toner, a cyan toner can be obtained.

  A full color toner that forms a full color image can be obtained by combining the black toner, yellow toner, magenta toner, and cyan toner.

  These colorants can be used alone or in combination and further in the form of a solid solution. The colorant of the present invention is appropriately selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHP transparency, and dispersibility in the toner. The addition amount of the colorant is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  A charge control agent may be used in combination with the toner of the present invention. The following substances are used for controlling the toner to be negatively charged.

  For example, organometallic compounds and chelate compounds are effective, and there are monoazo metal compounds, acetylacetone metal compounds, aromatic oxycarboxylic acids, aromatic dicarboxylic acids, oxycarboxylic acids, and dicarboxylic acid-based metal compounds. Other examples include aromatic oxycarboxylic acids, aromatic mono- and polycarboxylic acids and their metal salts, anhydrides, esters, and phenol derivatives such as bisphenol.

  Furthermore, urea derivatives, metal-containing salicylic acid compounds, metal-containing naphthoic acid compounds, boron compounds, quaternary ammonium salts, calixarene, resin charge control agents, and the like can be given.

  In particular, in the present invention, it is preferable to contain a salicylic acid-based metal compound as a charge control agent in the toner, and it is more preferable that the metal is aluminum or zirconium.

  The following substances are used to control the toner to be positively charged.

Nigrosine-modified products of nigrosine and fatty acid metal salts, etc .; guanidine compounds; imidazole compounds; quaternary ammonium salts such as tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylammonium tetrafluoroborate, and the like Phosphonium salts and other onium salts and their lake pigments; triphenylmethane dyes and their lake pigments (as rake agents, phosphotungstic acid, phosphomolybdic acid, phosphotungsten molybdic acid, tannic acid, lauric acid, gallic acid Acid, ferricyanide, ferrocyanide, etc.); metal salt of higher fatty acid; diorganotin oxide such as dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide; DOO, dioctyl tin borate, such as diorganotin tin borate such dicyclohexyl tin borate; resin charge control agent and the like. These can be used alone or in combination of two or more.

  The charge control agent is used in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the binder resin.

  The toner of the present invention has inorganic fine particles for charging stability, developability, fluidity, suppression of member adhesion, and improvement of durability. Among the inorganic fine particles used in the present invention, examples of the lubricant include fluorine-based resin powders (such as polyvinylidene fluoride and polytetrafluoroethylene) and fatty acid metal salts (such as zinc stearate and calcium stearate). Of the above, polyvinylidene fluoride is preferably used.

  In addition, charge controllable particles can be contained as the inorganic fine particles. Examples of the charge controllable particles include metal oxides (tin oxide, titania, zinc oxide, silica, alumina, etc.), carbon black, and the like.

  Among the inorganic fine particles, abrasives include metal oxides (such as strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, and chromium oxide), nitrides (such as silicon nitride), carbides (such as silicon carbide), and metals. And salts (calcium sulfate, barium sulfate, calcium carbonate, etc.). Of these, strontium titanate is preferably used as the abrasive.

  Among the inorganic fine particles, examples of the fluidity-imparting agent include metal oxides (silica, alumina, titania, etc.), carbon fluoride, and the like. Each of them is more preferably hydrophobized. In particular, as described above, silica, alumina, and titania are preferable from the viewpoint of maintaining good fluidity and chargeability of the toner and high adsorbability on the toner particles of the present invention. Is also a good mode. Among these, it is most preferable that at least silica is contained from the compatibility with the tin compound of the alkyl carboxylic acid having 5 to 15 carbon atoms of the present invention.

  The total amount of the inorganic fine powder added to the toner in the present invention is preferably 0.5 to 4.5 parts by mass, more preferably 0.8 to 3.5 parts by mass with respect to 100 parts by mass of the toner particles. If the total amount of the inorganic fine powder is less than 0.5 parts by mass, the fluidity of the toner becomes insufficient, the fogging accompanying the decrease in chargeability, and the toner scattering occur, and the effects of the present invention can be fully exerted. Absent. On the other hand, when the total addition amount exceeds 4.5 parts by mass, adverse effects such as toner scattering, fixing property deterioration, photoreceptor fusing, and toner charge reduction due to charge imparting member contamination occur.

Titania, silica, and alumina preferably added as the inorganic fine particles have a specific surface area of 20 to 400 m ² / g, more preferably 35 to 300 m ² / g, more preferably 50 to 230 m ² / g as measured by the BET method. Those within the range are good. If it is less than 20 m ² / g, it is difficult to ensure sufficient fluidity of the toner particles. On the other hand, if it is greater than 400 m ² / g, the rate of change in the presence state of the inorganic fine particles on the toner during continuous paper passing increases and the degree of aggregation of the toner particles decreases. Further, the TB-TA value defined in the present invention is likely to be larger than 60, and adverse effects such as fogging, scattering, and color variation in a color image are likely to occur.

  The inorganic fine particles as the fluidity-imparting agent are silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, and others for the purpose of improving hydrophobicity, chargeability, and transferability. The treatment is preferably performed by using a treating agent such as an organosilicon compound alone or in combination.

  The shape of the toner particles is preferably close to a sphere. Specifically, the toner particle has a shape factor of SF-1 of 100 to 150, more preferably 100 to 140, and even more preferably 100 to 130. . Moreover, SF-2 is in the range of 100 to 140, more preferably 100 to 130, and still more preferably 100 to 120.

  When the toner shape factor SF-1 exceeds 150 or SF-2 exceeds 140, the toner transfer efficiency decreases, the toner retransfer increases, and the latent image carrier surface wear increases. It becomes easy and is not preferable.

  It is also a preferred embodiment of the present invention that the toner of the present invention is mixed with a carrier and used as a two-component developer. The carrier used in the present invention is preferably a carrier in which core particles made of a magnetic material or a mixture of a magnetic material and a nonmagnetic material are coated with a resin and / or a silane compound. Here, a carrier using a magnetic material-dispersed resin carrier for the core particles is preferable in terms of image characteristics and long-term durability. In particular, when used in a mixture with a negatively chargeable toner, it is preferable to coat the core material particles with a coating layer containing an aminosilane compound. Since the toner having a fine particle diameter of 10 μm or less of the present invention tends to contaminate the surface of the carrier particles, a carrier in which the surface of the core particles is coated with a resin is preferable in order to prevent this.

  The carrier whose surface is coated with a resin is advantageous in terms of durability when applied to a high-speed machine, and is excellent in controlling the charge of the toner.

  As the resin for forming the coating layer that covers the surface of the carrier, for example, a fluorine-based resin, a silicone-based resin, and a silicone-based compound can be preferably used.

  Examples of the fluororesin that forms the carrier coating layer include halofluoropolymers such as polyvinyl fluoride, polyvinylidene fluoride, polytrifluoroethylene, and polytrifluorochloroethylene; polytetrafluoroethylene, polyperfluoropropylene, Copolymers of vinylidene fluoride and acrylic monomers, copolymers of vinylidene fluoride and trifluorochloroethylene, copolymers of tetrafluoroethylene and hexafluoropropylene, vinyl fluoride and vinylidene fluoride Copolymer, copolymer of vinylidene fluoride and tetrafluoroethylene, copolymer of vinylidene fluoride and hexafluoropropylene, copolymer of terpolymer of tetrafluoroethylene, vinylidene fluoride and non-fluorinated monomer Fluoroterpolymers such as polymers are preferred Used properly.

  The fluororesin preferably has a weight average molecular weight of 50,000 to 400,000 (more preferably 100,000 to 250,000).

  As the resin for forming the carrier coating layer, the above fluororesins may be used alone, or a blend of these may be used. Further, a non-fluorinated polymer may be blended with the fluororesin.

As the non-fluorine polymer, a monomer homopolymer or copolymer as described below is used.

Styrene derivatives such as styrene, α-methylstyrene, p-methylstyrene, pt-butylstyrene, p-chlorostyrene, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, methacrylic acid Hexyl, heptyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate, glycidyl methacrylate, methoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, methoxydiethylene glycol methacrylate, Ethoxyethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxy methacrylate Propylene glycol, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxytetraethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, methacrylic acid N-vinyl-2-pyrrolidone, methacrylonitrile, methacrylamide, N-methylol methacrylamide, ethyl methacrylate, diacetone acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, acrylic Hexyl acrylate, heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, acrylic Undecyl silylate, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, Methoxydipropylene glycol acrylate, phenoxyethyl acrylate, phenoxytetraethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentyl acrylate, dicycloacrylate Pentenyloxyethyl, N-vinyl-2-pyrrolidone acrylate, Glyci acrylate , Acrylonitrile, acrylamide, N-methylol acrylamide, diacetone acrylamide, vinyl morpholine acrylate, vinyl pyridine, vinyl monomer having one vinyl group in one molecule; divinyl benzene; glycol and methacrylic acid or acrylic acid Reaction products of, for example, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentadiol dimethacrylate, 1,6-hexanediol methacrylate, neopentyl glycol di Methacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate Rate, hydroxypivalate neopentyl glycol ester dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, trismethacryloxyethyl phosphate, tris (methacryloyloxyethyl) isocyanurate, ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate Acrylate, polyethylene glycol diacrylate, tripropylene diacrylate, Hydroxypivalate neopentyl glycol diacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, tris (methacryloyloxyethyl) isocyanurate, glycidyl methacrylate and methacrylic acid or acrylic Vinyl compounds having two or more vinyl groups in one molecule such as acid half esterified products, bisphenol type epoxy resins and methacrylic acid or acrylic acid half esterified products, glycidyl acrylate and methacrylic acid or acrylic acid half esterified products, etc. Monomer: 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy acrylate Examples thereof include vinyl monomers having a hydroxy group such as 3-phenyloxypropyl, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, 2-hydroxy-3-phenyloxypropyl methacrylate. .

  These monomers are copolymerized by a known method such as suspension polymerization, emulsion polymerization, or solution polymerization. These copolymers are preferably those having a weight average molecular weight of 10,000 to 70,000. Further, this copolymer may be crosslinked with melamine aldehyde or isocyanate.

  The mass-based blend ratio of the fluororesin and other polymer is preferably 20 to 80:80 to 20, and particularly preferably 40 to 60:60 to 40.

  Polysilicone such as dimethylpolysiloxane and phenylmethylpolysiloxane is used as the silicone resin or silicone compound for forming the carrier coating layer. Modified silicone resins such as alkyd-modified silicone, epoxy-modified silicone, polyester-modified silicone, urethane-modified silicone, and acrylic-modified silicone can also be used. Examples of the modification include a block copolymer, a graft copolymer, and a comb-shaped graft copolymer.

  When applying the coating layer to the surface of the core material particles, fluorine resin, silicone resin or silicone compound (solid methyl silicone varnish, solid phenyl silicone varnish, solid methyl phenyl silicone varnish, solid ethyl silicone varnish, various modified silicone varnishes) For example, a method in which a silicone resin) is made into a varnish and the magnetic particles are dispersed therein, or a method in which the varnish is sprayed onto the magnetic particles is used.

  The amount of the resin of the coating layer is 0.1 to 30% by mass (preferably 0.5 to 20% by mass) with respect to the carrier core material from the viewpoint of film formability and durability of the coating material. preferable.

  The volume average particle size of the carrier used in the present invention is preferably 25 to 55 μm (preferably 30 to 50 μm) in matching with a small particle size toner. When the volume average particle diameter of the carrier is less than 25 μm, the carrier is easily developed on the latent image holding member together with the toner in the developing step, and the latent image holding member and the cleaning blade are easily damaged. On the other hand, if the volume average particle diameter of the carrier is larger than 55 μm, the toner holding ability of the carrier is lowered, the solid image becomes non-uniform, and toner scattering, fogging and the like are likely to occur.

  In the present invention, it is preferable to mix the carrier and the toner so that the toner concentration is 3 to 12% by mass (more preferably 5 to 10% by mass) in order to satisfactorily satisfy the image density and image characteristics. .

In the present invention, the specific resistance of the carrier is preferably 1 × 10 ⁸ to 1 × 10 ¹⁶ Ω · cm, and more preferably 1 × 10 ⁹ to 1 × 10 ¹⁵ Ω · cm. If the specific resistance of the carrier is less than 1 × 10 ⁸ Ω · cm, the carrier easily adheres to the surface of the latent image carrier, and the latent image carrier is scratched or directly transferred onto paper. Prone to defects. Further, the developing bias may leak through the carrier, and the electrostatic latent image drawn on the latent image carrier may be disturbed.

If the specific resistance of the carrier exceeds 1 × 10 ¹⁶ Ω · cm, an edge-enhanced image is likely to be formed, and further, the charge on the carrier surface is difficult to leak. In some cases, fogging and scattering may occur due to the inability to charge the newly supplied toner. Further, the toner is charged with a substance such as the inner wall of the developing device, and the charge amount of the toner to be originally applied may become non-uniform. In addition, it tends to cause image defects such as electrostatic external additives.

The magnetic properties of the carrier are such that the magnetization strength at 1000 / 4π (kA / m) is a low magnetic force of 30 to 60 (Am ² / kg), more preferably 35 to 55 (Am ² / kg). Is good.

When the magnetization strength of the carrier exceeds 60 (Am ² / kg), the agent compression at the regulating blade portion on the developer carrying member becomes strong, and even when the toner of the present invention is used, the carrier by the release agent. Spent of. For this reason, defective coating due to a deterioration in carrier transportability on the sleeve, fogging in the latter half of the durability due to a decrease in charge imparting performance to the toner, toner scattering, and the like may occur. In addition, although related to the carrier particle size, the density of the magnetic brush formed on the developing sleeve at the developing pole decreases, the head length becomes long, and the stiffening occurs, so that unevenness of the sweep is present on the copy image. Prone to occur.

If the magnetization strength of the carrier is less than 30 (Am ² / kg), even if the carrier fine powder is removed, the magnetic force of the carrier is reduced, carrier adhesion is likely to occur, and toner transportability is likely to be reduced.

