JP2007108731A - Toner for developing electrostatic charge image, method and apparatus for manufacturing same, developer, container with toner, process cartridge, image forming method, and image forming apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a toner for developing an electrostatic charge image etc. capable of stably forming a high-quality and high-definition color image regardless of the environments and elapsed time as well as capable of forming a clear high-quality image with a good transferability and good cleaning properties, which can keep charge stable under high-temperature and high-humidity. <P>SOLUTION: In the toner for developing the electrostatic charge image containing at least a binder resin and a colorant, when the cross-section of a toner particle is divided by 20 nm square, the average value of the ratio (F/C) of fluorine atom and carbon atom, in a section including a surface and a section abutting on the section including the surface, is ≥0.8 and ≤1.2. Moreover, the average value of the ratio (F/C) of fluorine atom and carbon atom, in any section of 20 nm square which is ≥500 nm away from the surface, is ≤0.02. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an electrostatic charge image developing toner, a manufacturing method, and a manufacturing apparatus, which are used when developing an electrostatic charge image formed by an electrophotographic method, an electrostatic recording method, an electrostatic printing method or the like with a developer. The present invention relates to a developer, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus.

  In general, electrophotographic methods include various types of photoconductors using photoconductive substances (hereinafter also referred to as “electrostatic latent image carrier”, “image carrier”, and “electrophotographic photoconductor”). An electrostatic latent image forming step for forming an electrostatic latent image using the above means, a developing step for developing the electrostatic latent image by using toner to form a toner image, and transferring the toner image to a recording medium such as paper. The process includes a transfer process, a fixing process for fixing the toner image transferred to the recording medium to the recording medium by heating, pressure, thermal pressure, solvent vapor, and the like, and a cleaning process for removing the toner remaining on the photoreceptor.

  Developers used in electrophotography, electrostatic recording, electrostatic printing, and the like are once developed in an image carrier such as an electrostatic latent image carrier on which an electrostatic image is formed in the development process. Then, after being transferred from the electrostatic latent image carrier to a transfer medium such as transfer paper in the transfer step, it is fixed on the paper surface in the fixing step. At that time, as a developer for developing the electrostatic image formed on the latent image holding surface, a two-component developer composed of a carrier and a toner, and a one-component developer that does not require a carrier (magnetic toner, Non-magnetic toners are known.

  The toner used in the electrophotographic method is required to be manufactured using a method that saves energy and has little influence on the environment.

  Conventionally, dry toners used for electrophotography, electrostatic recording, electrostatic printing, etc. are obtained by melt-kneading a binder resin such as a styrene resin or a polyester resin together with an internal additive such as a colorant and then finely pulverizing it. So-called pulverized toner is widely used.

  In the toner manufacturing method by the pulverization method, it is important to uniformly disperse and pulverize each constituent material in order to ensure the uniformity of the shape of the obtained toner. Basically, the shape of the pulverized toner is indefinite, and the pulverized cross section becomes random, so it is difficult to control the shape and structure. In addition, when a large amount of an internal additive such as a colorant, a release agent, and a charge control agent is added, the internal additive is applied to the surface by grinding at the interface between the internal additive and the binder resin during the pulverization step. There is a problem in that exposure is easy and uneven charging occurs in individual toner particles, and quality such as toner characteristics such as fluidity and charging performance deteriorates.

  Recently, a toner production method using a chemical method for producing a toner in a solvent (for example, suspension polymerization method, emulsion polymerization aggregation method, dissolution suspension method, polyester elongation method, phase inversion emulsification method, etc.) has been studied. Yes.

In the suspension polymerization method, a colorant, a release agent, a charge control agent and other internal additives and a polymerization initiator are dispersed in a monomer, and the dispersion is suspended in an aqueous medium having a dispersant. In this method, oil droplets are formed, and then the temperature is raised to cause a monomer in the droplets to undergo a polymerization reaction (see Non-Patent Document 1).
An example of the emulsion polymerization aggregation method is shown. First, the colorant is dispersed in an aqueous surfactant solution. On the other hand, a polymerization initiator, a styrene monomer, and an acrylic monomer are added to an aqueous surfactant solution to produce a resin emulsion by emulsion polymerization. Mix the colorant dispersion and resin emulsion, and dispersion of other internal additives such as mold release agents and charge control agents as appropriate, and grow them by associating them to the desired particle size by adjusting the pH or adding a flocculant. Then, the toner is manufactured by fusing each fine particle by heating and stirring (see Patent Document 1 and Non-Patent Document 2).

  The dissolution suspension method includes a step of preparing a suspension in which an oily component obtained by dissolving a binder resin in an organic solvent in which the binder resin can be dissolved is suspended in an aqueous component; And a method of removing the organic solvent from the liquid, and having a volume shrinkage. In addition to the binder resin, internal additives such as a colorant, a release agent, and a charge control agent are dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and this is suspended in an aqueous medium in which a dispersant is present. The volatile solvent is removed after the droplets are formed. Unlike the suspension polymerization method and the emulsion polymerization aggregation method, this method has a wide range of versatility in the resin that can be used. It is excellent in that a polyester resin useful for a full-color process that requires smoothness can be used (see Patent Document 2 and Non-Patent Document 3).

  In the polyester elongation method, an oily component obtained by dissolving a polyester resin containing a reactive resin, which is a binder resin, in an organic solvent in which the polyester resin can be dissolved is emulsified and dispersed in an aqueous component. It is a construction method having a step of preparing a liquid and a step of performing a polyester elongation reaction while removing the organic solvent from the dispersion. Unlike the suspension polymerization method and emulsion polymerization aggregation method, this method is excellent in that a polyester resin useful for a full color process requiring transparency and smoothness of an image portion after fixing can be used, and elongation is also achieved. By performing the reaction, it becomes possible to control the viscoelasticity of the toner and to fix the toner in a wide temperature range (see Non-Patent Document 4).

  In the phase inversion emulsification method, a binder resin and internal additives such as a colorant, a release agent, and a charge control agent are dispersed and dissolved in a volatile solvent such as a low-boiling organic solvent, and a continuous aqueous phase is injected therein. The volatile solvent is removed after forming oil droplets by phase inversion from the W / O dispersion to the O / W dispersion. This method is also excellent in that it can be used for a full-color process in which the resin that can be used is versatile and particularly requires transparency and smoothness of the image area after fixing (patent) Reference 3 and Patent Document 4).

  As a toner manufactured using such a chemical method, a toner having a form capable of effectively expressing a desired function, such as a capsule toner and a core-shell toner, from the viewpoint of considering environmental problems in recent years. Are known.

  The chemical method can produce a toner having a small particle size and a narrow particle size distribution compared to the pulverization method. However, since the toner is granulated in water or in a hydrophilic solvent, the surface of the toner becomes hydrophilic, causing deterioration in charging performance, stability with time and instability of environmental characteristics, development and transfer failure, toner It has the potential to induce problems such as scattering and image quality degradation. Furthermore, the chemical method has problems such as a large amount of waste liquid and large energy for drying the toner, which is not preferable from the viewpoint of environmental load.

  As an alternative toner manufacturing method, there has been proposed a method in which fine droplets are formed using a piezoelectric pulse and then dried and solidified to form a toner (see Patent Document 5). Furthermore, a method has also been proposed in which fine droplets are formed using the thermal expansion in the liquid chamber, which is further dried and solidified to form a toner (see Patent Document 6). Furthermore, a method of performing the same processing using an acoustic lens has been proposed (see Patent Document 7).

  However, a toner manufactured by such a method is added with a charge control agent in order to develop a charge control effect which is an important characteristic of the toner. In many cases, it is difficult to discharge stably from a minute discharge hole, and it is difficult to stably discharge without blocking the discharge hole. In order to keep the state for a certain period of time, it was necessary to treat with a large amount of dispersion stabilizer.

  In addition, as a method for producing particles, droplet formation using a vibrating orifice (see Patent Document 8), droplet formation by applying mechanical vibration (see Patent Document 9), and a method using a pressure vibration injection granulator (See Patent Document 10), but these methods have not yet been applied to a toner manufacturing method.

  On the other hand, recently, a toner production method using a supercritical fluid has been developed. As a toner manufacturing method using such a supercritical fluid, for example, Patent Document 11 proposes a method of granulating toner particles using a Rapid Expansion of Supercritical Solutions (RESS) method. However, this proposed method can use only a resin that is soluble in a supercritical fluid, and the selection range of the resin that can be used is small. For example, the solubility in supercritical fluids such as high-molecular weight components (gels) required in toners and inexpensive, high-performance styrene-acrylic resins and polyester resins that are commonly used in the toner field are extremely high. There is a problem that it is low and usually cannot be used as it is.

  In order to improve the above problem, for example, in Patent Document 12, Patent Document 13, and Patent Document 14, instead of dissolving a resin in a supercritical fluid, a colored resin that has been previously melt-kneaded is used in an insoluble state. It proposes a method of using and applying a shearing force to form particles. However, these methods have a disadvantage that the range of material selection is widened, but the particle size distribution is widened. In particular, in order to obtain a high-definition image required by recent toners, the particle size distribution is wide. Is a fatal drawback.

  Therefore, it has a sharp particle size distribution, good toner characteristics such as chargeability, environmental friendliness, stability over time, no waste liquid, no residual monomer, and no drying process is required. However, as for the low-cost toner production method, the toner produced by the toner production method, and the image forming method using the toner, there are currently no sufficiently satisfactory performances. is there.

  Since the toner is developed and transferred by the electrostatic charge on the surface of the toner itself, the size of the toner is greatly affected by the quality of the image. It is well known that stable negative charge can be obtained when there are many fluorine atoms.

  In order to control the transferability and cleaning properties of the toner, it is effective to reduce the adhesion of the toner to the photoconductor and intermediate transfer body. In conventional toners, it has been usual to deposit inorganic or organic fine particles on the surface of the toner and reduce the adhesion of the toner by the effect of these surface fine particles. However, these external additives held on the toner surface are constantly subjected to mechanical stress in the developing machine, the transfer unit, the cleaning unit, etc. under the use of a copying machine, a printer, etc. As a result, the adhesiveness increased with time due to burying from the inside to the inside and the removal of the external additive, resulting in a decrease in transfer efficiency and a decrease in cleaning reliability. For this reason, it is known that it is preferable to obtain a sufficiently low surface energy only with toner base particles having no external additive, and it is advantageous that there are many fluorine atoms on the surface.

