JP2005062818A - Toner - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide toner which has excellent low-temperature fixing performance, high-temperature anti-offset properties and transferability, and with which an image having high fineness and high grade is stably obtained. <P>SOLUTION: The toner includes toner particles containing at least a colorant, a release agent, and a polar resin, and an inorganic fine powder. The polar resin contains (i) a polyester resin obtained by carrying out polymerization in the presence of at least a titanium chelate compound as a catalyst, and (ii) has an acid value ranging from 3 to 35 (mgKOH/g). The toner particles are granulated in an aqueous medium and have a weight-average particle diameter ranging from 4 to 10 μm. <P>COPYRIGHT: (C)2005,JPO&NCIPI

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. . Moreover, it has been used for a copy of high-definition images such as a digital printer or graphic design as an output of a computer as well as an office copy machine for copying an original document. 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 an example of a difficult electrophotographic image forming process for improving image quality, high definition, and high stability of an image, which is a user requirement.

  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 due to long-term use, and the charge imparting member such as the sleeve and the 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 the 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 and collision between the toner and the sleeve in the case of a one-component developer and between the toner and the carrier in the case of a two-component developer. (Sleeve carrier) and all the regulating members will be damaged. 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, the investigation on the charging series and resistance of the charge imparting member has been the focus. 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 the copying machine or the 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.

  In the pressure heating method, a toner image surface of a fixing sheet is applied to a pressure member on the surface of a fixing member having a heating source whose surface is formed of a material releasable with respect to toner (silicone rubber or fluororesin). Fixing is carried out by passing the film while contacting under pressure. 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 soiled (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, the transparency film (OHT film) that uses an overhead projector, which is increasingly used for presentations, has a low oil absorption capacity unlike paper, so stickiness on the surface of the OHT film after fixing becomes a problem. Yes. 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 fixing the toner at a low temperature or at a high temperature and for improving the fixability at the time of fixing at a low temperature. 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 publications have devised an invention that makes both OHT transparency and high-temperature offset resistance compatible 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, where the temperature of the heated body is drastically reduced during continuous paper feeding, fixing problems such as low-temperature fixing defects, so-called low-temperature offset phenomenon, paper discharge / stacking defects, etc., and long-term stable developability However, it has some problems.

  Some explanation will be given on the above-mentioned paper discharge / stacking failure. 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 leading end of the discharge side 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 discharge failure, a member such as a separation claw is brought into contact with the fixing member 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 body and damages the surface of the fixing body. 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 the phenomenon, attempts have been made to bring a web impregnated with silicone oil or the like into contact, but this is contrary to the reduction in size and cost of the fixing device. 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 or 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 sharp melt properties, 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. Specifically, the environmental characteristics such as excessive charging (so-called charge-up) under low humidity and insufficient charge amount under high humidity, and the slow rise rate of the charge amount.

  As a polymerization catalyst for producing a polyester resin for toner, it has been generally performed to use a tin-based catalyst such as dibutyltin oxide or an antimony-based antimony trioxide. These technologies satisfy the color reproducibility such as low temperature fixability and high temperature offset resistance, color mixing properties and transparency required for full color copiers in recent years, as well as the rising characteristics of charge amount, toner However, there are some problems in stably controlling the amount of charge.

  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 OHT sheet, transparency is obstructed when projected with OHT, 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 in OHT, low-temperature fixability at the time of heat and pressure fixing, and high-temperature offset resistance.

  In addition, none of the toners containing the release agent described above can stably provide good development characteristics, in particular, charge rising characteristics over a long period of time due to the presence of the release agent on the toner surface.

  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 having excellent low-temperature fixability and high-temperature offset resistance.

  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 a toner capable of achieving a high-quality image by having a quick rise in charge and having a stable charge amount in any environment.

  As a result of intensive studies, the present inventors have found that the above requirements can be satisfied by using a binder resin synthesized with a specific polymerization catalyst, and the present invention has been achieved. That is, the above object can be achieved by using the following toner.

(1) In a toner comprising toner particles containing at least a colorant, a release agent, and a polar resin, and an inorganic fine powder,
The polar resin contains (i) a polyester resin polymerized using at least a titanium chelate compound as a catalyst, and (ii) has an acid value of 3 to 35 (mgKOH / g),
The toner particles are granulated in an aqueous medium, and the toner has a weight average particle diameter of 4 to 10 μm.
(2) The toner according to (1), wherein in the titanium chelate compound, the chelate compound is a diol, a dicarboxylic acid, or an oxycarboxylic acid.
(3) The toner according to (1) or (2), wherein the titanium chelate compound is represented by the general formula (I) to the general formula (VIII) or a hydrate thereof.
(4) The toner according to (3), wherein the titanium chelate compound is represented by the general formula (II), (III), (VI) and (VII) or a hydrate thereof.
(5) In the water / methanol wettability test of the toner particles and the toner, methanol mass% until the transmittance reaches 50% of the initial value satisfies the following relational expressions (1) to ( The toner according to 4).
10 ≦ TA ≦ 70
30 ≦ TB ≦ 90
TB-TA ≦ 60
(TA: methanol mass% of toner particles, TB: methanol mass% of toner)
(6) The toner has a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. in a range of 50 to 120 ° C. in an endothermic curve in differential thermal analysis (DSC) measurement (1) Toner according to (5).
(7) The toner according to (1) to (6), wherein the toner contains a salicylic acid-based metal compound as a charge control agent.
(8) The toner according to (7), wherein the metal of the salicylic acid-based metal compound used as the charge control agent is aluminum or zirconium.
(9) The toner according to (1) to (8), wherein the polar resin has a hydroxyl value of 5 to 40 (mgKOH / g).
(10) The toner particles are obtained by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a release agent, a charge control agent, and a polymerization initiator in an aqueous medium, The toner according to (1) to (9), wherein the toner particles are produced by granulating and polymerizing a polymerizable monomer.

  In the toner of the present invention, by using a toner containing a polyester resin having an appropriate acid value that is polymerized using a titanium chelate compound as a catalyst, the rising speed of charging is high, and a large number of sheets are continuously printed. However, the image density is stable, and an image excellent in durability stability without fog is obtained. In addition, the interaction between the polar resin and the release agent makes it possible to provide a toner having a wide fixing region without causing deterioration in developability.

  According to the present invention, it is possible to provide a stable image over a long period of time.

The toner of the present invention has toner particles containing at least a colorant, a release agent, and a polar resin, and inorganic fine powder,
The polar resin contains at least a polyester resin polymerized using a titanium chelate compound as a catalyst, and has an acid value of 3 to 35 (mgKOH / g),
The toner particles are granulated in an aqueous medium;
The toner has a weight average particle diameter of 4 to 10 μm.

  As a result of intensive studies, the present inventors have found the following. The toner used in the present invention is greatly characterized in that a polar resin having a polyester unit contained in the toner is synthesized using a titanium chelate compound as a catalyst.

  The relationship between the performance of the toner of the present invention and each component is roughly as follows.

  By using a polar resin having a polyester unit, the low-temperature fixing performance is improved and the color toner has excellent color reproducibility such as color mixing and transparency. Furthermore, by using a titanium chelate compound as a polyester polymerization catalyst and maintaining an appropriate acid value in the resin, the interaction can increase the charging speed and saturation charge of the toner, thereby suppressing charge-up. Is also possible. In addition, the polar resin having the polyester unit satisfies the low-temperature fixability and the high-temperature offset resistance by an appropriate affinity with the release agent, and can secure a wide fixing area. That is, the release agent compatible with the polar resin functions plastically and improves the low-temperature fixability. On the contrary, the incompatible part exhibits a releasing effect from the original fixing body of the releasing agent at the time of fixing. This effect becomes remarkable in the case of a toner obtained by a suspension polymerization method in which a polar resin can exist on the toner surface. By using this titanium chelate catalyst, it becomes possible to stably hold the inorganic fine powder that controls the fluidity and charging stability of the toner on the toner surface for a long period of time. By applying to, high-quality images can be provided.