The apparent density of the carrier is preferably 2.3 g / cm ³ or less, and preferably 2.1 g / c.
More preferably, it is m ³ or less. If the apparent density is greater than 2.3 g / cm ³ , the spent of the carrier due to the release agent in the developing device occurs, resulting in poor coating due to poor carrier transportability on the developing sleeve, and durability due to a decrease in charge imparting performance to the toner. In the latter half, fogging, toner scattering, etc. occur.

  The shape factor SF-1 of the carrier is preferably 100 to 130, and more preferably 100 to 120. When SF-1 is larger than 130, the carrier is markedly contaminated with toner particles or inorganic fine powder, the charge imparting performance to the toner in long-term durable use is deteriorated, and problems such as toner scattering and fogging occur. .

  The carrier is preferably a magnetic material-dispersed resin carrier from the viewpoint of satisfying all the various physical properties.

  Hereinafter, various measurement methods according to the present invention will be described.

(1) Measurement of molecular weight distribution of toner A specific GPC measurement method for toner is as follows. The toner is extracted beforehand with a toluene solvent using a Soxhlet extractor for 20 hours, and then the toluene is distilled off with a rotary evaporator. Next, if necessary, the wax contained in the toner dissolves, but the resin component cannot be dissolved, and an organic solvent such as chloroform is added to perform sufficient washing. Thereafter, the washed toner component is dissolved in THF (tetrahydrofuran), and the obtained solution is filtered through a solvent-resistant membrane filter having a pore diameter of 0.3 μm as a measurement sample. The molecular weight distribution of the above sample is measured using a standard polystyrene resin calibration curve in a column configuration in which A-801, 802, 803, 804, 805, 806, and 807 manufactured by Showa Denko are connected using 150C manufactured by Waters. . A weight average molecular weight (Mw) and a number average molecular weight (Mn) are calculated from the obtained molecular weight distribution.

(2) Measurement of endothermic peak temperature, half width and glass transition temperature in DSC endothermic curve of toner Measured in accordance with ASTM D3418-82. In the present invention, “DSC-7”
(Perkin Elmer) is used. The melting point of indium and zinc is used for temperature correction of the device detection unit, and the heat of fusion of indium is used for correction of heat quantity. The measurement sample is accurately weighed within the range of 10 mg. Obtained when a sample in an aluminum pan and a sample with only an aluminum pan (empty pan) are set for control and the temperature of a 30 to 2000 ° C. measurement region is raised at a rate of 10 ° C./min. The main endothermic peak value is determined from the DSC curve obtained as the endothermic peak value of the toner used in the present invention. The half-value width of the endothermic peak is the temperature width of the endothermic chart that is half the height of the peak from the baseline in the endothermic peak. Incidentally, in the case of measuring only the releasing agent (wax component) is heated at the measurement time of the same conditions - to start the measurement after removing the previous history performed later temperature. Further, when measuring the wax component contained in the toner, the measurement is performed as it is without performing the operation of removing the previous history.

(3) Molecular weight measurement of release agent Measured by GPC under the following conditions.
Apparatus: GPC-150C (manufactured by Waters)
Column: GMH-MT30cm ² series (made by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml of 0.15% sample was injected

  Measure under the above conditions. In calculating the molecular weight of the sample, a molecular weight calibration curve prepared using a monodisperse polystyrene standard sample is used. Furthermore, it calculates by converting into polyethylene by the conversion formula derived from the Mark-Houwink viscosity formula.

(4) Water / methanol wettability test method Using a powder wettability tester WET-100P manufactured by Reska Co., Ltd., a methanol dropping transmittance curve measured under the following conditions and procedures is used.
First, 50 ml of a methanol / water mixed solvent (methanol concentration 0%) is placed in a flask and the transmittance is measured. The transmittance is measured with the transmittance at this time being 100% and the state in which no light is transmitted at all being 0%. That is, the methanol mass% when the transmitted light intensity at the time of measurement is half of the transmitted light intensity when the methanol / water mixed solvent (methanol concentration 0%) is transmitted is TA and TB of the present invention.

The transmittance is measured as follows.
A magnetic stirrer is placed in a flask containing 50 ml of a methanol / water mixed solvent (methanol concentration 0%). Then, 0.1 g of toner or toner particles sieved with a mesh having a mesh size of 150 μm is precisely weighed and placed in the flask. Next, stirring was started with a magnetic stirrer at a stirring speed of 300 rpm (5 revolutions / second), and methanol was continuously added into the sample solution for measurement at a rate of 1.3 ml / min with a glass tube while a wavelength of 780 nm was added. The light transmittance is measured and a methanol dropping transmittance curve is prepared. In this case, methanol is used as a titration solvent because it is less affected by elution of dyes, pigments, charge control agents and the like contained in the toner, and the surface state of the toner can be observed more accurately.

  In this measurement, the flask used was a circular 5 cm diameter and made of 1.75 mm glass, and the magnetic stirrer was a spindle with a length of 25 mm and a maximum diameter of 8 mm, and a Teflon (registered trademark) coating. What was given was used.

(5) Measurement of the penetration of the release agent The penetration of the release agent is measured according to JIS K2235. The measurement temperature is 25 ° C.

(6) Measurement of Melt Index (MI) of Toner Using a device described in JIS K7210, measurement was performed by a manual cutting method. The measurement conditions are as follows: measurement temperature: 135 ° C., load: 1.75 kg, sample filling amount: 5 to 10 g. In addition, a measured value is converted into a 10 minute value.

(7) Measurement of toner weight average particle size (D4) and toner particle size distribution The toner average particle size and particle size distribution can be measured using a Coulter Counter TA-II or Coulter Multisizer II (manufactured by Coulter Co.). However, in the present invention, Coulter Multisizer II (manufactured by Coulter Inc.) is used, and an interface (manufactured by Nikkaki Co., Ltd.) for outputting the number distribution and volume distribution and a PC 9801 personal computer (manufactured by NEC) are connected for measurement. As the electrolytic solution, a 1% NaCl aqueous solution is prepared using primary sodium chloride. For example, ISOTON R-II (manufactured by Coulter Scientific Japan) can be used. As a measuring method, 0.1 to 5 ml of a surfactant, preferably alkylbenzene sulfonate, is added as a dispersant to 100 to 150 ml of the electrolytic aqueous solution, and 2 to 20 mg of a measurement sample is further added. The electrolyte in which the sample is suspended is dispersed for about 1 to 3 minutes using an ultrasonic disperser, and the volume and number of toner particles having a particle diameter of 2 μm or more are measured using the 100 μm aperture as the aperture by the Coulter Multisizer. Then, the volume distribution and the number distribution are calculated. Using these values, the weight average particle diameter (D4) based on weight (representing the representative value of each channel as the representative value for each channel), the number% of toner having a particle diameter of 4.0 μm or less, and the particle diameter of 12 Determine the volume% of toner of 7 μm or more.

(8) Measurement of acid value and hydroxyl value of toner and polar resin <Acid value>
(A) Reagent (a) As the solvent, an ethyl ether-ethyl alcohol mixed solution (1 + 1 or 2 + 1) or a benzene-ethyl alcohol mixed solution (1 + 1 or 2 + 1) was used, and these solutions were mixed with phenolphthalein as an indicator immediately before use. Neutralize with 1 mol / liter potassium hydroxide ethyl alcohol solution.
(B) Phenolphthalein solution: 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(C) 0.1 mol / liter potassium hydroxide-ethyl alcohol solution: Dissolve 7.0 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. . The standardization is performed according to JIS K 8006 (basic matters concerning titration during the reagent content test).

  (B) Operation: 1-20 g of a sample (toner or polar resin) is weighed correctly, 100 ml of a solvent and a few drops of a phenolphthalein solution as an indicator are added thereto, and shaken sufficiently until the sample is completely dissolved. In the case of a solid sample, dissolve it by heating on a water bath. After cooling, this is titrated with a 0.1 mol / liter potassium hydroxide ethyl alcohol solution, and the end point of neutralization is taken when the indicator is slightly red for 30 seconds.

  (C) Calculation formula The acid value is calculated by the following formula (4).

ここで、
Ａ：酸価（ｍｇＫＯＨ／ｇ）
Ｂ：０．１ｍｏｌ／リットル水酸化カリウムエチルアルコール溶液の使用量（ｍｌ）
ｆ：０．１ｍｏｌ／リットル水酸化カリウムエチルアルコール溶液のファクター
Ｓ：試料（ｇ）を表す。

here,
A: Acid value (mgKOH / g)
B: Amount of 0.1 mol / liter potassium hydroxide ethyl alcohol solution (ml)
f: Factor of 0.1 mol / liter potassium hydroxide ethyl alcohol solution S: Represents sample (g).

<Hydroxyl value>
(A) Reagent (a) Acetylation reagent: Add 25 g of acetic anhydride to a 100 ml volumetric flask, add pyridine to make a total volume of 100 ml, and shake well. The acetylating reagent should be kept away from moisture, carbon dioxide and acid vapors and stored in a brown bottle.
(B) Phenolphthalein solution 1 g of phenolphthalein is dissolved in 100 ml of ethyl alcohol (95 vol%).
(C) N / 2 potassium hydroxide-ethyl alcohol solution Dissolve 35 g of potassium hydroxide in as little water as possible, add ethyl alcohol (95 vol%) to 1 liter, leave it for 2 to 3 days, and filter. The orientation is performed according to JIS K 8006.

  (B) Operation: 0.5-2.0 g of a sample is correctly weighed in a round bottom flask, and 5 ml of an acetylating reagent is correctly added thereto. Put a small funnel over the mouth of the flask and immerse the bottom of about 1 cm in a glycerin bath at 95-100 ° C. and heat. At this time, in order to prevent the temperature of the neck of the flask from rising due to the heat of the bath, a cardboard disk with a round hole in it is put on the base of the neck of the flask. After 1 hour, the flask is removed from the bath, and after cooling, 1 ml of water is added from the funnel and shaken to decompose acetic anhydride. In order to further complete the decomposition, the flask was again heated in a glycerin bath for 10 minutes, allowed to cool, and then the funnel and the wall of the flask were washed with 5 ml of ethyl alcohol, and N / 2 potassium hydroxide ethyl alcohol using a phenolphthalein solution as an indicator. Titrate with solution. A blank test is performed in parallel with the main test.

  (C) Calculation formula The hydroxyl value is calculated by the following formula (5).

here,
A: Hydroxyl value B: Amount used of N / 2 potassium hydroxide ethyl alcohol solution in blank test (ml)
C: Amount of use of N / 2 potassium hydroxide ethyl alcohol solution in this test (ml)
f: Factor of N / 2 potassium hydroxide ethyl alcohol solution S: Sample (g)
D: represents an acid value.

(9) Measurement of toner particle and carrier shape factors (SF-1, SF-2) Using a Hitachi FE-SEM (S-800), 100 toner images were randomly sampled at a magnification of 3000 times. The image information is introduced into an image analysis apparatus (Luzex3) manufactured by Nireco Corporation via an interface, analyzed, and defined as a value obtained by calculation from the following equations (6-1) and (6-2). Yes.

（ここで、ＭＸＬＮＧ：絶対最大長、ＡＲＥＡ：トナー投影面積、ＰＥＲＩ：周長を表す。）

(Here, MXLNG: absolute maximum length, AREA: toner projection area, PERI: circumference)

  The shape factor SF-1 indicates the degree of sphere, and gradually increases from 100 to become indefinite as it increases from 100. SF-2 indicates the degree of unevenness, and as the value increases from 100, the unevenness on the surface of the toner becomes more prominent.

(10) Measurement of carrier particle size The carrier particle size is measured under the conditions of a feed air pressure of 3 bar and a suction pressure of 0.1 bar using a laser diffraction particle size distribution measuring device (Hellos <HELOS>). The average particle diameter of the carrier means a 50% particle diameter based on the volume of the carrier particles.

(11) Measurement of carrier magnetic properties The carrier magnetic properties were measured using a vibrating magnetic field type magnetic property automatic recording apparatus BHV-35 manufactured by Riken Denshi Co., Ltd. Upon measurement, an external magnetic field of 1000 / 4π (kA / m) was created, and the magnetization strength at that time was determined. Make the carrier packed in a cylindrical plastic container so that the carrier particles do not move sufficiently, measure the magnetization moment in this state, measure the actual weight when the sample is put in , Magnetization strength (Am ² / k
g) was determined.
When measuring the carrier physical properties from the developer, the developer is washed with ion-exchanged water containing 1% of Contaminone N (surfactant) to separate the toner and the carrier, and then the above measurement is performed.

(12) Method for measuring specific resistance of carrier The specific resistance of the carrier was measured using a powder insulation resistance measuring instrument manufactured by Vacuum Riko Co., Ltd. Measurement conditions were 23 ° C. and 60% relative humidity for 24 hours or more in a measurement cell having a diameter of 20 mm (0.283 cm ² ), sandwiched between 120 g / cm ² load electrodes, and the cell thickness. Was 2 mm, and the applied voltage was measured at 500V.

(13) Method for measuring apparent density of carrier This is performed according to JIS-Z02504.

<Image Forming Method Using Toner of the Present Invention>
Hereinafter, an image forming method using the toner of the present invention (hereinafter also referred to as the image forming method of the present invention) will be described in detail.

As described above, the image forming method of the present invention performs image formation using the toner of the present invention, and includes a charging step for charging the surface of the photoreceptor; and an electrostatic latent image on the surface of the charged photoreceptor. A latent image forming step of forming an electrostatic latent image by an action of an electric field between a developer carrying member that carries a developer containing toner in a developing unit and a photosensitive member carrying an electrostatic latent image. A developing step of forming a toner image by supplying toner and visualizing an electrostatic latent image; a transfer step of transferring the toner image onto a transfer material with or without an intermediate transfer member; and a fixing member; The image forming method includes a fixing step in which the transfer material is passed through a nip portion formed by the pressure member pressed against the fixing member, and the toner image is heated and pressed against the transfer material. In the image forming method of the present invention, in the fixing step, the fixing member includes only a pressure member as a contact member, and the fixing member includes a non-contact type temperature detecting means as a means for detecting a surface temperature. It may be provided on the fixing member other than the portion of L / 6 from both ends of the fixing member when the longitudinal length of the fixing member is L.