  On the other hand, when there are many elements that bring about low surface energy such as fluorine element, the toner is transferred to a transfer medium, for example, paper, and after fixing, the affinity with the transfer medium such as paper is poor. There is also a problem that images are easily lost.

  In view of these, there has been proposed a toner having a configuration in which a large amount of fluorine element exists only on the outermost surface, and the toner has almost no fluorine element inside.

  In Patent Document 15, the ratio of fluorine atoms and carbon atoms (F / C) and / or the ratio of silicon atoms to carbon atoms (Si / C) in the resin component at a depth of less than 1 μm from the toner surface is 0. The ratio of fluorine atoms to carbon atoms (F / C) and / or the ratio of silicon atoms to carbon atoms in the resin component at a depth of 1 to 1 μm or more from the toner surface (Si / A toner is proposed in which C) is 0.01 or less.

  However, in Patent Document 15, copolymer resin fine particles having about 1% perfluoroacrylate or pentamethyldisiloxanyl methacrylate are arranged on the toner surface, and more fluorine element or silicon element is arranged on the surface. However, this method has a low copolymerization ratio of the fluorine-containing and silicon-containing acrylic monomer of the copolymer resin fine particles to be arranged on the surface, and has resulted in sufficiently arranging low surface energy elements on the surface. In addition, the upper limit of the ratio of fluorine atoms to carbon atoms (F / C) was 0.19.

  Further, in a toner containing at least a colorant and a resin, at least a fluorine compound is present on the surface, and the atomic ratio (F / C) of fluorine atoms to carbon atoms on the toner particle surface is 0.010 to 0.054. An electrostatic charge image developing toner is proposed (see Patent Document 16). This patent is intended to stabilize the charging, but is different from the present invention in the ratio (F / C) ratio of fluorine atoms to carbon atoms, and can be said to be a technology in a different technical field.

Japanese Patent No. 3141784 JP-A-7-152202 Japanese Patent No. 3063269 JP-A-8-21655 JP 2003-262976 A JP 2003-280236 A Japanese Patent Laid-Open No. 2003-262977 Japanese Patent No. 3344003 WO03 / 000741 pamphlet JP 2006-77252 A JP 2001-312098 A JP 2004-161824 A JP 2004-144778 A JP-A-2005-107405 JP 2005-274615 A JP 2005-115213 A Journal of the Imaging Society of Japan, Vol.43, No.1, 33-39 (2004) Journal of the Imaging Society of Japan, Vol. 43, No. 1, 40-47 (2004) Journal of the Imaging Society of Japan Vol.43 No.1, 48-53 (2004) Journal of the Imaging Society of Japan, Vol. 43, No. 1, 54-59 (2004)

  This invention is made | formed in view of this present condition, and makes it a subject to solve the said various problems in the past and to achieve the following objectives. That is, according to the present invention, by placing a significantly high concentration of fluorine atoms only on the extreme outermost surface of the toner particles, the transferability and cleaning properties are good and a clear high-quality image can be formed. In addition to electrostatic charge image developing toner that can stably form a high-quality and high-quality color image regardless of the environment or time, without lowering the charge even under high temperature and high humidity, a manufacturing method, and a manufacturing apparatus Another object of the present invention is to provide a developer using the toner, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus.

  In addition, the present invention has a low fixing temperature range, a wide fixing temperature range excellent in hot offset property, and good adhesion to the transfer paper, so that the toner does not detach from the transfer paper due to rubbing after fixing. It is an object of the present invention to provide a toner for developing a charge image, a manufacturing method and a manufacturing apparatus, and a developer, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus using the toner.

  In addition, the present invention has a low environmental impact during production, can produce toner efficiently, and is a particle having a monodispersibility with an unprecedented particle size. Electrostatic charge images in electrophotography, electrostatic recording, electrostatic printing, etc., with no or very little variation in the properties required for toners due to particles seen in previous production methods For developing electrostatic image used as developer for developing toner, manufacturing method and manufacturing apparatus, developer using the toner, container containing toner, process cartridge, image forming method, and image forming apparatus The purpose is to provide.

  As a result of intensive studies by the present inventors in order to solve the above problems, in a system in which a specific compound having a fluorine atom exists, the interface between air and a toner material in a fluid state, or supercritical carbon dioxide and fluid It has been found that the specific compound having fluorine atoms is oriented at the interface of the toner material in a state, and a very thin layer having a high concentration of fluorine atoms can be formed on the toner surface.

  As a specific first method, in a step of dissolving and adding a specific compound having a fluorine atom having an excellent negative charge control effect, and drying and solidifying the discharged droplet from the formation of the droplet in a fluid state Utilizing the property of orientation, the target charge control is hardly affected by the fixing inhibition effect derived from fluorine atoms by selectively moving and fixing fluorine atoms with excellent negative charge control effect on the toner surface. It was found that only sex can be acquired.

  As a specific second method, a specific compound having a fluorine atom excellent in negative charge control effect is dissolved and added in supercritical or subcritical carbon dioxide, and then added in supercritical or subcritical carbon dioxide. Utilizes the property that a specific compound having a fluorine atom is oriented on the toner surface at least in the process of polymerizing the polymerizable monomer, and selectively moves the fluorine atom excellent in negative charge control effect to the toner surface for fixation. As a result, it has been found that only the target charge controllability can be obtained without substantially receiving the fixability-inhibiting effect derived from fluorine atoms.