  Details are described below. In the charging characteristics of the toner, it is considered that the carboxyl group of the polyester resin improves the charging speed, and the OH group of the polyester resin has a function of reducing the saturation charge amount.

  Since the carboxyl group is a very polar functional group, the carboxyl groups are associated with each other, and from this association, the polymer chain is spread around. For example, when two carboxyl groups are associated, it is considered that the state is as follows, and a stable associated state is considered to be formed. Therefore, as shown in the present invention, it is possible to suppress the charge-up while increasing the charging speed and the saturation charge amount by controlling the acid value. Thereby, in any environment, a high image density can be stably maintained from the beginning.

  Next, in view of the bond angle between C—O, it is considered that four or more carboxyl groups form an aggregate of association. Since the aggregate of carboxyl groups formed in this way is like a hole, it is presumed that it easily accepts free electrons and thus has a function of improving the charging speed of the toner. If this state of association is maintained, it is resistant to attacks from the outside, and it is difficult to coordinate even when water molecules try to coordinate. Therefore, the environmental stability of the toner is also good.

  In contrast to the carboxyl group, for example, when two OH groups are associated,

の様になり、１つのときよりも極性が強くなり、カルボキシル基が会合するときのように、電荷が安定な状態で存在することができず、外側からの攻撃を受けやすくなる。結果、水分子の影響を受け易いものと推察される。

Thus, the polarity becomes stronger than that of one case, and the charge cannot exist in a stable state as in the case where the carboxyl groups are associated with each other, and is susceptible to attack from the outside. As a result, it is presumed to be easily affected by water molecules.

  By polymerizing a polyester resin exhibiting such charging characteristics with a titanium chelate catalyst, the charge can exist stably due to the interaction between the titanium compound remaining in the polyester resin and the OH group of the polyester. Therefore, it becomes difficult to be influenced by moisture, and the decrease in the saturation charge amount is suppressed.

  In this way, the interaction between the polyester resin having an appropriate acid value and hydroxyl value and the residue of the titanium chelate used as a catalyst increases the charging speed and the saturation charge amount, and also increases the charge under low humidity and high humidity. It becomes the resin composition which can suppress the fall of the amount of charge below.

  Furthermore, although the toner of the present invention contains a release agent, the inclusion of a low crystalline release agent is preferably used when used for a color toner. In particular, it is preferable that at least an ester wax is contained in the toner because of appropriate compatibility with the polyester resin. This not only improves the color mixing and transparency of the color toner, but also allows the release agent to be present near the toner surface at a level that does not impair the developability. Can be solved.

  In addition, although the toner of the present invention contains inorganic fine particles, silica, alumina, titania and the like are particularly preferably used from the viewpoint of imparting fluidity to the toner and charging stability. The present inventors have found an unexpected effect in a toner using a titanium chelate catalyst. Although the reason is not clear, the toner obtained by adding the above-mentioned inorganic fine powder to the polyester resin-containing toner particles using a titanium chelate catalyst has a high adsorption state, and the inorganic fine powder is released from the toner particles even when continuous printing is performed. Since the ratio was small, it was possible to provide high image quality stably over a long period of time. The height of the adhesion state is presumed to be due to the charge rate and saturation charge required of the polyester resin, or the interaction between the surface hydroxyl groups of the inorganic fine powder and the titanium chelate catalyst residue in the resin.

  In the titanium chelate compound used in the present invention, the ligand is preferably any one of diol, dicarboxylic acid, and oxycarboxylic acid. Among these, the ligand is particularly preferably an aliphatic diol, dicarboxylic acid, or oxycarboxylic acid. Aliphatic ligands are preferred because they have higher catalytic activity than aromatic ligands, are preferable in terms of shortening the reaction time and temperature control, and the resin physical properties are likely to be sharp in molecular weight distribution.

  Specific examples of the ligand include 1,2-ethanediol, 1,2-propanediol, and 1,3-propanediol as the diol. Dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, and oxycarboxylic acid, such as glycolic acid, lactic acid, hydroxyacrylic acid, α-oxybutyric acid, glyceric acid, tartronic acid, malic acid , Tartaric acid, citric acid.

  Moreover, it is preferable that a titanium chelate compound is represented by either the following general formula (I) thru | or general formula (VIII), or its hydrate.

（一般式（Ｉ）において、Ｒ₁は、炭素数２乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In the general formula (I), R ₁ is an alkylene group having 2 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

（一般式（ＩＩ）において、Ｒ₂は、炭素数１乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In General Formula (II), R ₂ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

（一般式（ＩＩＩ）において、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In general formula (III), M represents a counter cation, m represents the number of cations, n represents the valence of the cation, and when m = 1, n = 2 and when m = 2. N = 1 and M is a hydrogen ion, an alkali metal ion, an ammonium ion or an organic ammonium ion when n = 1, and an alkaline earth metal ion when n = 2.)

（一般式（ＩＶ）において、Ｒ₃は、炭素数１乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In General Formula (IV), R ₃ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, and may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

（一般式（Ｖ）において、Ｒ₄は、炭素数２乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In the general formula (V), R ₄ is an alkylene group having 2 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

（一般式（ＶＩ）において、Ｒ₅は、炭素数１乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In General Formula (VI), R ₅ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

（一般式（ＶＩＩ）において、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In General Formula (VII), M represents a counter cation, m represents the number of cations, n represents the valence of the cation, and when m = 1, n = 2 and when m = 2. N = 1 and M is a hydrogen ion, an alkali metal ion, an ammonium ion or an organic ammonium ion when n = 1, and an alkaline earth metal ion when n = 2.)

（一般式（ＶＩＩＩ）において、Ｒ₆は、炭素数１乃至１０のアルキレン基、アルケニレン基であり、置換基を有してもよく、Ｍは対陽イオンを表し、ｍは陽イオンの数、ｎは陽イオンの価数を表し、ｍ＝１のとき、ｎ＝２であり、ｍ＝２のとき、ｎ＝１であり、Ｍは、ｎ＝１の場合、水素イオン、アルカリ金属イオン、アンモニウムイオン、有機アンモニウムイオンであり、ｎ＝２の場合、アルカリ土類金属イオンを表す。）

(In General Formula (VIII), R ₆ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

  In particular, the titanium chelate compound has the above general formula (II), general formula (III), general formula (VI), general formula (VII) or each hydrate, and the toner chargeability is excellent in durability stability. This is preferable because an image maintaining the image quality can be obtained.

  The counter cation M in the general formulas (I) to (VIII) is preferably an alkali metal, and examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Among these, lithium, sodium are preferable. Potassium, and particularly preferred are sodium and potassium. Two or more of these titanium chelate compounds are used in combination and used as a catalyst is also a good form of the present invention.

  Moreover, when superposing | polymerizing the polyester resin of this invention, as addition amount of this titanium chelate compound, 0.01 mass%-2 mass% with respect to the total amount of polyester unit components, Preferably it is 0.05 mass%-1 mass. %, More preferably 0.1% by mass to 0.7% by mass. When it is less than 0.01% by mass, the reaction time during the polymerization of the polyester becomes long and the molecular weight distribution becomes broad, making it difficult to give good fixability when the toner is used. On the other hand, when the content exceeds 2% by mass, the charging characteristics of the toner are affected, and the fluctuation of the charge amount due to the environment tends to increase.

  The polar resin contained in the toner of the present invention may be a resin having at least a polyester unit, and the polyester unit component contained in the total resin is 3% by mass or more, thereby exhibiting the effect of the present invention. Therefore, it is preferable. 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 20 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.

  Moreover, the hydroxyl value (mgKOH / g) of the polar resin used in the present invention is 5 or more and 40 or less, so that the effects of the present invention can be further exhibited. The hydroxyl value is preferably 10 or more and 35 or less, more preferably 15 or more and 30 or less.

  When the hydroxyl value is less than 5, the toner charge rises slowly and causes image defects such as fogging and scattering before the charge rises.

  On the other hand, when the hydroxyl value is larger than 40, the decrease in the charge amount becomes remarkable particularly in a high humidity environment, causing image defects such as fogging and scattering.