  The toner of the present invention is a full-color product such as a black and white copying machine such as IR6000 or IR3000 manufactured by Canon, a laser beam printer such as LBP720 or LBP950, a modified two-component machine thereof, LBP2040, CLC500, CLC700, CLC1000, CP2150, CP660, or IRC3200. It can be preferably used in the machine.

A preferred example of the image forming method of the present invention using the toner of the present invention will be described below with reference to the drawings. FIG. 1 is a partial schematic view showing an example of an image forming apparatus to which the image forming method of the present invention is applied. Although details will be described later, this image forming apparatus includes a photosensitive drum 1 as a photosensitive member carrying an electrostatic latent image, a charging means 2 for charging the surface of the photosensitive drum 1, and a surface on the surface of the charged photosensitive drum 1. electrostatic and latent image (not shown) information writing means for forming a (laser exposure or the like), an electrostatic latent image formed on the photosensitive drum 1 surface is visualized with toner, and the developing device 4 that forms form a toner image, developing A transfer blade 27 is provided as transfer means for transferring the toner image formed by the apparatus 4 to the transfer material 25.

  As a developing method using the toner of the present invention, for example, development can be performed using a two-component developing unit as shown in FIG. In the present invention, the development process is performed by applying a voltage in which an alternating current component is superimposed on a direct current component to the developer carrying member to form an oscillating electric field between the developer carrying member and the surface of the photosensitive member. It is preferable that it is a process. Specifically, the alternating voltage shown in FIG. 2 is applied to the developer carrying member, and development is performed in a state where the magnetic brush formed by the carrier on the developer carrying member is in contact with the photosensitive member that is the latent image carrying member. It is preferable.

  The distance B between the developer carrying member (developing sleeve) 11 and the photosensitive drum 1 (SD distance) B is preferably 100 to 800 μm from the viewpoint of preventing carrier adhesion to the photosensitive member and improving dot reproducibility. . If the SD distance is narrower than 100 μm, the supply of the developer to the photoreceptor tends to be insufficient, and the image density becomes low, and if it exceeds 800 μm, the lines of magnetic force from the magnetic pole S1 spread and the density of the magnetic brush decreases, The dot reproducibility is inferior, or the force for restraining the magnetic coat carrier is weakened, and the carrier adheres easily.

  The voltage between the peaks of the alternating electric field is preferably 300 to 3000 V, and the frequency is 500 to 10000 Hz, preferably 1000 to 7000 Hz, which can be appropriately selected depending on the process. In this case, a triangular wave, a rectangular wave, a sine wave, a waveform with a changed duty ratio, an intermittent alternating superimposed electric field, or the like can be selected and used as the waveform. When the applied voltage is lower than 300 V, it is difficult to obtain a sufficient image density, and the fog toner in the non-image portion may not be recovered well. If the voltage exceeds 3000 V, the latent image may be disturbed via the magnetic brush, leading to a reduction in image quality.

  By using a two-component developer with well-charged toner, the anti-fogging voltage (Vback) can be lowered and the primary charge of the photoreceptor can be lowered, thus extending the life of the photoreceptor. it can. Vback is 350 V or less, more preferably 300 V or less, although it depends on the developing system.

  The contrast potential is preferably 100 to 500 V so that a sufficient image density is obtained.

When the frequency is lower than 500 Hz, although it is related to the process speed, when the toner in contact with the photosensitive member is returned to the developing sleeve, sufficient vibration is not applied and fogging is likely to occur. If it exceeds 10,000 Hz, the toner cannot follow the electric field, and the image quality is likely to deteriorate.

  What is important in the developing method of the present invention is that the contact width of the magnetic brush on the developing sleeve 11 with the photosensitive drum 1 in order to achieve a sufficient image density, excellent dot reproducibility and development without carrier adhesion ( The development nip C) is preferably 3 to 8 mm. If the development nip C is narrower than 3 mm, it is difficult to satisfactorily satisfy a sufficient image density and dot reproducibility. If the development nip C is wider than 8 mm, developer packing occurs and the operation of the machine stops or the carrier adheres. It is difficult to sufficiently suppress As a method for adjusting the developing nip, the nip width is appropriately adjusted by adjusting the distance A between the regulating blade 15 as the developer regulating member and the developing sleeve 11 or by adjusting the distance B between the developing sleeve 11 and the photosensitive drum 1. Can be adjusted.

  The image forming method of the present invention uses the developer and the developing method of the present invention, particularly in the output of an image that places importance on halftone, and in combination with a developing system that has formed a digital latent image, through the toner. Therefore, it is possible to develop the dot latent image faithfully without disturbing the latent image. Even in the transfer process, a high transfer rate can be achieved by using a toner having a fine particle size distribution that has been finely powder-cut. Therefore, high image quality can be achieved in both the halftone part and the solid part.

  In addition to the improvement in the initial image quality, the use of the above-mentioned two-component developer makes the change in the toner charge amount in the developing device small, and the effect of the present invention is sufficient without causing a deterioration in image quality even when copying many sheets. Can demonstrate.

  Preferably, a developing device for magenta, cyan, yellow, and black is provided, and black development is performed last, so that a tighter image can be presented.

  The image forming method of the present invention will be further described with reference to the drawings.

  In FIG. 1, a magnetic brush made of magnetic particles 23 is formed on the surface of the conveying sleeve 22 by the magnetic force of the magnet roller 21, and the photosensitive drum 1 is charged by bringing the magnetic brush into contact with the surface of the photosensitive drum 1. A charging bias is applied to the conveying sleeve 22 by a bias applying means (not shown).

  A digital electrostatic latent image is formed by irradiating the charged photosensitive drum 1 with a laser beam 24 by an exposure device (not shown) as a latent image forming unit. The electrostatic latent image formed on the photosensitive drum 1 is developed by the toner 19a in the developer 19 carried on the developing sleeve 11 containing the magnet roller 12 and applied with a developing bias by a bias applying device (not shown). Is done.

  The developing device 4 is divided into a developer chamber R1 and a stirring chamber R2 by a partition wall 17, and developer transport screws 13 and 14 are installed, respectively. Above the agitating chamber R2, a toner storage chamber R3 containing replenishing toner 18 is installed, and a supply port 20 is provided below the storage chamber R3.

The developer conveying screw 13 rotates to convey the developer in the developer chamber R1 in one direction along the longitudinal direction of the developing sleeve 11 while stirring. The partition wall 17 is provided with openings (not shown) on the front side and the back side of the drawing, and the developer conveyed to one side of the developer chamber R1 by the screw 13 is stirred through the opening of the partition wall 17 on one side. It is fed into the chamber R2 and delivered to the developer conveying screw 14. The direction of rotation of the screw 14 is opposite to that of the screw 13, while stirring and mixing the developer in the stirring chamber R 2, the developer delivered from the developer chamber R 1 and the toner replenished from the toner storage chamber R 3. In the opposite direction, the toner is conveyed through the stirring chamber R2 and fed into the developer chamber R1 through the other opening of the partition wall 17.

  In order to develop the electrostatic latent image formed on the photosensitive drum 1, the developer 19 in the developer chamber R <b> 1 is drawn up by the magnetic force of the magnet roller 12 and is carried on the surface of the developing sleeve 11. The developer carried on the developing sleeve 11 is conveyed to a regulating blade 15 as the developing sleeve 11 rotates, and after being regulated to a developer thin layer having an appropriate layer thickness, the developing sleeve 11, the photosensitive drum 1, and the like. Reaches the opposite development area. A magnetic pole (development pole) N1 is located at a position corresponding to the development area of the magnet roller 12, and the development pole N1 forms a development magnetic field in the development area, and the developer spikes by this development magnetic field, A developer magnetic brush is generated in the development area. Then, the magnetic brush comes into contact with the photosensitive drum 1, and the toner adhering to the magnetic brush and the toner adhering to the surface of the developing sleeve 11 are transferred to the electrostatic image area on the photosensitive drum 1 by the reversal development method. The electrostatic latent image is developed and a toner image is formed.

  The developer that has passed through the developing region is returned to the developing device 4 as the developing sleeve 11 rotates, and is peeled off from the developing sleeve 11 by the repulsive magnetic field between the magnetic poles S1 and S2, and the developer chamber R1 and the stirring chamber R2 are removed. It is dropped and collected.

  When the T / C ratio of the developer 19 in the developing device 4 (mixing ratio of toner and carrier, that is, the toner concentration in the developer) is reduced by the above developing process, the replenishing toner 18 is developed from the toner storage chamber R3. The stirring chamber R2 is replenished with an amount that matches the amount consumed, and the T / C of the developer 19 is maintained at a predetermined amount. To detect the T / C ratio of the developer 19 in the container 4, a toner concentration detection sensor that measures the change in the magnetic permeability of the developer using the inductance of the coil is used. The toner concentration detection sensor has a coil (not shown) therein.

The regulating blade 15 that is disposed below the developing sleeve 11 and regulates the layer thickness of the developer 19 on the developing sleeve 11 is a nonmagnetic blade made of a nonmagnetic material such as aluminum or SUS316. The distance between the end portion and the surface of the developing sleeve 11 is 150 to 1000 μm, preferably 250 to 900 μm. If this distance is less than 150 μm, the magnetic carrier is clogged in the meantime, and the developer layer is likely to be uneven, and it is difficult to apply the developer necessary for good development, and a developed image with a small density and unevenness is formed. Easy to be. This distance in order to prevent uneven coating due to unnecessary particles are mixed in the developer (so-called blade jam) is preferably at least 250 [mu] m. If it is larger than 1000 μm, the amount of developer applied on the developing sleeve 11 increases, and it is difficult to regulate the predetermined developer layer thickness, and the magnetic carrier particles adhere to the photosensitive drum 1 more and the developer is circulated and regulated. Development regulation by the blade 15 is weakened, and toner tribo is lowered and fogging is easily caused.

  Further, the developed toner image is transferred onto a transfer material (recording material) 25 being conveyed by a transfer blade 27 which is a transfer device to which a transfer bias is applied by a bias applying device 26, and onto the transfer material. The transferred toner image is fixed on the transfer material by a fixing device (not shown). In the transfer process, the transfer residual toner that has not been transferred to the transfer material and remains on the photosensitive drum 1 is adjusted in the charging state in the charging process and collected during development.

  Further, an example of the image forming method of the present invention having a charge amount control step will be described with reference to FIG.

  As shown in FIG. 10, a predetermined charging bias is applied to the charging roller 2 from the power source S1 to charge the photosensitive drum. At this time, the bias voltage is preferably an oscillating voltage obtained by superimposing a DC voltage (Vdc) and an AC voltage (Vac). Thereafter, image exposure is performed by the laser system 3 to form a latent image.

  The developing sleeve 4b is disposed opposite to the latent image so as to be close to the photosensitive drum 1. A facing portion between the photosensitive drum 1 and the developing sleeve 4b is a developing portion c. The developing sleeve 4b is preferably driven to rotate in the direction opposite to the traveling direction of the photosensitive drum 1 in the developing portion c. A part of the two-component developer 4e in the developing container 4a is adsorbed and held as a magnetic brush layer on the outer peripheral surface of the developing sleeve 4b by the magnetic force of the magnet roller 4c in the sleeve, and is rotated and conveyed as the sleeve rotates. Then, a predetermined thin layer is formed by the developer coating blade 4d, and in contact with the surface of the photosensitive drum 1 at the developing portion c, the surface of the photosensitive drum is rubbed appropriately.

  A predetermined developing bias is applied to the developing sleeve 4b from the power source S2. In this example, the developing bias voltage for the developing sleeve 4b is an oscillating voltage obtained by superimposing a DC voltage (Vdc) and an AC voltage (Vac). As a result, the latent image on the photosensitive drum is developed with the toner in the developer 4e. The developed toner is transferred to a transfer material, an intermediate transfer body, or the like by a transfer roller 5 at a transfer portion d. The toner remaining on the photosensitive drum undergoes the next charge amount control step. That is, the normal polarity is adjusted by the residual toner on the photosensitive drum coming into contact with the brush contact portion e on the charge amount control member 7 to which a predetermined voltage is applied from the power source S4. In the case of negatively charged toner, a negative voltage is applied to the photosensitive drum, and in the case of positively charged toner, a positive voltage is applied to the photosensitive drum. By passing through such a process, in the case of a cleaner-less system, the transfer residual toner can be recovered well during development. Although not clearly shown in FIG. 10, the same member as in the charge amount control process is used between the transfer process and the charge amount control process for the purpose of removing the residual charge on the photosensitive drum and improving the drum ghost. It is also an effective means to give the photosensitive drum a potential difference of opposite polarity applied in the charging step.

  FIG. 3 is a schematic view in which the image forming method of the present invention is applied to a full-color image forming apparatus.

  The full-color image forming apparatus main body is provided with a first image forming unit Pa, a second image forming unit Pb, a third image forming unit Pc, and a fourth image forming unit Pd. It is formed on a transfer material through development and transfer processes.

  The configuration of each image forming unit provided in the image forming apparatus will be described by taking the first image forming unit Pa as an example.

  The first image forming unit Pa includes an electrophotographic photosensitive drum 61a having a diameter of 30 mm as a photosensitive member that is an electrostatic latent image carrier, and the photosensitive drum 61a is rotated in the direction of arrow a. Reference numeral 62a denotes a primary charger as charging means, which is arranged so that a magnetic brush formed on the surface of a sleeve having a diameter of 16 mm comes into contact with the surface of the photosensitive drum 61a. 67a is a laser beam for forming an electrostatic latent image on the photosensitive drum 61a whose surface is uniformly charged by the primary charger 62a, and is irradiated by an exposure device (not shown). Reference numeral 63a denotes a developing device as developing means for developing the electrostatic latent image carried on the photosensitive drum 61a to form a color toner image, and holds the color toner. Reference numeral 64a denotes a transfer blade as transfer means for transferring a color toner image formed on the surface of the photosensitive drum 61a onto the surface of a transfer material (recording material) conveyed by a belt-like transfer material carrier 68. The transfer blade 64a can contact the back surface of the transfer material carrier 68 and apply a transfer bias.