The present invention is based on the above findings by the present inventors, and means for solving the above problems are as follows. That is,
<1> In an electrostatic charge image developing toner containing at least a binder resin and a colorant, when a toner particle cross section is divided by 20 nm square, fluorine in a section including the surface and a section adjacent to the section including the surface The average value of the ratio of atoms to carbon atoms (F / C) is 0.8 or more and less than 1.2, and the ratio of fluorine atoms to carbon atoms in any 20 nm square section separated by 500 nm or more from the surface ( F / C) is an electrostatic charge image developing toner having an average value of 0.02 or less.
<2> Ratio of fluorine atom and carbon atom that is 0.8 times or more the average value of the ratio of fluorine atom and carbon atom (F / C) in the section including the surface and the section adjacent to the section including the surface The toner for developing an electrostatic charge image according to <1>, wherein the layer representing (F / C) has a thickness of 20 nm or more and less than 400 nm.
<3> From the above <1> obtained by discharging a toner composition liquid containing a surfactant having a fluorine atom from a discharge hole, converting the toner composition liquid into droplets, and turning the droplets into solid particles in the granulation space. <2> The electrostatic image developing toner according to any one of <2>.
<4> The surfactant having a fluorine atom is the electrostatic image developing toner according to <3>, which contains a structure represented by the following general formula (1).
(Wherein R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 substituted or unsubstituted alkylene group, and Rf represents a C1-C20 perfluoroalkyl group.)
<5> The electrostatic image developing toner according to any one of <3> to <4>, wherein the surfactant having a fluorine atom is a block copolymer containing a structure represented by the general formula (1) It is.
<6> The surfactant having a fluorine atom is the electrostatic image developing toner according to <3>, which has a structure represented by the following general formula (2).
(Chemical formula 2)
Rf-X General formula (2)
Wherein X represents —COOM, SO ₃ M, —O—C ₆ H ₄ —SO ₃ M, —N (R ₁ ) ₃ , or —SO ₂ —N—Y ₂ , wherein R ₁ is Represents a hydrogen atom or a methyl group, M represents an alkali metal such as Na, K, or Li and an ammonium salt such as NH ₄ ; Y represents a hydrogen atom or a terminal hydroxyl group, a carboxy group or a salt thereof, amino An alkyl group which may have a group or a salt thereof, and Rf represents a C5-C8 perfluoroalkyl group, wherein R ₁ and Y may be the same group or different groups.
<7> The electrostatic charge image according to any one of <3> to <6>, wherein the content of the surfactant having a fluorine atom is 0.03 to 1 part by weight with respect to 100 parts by weight of the toner composition. Development toner.
<8> For electrostatic image development according to any one of <1> to <2>, obtained by polymerizing and granulating at least a polymerizable monomer in a supercritical fluid or a subcritical fluid. Toner.
<9> At least one of the supercritical fluid and the subcritical fluid contains a surfactant having a fluorine atom, and the polymer of the polymerizable monomer is at least one of the supercritical fluid and the subcritical fluid. The toner for developing an electrostatic charge image according to <8>, which is insoluble in water.
<10> The electrostatic image developing toner according to <9>, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.
<11> The electrostatic image developing toner according to any one of <9> to <10>, wherein the surfactant having a fluorine atom is a compound having a structural unit represented by the following general formula (1): is there.
In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.
<12> The electrostatic image developing toner according to <11>, wherein the composition ratio of the structural unit represented by the general formula (1) in the surfactant having a fluorine atom is 50 to 100 mol%. is there.
<13> The electrostatic charge image according to any one of <9> to <10>, wherein the surfactant having a fluorine atom is a compound obtained by reacting a compound represented by the following general formula (3): Development toner.
In the general formula (3), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.
<14> The electrostatic image developing toner according to <13>, wherein the reaction is performed in supercritical carbon dioxide.
<15> The electrostatic image developing toner according to any one of <13> to <14>, wherein the reaction is one of bulk polymerization and living radical polymerization.
<16> The electrostatic image developing toner according to any one of <9> to <15>, wherein the surfactant having a fluorine atom has a weight average molecular weight of 5,000 to 500,000.
<17> The electrostatic charge according to any one of <9> to <16>, wherein the content of the surfactant having a fluorine atom is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer. This is an image developing toner.
<18> The electrostatic image developing toner according to any one of <9> to <17>, wherein the polymerizable monomer is polymerized under a pressure of 8 to 100 MPa.
<19> The electrostatic image developing toner according to any one of <9> to <18>, wherein the polymerizable monomer is polymerized under heating at 30 to 150 ° C.
<20> The electrostatic image developing toner according to any one of <9> to <19>, wherein a release agent is contained in at least one of the supercritical fluid and the subcritical fluid.
<21> The weight average particle diameter is 1 to 10 μm, and the ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) is 1.00 to 1.15 < The toner for developing an electrostatic charge image according to any one of <9> to <20>.
<22> A production method for producing the electrostatic image developing toner according to any one of <1> to <8>, comprising at least a binder resin and a colorant, A discharge step of discharging a toner composition liquid containing a fluorine atom-containing surfactant from a discharge hole of the nozzle plate, a droplet forming step of converting the toner composition liquid into droplets; A method for producing a toner for developing an electrostatic charge image, comprising: a particle forming step of forming solid particles in a granulation space.
<23> In the discharging step, the toner composition liquid is continuously discharged from the discharge holes of the nozzle plate by applying pressure to the toner composition liquid in which the toner composition containing at least the binder resin and the colorant is liquefied. Then, a columnar state is formed, and in the droplet forming step, the toner composition liquid is formed into droplets by applying vibration to the toner composition liquid. Is the method.
<24> The nozzle plate according to any one of <22> to <23>, wherein the nozzle plate is formed of a metal plate having a thickness of 5 to 50 μm, and an opening diameter of a discharge hole on the nozzle plate is 3 to 35 μm. This is a method for producing a toner for developing an electrostatic image.
<25> The method for producing a toner for developing an electrostatic charge image according to any one of <22> to <24>, wherein a plurality of ejection holes are present on the nozzle plate.
<26> The toner composition liquid includes an organic solvent, and solidification of the toner composition liquid formed into droplets is performed by removing the organic solvent, and any one of the items <22> to <25> And a method for producing a toner for developing an electrostatic image.
<27> An air flow is generated by flowing a dry gas in the same direction as the droplet discharge direction, and the air flow causes the droplets to be transported in a solvent removal facility, and the solvent in the droplets is removed during the transport. The method for producing a toner for developing an electrostatic charge image according to <26>, wherein the toner particles are formed by forming the toner particles.
<28> The method for producing a toner for developing an electrostatic charge image according to <27>, wherein the dry gas is either air or nitrogen gas.
<29> The method for producing a toner for developing an electrostatic charge image according to any one of <27> to <28>, wherein the temperature of the dry gas is 40 to 200 ° C.
<30> The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged in a polarity opposite to the charge of the droplet, and the droplet is allowed to pass through the transport path <22 > To <29>. The method for producing a toner for developing an electrostatic image according to any one of <29>.
<31> The electrostatic charge image according to any one of <22> to <30>, wherein the toner particles have a volume average particle diameter / number average particle diameter (Dv / Dn) in a range of 1.00 to 1.15. This is a method for producing a developing toner.
<32> The method for producing a toner for developing an electrostatic charge image according to any one of <22> to <31>, wherein the volume average particle diameter is 1 to 10 μm.
<33> A method for producing the electrostatic image developing toner according to any one of <1> to <2> and <8> to <21>, comprising at least a binder resin and a colorant And a method for producing a toner for developing an electrostatic image in which a fluorine-containing layer is formed on a toner particle surface, wherein at least a polymerizable monomer is polymerized in a supercritical fluid or a subcritical fluid. A method for producing a toner for developing an electrostatic charge image, characterized in that the toner is granulated.
<34> At least one of the supercritical fluid and the subcritical fluid contains a surfactant having a fluorine atom, and the polymer of the polymerizable monomer is at least one of the supercritical fluid and the subcritical fluid. The method for producing a toner for developing an electrostatic charge image according to <33>, which is insoluble in.
<35> The method for producing a toner for developing an electrostatic charge image according to <34>, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.
<36> The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <35>, wherein the surfactant having a fluorine atom has a weight average molecular weight of 5,000 to 500,000.
<37> The electrostatic charge according to any one of <34> to <36>, wherein the content of the surfactant having a fluorine atom is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer. This is a method for producing an image developing toner.
<38> The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <37>, wherein the polymerizable monomer is polymerized under a pressure of 8 to 100 MPa.
<39> The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <38>, wherein the polymerizable monomer is polymerized under heating at 30 to 150 ° C.
<40> The method for producing a toner for developing an electrostatic charge image according to any one of <34> to <39>, wherein a release agent is contained in at least one of the supercritical fluid and the subcritical fluid.
<41> A production apparatus for producing the electrostatic image developing toner according to any one of <1> to <7>, wherein the toner composition containing at least a binder resin and a colorant is liquefied. The toner composition liquid is ejected from a nozzle plate oscillated at a constant frequency, and droplets are formed by removing droplet forming means for forming droplets and the solvent contained in the droplets, An apparatus for producing toner for developing an electrostatic image, comprising toner particle forming means for forming toner particles.
<42> The apparatus for producing an electrostatic charge image developing toner according to <41>, wherein the droplet forming unit includes a vibrating unit that directly vibrates the nozzle plate.
<43> The apparatus for producing an electrostatic charge image developing toner according to <42>, wherein the vibration unit vibrates the nozzle plate at the same time as the toner composition liquid containing the toner composition is passed.
<44> Any one of <41> to <43>, further comprising: a storage unit that stores a toner composition liquid in which the toner composition is in a liquid state, and that supplies the toner composition liquid in a liquid state to the droplet forming unit An electrostatic charge image developing toner manufacturing apparatus according to claim 1.
<45> From the above <41> to <44>, wherein the nozzle plate is vibrated at a constant frequency by expansion and contraction of the piezoelectric body, and the number of ejection holes on the nozzle plate vibrated by one piezoelectric body is 1 to 5000. 4. An apparatus for producing a toner for developing an electrostatic image according to any one of the above.
<46> The apparatus for producing an electrostatic charge image developing toner according to any one of <41> to <45>, wherein the constant frequency is 50 kHz to 50 MHz.
<47> The apparatus for producing an electrostatic charge image developing toner according to any one of <41> to <46>, wherein the constant frequency is 100 kHz to 10 MHz.
<48> A production apparatus for producing the electrostatic image developing toner according to any one of <1> to <7>, wherein the toner composition containing at least a binder resin and a colorant is liquefied. A storage unit that stores the toner composition liquid, a droplet forming unit that discharges the toner composition liquid supplied from the storage unit vibrated at a constant frequency from the discharge hole, and forms a droplet; And a toner particle forming unit that forms toner particles by drying the droplets by removing the solvent contained in the toner.
<49> The apparatus for producing an electrostatic charge image developing toner according to <48>, wherein the droplet forming unit includes a vibrating unit that directly vibrates the storage unit.
<50> The electrostatic charge according to any one of <41> to <49>, wherein the electrostatic charge has a plurality of nozzle plates, and the droplets discharged from the discharge holes on each nozzle plate are dried by one solvent removal facility. An image developing toner manufacturing apparatus.
<51> The toner particles formed by allowing the droplets to pass through the conveyance path are temporarily neutralized by a static eliminator, and then the toner particles are accommodated in the toner collecting unit <41>. To <50>, the electrostatic image developing toner manufacturing apparatus.
<52> The apparatus for producing an electrostatic charge image developing toner according to <51>, wherein the charge removal by the charge eliminator is performed by soft X-ray irradiation.
<53> The apparatus for producing an electrostatic charge image developing toner according to <51>, wherein the charge removal by the charge eliminator is performed by plasma irradiation.
<54> The toner collecting portion for collecting the toner particles has a tapered surface whose opening diameter is gradually reduced, and the toner particles are dried from the outlet portion where the opening diameter is reduced from the inlet portion by using dry gas. The apparatus for producing an electrostatic charge image developing toner according to any one of <41> to <53>, wherein the dry gas flow is formed and the toner particles are transferred to the toner storage container by the dry gas flow. is there.
<55> The apparatus for producing an electrostatic charge image developing toner according to <54>, wherein the flow of the dry gas is a vortex.
<56> The toner for developing an electrostatic charge image according to any one of <41> to <55>, wherein the toner collecting portion and the toner storage container are formed of a conductive material, and are grounded. It is a manufacturing device.
<57> The apparatus for producing an electrostatic charge image developing toner according to any one of <41> to <56>, which is an exposure prevention specification.
<58> A developer comprising the electrostatic image developing toner according to any one of <1> to <21>.
<59> A toner-containing container, wherein the electrostatic image developing toner according to any one of <1> to <21> is contained in a container.
<60> An electrostatic latent image carrier, and the electrostatic latent image can be developed on the electrostatic latent image carrier with the electrostatic image developing toner according to any one of <1> to <21>. A process cartridge having at least developing means for forming a visual image and detachable from an image forming apparatus main body.
<61> An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image development according to any one of <1> to <21> A developing process for forming a visible image by developing with the toner for use, a transferring process for transferring the visible image to a recording medium, and a roller-shaped or belt-shaped fixing member for transferring the transferred image to the recording medium And an image forming method characterized in that it includes at least a fixing step of fixing by heating and pressurizing using.
<62> An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image of <1> to <21> Developing means for developing a visible image by developing using any one of the electrostatic charge image developing toners, a transfer means for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium The image forming apparatus includes at least a fixing unit that heats and presses the toner using a roller-shaped or belt-shaped fixing member.

  According to the present invention, by arranging a remarkably high concentration of fluorine atoms only on the outermost surface of the toner particles as compared with the conventional case, various problems in the past can be solved, transferability and cleaning properties are good, and a clear high A toner for developing electrostatic images that not only enables the formation of high-quality images, but also has a stable charge even under high temperature and high humidity, and can stably form high-quality and high-quality color images regardless of the environment or time. , A manufacturing method, a manufacturing apparatus, a developer using the toner, a container containing toner, a process cartridge, an image forming method, and an image forming apparatus.

  In addition, according to the present invention, the fixing temperature range having a low temperature fixing property and excellent hot offset property is wide, the adhesiveness to the transfer paper is good, and the toner is not detached from the transfer paper by rubbing after fixing. An electrostatic charge image developing toner, a manufacturing method, and a manufacturing apparatus, and a developer, a toner-containing container, a process cartridge, an image forming method, and an image forming apparatus using the toner can be provided.

  In addition, according to the present invention, conventional problems can be solved, the environmental load during production can be reduced, toner can be produced efficiently, and monodispersibility with an unprecedented particle size can be achieved. As a result of these particles, there are no or very few fluctuations due to particles seen in conventional production methods in many of the characteristic values required for toners such as even better charging characteristics. Electrostatic image developing toner used as a developer for developing an electrostatic image in electrostatic recording, electrostatic printing, and the like, a production method and a production apparatus, and a developer and toner containing the toner A container, a process cartridge, an image forming method, and an image forming apparatus can be provided.

  Specifically, there are no fluctuations due to particle variations seen in the conventional production methods for pulverized toners and chemical toners, or even extremely small fluctuations that can be almost ignored. Has characteristics. The realization of these characteristics can be said to be a characteristic that can be obtained only by the present invention. However, the realization of this characteristic makes it possible to form an image almost faithful to the latent image formed on the photosensitive member. In addition, the same feature makes it possible to maintain the effect over a long period of time. In other words, by achieving uniformity in particle size distribution, uniformity in shape, and uniformity in surface condition, the mechanical stress required to reach the toner charge amount set in the electrophotographic process is extremely small and wasteful. This is presumably due to a dramatic increase in toner life. This makes it possible to obtain an image with excellent image quality over a long period of time.