  The toner particles of the present invention can exhibit the effects of the present invention by using particles that are granulated in an aqueous system such as suspension polymerization, emulsion polymerization, suspension granulation. 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 them, the suspension polymerization method is one of the most preferable forms 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 4 to 10 μm, and thus the effects of the present invention can be exhibited. Preferably it is 5-9 micrometers, More preferably, 6-7.5 micrometers is good.

  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 the thickness 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 of 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, Preferably 20 or more and 50 or less are good.

  Similarly, in the water / methanol wettability test of the toner, the methanol mass% (TB) until the transmittance reaches 50% of the initial value is 30 to 90, preferably 35 to 80, and more 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 is likely to occur in the second half of the image printing durability in which the external additive has deteriorated.

  Conversely, if TA is greater than 70 due to the toner surface exposure or modification of the release agent, or if TB exceeds 90 due to hydrophobicity increase and addition of a large amount of inorganic fine powder, the water repellency is too high. In particular, in a low humidity environment, it causes adverse effects such as deterioration of the coating uniformity of the developing sleeve due to the charge-up phenomenon, thin image density, and toner adhesion to the charge imparting 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.

  The difference between the toner particle and toner water / methanol wettability test value, so-called TB-TA, is preferably 0 or more and 60 or less, preferably 5 or more and 45 or less, and more preferably 10 or more and 30 or less.

  For toner particles that are easily wetted by water, it is necessary to suppress the wettability of the toner to water by the type and amount of additives such as inorganic fine powder, but if it is too excessive, that is, (TB-TA) When the value is larger than 60, even if an image having no problem is obtained initially, the durability stability is insufficient. Specifically, it causes adverse effects such as fogging and scattering in the second half of the endurance. 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 color tone of the initial image when the same image is output and the color of the image at the time of continuous paper passing is too different is likely to occur.

  Conversely, when highly hydrophilic inorganic fine particles are added, (TB-TA) may be smaller than zero. This causes a decrease in chargeability in a high humidity environment, resulting in image defects such as fogging and scattering.

  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. The endothermic curve in differential thermal analysis (DSC) measurement shows a maximum in a temperature range of 30 to 200 ° C. The peak temperature of the endothermic peak is preferably in the range of 50 to 120 ° C, more preferably in the range of 55 to 100 ° C, and still more preferably in the range of 60 to 75 ° C.

  This maximum endothermic peak is determined by 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 mold release agents is also a method that can be suitably used to achieve the present invention, but it is essential that the maximum peak temperature range be within 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 plasticizing effect on 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, a release agent cannot be satisfactorily interposed between the good fixing member and the toner, and the transfer paper sticks to the fixing member (so-called fixing sticking) phenomenon. It tends to happen.

  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 fogging 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. When the number average molecular weight (Mn) is less than 2000, the elasticity of the toner particles themselves is too low, and high temperature offset is likely 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 control the above physical properties, it can be controlled by the reaction temperature and the kind and amount of a polymerization initiator, a crosslinking agent, a chain transfer agent, and a release agent when a resin or a polymerized toner is produced.

  In order for the toner of the present invention to achieve an appropriate medium gloss, the melt index (MI) value at 125 ° C. is preferably 1 to 50, and 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. Conversely, if 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 wax 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, it is particularly preferable that an ester wax is contained in the toner as shown by the following general structural formula.

（式中、ａ及びｂは０〜４の整数を示し、ａ＋ｂは４であり、Ｒ₁及びＲ₂は炭素数が１〜４０の有機基であり、且つＲ₁とＲ₂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 carbon number 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、Ｒ₁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 is 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、Ｒ₁及びＲ₂は炭素数が１〜４０の有機基であり、且つＲ₁とＲ₂との炭素数差が３以上である基を示し、Ｒ₃は炭素数が１以上の有機基を示し、ｋは１乃至３の整数であるり、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。）

(Wherein, a and b represent an integer 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. R ₃ represents a group having a number difference of 3 or more, R ₃ represents an organic group having 1 or more carbon atoms, k is an integer of 1 to 3, n and m are integers of 0 to 40, and n and m is 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, and fogging, fusion, etc. It is easy to cause image defects.

  Specific examples of the titanium chelate compound used in the present invention are shown below.

  The “polyester unit” used in the present invention means a part derived from polyester. Specifically, as a component constituting the polyester unit, a divalent or higher valent alcohol monomer component and a divalent or higher carboxylic acid, It means an acid monomer component such as a divalent or higher carboxylic acid anhydride and a divalent or higher carboxylic acid ester.

  The toner of the present invention is characterized in that a component having these polyester units is used as a part of a raw material and a resin having a condensation-polymerized portion is used.

  As a dihydric or higher alcohol monomer component which is a polyester unit component, specifically, as a dihydric alcohol monomer component, polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane, poly Oxypropylene (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 oxides of bisphenol A Adduct, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-pro Lenglycol, 1,3-propylene glycol, 1,4-butanediol, neopentyl glycol, 1,4-butenediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, Examples include dipropylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A, and hydrogenated bisphenol A.

  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 phenol resins; trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid and anhydrides thereof, etc. 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 resins obtained by condensation polymerization with these polyester unit components have good charging characteristics. Therefore, it 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.)

  As the binder resin for the toner, polystyrene; a homopolymer of a styrene substitution product such as poly-p-chlorostyrene and polyvinyltoluene; a styrene-p-chlorostyrene copolymer, a styrene-vinyltoluene copolymer, and a styrene-vinyl. Naphthalene 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 copolymers such as styrene-vinyl ethyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer; acrylic Resin; Methacrylic resin; Polyvinegar Vinyl; silicone resins; polyester resins; polyamide resin; furan resins, epoxy resins, xylene resins. These resins are used alone or in combination.

  As the main component of the binder resin, a polyester resin and / or a styrene copolymer which is a copolymer of styrene and another vinyl monomer is preferable in terms of developability and fixability.

  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 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 single monomer in which a polymerizable monomer, a colorant, 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 dosage system 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.

  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 And 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. 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 adjusting the color and toner resistance by mixing the following coloring materials is one of the good forms.

  As the yellow colorant, compounds represented by condensed azo compounds, isoindolinone compounds, anthraquinone compounds, azo metal complex methine compounds, and allylamide compounds are used as pigments. Specifically, C.I. I. Pigment Yellow 3.7.10.12.12.14.15.17.233.24.60.62.7.74.75.5.83.93.95.99.9.100.101.104.108.109.110 111.117.123.128.129.138.139.147.148.1500.155.166.168.169.177.179.180.181.183.185.191: 1.191.192.193 .199 or the like 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 is particularly preferable. 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 can be 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 selected from the viewpoints of hue angle, saturation, brightness, weather resistance, OHT transparency, and dispersibility in the toner. The added amount of the colorant is used by adding 1 to 20 parts by mass with respect to 100 parts by mass of the binder resin.

  In the toner of the present invention, it is preferable to use a charge control agent in order to keep the toner chargeability stable. 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.

  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.

  Among these, in order to sufficiently exhibit the effects of the present invention, a metal-containing salicylic acid compound is preferable, and the metal is particularly preferably aluminum or zirconium. As the most preferred control agent, an aluminum salicylate compound is preferred.

  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.

  In the present invention, the use of a lubricant in order to reduce component contamination takes a suitable form. Examples of the lubricant include fluorine resin powder (polyvinylidene fluoride, polytetrafluoroethylene, etc.), fatty acid metal salt (zinc stearate, calcium stearate, etc.) and the like. Of the above, polyvinylidene fluoride is preferably used.

  The toner of the present invention has inorganic fine particles for charging stability, developability, fluidity, member adhesion suppression, and durability improvement.

  Examples of the charge controllable particles among the inorganic fine particles include metal oxides (such as tin oxide, titania, zinc oxide, silica, alumina) and carbon black.

  Abrasives include metal oxides (strontium titanate, cerium oxide, aluminum oxide, magnesium oxide, chromium oxide, etc.), nitrides (silicon nitride, etc.), carbides (silicon carbide, etc.), metal salts (calcium sulfate, barium sulfate, etc.) , Calcium carbonate, etc.). Of these, strontium titanate is preferably used as the abrasive.