The first image forming unit Pa uniformly charges the photosensitive drum 61a with the primary charger 62a, then forms an electrostatic charge image on the photosensitive member with the exposure device 67a, and develops the electrostatic latent image with the developing device 63a. The back side of a belt-like transfer material carrier 68 that develops using toner and carries the developed toner image on the first transfer portion (contact position between the photosensitive drum 61a and the transfer material). By applying a transfer bias from the transfer blade 64a that is in contact with the toner, the image is transferred to the surface of the transfer material.

  When the toner is consumed by the development and the T / C ratio decreases, the decrease is detected by the toner concentration detection sensor 85 that measures the change in the magnetic permeability of the developer using the inductance of the coil, and the amount of consumed toner is calculated. Accordingly, the replenishment toner 65a is replenished. The toner concentration detection sensor 85 has a coil (not shown) inside.

  This image forming apparatus has the same configuration as that of the first image forming unit Pa, and the second image forming unit Pb, the third image forming unit Pc, and the fourth image forming unit having different color toner colors held in the developing device. The image forming unit Pd is provided with four image forming units. For example, yellow toner is used for the first image forming unit Pa, magenta toner is used for the second image forming unit Pb, cyan toner is used for the third image forming unit Pc, and black toner is used for the fourth image forming unit Pd. An image is formed on a photoreceptor provided for each color of toner, and transfer of each color toner onto a transfer material is sequentially performed at a transfer portion of each image forming unit. In this step, the color toners are superimposed on each other by moving the transfer material once on the same transfer material while aligning the registration. When the transfer is completed, the transfer material is separated from the transfer material carrier 68 by the separation charger 69. Then, it is sent to the fixing device 70 by a conveying means such as a conveying belt, and a final full-color image is obtained by only one fixing.

  The fixing device 70 has a pair of a fixing roller 71 having a diameter of 40 mm and a pressure roller 72 having a diameter of 30 mm. The fixing roller 71 has heating means 75 and 76 inside.

  The unfixed color toner image transferred onto the transfer material passes through the pressure contact portion between the fixing roller 71 and the pressure roller 72 of the fixing device 70 and is fixed onto the transfer material by the action of heat and pressure. The

  In FIG. 3, a transfer material carrier 68 is an endless belt-like member, and this belt-like member is moved in the direction of arrow e by 80 drive rollers. 79 is a transfer belt cleaning device, 81 is a belt driven roller, and 82 is a belt static eliminator. Reference numeral 83 denotes a pair of registration rollers for conveying the transfer material in the transfer material holder to the transfer material carrier 68.

  As the transfer means, in place of the transfer blade that contacts the back side of the transfer material carrier, a contact transfer means that can contact the back side of the transfer material carrier such as a roller-like transfer roller and directly apply a transfer bias. Can be used.

  Further, a non-contact transfer unit that performs transfer by applying a transfer bias from a corona charger arranged in a non-contact manner on the back side of a transfer material carrier that is generally used instead of the contact transfer unit described above. It is also possible to use.

  However, it is more preferable to use the contact transfer means in that the amount of ozone generated when the transfer bias is applied can be controlled.

  Next, an example of another image forming method of the present invention will be described with reference to FIG.

  FIG. 4 is a schematic configuration diagram showing an example of an image forming apparatus capable of performing the image forming method of the present invention.

This image forming apparatus is configured as a full-color copying machine. The full-color copier is shown in Fig. 4.
As shown, the digital color image reader unit 35 is provided in the upper part, and the digital color image printer unit 36 is provided in the lower part.

  In the image reader unit, the original 30 is placed on the original platen glass 31 and exposed and scanned by the exposure lamp 32, whereby the reflected light image from the original 30 is condensed on the full color sensor 34 by the lens 33, and the color color separation image signal is obtained. Get. The color separation image signal is processed by a video processing unit (not shown) through an amplifier circuit (not shown) and sent to a digital image printer unit.

  In the image printer unit, a photosensitive drum 1 as a photosensitive member which is an electrostatic latent image carrier is a photosensitive member such as an organic photoconductor, and is supported rotatably in the direction of an arrow. Around the photosensitive drum 1, there are a pre-exposure lamp 11, a corona charger 2 as a primary charging member, a laser exposure optical system 3 as a latent image forming means, a potential sensor 12, and four developers 4Y and 4C of different colors. 4M, 4K, on-drum light amount detection means 13, a transfer device 5A and a cleaning device 6 are arranged.

  In the laser exposure optical system 3, an image signal from the reader unit is converted into an optical signal for image scan exposure by a laser output unit (not shown), and the converted laser beam is reflected by the polygon mirror 3a, and the lens 3b. Then, the light is projected onto the surface of the photosensitive drum 1 via the mirror 3c.

  At the time of image formation, the printer unit rotates the photosensitive drum 1 in the direction of the arrow, neutralizes the charge with the pre-exposure lamp 11, and then uniformly charges the photosensitive drum 1 with the charger 2, so that the optical image E for each separated color. To form a latent image on the photosensitive drum 1.

  Next, a predetermined developing device is operated to develop the latent image on the photosensitive drum 1, and a visible image, that is, a toner image is formed on the photosensitive drum 1 using a negatively chargeable toner having a resin as a base. The developing units 4Y, 4C, 4M, and 4K perform development by alternately approaching the photosensitive drum 1 according to the respective separation colors by the operations of the eccentric cams 24Y, 24C, 24M, and 24K.

  The transfer device 5A includes a transfer drum 5, a transfer charger 5b, an adsorption charger 5c for electrostatically adsorbing a recording material, and an adsorption roller 5g opposed thereto, an inner charger 5d, an outer charger 5e, and a separation charger. 5h. The transfer drum 5 is pivotally supported so as to be rotationally driven, and a transfer sheet 5f which is a recording material carrier that carries a recording material (transfer material) in an opening area around the transfer drum 5 is integrally adjusted in a cylindrical shape. A polycarbonate film or the like is used for the transfer sheet 5f.

  The recording material is conveyed from the recording material cassette 7a, 7b or 7c to the transfer drum 5 through the recording material conveyance system, and is carried on the transfer sheet 5f. The recording material carried on the transfer drum 5 is repeatedly conveyed to the transfer position facing the photosensitive drum 1 as the transfer drum 5 rotates, and is transferred onto the recording material by the action of the transfer charger 5b in the process of passing through the transfer position. The toner image on the photosensitive drum 1 is transferred to the surface.

  The above-described image forming process is repeated for yellow (Y), magenta (M), cyan (C), and black (K), and a color image in which four color toner images are transferred onto the recording material on the transfer drum 5 is transferred. Is obtained.

In the case of image formation on one side, the recording material onto which the four color toner images have been transferred in this way is separated from the transfer drum 5 by the action of the separation claw 8a, separation push-up roller 8b, and separation charger 5h. It is sent to the heat fixing device 9. The heat fixing device 9 includes a heat fixing roller 9a and a pressure roller 9b each having a heating means. When the recording material passes through the pressure contact portion between the heat fixing roller 9a and the pressure roller 9b as the heating member, the full-color image carried on the recording material is fixed to the recording material. That is, the toner mixing, coloring, and fixing to the recording material are performed by this fixing process, and after being formed into a full-color permanent image, it is discharged to the tray 10 and one full-color copy is completed. On the other hand, the photosensitive drum 1 is subjected to an image forming process again after residual toner on the surface is removed by cleaning with a cleaning device 6.

  In the image forming method of the present invention, a toner image obtained by developing the electrostatic latent image formed on the latent image carrier can be transferred to a recording material via an intermediate transfer member.

  That is, in this image forming method, a step of transferring a toner image formed by developing an electrostatic latent image formed on an electrostatic charge image bearing member to an intermediate transfer member and a toner image transferred to the intermediate transfer member are recorded. It has the process of transferring to a material.

  An example of an image forming method using the intermediate transfer member will be specifically described with reference to FIG.

  In the apparatus system shown in FIG. 5, the cyan developing unit 54-1, the magenta developing unit 54-2, the yellow developing unit 54-3, and the black developing unit 54-4 have cyan developer and magenta toner having cyan toner, respectively. A magenta developer, a yellow developer having a yellow toner, and a black developer having a black toner have been introduced. An electrostatic latent image is formed on the photosensitive member 51 as a latent image holding member by a latent image forming means 53 such as a laser beam. The electrostatic latent image formed on the photosensitive member 51 is developed with these developers by a developing method such as a magnetic brush developing method, a non-magnetic one-component developing method, or a magnetic jumping developing method, and each color toner image is formed on the photosensitive member 51. It is formed. The photosensitive member 51 is a photosensitive drum or photosensitive belt having a conductive substrate 51b and a photoconductive insulating material layer 51a formed on the conductive substrate 51b, such as amorphous selenium, cadmium sulfide, zinc oxide, organic photoconductor, and amorphous silicon. is there. The photoconductor 51 is rotated in the direction of the arrow by a driving device (not shown). As the photoreceptor 51, a photoreceptor having an amorphous silicon photosensitive layer or an organic photosensitive layer is preferably used.

  The organic photosensitive layer may be a single layer type in which the photosensitive layer contains a charge generation material and a material having charge transport performance in the same layer, or a function-separated type photosensitive layer comprising a charge transport layer and a charge generation layer as components. It 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.

  As the binder resin for the organic photosensitive layer, polycarbonate resin, polyester resin, and acrylic resin have good cleaning properties, and poor cleaning, fusion of toner to the photoreceptor, and filming of external additives are unlikely to occur.

  In the charging process, there are a non-contact type method using the photoconductor 51 using a corona charger and a contact type method using a contact charging member such as a roller. A contact type as shown in FIG. 5 is preferably used for efficient uniform charging, simplification, and low ozone generation.

  The charging roller 52 as a primary charging member has a basic configuration of a central core metal 52b and a conductive elastic layer 52a formed on the outer periphery thereof. The charging roller 52 is pressed against the surface of the photoconductor 51 with a pressing force, and is driven to rotate as the photoconductor 51 rotates.

  As a preferable process condition when using the charging roller, when the contact pressure of the roller is 5 to 500 g / cm and an AC voltage is superimposed on a DC voltage, AC voltage = 0.5 to 5 kVpp, AC Frequency = 50 Hz to 5 kHz, DC voltage = ± 0.2 to ± 5 kV.

  Other contact charging members include a method using a charging blade and a method using a conductive brush. These contact charging members are effective 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 member 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 fluorine acrylic resin can be applied.

  The toner image on the photosensitive member is transferred to the intermediate transfer member 55 to which a voltage (for example, ± 0.1 to ± 5 kV) is applied. The intermediate transfer body 55 includes a pipe-shaped conductive core 55b and a medium-resistance elastic body layer 55a formed on the outer peripheral surface thereof. The core metal 55b may be a plastic surface provided with a conductive layer (for example, conductive plating).

The medium resistance elastic layer 55a is made of elastic material such as silicone rubber, fluororesin rubber, chloroprene rubber, urethane rubber, EPDM (terpolymer of ethylene propylene diene), carbon black, zinc oxide, tin oxide, carbonized carbon. It is a solid or foamed meat layer in which a conductivity imparting material such as silicon is blended and dispersed to adjust the electric resistance value (volume resistance value) to a medium resistance of 10 ⁵ to 10 ¹¹ Ω · cm.

  The intermediate transfer member 55 is disposed in parallel with the photosensitive member 51 and is in contact with the lower surface portion of the photosensitive member 51, and rotates in the counterclockwise direction indicated by the arrow at the same peripheral speed as the photosensitive member 51.

  In the process in which the first color toner image formed and supported on the surface of the photoconductor 51 passes through the transfer nip where the photoconductor 51 and the intermediate transfer body 55 are in contact with each other, the transfer nip region is applied with the transfer bias applied to the intermediate transfer body 55. The intermediate transfer is sequentially performed on the outer surface of the intermediate transfer member 55 by the electric field formed on the intermediate transfer member 55.

  The untransferred toner on the photoconductor 51 that has not been transferred to the intermediate transfer body 55 is cleaned by the photoconductor cleaning member 58 and collected in the photoconductor cleaning container 59.

  The transfer unit 57 is supported in parallel with the intermediate transfer member 55 and is disposed in contact with the lower surface portion of the intermediate transfer member 55. The transfer means 57 is, for example, a transfer roller or a transfer belt, and rotates in the clockwise direction of the arrow at the same peripheral speed as that of the intermediate transfer body 55. The transfer unit 57 may be disposed so as to be in direct contact with the intermediate transfer member 55, or a belt or the like may be disposed between the intermediate transfer member 55 and the transfer unit 57.

  In the case of a transfer roller, the basic configuration is a central core 57b and a conductive elastic layer 57a that forms the outer periphery thereof.

  Common materials can be used for the intermediate transfer member and the transfer roller. By setting the volume resistivity of the elastic layer of the transfer roller to be smaller than the volume resistivity of the elastic layer of the intermediate transfer member, the voltage applied to the transfer roller can be reduced, and a good toner image is formed on the transfer material. In addition, it is possible to prevent the transfer material from being wound around the intermediate transfer member. In particular, the volume specific resistance value of the elastic layer of the intermediate transfer member is particularly preferably 10 times or more than the volume specific resistance value of the elastic layer of the transfer roller.

The hardness of the intermediate transfer member and the transfer roller is measured according to JIS K-6301. The intermediate transfer member used in the present invention is preferably composed of an elastic layer belonging to a range of 10 to 40 degrees. On the other hand, the hardness of the elastic layer of the transfer roller is harder than the hardness of the elastic layer of the intermediate transfer member. Those having a value of ˜80 degrees are preferable for preventing the transfer material from being wound around the intermediate transfer member. When the hardness of the intermediate transfer member and the transfer roller are reversed, a recess is formed on the transfer roller side, and the transfer material is likely to be wound around the intermediate transfer member.