  In particular, by using a surfactant having a fluorine atom, which is the essence of the present invention, it can be selectively oriented on the surface of the toner particle, and a significantly higher concentration of fluorine only on the extreme outermost surface of the toner particle as compared with the prior art. It becomes possible to arrange atoms. Not only does it have excellent charging characteristics, and it can form clear, high-quality images, but it does not decrease charging even under high temperature and high humidity, and it can stably produce high-quality and high-quality colors regardless of the environment or time. It is an object of the present invention to provide an electrostatic charge image developing toner capable of forming an image.

  The electrostatic charge image developing toner of the present invention is an electrostatic charge image developing toner containing at least a binder resin and a colorant. In the electrostatic charge image developing toner, fluorine atoms having an excellent negative charge control effect are arranged and fixed only on the outermost surface layer, In this case, only the target charge controllability can be obtained without substantially receiving the fixability-inhibiting effect derived from fluorine atoms.

  Here, the distribution of fluorine atoms in the toner can be determined as follows.

  Toner particles are embedded in an epoxy resin, and a measurement sample is prepared in which the toner is ultrathinned to about 100 nm using a microtome MT6000-XL (Keiwa Corporation). Thereafter, the measurement target range was confirmed with a transmission electron microscope image (TEM image) with a transmission electron microscope JEM-2010 (manufactured by JEOL Ltd.) equipped with an EDS (energy dispersive X-ray analyzer). Element distribution measurement was performed with the line acceleration voltage set to 200 kV. Under such conditions, the ratio of fluorine to carbon for every 20 nm square of the toner cross section can be obtained.

  In addition, after obtaining a measurement sample having an ultrathin section as described above, a transmission electron microscope JEM-2100F (manufactured by JEOL Ltd.) attached with an electron energy loss spectrometer (manufactured by Gatan) By measuring the electron energy loss spectrum, the ionization breaks obtained from theoretical calculations using the Gatan analysis program from the edge jump strengths of the carbon K absorption edge (284 eV) and the fluorine K absorption edge (685 eV). It can correct | amend using an area and can calculate the ratio (F / C) of a fluorine atom and a carbon atom.

  The abundance ratio of fluorine atoms on the outermost layer of the toner is determined by dividing the toner particle cross section by 20 nm square by the procedure as described above, and the fluorine atoms and carbon in the section adjacent to the section including the surface of the toner It can be determined by the average value of the ratio with atoms (F / C).

  When the average value of the ratio of fluorine atoms to carbon atoms (F / C) on the outermost layer of the toner is 0.8 or more and less than 1.2, stable negative charging independent of temperature and humidity can be obtained.

  Further, the thickness of the fluorine-containing layer was determined by examining a 20 nm square section indicating 0.8 times or more of the average value of the ratio of fluorine atoms to carbon atoms (F / C) in the toner cross section in the toner cross section, The total area of the sections can be obtained by dividing by the toner circumference measured on the toner cross section.

  In the method of measuring the electron energy loss spectrum, element mapping is performed using the fluorine K absorption edge (685 eV) and the carbon K absorption edge (284 eV) to obtain a carbon element map image and a fluorine element map image of the toner. Furthermore, from the intensity map of the contrast of the image converted into the element ratio by correction, an area showing 0.8 times or more of the average value of the ratio of fluorine atoms to carbon atoms (F / C) on the toner outermost layer is mapped. The thickness of the fluorine-containing layer can also be obtained by calculating the area and dividing by the toner circumference.

  A fluorine-containing layer, that is, a fluorine atom and a carbon atom that are 0.8 times or more the average value of the ratio (F / C) of fluorine atoms and carbon atoms in a section including the surface and a section adjacent to the section including the surface; When the thickness of the layer showing the ratio (F / C) is 20 nm or more and less than 400 nm, both stable negative charging and fixed image strength can be achieved.

  Here, if the thickness of the fluorine-containing layer is thinner than 20 nm, stable negative charging not depending on the target temperature and humidity cannot be obtained, and if it is thicker than 400 nm, the affinity with a transfer medium such as paper is poor, and mechanical There is a possibility that a toner image may be easily lost due to rubbing.

  The abundance ratio of fluorine in the toner can be expressed by an average value of the ratio of fluorine atoms to carbon atoms (F / C) in an arbitrary 20 nm square section separated by 500 nm or more from the surface, and is 0.02 or less. As a result, sufficient fixing strength can be obtained.

  Here, if it is 0.02 or more, the affinity with a transfer medium such as paper is poor, and there is a possibility that a toner image is easily lost due to mechanical rubbing.

  As a method for producing the toner for developing an electrostatic charge image, a toner composition liquid containing a fluorine atom-containing surfactant is discharged from a discharge hole of a nozzle plate, the toner composition liquid is formed into droplets, and the droplets are solid in a granulation space. There are a first method of forming particles and a second method of polymerizing at least a polymerizable monomer in a supercritical fluid or a subcritical fluid, and granulating.

  Hereinafter, details of the toner for developing an electrostatic charge image of the present invention will be clarified through the description of the method for producing the toner for developing an electrostatic charge image of the present invention.

  The first method is obtained by discharging a toner composition liquid containing a surfactant having a fluorine atom from a discharge hole, forming a droplet of the toner composition liquid, and turning the liquid droplet into a solid particle in the granulation space. In the process of drying in the gas phase, the amount of fluorine element on the toner surface is arranged to be extremely large by causing the compound having fluorine atoms to ooze out on the particle surface.

  That is, a specific compound having a fluorine atom having an excellent negative charge control effect is dissolved and added, and the property of orienting in the gas phase in the process of drying and solidifying the ejected droplets is selectively used on the toner surface. It is moved and fixed. As a result, only the target charge controllability can be obtained without substantially receiving the fixing property inhibiting effect derived from fluorine atoms.

  Hereinafter, the first method will be described.

(Toner production method)
In the first method, a solution or dispersion of a toner material containing at least a resin and a colorant is discharged from a nozzle plate oscillated at a constant frequency to form droplets, and the droplets are dried. It is characterized by making it.

-Droplet phenomenon-
The phenomenon of uniform droplet formation in a liquid column is described in Rayleigh, Lord “On the Instability of Jets” Proc. London Math. Soc. 110: 4 [1878], the wavelength condition λ at which the liquid column is most unstable is expressed by the following equation (1) using the liquid column diameter dj.
λ = 4.5dj (1)

Here, the frequency f of the disturbance phenomenon that occurs can be expressed by the following equation (2), where v is the velocity of the liquid column.
f = v / λ (2)

Schneider J. et al. M.M. , C.I. D. Hendricks, Rev. Instrum. 35 (10), 1349-50 [1964] As a result of deriving conditions for forming uniform particles stably experimentally, uniform particles are stably formed under the condition of the following formula (3). It is possible to do.
3.5 <λ / dj <7.0 (3)

Furthermore, Lindblad N. R. and J. et al. M.M. Schneider, J.A. Sci. Instrum. 42, 635 [1965], the minimum jet v _min velocity at which the liquid discharged from the discharge hole forms a liquid column based on the law of conservation of energy is expressed as the following equation (4). Is done.
v _min = (8σ / ρdj) ^1/2 (4)

  In Equation (4), σ represents the surface tension of the liquid, ρ represents the liquid density, and dj represents the diameter of the liquid column. The conditional expressions (1) to (4) are useful for estimating the conditions for reproducing such a phenomenon. However, we consider that these relational expressions are the types of liquid substances, mixtures, and dispersions. It is confirmed that the liquid column can be changed into droplets by the above disturbance by attaching the vibrator to the reservoir and vibrating the vibrator at the frequency f. Was established.

-Device-
An apparatus used in the toner manufacturing method of the present invention (hereinafter also referred to as “toner manufacturing apparatus”) is not particularly limited as long as it is an apparatus capable of manufacturing toner by the manufacturing method, and is appropriately selected. Droplet formation that can be used but forms a liquid droplet by discharging a liquid toner composition liquid containing at least a resin and a colorant from a nozzle plate that is vibrated at a constant frequency. It is preferable to use a toner manufacturing apparatus that includes a means and a toner particle forming unit that forms toner particles by drying the droplets by removing the solvent contained in the droplets. In the toner manufacturing apparatus, the droplet forming unit includes a vibration generating unit that directly vibrates the nozzle plate, and the vibration generating unit vibrates the nozzle plate simultaneously with the passage of the liquid toner composition liquid. preferable. It is more preferable to have a storage unit that stores a toner composition liquid in which the toner composition is in a liquid state and supplies the toner composition liquid in a liquid state to the droplet forming unit.

  For example, as shown in FIG. 1 and FIG. 2, a reservoir 1 containing a raw material solution containing a surfactant having fluorine atoms is connected to a liquid supply pipe 8 that supplies a liquid to the reservoir 1, and a discharge hole 4. A structure provided with a housing 9 for holding a plate having the above is desirable. A vibrating means 2 that vibrates the entire storage unit 1 is in contact with the storage unit 1. The vibrating means 2 is connected to the waveform generator 10 via the lead wire 11 and is preferably controlled. In addition, it is preferable for production to provide a drain 12 for draining the liquid in the reservoir 1 in order to create different varieties.

  Since the storage unit 1 needs to be held at least in a state where the toner composition liquid is pressurized, the storage unit 1 is made of a member such as a metal such as SUS or aluminum, and preferably has a pressure resistance of about 10 MPa. This is not a limitation.

Moreover, it is preferable that the vibration means 2 excites the whole storage part 1 which has the discharge hole 4 by one vibration means. The vibration means 2 for applying vibration to the storage unit 1 is not particularly limited as long as it can provide reliable vibration at a constant frequency, and can be appropriately selected and used. The piezoelectric body has a function of converting electrical energy into mechanical energy. Specifically, it is expanded and contracted by applying a voltage, and the discharge hole 4 can be vibrated by the expansion and contraction. Examples of the piezoelectric body include piezoelectric ceramics such as lead zirconate titanate (PZT). Generally, since the amount of displacement is small, the piezoelectric body is often used by being laminated. In addition, piezoelectric polymers such as polyvinylidene fluoride (PVDF), single crystals such as quartz, LiNbO ₃ , LiTaO ₃ , KNbO ₃ , and the like can be given.