  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 form. Among them, it is most preferable that at least titanium oxide is contained because of compatibility with the titanium chelate compound 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, fogging caused by a decrease in chargeability, and toner scattering may occur, and the effects of the present invention can be sufficiently exerted. Absent. On the other hand, when the total addition amount is more than 4.5 parts by mass, adverse effects such as toner scattering, deterioration of fixability, fusion of the photosensitive member, and reduction of the toner charge amount due to contamination of the charging member 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 increases. Further, the TB-TA defined in the present invention tends 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.

  Other inorganic fine particles include an anti-caking agent; a conductivity imparting agent such as zinc oxide, antimony oxide, tin oxide; and a developability improver. The addition amount of these additives is preferably 0.01 to 2 parts by mass, more preferably 0.1 to 1 part by mass with respect to 100 parts by mass of the toner.

  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, Ethoxydiethylene glycol methacrylate, methoxyethylene glycol methacrylate, butoxytriethylene glycol methacrylate, methoxy methacrylate Propylene glycol, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxydiethylene glycol methacrylate, benzyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, N-methacrylate Vinyl-2-pyrrolidone, methacrylonitrile, methacrylamide, N-methylol methacrylamide, ethyl methacrylate, diacetone acrylamide, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate , Heptyl acrylate, octyl acrylate, nonyl acrylate, decyl acrylate, acrylic Undecyl acid, dodecyl acrylate, glycidyl acrylate, methoxyethyl acrylate, propoxyethyl acrylate, butoxyethyl acrylate, methoxydiethylene glycol acrylate, ethoxydiethylene glycol acrylate, methoxyethylene glycol acrylate, butoxytriethylene glycol acrylate, acrylic Acid methoxydipropylene glycol, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxytetraethylene glycol acrylate, benzyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, dicyclopentyl acrylate, dicyclopentenyloxyethyl acrylate N-vinyl-2-pyrrolidone acrylate, glycidyl acrylate, a Vinyl monomers having one vinyl group in one molecule such as rilonitrile, acrylamide, N-methylol acrylamide, diacetone acrylamide, ethyl morpholine acrylate and vinyl pyridine; divinyl benzene; reaction of glycol with methacrylic acid or acrylic acid Products such as ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,5-pentadiol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate , Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, tripropylene glycol dimethacrylate , Hydroxypivalate neopentyl glycol ester dimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetramethacrylate, trismethacryloxyethyl phosphate, tris (acryloyloxyethyl) 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 , Polyethylene glycol diacrylate, tripropylene diacrylate, hydroxy Cypivalic acid neopentyl glycol diacrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, trisacryloxyethyl phosphate, tris (methacryloyloxyethyl) isocyanurate, glycidyl methacrylate and methacrylic acid or acrylic acid A vinyl monomer having two or more vinyl groups in one molecule, such as a half esterified product of bisphenol type epoxy resin and methacrylic acid or acrylic acid, a glycidyl acrylate and methacrylic acid or acrylic acid half esterified product, etc. ; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, hydroxybutyl acrylate, 2-hydroxy-3-acrylate Sulfonyloxy propyl, 2-hydroxyethyl methacrylate, may be mentioned 2-hydroxypropyl methacrylate, hydroxybutyl methacrylate, a vinyl monomer having a hydroxy group such as methacrylic acid 2-hydroxy-3-phenyloxypropyl.

  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 on 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 deterioration of carrier transportability on the sleeve, fogging in the latter half of the endurance due to a decrease in charge imparting performance to the toner, and toner scattering 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, more preferably 2.1 g / cm 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, and the charge imparting performance to the toner in long-term durable use is deteriorated, resulting in problems such as toner scattering and fogging. .

  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 resin component of toner The specific GPC measurement method for the resin component of the toner is as follows. The toner is previously extracted with a toluene solvent for 20 hours using a Soxhlet extractor, and then the toluene is distilled off using 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, endothermic peak half-value width and glass transition temperature in the DSC endothermic curve of the toner Measured in accordance with ASTM D3418-82. In the present invention, “DSC-7” (manufactured by PerkinElmer) 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 containing only an aluminum pan (empty pan) are set for control and the temperature of a 30 to 200 ° 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 release agent used in the present invention. The half-value width of the endothermic peak is the temperature width of the endothermic chart at a portion corresponding to one half of the peak height from the base line in the endothermic peak. In the case of measuring only the wax component, the measurement is started after the temperature is raised and lowered under the same conditions as in the measurement to remove the previous history. 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-MT 30 cm 2 series (manufactured by Tosoh Corporation)
Temperature: 135 ° C
Solvent: o-dichlorobenzene (0.1% ionol added)
Flow rate: 1.0 ml / min
Sample: 0.4 ml injection of 0.15% sample Measured 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 beaker 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 put into 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, a glass beaker having a diameter of 5 cm was used as the beaker, and a magnetic stirrer having a spindle shape of 25 mm in length and a maximum diameter of 8 mm and coated with Teflon (registered trademark) 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 binder resin <Acid value>
The acid value is determined as follows. Basic operation conforms to JIS-K0070.

(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 orientation is JIS K
8006 (basic matters concerning titration during reagent content test).

  (B) Operation: 1-20 g of a sample (toner or binder 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.

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

<Hydroxyl value>
The hydroxyl value is determined as follows. Basic operation conforms to JIS-K0070.

(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.

here,
A: Hydroxyl value B: Amount used of N / 2 potassium hydroxide ethyl alcohol solution for 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: Acid value

(9) Measurement of toner and carrier shape factors (SF-1, SF-2) Using Hitachi FE-SEM (S-800), 100 toner images were randomly sampled at a magnification of 3000 times. Image information is introduced into an image analysis apparatus (Luxex 3) manufactured by Nireco Corporation via an interface, analyzed, and defined as a value obtained by calculation from the following equation.
SF-1 = {(MXLNG) ² / AREA} × (π / 4) × 100
SF-2 = {(PERI) ² / AREA} × (1 / 4π) × 100
(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 The magnetization strength (Am ² / kg) 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) Measuring method of carrier resistivity:
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 of the Present Invention>
Hereinafter, 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.

  The toner of the present invention is manufactured by Canon, black and white copying machines such as IR6000 and IR3000, laser beam printers such as LBP720 and LBP950, these two-component modified machines, LBP2040, LBP2810, LBP2710, LBP2410, CLC500, CLC700, CLC1000, CP2150, It can be preferably used for full-color machines such as CP660 and IRC3200.

  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. An information writing means 24 (not shown) for forming an electrostatic latent image, a developing device 4 for visualizing the electrostatic latent image formed on the surface of the photosensitive drum 1 with toner and developing the toner image, and a developing device 4 A transfer blade 27 is provided as transfer means for transferring the formed toner image 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, as shown in FIG. 1, an alternating voltage is applied to the developer carrying member, and 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 to perform development.

  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 carrier adhesion is likely to occur.

  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. When the developing nip C is narrower than 3 mm, it is difficult to satisfactorily satisfy a sufficient image density and dot reproducibility. When the developing nip C is larger than 8 mm, the developer packing occurs and the operation of the machine is stopped or the carrier adheres. It becomes difficult to suppress it sufficiently. As a method for adjusting the developing nip, the distance A between the regulating blade 15 as the developer regulating member and the developing sleeve 11 is adjusted, or the distance B between the developing sleeve 11 and the photosensitive drum 1 is adjusted to appropriately adjust the nip width. 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) inside.

  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. In order to prevent non-uniform application (so-called blade clogging) due to unnecessary particles mixed in the developer, this distance is preferably 250 μm or more. 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.

  An example of the image forming method of the present invention having a charging polarity control step will be described with reference to FIG.

  As shown in FIG. 6, 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 charging polarity control process. 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. 6, the same member as in the charge polarity control step is used between the transfer step and the charge polarity control step in order to remove the residual charge on the photosensitive drum and improve 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 which is an electrostatic latent image carrier, and the photosensitive drum 61a is rotated and moved 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 toner image is developed with toner, and the developed toner image is transferred to the back side of a belt-shaped transfer material carrier 68 that carries and conveys the transfer material at the first transfer portion (contact position between the photosensitive drum 61a and the transfer material). Transfer is applied to the surface of the transfer material by applying a transfer bias from the abutting transfer blade 64a.