  The transfer means 57 is rotated with a difference in speed or peripheral speed from the intermediate transfer body 55. The transfer material 56 is conveyed between the intermediate transfer body 55 and the transfer means 57, and at the same time, a bias having a polarity opposite to the frictional charge of the toner is applied to the transfer means 57 from the transfer bias means. The toner image is transferred to the surface side of the transfer material 56.

  The transfer residual toner on the intermediate transfer member that has not been transferred to the transfer material 56 is cleaned by the intermediate transfer member cleaning member 60 and collected in the intermediate transfer member cleaning container 62. The toner image transferred to the transfer material 56 is fixed to the transfer material 56 by the heat fixing device 61.

  As the material of the transfer roller, the same material as that of the charging roller can be used. As a preferable transfer process condition, the contact pressure of the roller is preferably 2.94 to 490 N / m (3 to 500 g / cm), more preferably. Is 19.6 to 294 N / m, and DC voltage = ± 0.2 to ± 10 kV.

  If the linear pressure as the contact pressure is less than 2.94 N / m, it is not preferable because transfer of the transfer material and transfer failure are likely to occur.

For example, the conductive elastic layer 57b of the transfer roller 57 is blended with an elastic material such as polyurethane rubber or EPDM (ethylene propylene diene terpolymer) and a conductive agent such as carbon black, zinc oxide, tin oxide, or silicon carbide. The electrical resistance value (volume resistance value) is 10 ⁶ to 1
It is a solid or foamed layer adjusted to a medium resistance of 0 ¹⁰ Ω · cm.

  As a contact one-component developing method, it is possible to develop using a non-magnetic toner, for example, using a developing device 90 as shown in FIG.

  The developing device 90 includes a developing container 91 that stores a one-component developer 98 (hereinafter, simply referred to as “developer”) having magnetic or non-magnetic toner, and one component stored in the developing container 91. The developer carrier 92 for carrying the developer 98 and transporting it to the development area, the supply roller 95 for supplying the developer onto the developer carrier, and the developer layer thickness on the developer carrier are regulated. Therefore, an elastic blade 96 as a developer layer thickness regulating member and a stirring member 97 for stirring the developer 98 in the developing container 91 are provided.

  As the developer carrier 92, it is preferable to use an elastic roller having an elastic layer 94 formed of an elastic member such as rubber or resin having elasticity such as foamed silicone rubber on the roller base 93.

  The elastic roller (92) is formed on the photosensitive member by a one-component developer 98 applied to the surface of the elastic roller in pressure contact with the surface of the photosensitive drum 99 as a photosensitive member as a latent image holding member. The electrostatic latent image is developed, and unnecessary one-component developer 98 present on the photosensitive member after the transfer is recovered.

In the present invention, the developer carrying member 92 is substantially in contact with the surface of the photosensitive drum 99. This means that when the one-component developer is removed from the developer carrier, the developer carrier is in contact with the photoreceptor. At this time, an image having no edge effect is obtained through the developer by an electric field acting between the photosensitive member and the developer carrying member, and at the same time, cleaning is performed. It is necessary that the surface of the elastic roller as the developer carrying member or the vicinity of the surface has an electric potential between the surface of the photosensitive member and the surface of the elastic roller. Therefore, it is possible to use a method in which the elastic rubber of the elastic roller is resistance controlled to the middle resistance region to keep the electric field while preventing conduction with the surface of the photoconductor, or a method of providing a thin dielectric layer on the surface layer of the conductive roller. . Furthermore, there is a configuration in which a conductive resin sleeve in which the surface that contacts the surface of the photoreceptor is covered with an insulating material on the conductive roller or a conductive layer is provided on the surface that does not contact the photoreceptor with an insulating sleeve. Is possible.

  The elastic roller carrying the one-component developer may rotate in the same direction as the photosensitive drum, or may rotate in the opposite direction. When the rotations are in the same direction, the peripheral speed ratio is preferably greater than 100% with respect to the peripheral speed of the photosensitive drum. If it is 100% or less, problems such as poor line definition are likely to occur. The higher the peripheral speed ratio is, the more developer is supplied to the development site, the more frequently the developer is desorbed from the electrostatic latent image, and the unnecessary part of the developer is scraped off. An image faithful to the electrostatic latent image is obtained by repeatedly applying the developer to the portion. More preferably, the peripheral speed ratio is 100% or more.

  The developer layer thickness regulating member 96 is not limited to an elastic blade as long as it is in pressure contact with the surface of the developer carrying member 92 by an elastic force, and an elastic roller can also be used.

  As the elastic blade and elastic roller, rubber elastic bodies such as silicone rubber, urethane rubber and NBR; synthetic resin elastic bodies such as polyethylene terephthalate; metal elastic bodies such as stainless steel and steel can be used. Furthermore, even those complexes can be used.

  In the case of an elastic blade, the base which is the upper side of the elastic blade is fixedly held on the developer container side, and the lower side is bent in the forward or reverse direction of the developing sleeve against the elasticity of the blade. The inner surface side (the outer surface side in the case of the reverse direction) is brought into contact with the sleeve surface with an appropriate elastic pressure.

  The supply roller 95 is made of a foam material such as polyurethane foam, and rotates with a relative speed other than 0 in the forward or reverse direction with respect to the developer carrier, and supplies the one-component developer on the developer carrier. The developer after development (undeveloped developer) is also stripped off.

  When developing the electrostatic latent image on the photosensitive member with a one-component developer on the developer carrying member in the developing region, a direct and / or alternating development bias is provided between the developer carrying member and the photosensitive drum. It is preferable to apply and develop.

  Next, the non-contact jumping development method will be described.

  Examples of the non-contact jumping development method include a development method using a one-component magnetic developer having a non-magnetic toner. Here, a developing method using a one-component nonmagnetic developer having a nonmagnetic toner will be described based on a schematic configuration diagram shown in FIG.

  The developing device 170 includes a developing container 171 containing a one-component non-magnetic developer 176 having non-magnetic toner (hereinafter sometimes simply referred to as “developer”), and one component contained in the developing container 171. A developer carrier 172 for carrying a non-magnetic non-magnetic developer 176 and transporting it to the development area, a supply roller 173 for supplying a one-component non-magnetic developer onto the developer carrier 172, and a developer carrier An elastic blade 174 as a developer layer thickness regulating member for regulating the developer layer thickness on 172, and a stirring member 175 for stirring the one-component nonmagnetic developer 176 in the developing container 171 are provided. .

  Reference numeral 169 denotes a photosensitive member as an electrostatic latent image holding member, and the latent image is formed by electrophotographic process means or electrostatic recording means (not shown). Reference numeral 172 denotes a developing sleeve as a developer carrying member, which is a non-magnetic sleeve made of aluminum or stainless steel.

  As the developing sleeve, a rough tube of aluminum or stainless steel may be used as it is, but it is preferable that the surface is uniformly roughened by spraying glass beads, mirror-finished, or coated with a resin.

  The one-component nonmagnetic developer 176 is stored in the developing container 171 and is supplied onto the developer carrier 172 by the supply roller 173. The supply roller 173 is made of a foam material such as polyurethane foam, and rotates with a non-zero relative speed in the forward or reverse direction with respect to the developer carrier 172, and on the developer carrier 172 along with the supply of the developer. The developer after development (undeveloped developer) is also stripped off. The one-component nonmagnetic developer 176 supplied onto the developer carrier 172 is uniformly and thinly applied by an elastic blade 174 as a developer layer thickness regulating member.

  The contact pressure between the elastic coating blade and the developer carrying member is 0.3 to 25 kg / m, preferably 0.5 to 12 kg / m as the linear pressure in the developing sleeve bus direction. When the contact pressure is less than 0.3 kg / m, it is difficult to uniformly apply the one-component nonmagnetic developer, and the charge amount distribution of the one-component nonmagnetic developer becomes broad, which causes fogging and scattering. When the contact pressure exceeds 25 kg / m, a large pressure is applied to the one-component nonmagnetic developer, and the one-component nonmagnetic developer is deteriorated. Absent. Further, it is not preferable because a large torque is required to drive the developer carrying member. That is, by adjusting the contact pressure to 0.3 to 25 kg / m, it becomes possible to effectively loosen the aggregation of the one-component nonmagnetic developer using the toner of the present invention. It becomes possible to instantly raise the charge amount of the nonmagnetic developer.

  As the developer layer thickness regulating member, an elastic blade or an elastic roller can be used, and it is preferable to use a material of a triboelectric charge series suitable for charging the developer to a desired polarity.

  In the present invention, the material for the developer layer thickness regulating member is preferably silicone rubber, urethane rubber, or styrene butadiene rubber. Furthermore, an organic resin layer such as polyamide, polyimide, nylon, melamine, melamine cross-linked nylon, phenol resin, fluorine resin, silicone resin, polyester resin, urethane resin, styrene resin may be provided. It is also possible to use conductive rubber and conductive resin, and to disperse filler and charge control agent such as metal oxide, carbon black, inorganic whisker and inorganic fiber in the rubber and resin of the blade. It is preferable that the member can provide appropriate conductivity and charge imparting property and can charge the one-component non-magnetic developer appropriately.

  In this non-magnetic one-component development method, in a system in which a single-component non-magnetic developer is thinly coated on the developing sleeve 172 by the elastic blade 174, in order to obtain a sufficient image density, the one-component on the developing sleeve 172 is obtained. The thickness of the nonmagnetic developer layer is preferably made smaller than the opposing gap length β between the developing sleeve and the latent image holding member, and an alternating electric field is applied to this gap. That is, the bias power source 177 shown in FIG. 7 applies an alternating electric field or a developing bias in which a DC electric field is superimposed on the alternating electric field between the developing sleeve 172 and the photosensitive member 169, so that the developing sleeve 172 is applied to the photosensitive member 169. It is possible to facilitate the movement of the one-component nonmagnetic developer and obtain a higher quality image.

Next, the fixing process will be described. FIG. 8 is a schematic cross-sectional view showing an example of a fixing device preferably used in the present invention, and FIG. 9 is a perspective view showing a fixing roller and a pressure roller of FIG.

  The fixing device includes a cylindrical fixing roller 95 as a fixing body, a pressure roller 96 as a pressure body pressed against the fixing roller 95, and a non-contact type for detecting the surface temperature of the fixing roller 95. And a non-contact temperature detection sensor 91 as temperature detection means. The fixing roller 95 includes a hollow aluminum cored bar having a thickness of 2 mm, a silicone rubber layer as an intermediate layer provided on the cored bar, and a PTFE having a thickness of about 20 μm coated on the silicone rubber layer. It has a surface layer made of a fluororesin such as (polytetrafluoroethylene). The fixing roller 95 further includes a halogen heater 97 as a heating element for heating the fixing roller inside the cored bar. On the other hand, the pressure roller 96 includes a stainless steel core, a silicone rubber layer provided on the metal core, and a PFA (tetrafluoroethylene-perfluoro) having a thickness of about 50 μm coated on the silicone rubber layer. Alkyl vinyl ether copolymer resin) tube. The non-contact temperature detection sensor 91 is disposed to face the fixing roller 95 and includes an infrared absorption film that detects the amount of infrared rays emitted from the fixing roller 95.

  The transfer material 92 onto which the toner image has been transferred in the transfer step is passed through the nip formed by the pressure roller 96 being pressed against the fixing roller 95 by the transport body 98, whereby the toner 99 is transferred to the transfer material 92. To be established. At this time, the temperature of the image passing area 93 (the dark color portion of the fixing roller 95 in the figure) through which the transfer material passes is detected by the non-contact temperature detection sensor in the fixing roller 95, and an electric signal corresponding to the detected temperature. Is input to the control device 100. In response to an input signal to the control device, ON / OFF of the current to the halogen heater 97 is controlled, and the temperature of the fixing roller 95 is controlled to a constant temperature (190 ° C. in the present embodiment).

Further, as the process conditions of the present invention, the fixing speed when a normal transfer paper (105 g / m ² or less) is passed is 100 to 700 mm / s for a black and white machine, and 100 to 400 mm for a full color machine. / S is preferable.

  Furthermore, the width of the fixing nip is preferably 3 to 20 mm, and more preferably 5 to 15 mm.

  Specific examples of the present invention will be described below, but the present invention is not limited to these examples. “Part” means “part by mass”.

(Polar resin production example 1)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane (3.65 mol), isophthalic acid (6.21 mol), and trimetic anhydride (0.14 mol) were measured. 100 parts of these acids / alcohols and 0.2 part of tin compound of alkyl carboxylic acid having 8 carbon atoms (tin tin ethyl 2-ethylhexanoate: [CH ₃ (CH ₂ ) ₃ CHC ₂ H ₅ COO] ₂ Sn), made of glass The flask was placed in a 4-liter four-necked flask, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube were attached and placed in a mantle heater. The reaction was carried out at 220 ° C. in a nitrogen atmosphere, and when the acid value reached 12, heating was stopped and the resin was gradually cooled to obtain polar resin 1. This resin had a hydroxyl value of 15, Mw of 10,000, Mn5000, and Tg: 64.6 ° C.

(Polar resin production example 2)
Except for changing the alkylcarboxylic acid tin compound of Polar resin production example 1 to 0.4 part of tin compound of alkylcarboxylic acid having 15 carbon atoms (tin pentadecanoate: [CH ₃ (CH ₂ ) ₁₃ COO] ₂ Sn) Obtained Polar Resin 2 in the same manner. This resin had an acid value of 15, a hydroxyl value of 18, Mw of 23,000, Mn of 4700, and Tg: 63.6 ° C.

(Polar resin production example 3)
The tin alkyl alkylcarboxylic acid tin compound of Production Example 1 of polar resin was converted to a tin compound of an alkylcarboxylic acid having 5 carbon atoms (tin 2,2-dimethylpropanoate: [CH ₃ C (CH ₃ ) ₂ COO] ₂ Sn).
The polar resin 3 was obtained in the same manner except that it was changed to. This resin had an acid value of 14, a hydroxyl value of 16, Mw of 11,000, Mn of 5200, and Tg: 64.7 ° C.