  The constant frequency is not particularly limited and may be appropriately selected depending on the purpose. However, 100 kHz to 10 MHz is preferable, and 200 kHz to 2 MHz is more preferable from the viewpoint of generating micro droplets having a very uniform particle diameter. preferable.

  The vibration means 2 is in contact with the storage portion 1, and the storage portion 1 holds a plate having the discharge holes 4. The vibration means 2 and the plate having the discharge holes 4 are liquid columns generated from the discharge holes 4. It is most preferable to arrange them in parallel from the viewpoint of uniformly imparting vibrations to each other, and even if deformation occurs in the process of vibrations, it is desirable that the relationship be maintained within an inclination of 10 °.

  Although it is possible to produce particles even if only one discharge hole 4 is provided, a plurality of droplets discharged from each discharge hole are provided from the viewpoint of efficiently generating minute droplets having a very uniform particle diameter. Is preferably dried by one solvent removal equipment, in the illustrated example, by the solvent removal equipment 5.

  The support means 3 for fixing and supporting a part of the vibration means 2 is provided for fixing the storage unit 1 and the vibration means 2 to the apparatus, and the material is not particularly limited, but is a rigid body such as metal. I just need it. If necessary, a rubber material, a resin material, or the like as a vibration reducing material may be provided in part so as not to cause disturbance of vibration of the reservoir 1 due to excessive resonance.

  The discharge holes 4 are discharge holes for discharging the toner composition liquid as a liquid column. The material and shape of the nozzle plate having the discharge holes 4 are not particularly limited and may be appropriately selected. For example, the nozzle plate having the discharge holes 4 is formed of a metal plate having a thickness of 5 to 50 μm. In addition, when the opening diameter of the discharge hole 4 is 1 to 40 μm, particles that are very uniform at a vibration frequency of 100 kHz or more without blocking the fine particle dispersion of 1 μm or less contained in the toner composition liquid are obtained. It is preferable from the viewpoint of achieving both generation of fine droplets having a diameter. This is because the frequency region in which droplets can be stably obtained due to the droplet formation phenomenon decreases substantially as the diameter of the opening diameter of the discharge hole 4 increases. The above vibration frequency is assumed. The opening diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

  The liquid supply means 5 for supplying the liquid to the reservoir is preferably a metering pump such as a tube pump, a gear pump, a rotary pump, or a syringe pump. Moreover, the pump of the type pressurized and sent with compressed air etc. may be used. With these liquid supply means 5, the reservoir is filled with the toner composition liquid, and the pressure can be increased to a pressure at which droplets can be formed. The liquid pressure can be measured with a pressure gauge attached to the pump or a dedicated pressure sensor.

  The solvent removal equipment 6 is not particularly limited as long as the solvent of the droplets 13 can be removed, but an air flow is generated by flowing the dry gas 14 in the same direction as the discharge direction of the droplets 13, and the liquid is The toner particles 15 are preferably formed by transporting the droplets 13 in the solvent removal equipment 6 and removing the solvent in the droplets 13 during the transportation. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure. The dry gas is not particularly limited as long as it is a gas that can dry the droplets 13, and examples thereof include air and nitrogen gas.

  The toner collecting unit 7 is a member provided at the bottom of the toner particle manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner. The structure of the toner collecting portion 7 is not particularly limited as long as the toner can be collected and can be appropriately selected. From the above viewpoint, however, the toner collecting portion 7 has a tapered surface whose opening diameter is gradually reduced as in the illustrated example. Thus, the toner particles 15 are formed using the dry gas 14 from the outlet portion whose opening diameter is smaller than that of the inlet portion, and a flow of the dry gas 14 is formed. It is preferable to transport it.

  As a transfer method, as shown in the illustrated example, the toner particles 15 may be pumped to the toner storage container by the dry gas 14, or the toner particles 15 may be sucked from the toner storage container side.

  Although there is no restriction | limiting in particular as a flow of the dry gas 14, From a viewpoint which can generate | occur | produce a centrifugal force and can remove a fine powder, it is preferable that it is a vortex | eddy_current.

  Furthermore, from the viewpoint of more efficiently transporting the toner particles 15, it is more preferable that the toner collecting unit 7 and the toner storage container are formed of a conductive material and are connected to the ground. . Further, the toner manufacturing apparatus preferably has an exposure specification.

  Further, for example, as shown in FIG. 3, at least a slurry dispersion storage container 35 as the storage means, a nozzle plate 21 as the droplet forming means provided in the drying container 30, and an electrode 22 And a device having a solvent removal equipment 23, a static eliminator 24, and a toner collecting unit 25 as the toner particle forming means.

  In the toner manufacturing apparatus shown in FIG. 3, the dissolved or dispersed liquid stored in the slurry dispersion storage container 35 is appropriately adjusted by the liquid supply means 34 through the liquid supply pipe 29 to adjust the liquid supply flow. The toner particles 26 are ejected as droplets 31 from the ejection holes formed in the nozzle plate 21 through the passage 37, and the droplets 31 are charged by the electrodes 22, and then the solvent is removed by the solvent removal equipment 23 to form toner particles 26. The toner particles 26 are collected by the toner collecting unit 25 by the vortex 27 after being discharged by the charge eliminator 24 and conveyed to the toner storage container 32.

  Hereinafter, the toner production apparatus shown in FIG. 3 will be described in detail for each member.

--Nozzle plate and piezoelectric body--
As described above, the nozzle plate 21 shown in FIG. 3 is a member that discharges a toner composition liquid that is a liquid toner composition to form droplets.

  The material and shape of the nozzle plate 21 are not particularly limited and may be appropriately selected. For example, the nozzle plate 21 is formed of a metal plate having a thickness of 5 to 50 μm and has a discharge hole. When the solution has a diameter of 3 to 35 μm, when the solution is ejected from the nozzle plate 21, a vibration is applied to the reservoir 1 itself, so that a shearing force is applied and micro droplets having an extremely uniform particle size are formed. It is preferable from the viewpoint of generating. The opening diameter means a diameter if it is a perfect circle, and a minor diameter if it is an ellipse.

  The constant frequency is not particularly limited and may be appropriately selected according to the purpose. However, 50 kHz to 50 MHz is preferable, and 100 kHz to 10 MHz is preferable from the viewpoint of generating minute droplets having a very uniform particle diameter. More preferred is 100 kHz to 450 kHz.

  The nozzle plate 21 may be provided with only one ejection hole, but from the viewpoint of generating minute liquid droplets having a very uniform particle diameter, a plurality of liquid droplets 31 are ejected from each ejection hole. It is preferable to dry with one solvent removal equipment, in the illustrated example, with the solvent removal equipment 23.

  Referring to FIG. 4 further, the toner composition liquid supplied via the liquid supply flow path 37 provided with the nozzle plate 21 and the O-ring 39 is separated into droplets 31 and discharged into the drying facility by dispersed air. .

  The number of ejection holes formed in the nozzle plate 21 is not particularly limited, but is preferably 1 to 2000 in order to more surely generate micro droplets having a very uniform particle diameter, 200-1500 are preferable.

--Solvent removal equipment--
The solvent removal equipment 23 is not particularly limited as long as the solvent of the droplet 31 can be removed, but an air flow is generated by flowing a dry gas in the same direction as the discharge direction of the droplet 31, The toner particles 26 are preferably formed by transporting the droplets 31 in the solvent removal equipment 23 and removing the solvent in the droplets 31 during the transport. Here, “dry gas” means a gas having a dew point temperature of −10 ° C. or lower under atmospheric pressure.

  The dry gas is not particularly limited as long as it is a gas capable of drying the droplets 31, and examples thereof include air and nitrogen gas.

  Although there is no restriction | limiting in particular as a method of flowing the said dry gas to the solvent removal equipment 23, For example, as shown in FIG. 3, the method of flowing from the dry gas supply pipe 33 is mentioned.

  The temperature of the drying gas is preferably higher in terms of drying efficiency, and even if a drying gas having a boiling point higher than the solvent used is used due to the characteristics of spray drying, the constant rate drying region during drying is used. Thus, the droplet temperature does not rise above the boiling point of the solvent, and the resulting toner is not thermally damaged. However, since the main constituent material of the toner is a thermoplastic resin, when it is exposed to a dry gas that is higher than the boiling point of the resin to be used after drying, that is, in the rate-decreasing drying region, the toner is liable to be thermally fused. There is a risk that the monodispersibility may be impaired. Therefore, specifically, the temperature of the dry gas is preferably, for example, 40 to 200 ° C, more preferably 60 to 150 ° C, and particularly preferably 75 to 85 ° C.

  Further, as shown in FIG. 3, from the viewpoint of preventing the droplet 31 from adhering to the inner wall surface of the solvent removal equipment 23, the charge of the droplet 31 is opposite. It is preferable to provide an electric field curtain 28 charged to a polarity, to form a transport path whose periphery is covered with the electric field curtain 28, and to allow the droplet 31 to pass through the transport path.

--- Static eliminator--
The static eliminator 24 temporarily neutralizes the charge of the toner particles 26 formed by allowing the droplets 31 to pass through the conveyance path, and then accommodates the toner particles 26 in the toner collecting unit 25. It is a member for.

There is no particular limitation on the method of static elimination by the static eliminator 24, and a commonly known method can be appropriately selected and used. However, since static elimination is possible, for example, soft X-ray Preferably, the irradiation is performed by irradiation, plasma irradiation, or the like.
-Toner collection part-
The toner collecting unit 25 is a member provided at the bottom of the toner manufacturing apparatus from the viewpoint of efficiently collecting and transporting toner.

  The structure of the toner collecting portion 25 is not particularly limited as long as the toner can be collected, and can be appropriately selected. From the above viewpoint, a tapered surface whose opening diameter is gradually reduced is provided as in the illustrated example. The toner particles 26 are formed from the outlet portion whose opening diameter is smaller than that of the inlet portion, using the dry gas to form the flow of the dry gas, and the toner particles 26 are stored in the toner by the flow of the dry gas. It is preferably transferred to the container 32.

  As the transfer method, the toner particles 26 may be pumped to the toner storage container 32 by the dry gas as shown in the example, or the toner particles 26 may be sucked from the toner storage container 32 side.

  Although there is no restriction | limiting in particular as a flow of the said dry gas, From a viewpoint which can collect the toner particle 26 reliably by generating a centrifugal force, it is preferable that it is the vortex | eddy_current 27.