  When the toner is consumed by 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. Four image forming units such as the image forming unit Pd are provided side by side. 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 includes 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 includes heating means 75 and 76 therein.

  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, the 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 unit, a contact transfer unit capable of directly applying a transfer bias by contacting a transfer roller can be used instead of the transfer blade contacting the back surface side of the transfer material carrier.

  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.

  As a contact one-component developing method, it is possible to develop using 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. The peripheral speed ratio is more preferably 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 an 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 of the developing sleeve 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 fillers and charge control agents such as metal oxide, carbon black, inorganic whiskers and inorganic fibers in the blade rubber and resin. 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 developing 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 developing member 172 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, a bias power source 177 shown in FIG. 5 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 photosensitive member 169 is over the developing sleeve 172. It is possible to facilitate the movement of the one-component nonmagnetic developer and obtain a higher quality image.

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 / s for a full color machine. It is preferable that

  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 0.3 parts of the above-mentioned titanium chelate compound 4 were placed in a 4-liter glass four-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen introducing tube were attached and placed in a mantle heater. . The reaction was carried out at 220 ° C. under a nitrogen atmosphere, and when the acid value reached 12, heating was stopped and the mixture was gradually cooled to obtain Resin 1 having a polyester unit component. This resin had a hydroxyl value of 20, Mw of 12,000, Mn of 5200, and Tg: 65.7 ° C.

(Polar resin production example 2)
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, 0.2 mol of trimellitic anhydride are weighed, 100 parts of these, 0.27 parts of the above-mentioned titanium chelate compound 4 and 4 liters of 4 liters made of glass The flask was placed in a mantle heater with a thermometer, a stir bar, a condenser and a nitrogen inlet tube attached. 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 2 having a polyester unit component. This resin had an acid value of 11, a hydroxyl value of 19, Mw of 70,000, Mn of 5400, and Tg of 66.7 ° C.

(Polar resin production example 3)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2.75 mol Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.0 mol, isophthal The acid 6.1 mol and the trimet anhydride 0.15 mol were measured. 100 parts of these acids / alcohols and 0.27 parts of titanium chelate compound 1 (described above) are placed in a 4-liter 4-neck flask made of glass, and a thermometer, a stir bar, a condenser and a nitrogen inlet tube are attached and placed in a mantle heater. It was. The reaction was carried out at 220 ° C. in a nitrogen atmosphere, and when the acid value reached 13, heating was stopped and the mixture was gradually cooled to obtain a resin 3 having a polyester unit component. This resin has a hydroxyl value of 20, Mw1 It was 30,000, Mn 5300, Tg: 65.9 ° C.

(Polar resin production example 4)
In Resin Production Example 3, a resin 4 having a polyester unit component was obtained in the same manner except that the above-mentioned titanium chelate compound 3 was used instead of the titanium chelate compound 1. The polyester unit component in the resin is 100% by mass. This resin had an acid value of 13, a hydroxyl value of 20, Mw of 12,000, Mn of 5200, and Tg: 66.7 ° C.

(Polar resin production example 5)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2.61 mol, polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.74 mol, 3.91 mol of fumaric acid and 1.74 mol of trimetic anhydride were measured. Place 100 parts of these acid / alcohol and 0.3 part of titanium chelate compound 2 (described above) in a glass 4-liter four-necked flask, attach a thermometer, stir bar, condenser and nitrogen inlet tube and place in a mantle heater. It was. Under a nitrogen atmosphere, reaction was performed at 235 ° C. for 5 hours to obtain a resin 5 having a polyester unit component. This resin had an acid value of 10, a hydroxyl value of 18, Mw of 34,000, Mn of 3200, and Tg: 64.7 ° 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 4 in Polar resin production example 1. This resin had a hydroxyl value of 15, Mw of 19,000, Mn of 6700, and Tg: 65.7 ° C.

(Polar resin production example 7)
Polar resin 7 having a polyester unit component was obtained in the same manner except that the reaction was stopped when the acid value reached 22 in Polar resin production example 1. This resin had a hydroxyl value of 28, Mw of 11,000, Mn3700, and Tg: 66.3 ° C.

(Polar resin production example 8)
In Resin Production Example 3, a resin 8 having a polyester unit component was prepared in the same manner except that 0.15 part of titanium chelate compound 3 and 0.15 part of titanium chelate compound 4 were used instead of titanium chelate compound 1. Got. The polyester unit component in the resin is 100% by mass. This resin had an acid value of 12, a hydroxyl value of 20, Mw of 12,000, Mn of 5200, and Tg: 66.7 ° C.

(Polar resin production example 9)
Polyoxypropylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 2.75 mol Polyoxyethylene (2.2) -2,2-bis (4-hydroxyphenyl) propane 1.0 mol, isophthal The acid 6.1 mol and the trimet anhydride 0.15 mol were measured. 100 parts of these acids / alcohol and 0.27 parts of titanium chelate compound 9 (described above) dihydrate are put into a glass 4-liter four-necked flask, and a thermometer, a stirring rod, a condenser and a nitrogen inlet tube are attached. Placed in the mounting 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 mixture was gradually cooled to obtain a resin 9 having a polyester unit component. This resin had a hydroxyl value of 23, Mw of 12,000, Mn of 5200, and Tg: 68.0 ° C.

(Polar resin comparative production example 1)
In Resin Production Example 3, Comparative Resin 1 having a polyester unit component was obtained in the same manner except that tetramethyl titanate was used instead of titanium chelate compound 1. The polyester unit component in the resin is 100% by mass. This resin had an acid value of 21, a hydroxyl value of 29, an Mw of 13,000, an Mn of 5200, and a Tg of 65.7 ° C.

(Polar resin comparative production example 2)
In Resin Production Example 3, Comparative Resin 2 having a polyester unit component was obtained in the same manner except that dibutyltin oxide was used instead of titanium chelate compound 1. The polyester unit component in the resin is 100% by mass. This resin had an acid value of 21, a hydroxyl value of 29, an Mw of 14,000, an Mn of 5800, and a Tg of 67.6 ° C.

(Polar resin comparative production example 3)
In the polar resin production example 1, a comparative resin 3 having a polyester unit component was obtained in the same manner except that the reaction was stopped when the acid value reached 1. This resin had a hydroxyl value of 9, Mw of 21,000, Mn of 7700, and Tg of 66.7 ° C.

(Polar resin comparative production example 4)
Comparative Resin 4 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 a hydroxyl value of 42, Mw of 11,000, Mn3700, and Tg: 66.7 ° C.

<Toner Production Example 1>
For 100 parts of styrene monomer, 15 parts of copper phthalocyanine as a cyan colorant and 2.0 parts of aluminum compound of di-tertiary butylsalicylic acid [Bontron E101 (manufactured by Orient Chemical Industries)] 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, it was warmed to 0.1M-Na ₃ PO ₄ aqueous solution 450 parts turned to 60 ° C. in deionized water 710 parts, calcium phosphate compounds was slowly added 1.0 M-CaCl ₂ aqueous solution 67.7 parts 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)
7 parts of polar resin 1 (Mw: 12,000, Mn: 5200, Tg: 65.7 ° C., acid value: 12.0, hydroxyl group value: 20)
-0.075 part of divinylbenzene 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.

To 100 parts of the obtained cyan toner particles, 1.2 parts of hydrophobic silica treated with silicone oil having a specific surface area of 200 m ² / g by BET method and isobutyltrimethoxysilane having a specific surface area of 100 m ² / g After 0.2 part of the treated anatase-type titanium oxide was externally added with a Henschel mixer, coarse particles were removed with a turbo screener equipped with # 400 mesh. 1 was obtained. The toner had a mass average particle size of 6.9 μm, a TA value of 42, and a TB value of 61. The obtained toner No. The composition of No. 1 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 2>
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 2 and 10 parts were added. 2 was obtained. The obtained toner No. The composition of 2 is shown in Table 1, and the physical properties are shown in Table 2.