(Polar resin production example 4)
As a vinyl copolymer, 1.1 mol of styrene, 0.14 mol of 2-ethylhexyl acrylate, 0.1 mol of acrylic acid, and 0.05 mol of dicumyl peroxide are put into a dropping funnel. Moreover, 2.3 mol of polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2. 8 mol, 3.1 mol of terephthalic acid, 1.6 mol of isophthalic acid, and 0.2 mol of trimellitic anhydride are weighed, and 100 parts of these are tin compounds of alkyl carboxylic acid having 8 carbon atoms (tin tin ethyl 2-ethylhexanoate: [CH ₃ (CH ₂ ) ₃ CHC ₂ H ₅ COO] ₂ Sn) was placed in a 4-liter four-necked flask made of 0.26 parts of glass, and a thermometer, a stirring rod, a condenser and a nitrogen introduction tube were attached and placed in a mantle heater. . Next, after the inside of the flask was replaced with nitrogen gas, the temperature was gradually increased while stirring, and while stirring at a temperature of 145 ° C., the monomer of the vinyl resin, the crosslinking agent and the polymerization initiator were added from the previous dropping funnel. It was dripped over 4 hours. Next, the temperature was raised to 220 ° C. and the reaction was carried out for 5 hours to obtain a resin 4 having a polyester unit component. This resin had an acid value of 18, a hydroxyl value of 18, Mw of 69,000, Mn of 6200, and Tg: 67.4 ° C.

(Polar resin production example 5)
Except for changing the alkylcarboxylate tin compound of Production Example 1 of polar resin to 0.3 part of a tin compound of an alkylcarboxylic acid having 12 carbon atoms (tin tin dodecanoate: [CH ₃ (CH ₂ ) ₁₀ COO] ₂ Sn) Obtained the polar resin 5 in the same manner. This resin had an acid value of 14, a hydroxyl value of 17, Mw of 20,000, Mn of 4900, and Tg: 64.2 ° C.

(Polar resin production example 6)
Polar resin 6 having a polyester unit component was obtained in the same manner except that the reaction was stopped when the acid value reached 2 in Polar resin production example 1. This resin had an acid value of 2, a hydroxyl value of 8, Mw of 20,000, Mn of 7600, and Tg: 65.7 ° C.

(Polar resin production example 7)
In polar resin production example 1, except that it stops the reaction when the acid value of 6, thereby obtaining the polar resin 7 having Poriesu ether component in the same manner. This resin had an acid value of 6, a hydroxyl value of 13, Mw of 19,000, Mn of 6700, and Tg: 65.7 ° C.

(Polar resin production example 8)
Polar resin 8 having a polyester unit component was obtained in the same manner except that the reaction was stopped when the acid value reached 20 in Polar resin production example 1. This resin had an acid value of 20, a hydroxyl value of 29, an Mw of 11,000, an Mn of 3800, and a Tg of 66.3 ° C.

(Polar resin production example 9)
Polar resin 9 having a polyester unit component was obtained in the same manner except that the reaction was stopped when the acid value reached 38 in Polar resin production example 1. This resin had an acid value of 38, a hydroxyl value of 39, Mw of 8,000, Mn3400, and Tg: 65.8 ° C.

(Polar resin comparative production example 1)
Comparative Resin 1 in the same manner except that the alkylcarboxylic acid tin compound of Production Example 1 of polar resin is changed to a tin compound of alkylcarboxylic acid having 3 carbon atoms (tin propanoate: [CH ₃ CH ₂ COO] ₂ Sn). Got. This resin had an acid value of 15, a hydroxyl value of 18, Mw of 13,000, Mn of 5400, and Tg: 64.7 ° C.

(Polar resin comparative production example 2)
Other than adding the alkylcarboxylic acid tin compound of Polar Resin Production Example 1 to 0.5 part of a tin compound of alkyl carboxylic acid with 19 carbon atoms (tin nonadecanoate: [CH ₃ (CH ₂ ) ₁₇ COO] ₂ Sn) In the same manner, Comparative Resin 2 was obtained. This resin had an acid value of 17, a hydroxyl value of 20, Mw of 28,000, Mn of 4500, and Tg: 62.6 ° C.

(Polar resin comparative production example 3)
In Resin Production Example 1, a comparative resin 3 having a polyester unit component was obtained in the same manner except that tin compound 1 of alkylcarboxylic acid was changed to dibutyltin oxide. This resin had an acid value of 15, a hydroxyl value of 19, Mw of 14,000, Mn of 5800, and Tg of 67.6 ° C.

<Toner Production Example 1>
For 100 parts of the styrene monomer, 14 parts of cyan colourant copper phthalocyanine (CI Pigment Blue 15: 3) and 1.8 parts of an aluminum compound of di-tertiary butylsalicylic acid were prepared. These were introduced into an attritor and stirred at 200 rpm at 25 ° C. for 180 minutes using 1.25 mm zirconia beads to prepare a master batch dispersion 1.
On the other hand, 450 parts of 0.1M Na ₃ PO ₄ aqueous solution was added to 710 parts of ion-exchanged water and heated to 60 ° C., then 67.7 parts of 1.0M CaCl ₂ aqueous solution was gradually added to form a calcium phosphate compound. An aqueous medium containing was obtained.

next,
・ Master batch dispersion 1 53 parts ・ Styrene monomer 12 parts ・ N-butyl acrylate monomer 35 parts ・ Ester wax 20 parts (total carbon number: 34, half width: 4 ° C., DSC endothermic peak: 70 ° C., (Mw: 800, Mn: 600, penetration: 6 degrees)
-Polar resin (1 part)-Divinylbenzene (0.065 part) was heated to 60 ° C and stirred to uniformly dissolve and disperse. In this, 3 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition.

The pH of the aqueous medium is maintained at 6 and the polymerizable monomer composition is charged. The polymerizable monomer composition is stirred at 10000 rpm for 10 minutes in a homomixer at 60 ° C. under N ₂ atmosphere. The product was granulated. Thereafter, the mixture was transferred to a reaction vessel, the pH of the aqueous medium was maintained at 6, and the temperature was raised to 63 ° C. while stirring with a paddle stirring blade, and the reaction was performed for 5 hours. Furthermore, 1 part of potassium perphosphate was added, the temperature was raised to 80 ° C., and the reaction was carried out for 5 hours. After completion of the polymerization reaction, vacuum drying is performed sufficiently, and after cooling, hydrochloric acid is added to dissolve the calcium phosphate compound, followed by filtration, washing with water, drying under vacuum, classification with a multistage classifier and cyanide. Color toner particles were obtained.

The obtained 100 parts of the cyan toner particles, the specific surface area by BET method of 300 meters ² /
After adding 1.1 parts of hydrophobic silica treated with silicone oil (g) and 0.3 parts of isobutyltrimethoxysilane-treated aluminum oxide (specific surface area of 90 m ² / g) with a Henschel mixer, # 400 The coarse particles were removed with a turbo screener equipped with a mesh, and a cyan non-magnetic toner No. 1 was obtained. The toner had a mass average particle size of 6.8 μm, a TA value of 44, and a TB value of 63. As other toner physical properties, as shown in Table 1, the endothermic peak temperature in DSC is 70 ° C., the opposite value width is 4 ° C., Mn: 17,000 in GPC molecular weight distribution measurement, Mw: 110,000, in MI measurement, MI: 13, glass transition point (Tg) in DSC: 59.8 ° C., SF-1: 112, SF-2: 107.

<Toner Production Example 2>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin to be used is changed to the polar resin 2, the cyan toner No. 1 is used. 2 was obtained. The obtained toner No. The composition and physical properties of 2 are shown in Table 1.

<Toner Production Example 3>
In Toner Production Example 1, the same procedure as in Production Example 1 was used except that the polar resin used was changed to polar resin 3 and 10 parts were added. 3 was obtained. The obtained toner No. Table 1 shows the composition and physical properties of No. 3.

<Toner Production Example 4>
In the toner production example 1, the same procedure as in the above production example 1 was used except that the polar resin used was changed to the polar resin 4, and cyan toner No. 4 was obtained. The obtained toner No. The composition and physical properties of 4 are shown in Table 1.

<Toner Production Example 5>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin to be used is changed to the polar resin 5, the cyan toner No. 5 was obtained. The obtained toner No. The composition and physical properties of No. 5 are shown in Table 1.

<Toner Production Example 6>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin used is changed to the polar resin 6, the cyan toner No. 6 was obtained. The obtained toner No. The composition and physical properties of 6 are shown in Table 1.

<Toner Production Example 7>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin to be used is changed to the polar resin 7, the cyan toner No. 7 was obtained. The obtained toner No. Table 1 shows the composition and physical properties of No. 7.

<Toner Production Example 8>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin to be used is changed to the polar resin 8, a cyan toner No. 8 was obtained. The obtained toner No. The composition and physical properties of No. 8 are shown in Table 1.

<Toner Production Example 9>
In the toner production example 1, using the same method as in the production example 1 except that the polar resin to be used is changed to the polar resin 9, cyan toner No. 9 was obtained. The obtained toner No. The composition and physical properties of 9 are shown in Table 1.

<Toner Production Example 10>
In Toner Production Example 7, the amount of 0.1M-Na ₃ PO ₄ aqueous solution used was 600 parts, the homomixer rotation speed was 13000 rpm, the classification conditions of the multistage classifier were changed, and hydrophobic silica was changed to 1 except for using .5 parts using the same method as in production example 1, mass average particle diameter 3.5 [mu] m (4 [mu] m or less: 62.0 number%, 12.7 [mu] m or more: 0% by volume) cyan Iroto donors of No. 10 was obtained. The obtained toner No. The composition and physical properties of 10 are shown in Table 1.

<Toner Production Example 11>
In Toner Production Example 7, the amount of 0.1 M Na ₃ PO ₄ aqueous solution used was 570 parts, the homomixer rotation speed was 12000 rpm, the classification conditions of the multistage division classifier were changed, and hydrophobic silica was changed to 1 except for using .3 parts using the same method as in production example 1, mass average particle diameter 4.9 [mu] m (4 [mu] m or less: 50.0 number%, 12.7 [mu] m or more: 0% by volume) cyan Iroto donors of No. 11 was obtained. The obtained toner No. The composition and physical properties of 11 are shown in Table 1.

<Toner Production Example 12>
In Toner Production Example 8, the amount of 0.1 M Na ₃ PO ₄ aqueous solution used was 210 parts, the homomixer rotation speed was 5000 rpm, and the classification conditions of the multi-stage division classifier were changed to change the hydrophobic silica to 0 A cyan color having a mass average particle diameter of 9.2 μm (4 μm or less: 2.7% by number, 12.7 μm or more: 1.4% by volume) using the same method as in Production Example 1 except that the amount is 8 parts. Doo toner No. 12 was obtained. The obtained toner No. The composition and physical properties of 12 are shown in Table 1.

<Toner Production Example 13>
In Toner Production Example 8, the amount of 0.1 M Na ₃ PO ₄ aqueous solution used was 180 parts, the homomixer rotation speed was 4000 rpm, and the classification conditions of the multi-stage division classifier were changed to change the hydrophobic silica to 0 A cyan color having a mass average particle diameter of 11.0 μm (4 μm or less: 1.8% by number, 12.7 μm or more: 3.6% by volume) is used in the same manner as in Production Example 1 except that the amount is 0.6 parts. Doo toner No. 13 was obtained. The obtained toner No. The composition and physical properties of 13 are shown in Table 1.

<Toner Comparative Production Examples 1 to 3>
In Toner Production Example 1, Comparative Toner No. 1 was prepared in the same manner except that Comparative Resins 1 to 3 were used instead of Polar Resin 1 and the inorganic fine powder was only 0.9% by mass of silica. 1 to Comparative toner No. 3 was obtained.
The obtained comparative toner No. 1-No. Table 1 shows the composition and physical properties of No. 3.

<Toner Production Example 14>
In Toner Production Example 1, the polar resin to be used is the polar resin no. And 7, and 35 parts of the ester wax to be added, 1.8 parts of hydrophobic silica amount, similarly to the cyan Iroto toner except that 0.5 parts of hydrophobic alumina addition amount No. 14 was obtained. The obtained toner No. The composition and physical properties of 14 are shown in Table 1. In particular, both TA value: 71 and TB value: 91 showed high values.

<Toner Production Example 15>
In Toner Production Example 1, the polar resin to be used is the polar resin no. And 8, and 3 parts of the ester wax to be added, 1.0 parts of hydrophobic silica amount, similarly to the cyan Iroto toner except that 0.2 parts of hydrophobic alumina addition amount No. 15 was obtained. The obtained toner No. The composition and physical properties of 15 are shown in Table 1. In particular, TA values: 7 and TB values: 28 were shown as low values.

<Toner Production Example 16>
In Toner Production Example 15, 1.5 parts of hydrophobic silica amount, cyan Iroto toner except that 0.4 parts of hydrophobic alumina amount in the same manner No. 16 was obtained. The obtained toner No. The composition and physical properties of 16 are shown in Table 1. In particular, TB-TA was as high as 48.

<Toner Production Example 17>
In Toner Production Example 15, 1.8 parts of hydrophobic silica amount, cyan Iroto toner except that 0.5 parts of hydrophobic alumina amount in the same manner No. 17 was obtained. The obtained toner No. The composition and physical properties of 17 are shown in Table 1. In particular, TB-TA was as high as 62.

<Toner Production Example 18>
<Manufacture of magnetic body 1>
In ferrous sulfate aqueous solution, l. 0 to 1.1 equivalents of caustic soda solution and sodium silicate were mixed to prepare an aqueous solution containing ferrous hydroxide.