  Further, from the viewpoint of more efficiently transporting the toner particles 26, it is more preferable that the toner collecting portion 25 and the toner storage container 32 are formed of a conductive material and are connected to the ground. preferable. The toner manufacturing apparatus preferably has an exposure specification.

--- Droplet--
As described above, the droplet 31 is generated by discharging a solution or dispersion of a toner material containing a specific substance from the nozzle plate 21 oscillated at a constant frequency. The toner material will be described separately.

  There is no restriction | limiting in particular as a method of liquefying the said toner composition, The method used normally can be selected suitably. Specifically, a binder resin such as a styrene acrylic resin, a polyester resin, a polyol resin, or an epoxy resin may be melt-kneaded with a colorant or the like and finely pulverized, or obtained during the production. The kneaded product may be once dissolved in an organic solvent in which the resin component is soluble and then processed as fine droplets.

-Action-
According to the toner manufacturing method of the present invention described in detail above, the number of droplets 31 generated from the ejection holes formed in the nozzle plate 21 is very large, tens of thousands to several million per second. Further, it is easy to increase the number of discharge holes. In addition, it can be said to be the most suitable method for producing toner from the viewpoint of obtaining a very uniform droplet diameter and sufficient productivity. Further, in this production method, the particle diameter of the toner finally obtained can be accurately determined by the following calculation formula (1), and there is almost no change in the particle diameter depending on the material used.
〔a formula〕
Dp = (6QC / πf) ^1/3 (1)
However, Dp: solid particle diameter, Q: liquid flow rate (determined by pump flow rate and discharge hole diameter), f: vibration frequency, C: volume concentration of solid content.

The toner particle diameter can be accurately calculated only by the above formula (1), but more simply can be obtained by the following formula (2).
〔a formula〕
Solid content volume concentration (volume%) = (solid particle diameter / droplet diameter) ³ (2)

  That is, the diameter of the toner particles 26 obtained by the present invention is twice the opening diameter of the nozzle plate 21 regardless of the vibration frequency at which the droplets 31 are ejected. Therefore, the target solid particle diameter can be obtained by obtaining and adjusting the solid content concentration in advance from the relationship of the above formula (2). For example, when the diameter of the discharge hole is 7.5 μm, the droplet diameter is 15 μm. Therefore, if the solid content volume concentration is 6.40% by volume, 6.0 μm solid particles can be obtained. In this case, the vibration frequency is preferably higher from the viewpoint of productivity, but Q (liquid flow rate) is determined from the calculation formula (1) according to the vibration frequency determined here.

  In the conventional manufacturing method, the particle size often varies greatly depending on the material used. In this manufacturing method, the particle size as set is controlled by managing the droplet diameter and solid content concentration at the time of discharge. It becomes possible to continuously obtain particles having a diameter.

  Further, since the toner obtained by the present invention has a very uniform particle size, the fluidity in the toner base is very high. Therefore, even when an external additive is added for the purpose of reducing the adhesive force to a manufacturing apparatus or the like, the effect can be exhibited in an extremely small amount. Considering the deterioration of external additives due to stress and the safety of fine particles to the human body, it is preferable not to use such external additives as much as possible, which is also an advantage of the present invention.

(toner)
The toner of the present invention is a toner manufactured by the above-described toner manufacturing method of the present invention.

  As the toner, a toner having a monodispersed particle size distribution can be obtained by the toner manufacturing method.

  Specifically, the particle size distribution (weight average particle diameter / number average particle diameter) of the toner is preferably in the range of 1.00 to 1.15, and is preferably in the range of 1.00 to 1.05. Is more preferable. Moreover, as a weight average particle diameter, it is preferable that it is 1-10 micrometers.

  The toner material that can be used in the present invention can be the same as the conventional electrophotographic toner. That is, a binder resin such as a styrene acrylic resin, a polyester resin, a polyol resin, and an epoxy resin is dissolved in various organic solvents, a colorant is dispersed, and a release agent is dispersed or dissolved. The target toner particles can be produced by discharging from the discharge holes and drying and solidifying into fine droplets by the toner manufacturing method. Further, a liquid obtained by once dissolving or dispersing the kneaded material obtained by hot-melt kneading the above materials in various solvents is dried and solidified as fine droplets by the above-described toner production method, and the fluorine-based surfactant is added to the toner particles in the drying process. By moving to the surface layer, the target toner can be obtained.

-Toner material-
The toner material contains at least a resin, a colorant, and a fluorosurfactant and, if necessary, other components such as a carrier and wax.

--Resin--
Examples of the resin include at least a binder resin.

  As the binder resin, it is preferable to increase the viscoelasticity of the binder resin by acting with a reactive substance. Regarding its action, a covalent bond, an ionic bond, a hydrogen bond, etc. can be considered. Among the commonly used resins, it can be used in consideration of the reactivity as appropriate. For example, vinyl polymers such as acrylic acid and acrylic ester monomers, methacrylic acid and methacrylate monomers are used. Copolymers, copolymers of these monomers or two or more types, polyester polymers, polyol resins, phenol resins, silicone resins, polyurethane resins, polyamide resins, furan resins, epoxy resins, xylene resins, terpene resins, polymers Examples include a malon indene resin, a polycarbonate resin, and a petroleum resin.

  Styrene binder resins such as polystyrene, poly-p-chlorostyrene, polyvinyltoluene and other styrene and substituted polymers thereof; styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer Polymer, styrene-vinyl naphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methacrylic copolymer Acid methyl copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer Coalescence, styrene-vinylmethylke Styrene copolymer such as styrene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid copolymer, styrene-maleic acid ester copolymer Coalescence is mentioned. Examples of acrylic binders include polymethyl methacrylate and polybutyl methacrylate. In addition, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, and polyacrylic. Examples include acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, and paraffin wax.

  Examples of the acrylic acid and methacrylic acid ester monomers include acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, and acrylic acid. Examples include acrylic acid such as n-dodecyl, 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, or esters thereof.

  Examples of the methacrylic acid and methacrylic acid ester monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, and n methacrylate. -Dodecyl, 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, methacrylic acid such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, or esters thereof.

  The following (1)-(16) is mentioned as an example of the other monomer which forms the said vinyl polymer or a copolymer. (1) Vinyl halides such as vinyl chloride, vinyl chloride, vinyl bromide and vinyl fluoride; (2) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (3) Vinyl methyl ether and vinyl Vinyl ethers such as ethyl ether and vinyl isobutyl ether; (4) vinyl ketones such as vinyl methyl ketone, vinyl hexyl ketone and methyl isopropenyl ketone; (5) N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N -N-vinyl compounds such as vinylpyrrolidone; (6) vinylnaphthalenes; (7) acrylic acid or methacrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylamide, etc .; (8) maleic acid, citraconic acid, itaconic acid, alkenyl Succinic acid, fumaric acid, mesa Unsaturated dibasic acids such as acids; (9) unsaturated dibasic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, alkenyl succinic anhydride; (10) maleic acid monomethyl ester , Maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester, citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester (11) Unsaturated dibasic acid esters such as dimethylmaleic acid and dimethylfumaric acid; (12) α, β-unsaturated acids such as crotonic acid and cinnamic acid; ) Crotonic acid anhydride, cinnamic acid anhydride, etc. (14) anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides thereof and monoesters thereof (15) acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (16) 4- (1- Monomers having a hydroxy group such as hydroxy-1-methylbutyl) styrene and 4- (1-hydroxy-1-methylhexyl) styrene.

  Among resins that are usually used, there are resins having low reactivity, but they may be used in combination with the above-mentioned resins. For example, styrene monomers include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, p-phenyl styrene, p-ethyl styrene, 2,4-dimethyl styrene, pn-amyl 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 such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, p-nitrostyrene, or a derivative thereof.

  Examples of other monomers forming the vinyl polymer or copolymer include monoolefins such as ethylene, propylene, butylene and isobutylene; polyenes such as butadiene and isoprene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may be used in combination with a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the crosslinking agent used in this case include aromatic vinyl vinyl compounds such as divinylbenzene and divinylnaphthalene. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, and 1,6. And xanthdiol diacrylate, neopentyl glycol diacrylate, and those obtained by replacing acrylates of these compounds with methacrylate. Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, and dipropylene. Examples include glycol diacrylate and those obtained by replacing acrylate of these compounds with methacrylate.

  In addition, a diacrylate compound or a dimethacrylate compound linked by a chain containing an aromatic group and an ether bond is also included. Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku Co., Ltd.).

  These cross-linking agents are preferably used in an amount of 0.01 to 10 parts by weight, and 0.03 to 5 parts by weight, based on 100 parts by weight of the other monomers forming the vinyl polymer or copolymer. It is more preferable. Of these crosslinkable monomers, they are bonded to the toner resin by a bond chain containing one aromatic divinyl compound (particularly divinylbenzene), one aromatic group, and one ether bond from the viewpoint of fixability and offset resistance. Preferred are diacrylate compounds. Among these, a combination of monomers that becomes a styrene-acrylic copolymer is preferable.

  Examples of the polymerization initiator used in the production of the vinyl polymer or copolymer of the present invention include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile), dimethyl-2,2′-azobisisobutyrate, 1 , 1′-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) -isobutyronitrile, 2,2′-azobis (2,4,4-trimethylpentane), 2-phenylazo-2 ′ , 4'-dimethyl-4'-methoxyvaleronitrile, 2,2'-azobis (2-methylpropane), methyl ethyl ketone peroxide, acetylacetone peroxide, cyclohexanone Ketone peroxides such as oxide, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di -Tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α- (tert-butylperoxy) isopropylbenzene, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, benzoyl peroxide, m-tolyl peroxide, di-isopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate Di-n-propyl peroxydicarbonate, di-2-ethoxyethyl peroxycarbonate, di-ethoxyisopropyl peroxydicarbonate, di (3-methyl-3-methoxybutyl) peroxycarbonate, acetylcyclohexyl Sulfonyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxyisobutyrate, tert-butyl peroxy-2-ethylhexarate, tert-butyl peroxylaurate, tert-butyl-oxybenzoate, tert- Butyl peroxyisopropyl carbonate, di-tert-butyl peroxyisophthalate, tert-butyl peroxyallyl carbonate, isoamyl peroxy-2-ethylhexanoate, di-tert-butyl Kisa Hydro terephthalate to Rupaokishi, tert- butylperoxy azelate, and the like.