<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. The composition of No. 3 is shown in Table 1, and the physical properties are shown in Table 2.

<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 of 4 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 5>
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 5 and the number of parts added was 23 parts, and 20 parts of the release agent was added. Toner No. 5 was obtained. The obtained toner No. The composition of No. 5 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 6>
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 6, and cyan toner No. 1 was used. 6 was obtained. The obtained toner No. The composition of No. 6 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 7>
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 the polar resin 7, and cyan toner No. 1 was used. 7 was obtained. The obtained toner No. The composition of No. 7 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Comparative Production Examples 1 to 4>
In Toner Production Example 1, Comparative Resins 1 to 4 were used in place of Polar Resin 1, and polypropylene wax (half-width: 22 ° C., DSC endothermic peak: 129 ° C., Mw: 1.w) instead of ester wax as a release agent. 70, Mn: 1350, penetration: 0.5 degree) and 2.5 parts of inorganic fine powder were added in the same manner except that only silica was 0.9% by mass. 1-No. 4 was obtained. The obtained comparative toner No. The composition of 1-4 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Comparative Production Example 5>
Production Example 1 of toner, the resin 6 used as the polar resin, 600 parts of the amount of 0.1M-Na ₃ PO ₄ aqueous solution, the rotational speed of the homomixer and 13000 rpm, the classification conditions of the multi-division classifier, respectively The mass average particle diameter was 3.4 μm (4 μm or less: 62.0% by number, 12.7 μm or more: 0 or more) using the same method as in Production Example 1 except that 1.1 parts of hydrophobic silica was used. Volume%) cyan comparison toner No. 5 was obtained. The obtained comparative toner No. The composition of 5 is shown in Table 3, and the physical properties are shown in Table 4.

<Comparative Production Example 6 of Toner>
In Toner Production Example 1, resin 7 was used as the polar resin, the amount of 0.1M-Na ₃ PO ₄ aqueous solution used was 190 parts, the homomixer rotation speed was 4300 rpm, and the classification conditions of the multistage division classifier were respectively The mass average particle size was 10.9 μm (4 μm or less: 2.7% by number, 12.7 μm or more: 3) using the same method as in Production Example 1 except that 0.7 part of hydrophobic silica was used. .4 volume%) cyan comparative toner No. 6 was obtained. The obtained comparative toner No. The composition of 6 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Comparative Production Example 7>
In Toner Production Example 15, the same procedure was performed except that no polar resin was used. 7 was obtained. The obtained comparative toner No. The composition of No. 7 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 8>
In Toner Production Example 6, resin 6 was used as the polar resin, the amount of 0.1M-Na ₃ PO ₄ aqueous solution used was 520 parts, the homomixer rotation speed was 11500 rpm, and the classification conditions of the multistage division classifier were respectively The mass average particle size was 4.9 μm (4 μm or less: 49. 49 μm or less) using the same method as in Production Example 6 except that 1.5 parts of hydrophobic silica and 0.3 parts of hydrophobic titanium oxide were used. 0% by number, 12.7 μm or more: 0% by volume). 8 was obtained. The obtained toner No. The composition of No. 8 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 9>
In Toner Production Example 7, using the same method as in Production Example 7 except that Resin 7 was used as the polar resin, 0.7 part of hydrophobic silica and 0.1 part of hydrophobic titanium oxide were used. A cyan toner No. having an average particle size of 9.2 μm (4 μm or less: 8.0% by number, 12.7 μm or more: 2.1% by volume). 9 was obtained. The obtained toner No. The composition of 9 is shown in Table 1, and the physical properties are shown in Table 2.

<Example 10 of toner production>
In toner production example 6, using the same method as in production example 6 except that the ester wax to be added is 40 parts, the hydrophobic silica is 1.8 parts, and the hydrophobic titanium oxide is 0.5 parts. Cyan toner No. having a mass average particle diameter of 6.7 μm. 10 was obtained. The obtained toner No. The composition of 10 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 11>
In Toner Production Example 9, using the same method as in Production Example 9 except that the added ester wax was 3 parts, the hydrophobic silica was 1.2 parts, and the hydrophobic titanium oxide was 0.2 parts. Cyan toner No. having a mass average particle diameter of 6.8 μm. 11 was obtained. The obtained toner No. The composition of 11 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 12>
A toner having a mass average particle diameter of 6.7 μm was prepared in the same manner as in Production Example 11 except that 1.5 parts of hydrophobic silica and 0.3 parts of hydrophobic titanium oxide were used in Toner Production Example 11. Color toner No. 12 was obtained. The obtained toner No. The composition of 12 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 13>
A toner having a mass average particle diameter of 6.8 μm was prepared in the same manner as in Production Example 11 except that 1.8 parts of hydrophobic silica and 0.4 parts of hydrophobic titanium oxide were used. Color toner No. 13 was obtained. The obtained toner No. The composition of 13 is shown in Table 1, and the physical properties are shown in Table 2.

(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 being dried, 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, the fine particle component is removed by classification by a wet classification method using precipitation separation, and the obtained hydrophobic iron oxide particles are washed, filtered and dried by a conventional method, and then the slightly aggregated particles are separated. The magnetic body 1 was obtained by crushing.

<Toner Production Example 14>
After warming the 0.1M-Na ₃ PO ₄ aqueous solution 450 parts turned to 60 ° C. in deionized water 710 parts, water which was slowly added 1.0 M-CaCl ₂ aqueous solution 67.7 parts comprising calcium phosphate compounds A medium was obtained.
-77 parts of styrene-23 parts of n-butyl acrylate-17 parts of ester wax (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 1 (Mw: 12,000, Mn: 5200, Tg: 65.7 ° C., acid value: 12.0, hydroxyl group value: 20)
・ 0.075 part of divinylbenzene ・ aluminum compound of di-tertiary butylsalicylic acid [bontron E101 (manufactured by Orient Chemical Co., Ltd.)] 1 part ・ 100 parts of magnetic substance 1 is added to the aqueous medium heated to 60 ° C. , And uniformly dissolved and dispersed by stirring. In this, 3 parts of polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved to prepare a polymerizable monomer composition. Except for this, toner particles were obtained in the same manner as in Toner Production Example 1. To the toner particles, 1.2 parts of hydrophobic silica and 0.05 part of hydrophobic titanium oxide used in Toner Production Example 1 were added. 14 was obtained. The obtained toner No. The composition of 14 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 15>
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 type of homogenizer (manufactured by IKA: Ultra Tarrax), a shearing force was strongly applied to disperse, heated to 62 ° C. and held for 1 hour to prepare dispersion (A).

Preparation of colorant dispersion (B) 90 g of copper phthalocyanine pigment
(BASF: PV FAST BLUE)
Anionic surfactant 5g
(Daiichi Kogyo Seiyaku Co., Ltd .: Neogen SC)
200g of ion exchange water
Aluminum compound of di-tertiary butylsalicylic acid [Bontron E101 (manufactured by Orient Chemical Industries)] 10 g
The above was mixed, dissolved, and dispersed for 10 minutes using a rotor-stator type homogenizer (manufactured by IKA: Ultra Tarrax), and further dispersed for 5 minutes using an ultrasonic homogenizer to prepare a colorant dispersion (B). .

Preparation of release agent dispersion (C) Polypropylene wax (half-width: 22 ° C., DSC endothermic peak: 129 ° C., Mw: 170,000, 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 prepare a release agent dispersion (C).

--Preparation of aggregated particles--
Dispersion (A) 200g
Colorant dispersion (B) 10g
Release agent dispersion (C) 10g
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. Holding at 48 ° C. for 30 minutes gave aggregated particles.