While maintaining the pH of the aqueous solution at around 9, air was blown and an oxidation reaction was performed at 80 to 90 ° C. to prepare a slurry liquid for generating seed crystals. Subsequently, after adding ferrous sulfate aqueous solution so that it may become 0.9-1.2 equivalent with respect to the original alkali amount (sodium component of caustic soda) to this slurry liquid, the slurry liquid is maintained at pH 8 and air is supplied. The oxidation reaction was promoted while blowing, and the magnetic iron oxide particles produced after the oxidation reaction were washed, filtered, and taken out once. At this time, a small amount of water-containing sample was collected and the water content was measured. Next, this water-containing sample was re-dispersed in another aqueous medium without drying, and then the pH of the re-dispersed liquid was adjusted to about 6, and the silane coupling agent (n-C ₁₀ H _{21 was} thoroughly stirred. 1.2 parts of Si (OCH ₃ ) ₃ ) was added to magnetic iron oxide (the amount of magnetic iron oxide was calculated as a value obtained by subtracting the water content from the water-containing sample), and a coupling treatment was performed. Next, fine particles are removed by classification using the wet classification method used for precipitation separation , and the obtained hydrophobic iron oxide particles are washed, filtered and dried by conventional methods, and then the slightly aggregated particles are separated. The magnetic body 1 was obtained by crushing.

<Manufacture of Toner 18>
After adding 450 parts of 0.1 M Na ₃ PO ₄ aqueous solution to 710 parts of ion-exchanged water and heating to 60 ° C., 67.7 parts of 1.0 M CaCl ₂ aqueous solution is gradually added to form an aqueous system containing a calcium phosphate compound. A medium was obtained.

Styrene 77 parts n-butyl acrylate 23 parts Ester wax 17 parts (total carbon number: 34, half width: 4 ° C., DSC endothermic peak: 70 ° C., Mw: 800, Mn: 600, penetration: 6 degrees )
・ 7 parts of polar resin ・ 0.075 parts of divinylbenzene ・ 1 part of aluminum complex of ditertiary butylsalicylic acid ・ 100 parts of magnetic substance 1 is added to the aqueous medium heated to 60 ° C. and stirred to dissolve uniformly. Distributed. In this, 3 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. Except for this, the same procedure as in Toner Production Example 1 was followed, except for toner No. 18 was obtained. The obtained toner No. The composition and physical properties of 18 are shown in Table 1.

<Toner Production Example 19>
Preparation of dispersion (A) Polar resin 5 50 g
100 g of methylene chloride
The above was mixed and dissolved in a ball mill, dispersed in 155 g of pure water containing 10% polyethylene glycol and 0.7% cationic surfactant (manufactured by Kao Corporation: Sanizol B50), and rotor stator Using a homogenizer of the type (IKA: Ultra Tarrax), applying a strong shearing force to disperse, heat to 62 ° C., hold for 1 hour, and disperse resin particles having an average particle size of 820 nm A dispersion (A) was prepared.

Preparation of Colorant Dispersion (B) Copper Phthalocyanine Pigment 100g
(BASF: PV FAST BLUE)
Anionic surfactant 5g
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
200g of ion exchange water
The above is mixed, dissolved, and dispersed for 10 minutes using a rotor-stator type homogenizer (manufactured by IKA: Ultra Tarrax), and further dispersed for 5 minutes with an ultrasonic homogenizer, and a colorant having an average particle diameter of 100 nm is obtained. Dispersed colorant dispersion (B) was prepared.

Preparation of release agent dispersion (C) Polypropylene wax (half-width: 22 ° C., DSC endothermic peak: 129 ° C., Mw: 17,000, Mn: 1350, penetration: 0.5 degree) 5 g
Cationic surfactant 5g
(Manufactured by Kao Corporation: Sanizol B50)
200g of ion exchange water
The above was heated to 95 ° C. and dispersed using a homogenizer (manufactured by IKA: Ultra Turrax T50), and then dispersed with a pressure discharge homogenizer to disperse a release agent having an average particle size of 550 nm. A release agent dispersion liquid (C) was prepared.

<First Step> -Preparation of Aggregated Particles-
Dispersion (A) 183g
Colorant dispersion (B) 12g
Release agent dispersion (C) 5g
Cationic surfactant 2g
(Manufactured by Kao Corporation: Sanizol B50)
The above mixture was mixed and dispersed in a round stainless steel flask using a homogenizer (manufactured by IKA: Ultra Tarrax T50), and then heated to 48 ° C. in a heating oil bath while stirring the flask. After maintaining at 48 ° C. for 30 minutes, observation with an optical microscope confirmed that aggregated particles having an average particle diameter of about 5.8 μm were formed.

<Second step> -Preparation of adhered particles-
Here, 5 g of the colorant dispersion (B) as the colorant fine particle dispersion was slowly added, and the temperature of the heating oil bath was raised to 50 ° C. and held for 30 minutes. The temperature was further raised to 52 ° C. and held for 1 hour.

<Third step>
Thereafter, 2 g of an anionic surfactant (Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC) was added thereto, and then the stainless steel flask was sealed and stirring was continued using a magnetic seal. And it heated to 110 degreeC and hold | maintained for 3 hours. After cooling, the reaction product was filtered and thoroughly washed with ion exchange water to obtain a toner for developing an electrostatic image. Otherwise, toner No. 19 was obtained with the constitution shown in Table 1. The obtained toner No. The composition and physical properties of 19 are shown in Table 1.

<Toner Production Example 20>
[Mixing process]
The following composition was dispersed with a ball mill for 24 hours to obtain 200 parts of a toner composition mixed solution in which the polar resin 5 was dissolved.
-5 89 parts of polar resin-C.I. I. Pigment Blue (15: 3) 6.5 parts / polypropylene wax (half-width: 22 ° C., DSC endothermic peak: 129 ° C., Mw: 17,000, Mn: 1350, penetration: 0.5 °) 2 .5 parts ・ Aluminum complex of ditertiarybutylsalicylic acid 1 part ・ Ethyl acetate (solvent) 100 parts

[Dispersion suspension process]
Carboxymethylcellulose was dissolved by dispersing the following composition with a ball mill for 24 hours to obtain an aqueous medium.
・ Calcium carbonate (covered with acrylic acid copolymer) 20 parts ・ Carboxymethylcellulose 0.5 part (trade name: Serogen BS-H, manufactured by Daiichi Kogyo Co., Ltd.)
-Ion-exchanged water 99.5 parts Put 1200 g of the aqueous medium obtained from the above into a TK homomixer, add 1000 g of the toner composition mixture while stirring the rotating blade at a peripheral speed of 20 m / sec, and add 25 g While maintaining constant, the mixture was stirred for 1 minute to obtain a suspension.

[Solvent removal step]
While stirring 2200 g of the suspension obtained in the dispersion suspension step with a full zone blade (made by Shinko Pantech Co., Ltd.) at a peripheral speed of 45 m / min, the temperature is kept constant at 40 ° C. The upper gas phase was forcibly renewed and solvent removal was started. At that time, 15 minutes after the start of solvent removal, 75 g of ammonia water diluted to 1% as an ionic substance was added, then 25 g of ammonia water was added 1 hour after the start of solvent removal, and then from the start of solvent removal. Two hours later, 25 g of the aqueous ammonia was added, and finally 25 g of the aqueous ammonia was added 3 hours after the start of solvent removal, so that the total amount added was 150 g. Furthermore, while maintaining the temperature at 40 ° C., the toner dispersion was maintained for 17 hours from the start of solvent removal to remove the solvent (ethyl acetate) from the suspended particles.

[Washing and dehydration process]
To 300 parts of the toner dispersion obtained in the solvent removal step, 80 parts of 10 mol / l hydrochloric acid is added, neutralized with a 0.1 mol / l sodium hydroxide aqueous solution, and then washed with ion-exchanged water by suction filtration four times. Thus, a toner cake was obtained.

[Drying and sieving process]
The toner cake obtained above was dried with a vacuum dryer and sieved with a 45 μm mesh. Other than that, in the same manner as toner 1, toner No. 20 was obtained. The obtained toner No. The composition and physical properties of 20 are shown in Table 1.

<Toner Production Example 21>
C.I used in Toner Production Example 1 I. In the same manner as in Toner Production Example 1, except that 14 parts by mass of Pigment Yellow 93 was used instead of Pigment Blue 15: 3, Yellow Toner No. 21 was obtained. The obtained toner No. The composition and physical properties of 21 are shown in Table 1.

<Toner Production Example 22>
C.I used in Toner Production Example 1 I. In the same manner as in Toner Production Example 1, except that 14 parts by mass of dimethylquinacridone was used in place of Pigment Blue 15: 3, magenta toner No. 22 was obtained. The obtained toner No. The composition and physical properties of 22 are shown in Table 1.

<Toner Production Example 23>
C.I used in Toner Production Example 1 I. Black toner No. 1 was prepared in the same manner as in Toner Production Example 1 except that 20 parts by mass of carbon black was used instead of CI Pigment Blue 15: 3. 23 was obtained. The obtained toner No. The composition and physical properties of 23 are shown in Table 1.

<Manufacture example 1 of a magnetic carrier>
・ Phenol (hydroxybenzene) 50 parts ・ 37 parts by mass of formalin aqueous solution 80 parts ・ Water 50 parts ・ Alumina-containing magnetite fine particles surface-treated with KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.) 1 280 parts (number average particle size 0.22 μm, specific resistance 4 × 10 ⁵ Ω · cm)
120 parts of α-Fe ₂ O ₃ fine particles 1 surface-treated with KBM403 (number average particle diameter 0.40 μm, specific resistance 8 × 10 ⁹ Ω · cm)
-25 parts by mass of ammonia water 15 parts The above materials were put into a four-necked flask, heated to 85 ° C for 60 minutes with stirring and mixing, and reacted and cured for 120 minutes. After cooling to 30 ° C. and adding 500 parts of water, the supernatant was removed, the precipitate was washed with water and air-dried. Next, this was vacuum-dried for 24 hours to obtain a magnetic carrier core (A) having a phenol resin as a binder resin. In the magnetic carrier core (A), 0.4% by mass of adsorbed water was present after being left for 24 hours at 30 ° C./80% relative humidity.

  The surface of the obtained magnetic carrier core (A) was coated with a 5% by mass toluene solution of γ-aminopropyltrimethoxysilane represented by the following formula (2).

  The surface of the magnetic carrier core (A) was treated with 0.3% by mass of γ-aminopropyltrimethoxysilane. During coating, toluene was volatilized while coating while applying a shear stress to the magnetic carrier core (A) continuously. It was confirmed that the group represented by the following (3) was present on the surface of the magnetic carrier core (A).

  While stirring the magnetic carrier (A) treated with the silane coupling agent in the above processing machine at 70 ° C., the silicone resin KR-221 (manufactured by Shin-Etsu Chemical Co., Ltd.) was charged with 4 to the silicone resin solid content. % T-aminopropyltrimethoxysilane was added and diluted with toluene so that the silicone resin solid content was 25%, and then added under reduced pressure to perform resin coating. Thereafter, after stirring for 2 hours, heat treatment was performed at 140 ° C. for 2 hours in an atmosphere of nitrogen gas to loosen the agglomerates, and then coarse particles of 200 mesh or more were removed to obtain a magnetic carrier 1.

The obtained magnetic carrier 1 has an average particle size of 35 μm, a specific resistance of 1 × 10 ¹³ Ω · cm, a magnetization strength (σ ₁₀₀₀ ) at 1 K Oersted of 40 Am ² / kg, and an apparent density of 1.9 g / cm. cm ³ and SF-1 were 107.

<Manufacture example 2 of a magnetic carrier>
Li ₂ CO ₃ 14.0 mol%, Fe ₂ O ₃ 77.0 mol%, Mg (OH) ₂ 6.8 mol% and CaCO ₃ 2.2 mol% were pulverized in a wet ball mill for 5 hours, mixed and dried. It was held at 900 ° C. for 1 hour and pre-baked. This was pulverized with a wet ball mill for 7 hours to 3 μm or less. Appropriate amounts of a dispersant and a binder were added to the slurry, and then granulated and dried with a spray dryer, and held in an electric furnace at 1240 ° C. for 4 hours to perform main firing. Then, it was crushed and further classified to obtain a magnetic carrier 2 of ferrite particles having an average particle size of 40 μm.

<Toner Production Example 24>
In Toner Production Example 1, 0.8 parts of hydrophobic silica amount, cyan Iroto toner except that the hydrophobic aluminum oxide added amount 0.2 parts similarly No. 24 was obtained. The obtained toner No. The composition and physical properties of 24 are shown in Table 1.

<Toner Production Example 25>
In Toner Production Example 21, 0.8 parts of hydrophobic silica amount, yellow Iroto toner and hydrophobic aluminum oxide addition amount in the same manner except that the 0.2 parts No. 25 was obtained. The obtained toner No. The composition and physical properties of 25 are shown in Table 1.

<Toner Production Example 26>
In Toner Production Example 22, 0.8 parts of hydrophobic silica amount, the hydrophobic oxide to aluminum addition amount than that to 0.2 parts, the same procedure magenta Iroto toner No. 26 was obtained. The obtained toner No. The composition and physical properties of 26 are shown in Table 1.

<Toner Production Example 27>
In Toner Production Example 23, 0.8 parts of hydrophobic silica amount, black Iroto toner and hydrophobic aluminum oxide addition amount in the same manner except that the 0.2 parts No. 27 was obtained. The obtained toner No. The composition and physical properties of 27 are shown in Table 1.

<Toner Production Example 28>
In Toner Production Example 3, the same procedure as in toner No. 1 was used except that the release agent used was ester wax having an endothermic peak temperature of 48 ° C. 28 was obtained. The obtained toner No. The composition and physical properties of 28 are shown in Table 1.

<Toner Production Example 29>
In Toner Production Example 3, the same procedure as in toner No. 1 was used except that polyethylene wax having an endothermic peak temperature of 122 ° C. was used as the release agent. 29 was obtained. The obtained toner No. The composition and physical properties of 29 are shown in Table 1.

<Developer Production Examples 24-27>
Toner No. 24, 25, 26, and 27 and magnetic carrier 1 were adjusted so that the toner / carrier mass ratio was 8%. 24, 25, 26 and 27 were obtained.

<Developer Production Example 30>
Toner No. 24 and magnetic carrier 2 were adjusted so that the toner / carrier mass ratio would be 8%. 30 was obtained.