  When the binder resin is a styrene-acrylic copolymer, the molecular weight distribution by GPC soluble in the resin component tetrahydrofuran (THF) is at least 1 in the region of molecular weight 3,000 to 50,000 (in terms of number average molecular weight). A resin in which one peak exists and at least one peak exists in a region having a molecular weight of 100,000 or more is preferable in terms of fixing property, offset property, and storage property. Further, as the THF soluble component, a binder resin in which a component having a molecular weight distribution of 100,000 or less is 50 to 90% is preferable, and a binder resin having a main peak in a region having a molecular weight of 5,000 to 30,000. Is more preferable, and a binder resin having a main peak in the region of 5,000 to 20,000 is most preferable.

  In addition, the polyester resin can further reduce the melt viscosity while ensuring the stability during storage of the toner, as compared with the styrene or acrylic resin. Such a polyester resin can be obtained, for example, by a polycondensation reaction between an alcohol and a carboxylic acid. Examples of the alcohol include diols such as polyethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,4-propylene glycol, neopentyl glycol, 1,4-butenediol, , 4-Bis (hydroxymethyl) cyclohexane, bisphenol A, hydrogenated bisphenol A, polyoxyethylenated bisphenol A, polyoxypropylenated bisphenol A and other etherified bisphenols, which are saturated or unsaturated having 3 to 22 carbon atoms Divalent alcohol units substituted with the above hydrocarbon groups, other divalent alcohol units, sorbitol, 1,2,3,6-hexanetetrol, 1,4-sorbitan, pentaerythritol dipentaes Re , Tripentaerythritol, sucrose, 1,2,4-butanetriol, 1,2,5-pentanetriol, glycerol, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, Mention may be made of trihydric or higher alcohol monomers such as trimethylolethane, trimethylolpropane and 1,3,5-trihydroxymethylbenzene. Examples of the carboxylic acid used to obtain the polyester resin include monocarboxylic acids such as palmitic acid, stearic acid, and oleic acid, maleic acid, fumaric acid, mesaconic acid, citraconic acid, terephthalic acid, cyclohexanedicarboxylic acid, and succinic acid. Acids, adipic acid, sebacic acid, malonic acid, divalent organic acid monomers in which these are substituted with saturated or unsaturated hydrocarbon groups having 3 to 22 carbon atoms, anhydrides of these acids, lower alkyl esters and Dimer from linolenic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid, 1, 2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl 2-methylenecarboxypropane, tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid embol trimer acid, trivalent or higher polyvalent carboxylic acid monomers such as acid anhydrides thereof Can be mentioned.

  When the binder resin is a polyester resin, the toner has fixability and offset resistance because at least one peak exists in the molecular weight range of 3,000 to 50,000 in the molecular weight distribution of the THF soluble component of the resin component. In addition, as a THF soluble component, a binder resin in which a component having a molecular weight of 100,000 or less is 60 to 100% is preferable, and at least one peak exists in a region having a molecular weight of 5,000 to 20,000. More preferable is a binder resin.

  When the binder resin is a polyester resin, the acid value is preferably 0.1 mgKOH / g to 100 mgKOH / g, more preferably 0.1 mgKOH / g to 70 mgKOH / g, and 0.1 mgKOH / g. Most preferably, it is g-50 mgKOH / g.

  Epoxy resins include polycondensates of bisphenol A and epochrohydrin. For example, Epomic R362, R364, R365, R366, R367, R369 (manufactured by Mitsui Petrochemical Co., Ltd.), Epoto YD Commercially available products such as −011, YD-012, YD-014, YD-904, YD-017 (manufactured by Tohto Kasei Co., Ltd.), Epocoat 1002, 1004, 1007 (manufactured by Shell Chemical Co., Ltd.), and the like. Moreover, you may seal the epoxy group of the terminal of these epoxy resins with phenolic compounds, such as cumylphenol and alkylphenol.

  As a binder resin that can be used in the toner of the present invention, a resin containing a monomer component capable of reacting with both of these resin components in at least one of the vinyl polymer component and the polyester resin component is also used. Can do. Examples of monomers that can react with the vinyl polymer among the monomers constituting the polyester-based resin component include, for example, unsaturated dicarboxylic acids such as phthalic acid, maleic acid, citraconic acid, and itaconic acid, or anhydrides thereof. It is done. Examples of the monomer constituting the vinyl polymer component include those having a carboxyl group or a hydroxy group, and acrylic acid or methacrylic acid esters.

  In the present invention, the number average molecular weight and the weight average molecular weight of the binder resin are measured by GPC under the following conditions.

・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 1.0 ml / min ・ Sample: 0.1 ml of 0.05-0.6% concentration sample was injected

  From the molecular weight distribution of the binder resin measured under the above conditions, the number average molecular weight and the weight average molecular weight of the binder resin were calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

In the present invention, the acid value of the binder resin component of the toner composition is determined by the following method, and the basic operation conforms to JIS K-0070.
(1) The sample is used by removing additives other than the binder resin (polymer component) in advance, or the acid value and content of components other than the binder resin and the crosslinked binder resin are obtained in advance. . The sample pulverized product 0.5 to 2.0 g is precisely weighed, and the weight of the polymer component is defined as Wg. For example, when measuring the acid value of the binder resin from the toner, the acid value and content of the colorant or magnetic material are separately measured, and the acid value of the binder resin is obtained by calculation.
(2) A sample is put into a 300 (ml) beaker, and 150 (ml) of toluene / ethanol (volume ratio 4/1) is added and dissolved.
(3) Titrate with a potentiometric titrator using an ethanol solution of 0.1 mol / l KOH.
(4) The amount of KOH solution used at this time is S (ml), a blank is measured at the same time, the amount of KOH solution used at this time is B (ml), and the following equation (5) is used for calculation. However, f is a factor of KOH.
Acid value (mgKOH / g) = [(SB) × f × 5.61] / W (5)

  The toner binder resin and the composition containing the binder resin preferably have a glass transition temperature (Tg) of 35 to 80 ° C., more preferably 40 to 75 ° C., from the viewpoint of toner storage stability. If the Tg is lower than 35 ° C., the toner is likely to deteriorate in a high temperature atmosphere, and offset may easily occur during fixing. On the other hand, when Tg exceeds 80 ° C., fixability may be deteriorated.

--Colorant--
The colorant is not particularly limited, and a commonly used resin can be appropriately selected and used. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), cadmium yellow, yellow iron oxide, ocher, yellow lead, titanium yellow, polyazo yellow, oil yellow, Hansa yellow (GR, A, RN, R), pigment yellow L, benzidine yellow (G, GR), permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Red Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red, Antimon Zhu, Permanent Red 4R, Para Red, Fu Issey Red, Parachlor Ortho Nitroaniline Red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmin Min BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, Rhodamine Lake Y, Alizarin Lake, Thioindigo Red B, Thioindigo Maroon, Oil Red, Nacridone Red, Pyrazolone Red, Polyazo Red, Chrome Vermilion, Benzidine Orange, Perinone Orange, Oil Orange, Cobalt Blue, Cerulean Blue, Alkaline Blue Lake, Peacock Blue Lake, Victoria Blue Lake, Metal Free Phthalocyanine Blue, Phthalocyanine Blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Chrome Oxide , Pyridian, emerald green, pigment green B, naphthol green B, green gold, acid green , Malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and mixtures thereof.

  The colorant can be used by finely dispersing it in an organic solvent in the presence of a dispersant using a ball mill or a bead mill. It is also preferable to use a master batch described later and finely disperse it after dissolution.

  The content of the colorant is preferably 1 to 15% by weight, more preferably 3 to 10% by weight, based on the toner. When the content is less than 1% by weight, the coloring power of the toner is decreased. When the content is more than 15% by weight, the pigment is poorly dispersed in the toner, and the coloring power is decreased. May be reduced.

  The colorant used in the present invention can also be used as a master batch combined with a resin. You may mix | blend a pigment dispersant as needed. As the binder resin kneaded with the master batch, in addition to the above-mentioned modified and unmodified polyester resins, for example, styrene such as polystyrene, poly p-chlorostyrene, and polyvinyltoluene, and polymers of substituted products thereof; styrene -P-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, Styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate copolymer, styrene-α-chloro Methyl methacrylate copolymer, styrene-acrylonite Copolymer, styrene-vinyl methyl ether copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile-indene copolymer, styrene-maleic acid Copolymers, styrene copolymers such as styrene-maleic acid ester copolymers; acrylic binders such as polymethyl methacrylate and polybutyl methacrylate; polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester, epoxy resin, Epoxy polyol resin, polyurethane, polyamide, polyvinyl butyral, polyacrylic acid resin, rosin, modified rosin, terpene resin, phenol resin, aliphatic or alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, Raffin wax and the like. These may be used individually by 1 type and may be used in mixture of 2 or more types.

  The master batch can be obtained by mixing and kneading a resin for a master batch and a colorant under a high shear force. At this time, an organic solvent can be used to enhance the interaction between the colorant and the resin. Also, there is a method of removing the water and organic solvent components by mixing and kneading an aqueous paste containing water, which is a so-called flushing method, together with a resin and an organic solvent, and transferring the colorant to the resin side. Since the wet cake can be used as it is, it does not need to be dried and is preferably used. For mixing and kneading, a high shearing dispersion device such as a three-roll mill is preferably used.

  The amount of the master batch used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the binder resin.

  The resin for the masterbatch preferably has an acid value of 30 mgKOH / g or less, and more preferably 20 mgKOH / g or less. When the acid value exceeds 30 mgKOH / g, the chargeability under high humidity may be lowered.

  The pigment dispersant is preferably highly compatible with the binder resin in terms of pigment dispersibility. Specific commercial products include “Azisper PB821”, “Azisper PB822” (Ajinomoto Fine Techno Co., Ltd.). Product), “Disperbyk-2001” (manufactured by Big Chemie), “EFKA-4010” (manufactured by EFKA), and the like.

  The pigment dispersant is preferably blended in the toner at a ratio of 0.1 to 50% by weight with respect to the colorant. When the blending ratio is less than 0.1% by weight, the pigment dispersibility may be insufficient, and when it is more than 50% by weight, the chargeability under high humidity may be lowered.

  The pigment dispersant has a weight average molecular weight of 500 to 100,000, which is the maximum molecular weight of the main peak in terms of styrene equivalent weight by GPC, and from the viewpoint of pigment dispersibility, 3,000 to 100,000. Is more preferable. In particular, 5,000 to 50,000 are preferable, and 5,000 to 30,000 are most preferable. When the molecular weight is less than 500, the polarity increases and the dispersibility of the colorant may decrease. When the molecular weight exceeds 100,000, the affinity with the solvent increases and the dispersibility of the colorant decreases. There are things to do.