<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 sufficiently washed with ion exchange water to obtain toner particles for developing an electrostatic charge image. Other than that, the toner no. 15 was obtained. The obtained toner No. The composition of 15 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 16>
[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.
-Polar resin 5 85 parts-C.I. I. 6. 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 °) 5 parts-Aluminum compound of di-tertiary butylsalicylic acid [Bontron E101 (made by Orient Chemical Industries)] 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 (coated 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 to obtain toner particles. Otherwise, the same procedure as in Production Example 1 was performed, except that the toner No. 16 was obtained. The obtained toner No. The composition of 16 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 17>
C.I used in Toner Production Example 1 I. In the same manner as in Toner Production Example 1, except that 14 parts of Pigment Yellow 93 was used instead of Pigment Blue 15: 3, Yellow Toner No. 17 was obtained. The obtained toner No. The composition of 17 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 18>
C.I used in Toner Production Example 1 I. In the same manner as in Toner Production Example 1, except that 14 parts of dimethylquinacridone was used instead of CI Pigment Blue 15: 3, 18 was obtained. The obtained toner No. The composition of 18 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 19>
C.I used in Toner Production Example 1 I. A black toner No. 1 was prepared in the same manner as in Toner Production Example 1 except that 20 parts of carbon black was used instead of CI Pigment Blue 15: 3. 19 was obtained. The obtained toner No. The composition of 19 is shown in Table 1, and the physical properties are shown in Table 2.

<Toner Production Example 20>
In the same manner as in Toner Production Example 1, except that 1.0 part of hydrophobic silica and 0.4 part of hydrophobic titanium oxide were used, a cyan toner No. 1 having a mass average particle diameter of 6.9 μm was used. 20 was obtained. The obtained toner No. The composition of 20 is shown in Table 1, and the physical properties are shown in Table 2. Further, this toner and the following magnetic carrier 1 were mixed at a toner mass% of 8% to obtain a developer 20.

<Toner Production Example 21>
A similar procedure was used in Toner Production Example 17 except that 1.0 part of hydrophobic silica and 0.4 part of hydrophobic titanium oxide were used, and a yellow toner No. 1 having a mass average particle diameter of 6.8 μm was used. 21 was obtained. The obtained toner No. The composition of 21 is shown in Table 1, and the physical properties are shown in Table 2. Further, this toner and the following magnetic carrier 1 were mixed at a toner mass% of 8% to obtain a developer 21.

<Toner Production Example 22>
In the same manner as in Toner Production Example 18, except that 1.0 part of hydrophobic silica and 0.4 part of hydrophobic titanium oxide were used, a magenta toner No. 1 having a mass average particle diameter of 6.8 μm was used. 22 was obtained. The obtained toner No. The composition of 22 is shown in Table 1, and the physical properties are shown in Table 2. Further, this toner and the following magnetic carrier 1 were mixed at a toner mass% of 8% to obtain a developer 22.

<Toner Production Example 23>
A black toner No. 19 having a mass average particle diameter of 6.8 μm was used in the same manner as in Toner Production Example 19 except that 1.0 part of hydrophobic silica and 0.4 part of hydrophobic titanium oxide were used. 23 was obtained. The obtained toner No. The composition of 23 is shown in Table 1, and the physical properties are shown in Table 2. Further, this toner and the following magnetic carrier 1 were mixed at a toner mass% of 8% to obtain a developer 23.

<Toner Production Example 24>
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. 24 was obtained. The obtained toner No. The composition of 24 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 25>
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 124 ° C. was used as the release agent. 25 was obtained. The obtained toner No. The composition of 25 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 26>
In Toner Production Example 1, Toner No. 1 was similarly used except that no aluminum compound of di-tertiary butylsalicylic acid was used. 26 was obtained. The obtained toner No. The composition of 26 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 27>
Toner No. 1 was prepared in the same manner as in Toner Production Example 1 except that a zirconium compound of di-tertiary butyl salicylic acid [TN105 (manufactured by Hodogaya Chemical Co., Ltd.)] was used instead of the aluminum compound of di-tertiary butyl salicylic acid. 27 was obtained. The obtained toner No. The composition of 27 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 28>
Toner No. 1 was prepared in the same manner as in Toner Production Example 1 except that a zinc compound of di-tertiary butyl salicylic acid [Bontron E84 (manufactured by Orient Chemical Industries)] was used instead of the aluminum compound of di-tertiary butyl salicylic acid. 28 was obtained. The obtained toner No. The composition of 28 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 29>
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 8. 29 was obtained. The obtained toner No. The composition of 29 is shown in Table 3, and the physical properties are shown in Table 4.

<Toner Production Example 30>
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 9, and cyan toner No. 1 was used. 30 was obtained. The obtained toner No. The composition of 30 is shown in Table 3, and the physical properties are shown in Table 4.

<Manufacture example 1 of a magnetic carrier>
-50 parts of phenol (hydroxybenzene)-80 parts of 37% by weight formalin aqueous solution-50 parts of water-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.

  A 5% by mass toluene solution of γ-aminopropyltrimethoxysilane represented by the following formula was applied to the surface of the obtained magnetic carrier core (A).

  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. On the surface of the magnetic carrier core (A)

が存在しているのが確認された。

Was confirmed to exist.

  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. % Γ-aminopropyltrimethoxysilane was added, 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 diameter 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 / kg. cm ³ and SF-1 were 107.

<Manufacture example 2 of magnetic carrier>
Li ₂ CO ₃ 14.0 mol%, Fe ₂ O ₃ 77.0 mol%, Mg (OH) 26.8 mol% and CaCO ₃ 2.2 mol% were pulverized in a wet ball mill for 5 hours, mixed and dried, then 900 Preliminary firing was performed by maintaining at 1 ° C. for 1 hour. 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.

<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. The evaluation results are shown in Table 5. As can be seen from Table 5, 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 transfer paper) was output in 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: Unbearable in actual use.

(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 with a halftone image density of 0.5 cm in 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: A slight offset occurred at the end other than the part that passed through the A4 portrait, but this was not a problem in use.
C: A slight offset occurred in the end portion other than the portion that passed through the A4 portrait. Although it is at the level of practical use, there is no problem in normal copying.
D: Level in which offset occurs in the entire longitudinal direction, causing a problem in actual use.
E: An offset is generated from the first surface in the entire longitudinal direction, and it is not durable for actual use.

(4) Fog 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 ODEL TC-6DS” manufactured by Tokyo Denshoku Co., Ltd.) equipped with a filter of a complementary color of the measurement color. did. 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 expressed by the following formula: Fog (%) = Dr (%) − Ds (%)
Calculate from

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

(6) Drum Fusion In a 10,000 sheet endurance test under the H / H environment, the presence or absence of a fusion product on the drum was evaluated by visual and loupe according to the following evaluation criteria in six stages.
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 with a diameter of 0.1 to 0.4 mm exist on the drum, and although they are slightly generated on the image, they are not at a level that causes a problem in actual use.
D: A level in which there are 10 or more fused objects larger than 0.4 mm in diameter on the drum, which also occurs on the image, causing a problem.
E: There are 10 to 20 fusion objects having a diameter of 0.4 mm to 1 mm on the drum, and this is a problem level that occurs on the image.
F: A fused material larger than 1 mm in diameter exists on the entire surface of the drum, and a large number of images are generated on the drum. This is a problem level and cannot be used practically.

(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: Several defective cleanings with a length of 1 to 4 mm exist on the drum, and although they are slightly generated on the image, they are not at a level causing a problem in actual use.
D: A level in which 10 or more cleaning defects longer than 4 mm in length exist on the drum and also occur on the image, causing a problem.
E: A level in which there are 10 to 20 cleaning defects having a diameter of 4 mm to 10 mm on the drum, which also occurs on the image and causes a problem.
F: There are cleaning defects larger than 1 mm in diameter on the entire surface of the drum, and many images are generated on the drum. This is a problem level and cannot withstand actual use.

(8) Image quality evaluation After the endurance test under H / H environment, image quality evaluation (overall evaluation of 5-point characters, line images, and solid images) was performed visually and with a magnifying glass. The evaluation criteria are as follows.
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 recognized by the loupe check, but the solid image is uniform and good with no visual check.
C: Although a part scattered in the line image and the character image is visually confirmed, it is not a level that causes a problem in actual use.
D: There are many parts that are visually scattered in the line image and the character image, but at a level that does not cause any problem in general use.
E: Level causing a partial problem that is visually scattered in a line image and a character image.
F: Many parts are scattered in the line image and the character image by visual observation, and cannot be used in actual use.
G: Not only a line image and a character image but also a solid image is not uniform and is poor and cannot be used practically.