<Toner Production Example 30>
In Toner Production Example 1, di - but without the aluminum compound of tertiary butyl salicylic acid in the same manner Toner No. 30 was obtained. The obtained toner No. The composition and physical properties of 30 are shown in Table 1.

<Toner Production Example 31>
In Toner Production Example 1, di - instead of aluminum compounds of tertiary butyl salicylate, di - but using a zirconium compound of tertiary butyl salicylic acid in the same manner Toner No. 31 was obtained. The obtained toner No. The composition and physical properties of 31 are shown in Table 1.

<Toner Production Example 32>
In Toner Production Example 1, di - instead of aluminum compounds of tertiary butyl salicylate, di - but using zinc compound tertiary butyl salicylic acid in the same manner Toner No. 32 was obtained. The obtained toner No. The composition and physical properties of 32 are shown in Table 1.

<Example 1>
As an image forming apparatus, a commercially available color laser printer CP2810 (manufactured by Canon Inc.) was modified to a printer capable of outputting 20 sheets / min at a fixing speed of 150 mm / s.
Toner No. Using a developer 1 consisting of 1, an image pattern having a printing rate of 10% having 5 circles with a diameter of 20 mm and an image density of 1.5 measured by a 504 type reflection densitometer manufactured by X-Rite Co., Ltd. A sheet passing test of 10,000 sheets was performed in each environment of ° C / relative humidity 5% (N / L), 32.5 ° C / relative humidity 92% (H / H), and evaluation was performed based on the following evaluation methods. Here, the materials used are shown in Table 1, and the evaluation results are shown in Table 2. As can be seen from Table 2, generally good results were obtained for all the evaluation items.

(1) Low-temperature fixability Evaluation was performed using Xx64 g paper in an L / L (15 ° C., 10% RH) environment. Nine solid 5 cm square images were output on A4 paper. The amount of paste of the unfixed image at this time was 0.6 mmg / cm ² . The image was reciprocated five times with sylbon paper applied with a load of 4.9 kPa, and the temperature at which the density reduction rate was 20% or more was evaluated as the minimum fixing temperature.

(2) OHT Transparency Evaluation Using a transparency of CP2810, a solid image (0.6 mmg / cm ² on the transfer paper) was output under an N / N environment. Using a transmission type OHT projector, it was visually evaluated in five stages as follows.

A: Transparency is remarkably high and good.
B: Transparency is good.
C: Slightly dull but no problem in actual use.
D: The level is quite dull and slightly problematic.
E: Dullness is terrible.

(3) High-temperature offset resistance Evaluation was performed using Xx64 g paper in an N / N (23.5 ° C., 60% RH) environment. After 50 sheets of a solid white image were passed in A4 portrait orientation, an A4 landscape orientation image was printed on both sides of a halftone image having an image density of 0.5 across the entire area 5 cm from the tip and a solid white image other than that. The level of the offset appearing on the white background at this time was visually confirmed.

A: No offset occurs at all.
B: Although an offset slightly occurred at the end other than the portion where the paper was passed in the A4 portrait orientation, this level is not a problem in use.
C: A level slightly offset in actual use in which an offset is slightly generated at an end portion other than a portion where A4 paper is placed vertically, but this is not a problem in normal copying.
D: Level in which offset occurs in the entire longitudinal direction, causing a problem in actual use.
E: Offset occurs from the first surface in the entire longitudinal direction.

(4) Fog The fog was measured in a 10,000 sheet durability test under N / L and H / H environments. As a method, the average reflectance Dr (%) of plain paper before image printing is measured by a reflectometer ("REFLECTOMETER M ODEL TC-6DS" manufactured by Tokyo Denshoku Co., Ltd.) equipped with a complementary color filter for the measurement color. It was measured. On the other hand, a solid white image was drawn on plain paper, and then the reflectance Ds (%) of the solid white image was measured. The fog (%) is calculated from the following formula (7).

(5) Image Density Image density was measured with an X-Rite 504 reflection densitometer.

(6) Drum Fusion In a 10,000 sheet durability test in a H / H environment, the presence or absence of fusion material on the drum was evaluated by visual and loupe in six stages according to the following evaluation criteria.

A: There is no fused material.
B: Several fused objects having a diameter of 0.1 mm or less exist on the drum, but there is no problem on the image.
C: Several melts having a diameter of 0.1 to 0.4 mm are present on the drum and are slightly generated on the image.
D: Ten or more fusion objects having a diameter of 0.1 to 0.4 mm exist on the drum, and are also generated on the image.
E: There are 10 to 20 fusions larger than 0.4 mm in diameter on the drum, and they are also generated on the image.
F: A fused material having a diameter larger than 1 mm exists on the entire surface of the drum, and many images are generated on the image.

(7) Photoconductor cleaning defect evaluation A: There is no cleaning defect at all.
B: There are several cleaning defects of 1 mm or less on the drum, but there is no problem on the image.
C: Although several cleaning defects of 1 to 4 mm in length exist on the drum and are slightly generated on the image, they are not at a level causing a problem in actual use.
D: 10 or more cleaning defects having a length of 1 to 4 mm exist on the drum, and are also generated on the image.
E: 10 to 20 cleaning defects longer than 4 mm in length exist on the drum, and are also generated on the image.
F: A cleaning defect larger than 1 mm diameter exists on the entire surface on the drum, and many images are generated on the image.

(8) Image quality evaluation After the durability test under the H / H environment, image quality evaluation (total evaluation of 5-point characters, line images, and solid images) was performed visually and with a magnifying glass. The evaluation criteria are quasi-cheat below.

A: There is no scattering, the line image and the character image are clear, and the solid image is uniform and good.
B: Slight scattering is confirmed by the loupe check, but the solid image is uniform and good without any problem in the visual check.
C: Although a part slightly scattered in the line image and the character image is visually confirmed, it is not at a level causing a problem in actual use.
D: A level in which a scattered part in the line image and the character image is visually confirmed, but is a level that does not cause a problem in the general use.
E: Many splashes are confirmed visually in the line image and the character image.
F: Remarkable scattering is confirmed in the line image and the character image by visual observation.
G: Not only a line image and a character image but also a solid image is a poor image with no uniformity.

(9) Toner scattering evaluation After the durability test in the H / H environment, toner scattering was evaluated based on the amount of toner accumulated under the developing sleeve and in the machine.

A: Good with no toner under the developing sleeve and in the machine.
B: A toner layer is slightly observed under the developing sleeve, but there is no scattered toner in the apparatus, and it is good.
C: Toner slightly scattered under the developing sleeve and in the machine, but not at a problematic level.
D: Toner is scattered under the developing sleeve and in the machine.
E: A lot of toner is scattered under the developing sleeve and in the machine.
F: The inside of the machine is contaminated with toner color, and image defects frequently occur.

(10) Blocking test 10 g of toner was put in a 50 cc polycup. The state of the toner when this was left in a constant temperature layer at 53 ° C. for 3 days (72 hours) was visually judged as follows.

A: No blocking at all, almost the same as the initial state.
B: Slightly agglomerated, but collapsed by the rotation of the polycup, and there is no particular problem.
C: Although it is agglomerated, it is in a state where it is broken by hand.
D: Aggregation is intense.
E: Solidified.

(11) Measurement of transfer efficiency Transfer efficiency was confirmed at the end of the endurance test under H / H environment. Image glue amount 0.65m
A solid image of g / cm ² was developed on a drum and then transferred to EN100 (64 g paper) to obtain an unfixed image. The transfer efficiency was determined from the change in weight between the toner amount on the drum and the toner amount on the transfer paper (the transfer efficiency is 100% when the entire toner amount on the drum is transferred onto the transfer paper).

A: Transfer efficiency is 95% or more B: Transfer efficiency is 90% or more and less than 95% C: Transfer efficiency is 80% or more and less than 90% D: Transfer efficiency is 70% or more and less than 80% E: Transfer efficiency is less than 70%

(12) Color check 10 samples of photographic images including primary colors of Y, M, and C and secondary colors of R, G, and B were sampled at the initial stage and after endurance of 10,000 sheets. The initial and color only after the running at that time was made a visual check to the following evaluation.
A: There is no color fluctuation at all.
B: Almost no change in color.
C: There is a slight color variation, and it is pointed out to severe users.
D: There is a color fluctuation and is a level pointed out to general users.
E: Color is greatly different.

< Examples 2-9, 11, 12, 14-17, 21-23, and 26-28, and Reference Examples 10, 13, 18, 24, and 25 >
As shown in Table 1, Developers 2 to 33 were prepared in combination with toner or carrier. The developer was changed as shown in Table 2, and evaluation was performed using the same method as in Example 1. The results are shown in Table 2. In Examples 21, 22, and 23, evaluation was performed in cyan when a full-color image was output.
When using a two-component developer, a developer and a remodeling device adjusted as described below were used. First, 92 parts of a magnetic carrier and 8 parts of toner were mixed with a V-type mixer to obtain a two-component developer.

  For evaluation of the two-component developer, a commercially available digital copying machine CP2150 (manufactured by Canon Inc.) was changed to a copying apparatus capable of outputting 35 sheets / minute with a fixing speed of 150 mm / s. Further, the copying apparatus is modified so that the developing device and the charging device shown in FIG. 1 can be inserted, and the one using the developing bias shown in FIG. 2 is used. It changed to the roller which covered 2 micrometers, and changed into the form which removes all contact members other than pressure rollers, such as an oil application mechanism.

<Comparative Examples 1-3>
Using the comparative toners 1 to 3 shown in Table 1, the same experimental method and evaluation as in Example 1 were performed according to the image forming method shown in Table 2. The results are shown in Table 2.

It is a partial schematic diagram showing an example of an image forming apparatus in which the image forming method of the present invention is suitably used. It is a figure explaining the alternating electric field used with the image forming method of this invention. 1 is a schematic diagram illustrating an example of a full-color image forming apparatus in which an image forming method of the present invention is suitably used. It is a schematic explanatory drawing which shows the other example of the image forming apparatus with which the image forming method of this invention is used suitably. It is a schematic explanatory drawing which shows the other example of the image forming apparatus with which the image forming method of this invention is used suitably. It is a schematic explanatory drawing which shows the example of the image forming apparatus which applied the image forming method of this invention to the contact one-component developing method. It is a schematic explanatory drawing which shows the other example of the image forming apparatus which applied the image forming method of this invention to the non-contact one-component developing method. 1 is a schematic explanatory diagram illustrating an example of a fixing device in which an image forming method of the present invention is suitably used. 1 is a schematic explanatory diagram illustrating an example of a fixing device in which an image forming method of the present invention is suitably used. It is a schematic explanatory drawing which shows the other example of the image forming apparatus with which the image forming method of this invention is used suitably.

Claims (5)

A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a charge control agent and a release agent is dispersed in an aqueous medium, granulated, and polymerized. and the color toner particles obtained by suspending polymerization using an initiator, a color toner containing an inorganic fine powder,
The color toner particles contain at least the colorant, the release agent, the charge control agent, and the polar resin,
The polar resin is a polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, isophthalic acid, anhydrous , using a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst. Containing at least a polyester resin having an acid value of 3 to 35 mg KOH / g obtained by polymerizing a monomer containing at least trimellitic acid ,
The release agent is an ester wax, the release agent has a weight average molecular weight (Mw) of 300 to 1,500, and a weight average molecular weight / number average molecular weight ratio (Mw / Mn) of 1.5 or less. Yes, the penetration is 15 degrees or less,
The charge control agent is an aluminum salicylate compound, a zinc salicylate compound, or a zirconium salicylate compound;
In the endothermic curve in differential scanning calorimetry (DSC) measurement of the color toner, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is 50 to 120 ° C., and the half width of the maximum endothermic peak is 15 ° C. or less. ,
In the water / methanol wettability test for the color toner particles, TA which is methanol mass% at the time when the transmittance becomes 50% of the initial value is 7 to 71,
In the water / methanol wettability test for the color toner, TB which is methanol mass% when the transmittance reaches 50% of the initial value is 20 to 69,
Color toner weight average particle diameter of the color toner is characterized 4~10μm der Rukoto. The color toner according to claim 1, wherein a tin compound of an alkyl carboxylic acid having 7 to 12 carbon atoms is used as the catalyst. The color toner according to claim 1, wherein the acid value of the polar resin is 7 to 15 (mg KOH / g). The color toner according to any one of claim 1 to 3, wherein the weight average particle diameter of the toner is 6～7.5Myuemu. A polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a charge control agent and a release agent is dispersed in an aqueous medium, granulated, and polymerized. initiator to produce a color toner particle suspension polymerized to using a method for manufacturing a color toner externally added with inorganic fine powder in the color toner particles,
The color toner particles contain at least the colorant, the release agent, the charge control agent, and the polar resin,
The polar resin is a polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, isophthalic acid, anhydrous , using a tin compound of an alkyl carboxylic acid having 5 to 15 carbon atoms as a catalyst. Containing at least a polyester resin having an acid value of 3 to 35 mg KOH / g obtained by polymerizing a monomer containing at least trimellitic acid ,
The release agent is an ester wax, the release agent has a weight average molecular weight (Mw) of 300 to 1,500, and a weight average molecular weight / number average molecular weight ratio (Mw / Mn) of 1.5 or less. Yes, the penetration is 15 degrees or less,
The charge control agent is an aluminum salicylate compound, a zinc salicylate compound, or a zirconium salicylate compound;
In the endothermic curve in differential scanning calorimetry (DSC) measurement of the color toner, the peak temperature of the maximum endothermic peak in the temperature range of 30 to 200 ° C. is 50 to 120 ° C., and the half width of the maximum endothermic peak is 15 ° C. or less. ,
In the water / methanol wettability test for the color toner particles, TA which is methanol mass% at the time when the transmittance becomes 50% of the initial value is 7 to 71,
In the water / methanol wettability test for the color toner, TB which is methanol mass% when the transmittance reaches 50% of the initial value is 20 to 69,
Method for producing a color toner having a weight average particle diameter of the color toner is characterized 4~10μm der Rukoto.

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