(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: Although a slight toner layer is confirmed under the developing sleeve, there is no scattered toner in the machine, and it is good.
C: The toner is slightly scattered under the developing sleeve and in the machine, but this is not a problem level.
D: Toner is scattered under the developing sleeve and in the machine, causing a problem.
E: The toner is scattered under the developing sleeve and in the machine, and it cannot withstand actual use.
F: The inside of the machine is contaminated with toner color, image defects frequently occur, and cannot be used in actual use.

(10) Fixing roller winding property test Fixing winding property was confirmed at the initial stage in a durability test under an H / H environment. A solid image having an image amount of 1.1 mg / cm ² was placed on EN100 (64 g paper) completely humidity-controlled paper from a position 1 mm from the leading edge of the transfer paper to obtain an unfixed image. This was fixed using a fixing machine of IRC3200. At this time, the temperature at which the transfer paper is wound around the fixing roller when the fixing temperature is lowered by 5 ° C. is defined as the fixing roller winding temperature.

(11) 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 and can withstand some practical use.
D: Aggregation is severe, causing problems in actual use.
E: Solidified and cannot be used.

(12) Measurement of transfer efficiency The transfer efficiency was confirmed at the end of the durability test under H / H environment. A solid image having an image paste amount of 0.65 mg / cm ² was developed on a drum and 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%

(13) Color fluctuation test Ten 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. At that time, the initial and endurance colors were visually confirmed and evaluated as follows.
A: There is no color fluctuation at all.
B: Almost no change in color.
C: There is a slight color change, and it is pointed out to severe users.
D: There is a color fluctuation and is pointed out.
E: The color tone is greatly different, and the problem in actual use is great.

<Examples 2 to 26>
As shown in Tables 1 to 4, Developers 2 to 31 were prepared in combination with toner or carrier. The developer was changed as shown in Table 5, and evaluation was performed using the same method as in Example 1. The results are shown in Table 5. In Examples 17, 18, and 21, the evaluation was performed in cyan when a full-color image was output. Further, only in Example 31, the re-environment of 15,000 sheets was printed.

  When using a two-component developer, a developer and a remodeling device prepared 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 / min with a fixing speed of 150 mm / s as an image forming apparatus. 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 1-7>
Comparative toners 1 to 7 in Tables 3 and 4 were used, and the same experimental method and evaluation as in Example 1 were performed according to the image forming method in Table 5. The results are shown in Table 5.

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 which shows the alternating electric field used in Example 1. FIG. 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 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. 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.

Explanation of symbols

1, 61a Photosensitive member (photosensitive drum)
2, 62a Charging means 2a Conductive support made of stainless steel 2e Charge roller pressure contact member (spring)
Exposure device 4, 63a Developing device 4a Developing container 4a Developing container 4b, 11 Developer carrier (developing sleeve)
4c, 12 Magnet roller 4f, 13, 14 Developer conveying screw 4d, 15 Regulating blade 5 Transfer roller 6 Fixing device 7 Charge amount control means 8 Non-contact thermistor 17 Bulkhead 18, 65a Replenishing toner 19 Developer 19a Toner 19b Carrier 20 Supply port 21 Magnet roller 22 Conveying sleeve 23 Magnetic brush L, 24, 67a Laser light P, 25 Transfer material (recording material)
26 Bias application means 27, 64a Transfer blade 28 Toner density detection sensor 68 Transfer material carrier 69 Separation charger 70 Fixing device 71, 95 Fixing roller 72, 96 Pressure roller 73 Web 75, 76 Heating means 79 Transfer belt cleaning device 80 Driving roller 81 Belt driven roller 82 Belt neutralizer 83 Registration roller 85 Toner density detection sensor 100 Controller a Charging unit b Exposure unit c Developing unit d Transfer unit e Charge amount control unit S1, S2, S3, S4 Voltage application device

Claims (10)

In a toner comprising toner particles containing at least a colorant, a release agent, and a polar resin, and an inorganic fine powder,
The polar resin contains (i) a polyester resin polymerized using at least a titanium chelate compound as a catalyst, and (ii) has an acid value of 3 to 35 (mgKOH / g),
The toner particles are granulated in an aqueous medium,
The toner has a weight average particle diameter of 4 to 10 μm.   The toner according to claim 1, wherein in the titanium chelate compound, the chelate compound is a diol, a dicarboxylic acid, or an oxycarboxylic acid. The toner according to claim 1, wherein the titanium chelate compound is represented by the following general formula (I) to general formula (VIII) or a hydrate thereof.

(In General Formula (I), R ₁ is an alkylene group having 2 to 10 carbon atoms or an alkenylene group, and may have a substituent. M represents a counter cation, m represents the number of cations, n represents the valence of a cation, and when m = 1, n = 2, and when m = 2, n = 1, and when n = 1, M is a hydrogen ion, an alkali metal ion, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

(In the general formula (II), R ₂ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, and may have a substituent. M represents a counter cation, m represents the number of cations, n represents the valence of a cation, and when m = 1, n = 2, and when m = 2, n = 1, and when n = 1, M is a hydrogen ion, an alkali metal ion, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

(In general formula (III), M represents a counter cation, m represents the number of cations, n represents the valence of the cation, and when m = 1, n = 2 and when m = 2. N is 1. When n = 1, M is a hydrogen ion, an alkali metal ion, an ammonium ion, or an organic ammonium ion, and when n = 2, it represents an alkaline earth metal ion.)

(In the general formula (IV), R ₃ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, and may have a substituent. M represents a counter cation, m represents the number of cations, n represents the valence of a cation, and when m = 1, n = 2, and when m = 2, n = 1, and when n = 1, M is a hydrogen ion, an alkali metal ion, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

(In the general formula (V), R ₄ is an alkylene group having 2 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

(In General Formula (VI), R ₅ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)

(In General Formula (VII), M represents a counter cation, m represents the number of cations, n represents the valence of the cation, and when m = 1, n = 2 and when m = 2. N = 1 and M is a hydrogen ion, an alkali metal ion, an ammonium ion or an organic ammonium ion when n = 1, and an alkaline earth metal ion when n = 2.)

(In General Formula (VIII), R ₆ is an alkylene group having 1 to 10 carbon atoms or an alkenylene group, which may have a substituent, M represents a counter cation, m represents the number of cations, n represents the valence of the cation, n = 2 when m = 1, n = 1 when m = 2, and M is a hydrogen ion, an alkali metal ion when n = 1, (It is an ammonium ion or an organic ammonium ion. When n = 2, it represents an alkaline earth metal ion.)   The toner according to claim 3, wherein the titanium chelate compound is represented by the general formulas (II), (III), (VI) and (VII) or hydrates thereof. 5. The water content in the water / methanol wettability test of the toner particles and the toner, respectively, methanol mass% until the initial transmittance reaches 50% satisfies the following relational expression. The toner described in 1.
10 ≦ TA ≦ 70
30 ≦ TB ≦ 90
TB-TA ≦ 60
(TA: methanol mass% of toner particles, TB: methanol mass% of toner)   6. The toner according to claim 1, wherein a peak temperature of a maximum endothermic peak in a temperature range of 30 to 200 ° C. is in a range of 50 to 120 ° C. in an endothermic curve in differential thermal analysis (DSC) measurement. The toner according to any one of the above.   The toner according to any one of claims 1 to 6, wherein the toner contains a salicylic acid-based metal compound as a charge control agent.   The toner according to claim 7, wherein the metal of the salicylic acid-based metal compound used as the charge control agent is aluminum or zirconium.   The toner according to claim 1, wherein the polar resin has a hydroxyl value of 5 to 40 (mg KOH / g).   The toner particles are prepared by dispersing a polymerizable monomer composition containing at least a polymerizable monomer, a colorant, a polar resin, a release agent, a charge control agent, and a polymerization initiator in an aqueous medium and granulating it. The toner according to claim 1, wherein the toner particles are produced by polymerizing a polymerizable monomer.

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