  The amount of the pigment dispersant added is preferably 1 to 50 parts by weight and more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 1 part by weight, the dispersibility may be lowered, and if it exceeds 50 parts by weight, the chargeability may be lowered.

--Fluorine atom surfactant--
As the fluorosurfactant, a polymer having a structure represented by the following general formula (1) is preferable.

(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.)
In particular, the fluorosurfactant is more preferably a block copolymer.

  Examples of the method for producing the block copolymer include Japanese Patent Application Laid-Open Nos. 2003-171607, 2004-075780, 2003-154307, 2004-036018, 2003-221419, and 2002. No. 363495, JP-A No. 2002-266257, JP-A No. 2002-105152, JP-A No. 2002-097338, JP-A No. 2001-206952, JP-A No. 2000-169531, etc. For example, commercially available materials such as Daikin Unidyne TG-590, TG-490, TG-540, and Nippon Oil & Fats Modipers F200, F220, F600, F2020, and F3035 can also be used.

  Moreover, the structure represented by the following general formula (2) may be sufficient as surfactant which has a fluorine atom.

(Chemical formula 6)
Rf-X General formula (2)
(In the formula, X represents —COOM, SO ₃ M, —O—C ₆ H ₄ —SO ₃ M, —N (R ₁ ) ₃ , —SO ₂ —N—Y ₂ , R ₁ represents a hydrogen atom or A methyl group, M is an alkali metal such as Na or K, Li, and an ammonium salt such as NH ₄ ; Y is a hydrogen atom or a hydroxyl group at its terminal, a carboxy group or a salt thereof, an alkyl group that may have an amino group or a salt thereof , Rf represents a perfluoroalkyl group having C₅-C₈. wherein R ₁ and Y may be either different groups in the same group)

  Specifically, surfactants having fluorine atoms as shown in Table 1 are used.

<Wax>
In the present invention, a wax may be contained together with the binder resin and the colorant.

  The wax of the present invention is not particularly limited, and those that are usually used can be appropriately selected and used. For example, low molecular weight polyethylene, low molecular weight polypropylene, polyolefin wax, microcrystalline wax, paraffin wax, sax. Plant waxes such as aliphatic hydrocarbon waxes such as sol wax, oxides of aliphatic hydrocarbon waxes such as polyethylene oxide wax or block copolymers thereof, candelilla wax, carnauba wax, wood wax, jojoba wax, etc. Waxes mainly composed of animal waxes such as beeswax, lanolin and spermaceti, mineral waxes such as ozokerite, ceresin and petrolatum, and fatty acid esters such as montanic ester wax and castor wax. Deoxidized carnauba wax and other fatty acid esters that have been partially or wholly deoxidized are included.

  Examples of the wax further include saturated linear fatty acids such as palmitic acid, stearic acid, montanic acid, or linear alkyl carboxylic acids having a linear alkyl group, prandidic acid, eleostearic acid, and valinal acid. Unsaturated fatty acids such as stearyl alcohol, eicosyl alcohol, behenyl alcohol, carnapyl alcohol, seryl alcohol, mesyl alcohol, or long-chain alkyl alcohols, polyhydric alcohols such as sorbitol, linoleic acid amides, olefinic acids Fatty acid amides such as amide and lauric acid amide, methylene biscapric acid amide, ethylene bis lauric acid amide, hexamethylene bis stearic acid amide and other saturated fatty acid bisamides, ethylene bis oleic acid amide, hexamethylene bis Unsaturated fatty acid amides such as oleic acid amide, N, N′-dioleyl adipic acid amide, N, N′-dioleyl sepasinic acid amide, m-xylene bisstearic acid amide, N, N-distearyl isophthalic acid Grafting with aromatic bisamides such as amides, fatty acid metal salts such as calcium stearate, calcium laurate, zinc stearate and magnesium stearate, and aliphatic hydrocarbon waxes with vinyl monomers such as styrene and acrylic acid Examples thereof include waxes, partial ester compounds of fatty acids such as behenic acid monoglycerides and polyhydric alcohols, and methyl ester compounds having a hydroxyl group obtained by hydrogenating vegetable oils and fats.

  More preferable examples include polyolefins obtained by radical polymerization of olefins under high pressure, polyolefins obtained by purifying low molecular weight by-products obtained during polymerization of high molecular weight polyolefins, and polymerization using a catalyst such as a Ziegler catalyst or a metallocene catalyst under low pressure. Polyolefin, polyolefin polymerized using radiation, electromagnetic waves or light, low molecular weight polyolefin obtained by thermal decomposition of high molecular weight polyolefin, paraffin wax, microcrystalline wax, Fitzscher Tropsch wax, Jintole method, hydrocol method, age method Synthetic hydrocarbon waxes synthesized by, etc., synthetic waxes using a compound having 1 carbon atom, hydrocarbon waxes having a functional group such as a hydroxyl group or a carboxyl group, hydrocarbon waxes and carbonization having a functional group hydrogen A mixture of wax, styrene these waxes as a matrix, maleic acid ester, acrylate, methacrylate, graft-modified wax with such a vinyl monomer of maleic acid.

  In addition, these waxes have a sharp molecular weight distribution using a press perspiration method, a solvent method, a recrystallization method, a vacuum distillation method, a supercritical gas extraction method, or a solution liquid crystal deposition method, a low molecular weight solid fatty acid, a low A molecular weight solid alcohol, a low molecular weight solid compound, and other impurities are preferably used.

  The melting point of the wax is preferably 70 to 140 ° C., and more preferably 70 to 120 ° C., in order to balance the fixability and the offset resistance. If it is less than 70 degreeC, blocking resistance may fall, and if it exceeds 140 degreeC, an offset-proof effect may become difficult to express.

  Further, by using two or more different types of waxes in combination, the plasticizing action and the releasing action which are the actions of the wax can be expressed simultaneously.

  Examples of the types of wax having a plasticizing action include waxes having a low melting point, those having a branch on the molecular structure, and those having a polar group.

  Examples of the wax having a releasing action include a wax having a high melting point, and the molecular structure includes a linear structure and a non-polar one having no functional group. Examples of use include a combination of two or more different waxes having a melting point difference of 10 ° C. to 100 ° C., a combination of polyolefin and graft-modified polyolefin, and the like.

  When selecting two types of wax, in the case of a wax having the same structure, a wax having a relatively low melting point exhibits a plasticizing action, and a wax having a high melting point exhibits a releasing action. At this time, when the difference in melting point is 10 to 100 ° C., functional separation is effectively expressed. If it is less than 10 ° C., the function separation effect may be difficult to appear, and if it exceeds 100 ° C., the function may not be emphasized by interaction. At this time, the melting point of at least one of the waxes is preferably 70 to 120 ° C, and more preferably 70 to 100 ° C, because the function separation effect tends to be easily exhibited.

  As for the wax, those having a branched structure, those having a polar group such as a functional group, and those modified with a component different from the main component exhibit a plastic action, and those having a more linear structure or functional group Nonpolar or non-denatured straight materials that do not have a mold exhibit a releasing action. Preferred combinations include polyethylene homopolymers or copolymers based on ethylene and polyolefin homopolymers or copolymers based on olefins other than ethylene, polyolefins and graft modified polyolefins, alcohol waxes, fatty acid waxes or ester waxes. And hydrocarbon wax combinations, Fischer-Tropsch wax or polyolefin wax and paraffin wax or microcrystal wax combination, Fischer-Tropsch wax and polyolefin wax combination, paraffin wax and microcrystal wax combination, Carnauba Wax, Can Delila wax, rice wax or montan wax and hydrocarbon-based wax Like a combination of.

  In any case, since it becomes easy to balance the toner storage stability and the fixing property, the peak top temperature of the maximum peak is in the region of 70 to 110 ° C. in the endothermic peak observed in the DSC measurement of the toner. Preferably, it has a maximum peak in the region of 70 to 110 ° C.

  The total content of the wax is preferably 0.2 to 20 parts by weight and more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the binder resin.

  In the present invention, the peak top temperature of the endothermic peak of the wax measured by DSC is defined as the melting point of the wax.

  The wax or toner DSC measuring device is preferably measured with a high-precision internal heat input compensation type differential scanning calorimeter. As a measuring method, it carries out according to ASTM D3418-82. The DSC curve used in the present invention is one that is measured when the temperature is raised at a temperature rate of 10 ° C./min after once raising and lowering the temperature and taking a previous history.

  In the present invention, a known charge control agent generally used for an electrophotographic toner can be used in combination with the fluorosurfactant having the charge control effect of the present invention together with a binder resin and a colorant.

  As the charge control agent, when a colored material is used, the color tone may change. Therefore, a colorless or nearly white material is preferable, and the contained metal complex dye, a fluorine-modified quaternary ammonium salt, a metal salt of salicylic acid, a salicylic acid derivative A metal salt etc. are mentioned. In addition, although a metal can be suitably selected according to the objective, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

  Commercially available charge control agents include oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenol condensate E-89 (above, manufactured by Orient Chemical Industries), LRA-901, Examples thereof include LR-147 (manufactured by Nippon Carlit Co., Ltd.), a quinacridone, an azo pigment, a polymer compound having a sulfonic acid, a carboxylic acid, a quaternary ammonium salt, and the like, which are boron complexes.

  The amount of charge control agent used is determined by the type of binder resin, the presence or absence of additives used as necessary, and the toner production method including the dispersion method, and is not uniquely limited. However, it is preferably used in the range of 0.1 to 10 parts by weight with respect to 100 parts by weight of the binder resin. The range of 0.2 to 5 parts by weight is preferable. When the amount exceeds 10 parts by weight, the chargeability of the toner is too high, the effect of the main charge control agent is reduced, the electrostatic attractive force with the developing roller is increased, the flowability of the developer is reduced, and the image density is reduced. Incurs a decline.

  In addition, these charge control agents and release agents can be melt-kneaded together with the master batch and resin, and of course, it may be added when dissolved and dispersed in an organic solvent, but the discharge holes need not be blocked. Therefore, it is necessary to finely pulverize the charge control agent and disperse it in an organic solvent using a wet pulverizer such as a bead mill.

  Examples of the magnetic material that can be used in the present invention include (1) iron oxide containing magnetic iron oxide such as magnetite, maghemite, and ferrite, and other metal oxides, and (2) metals such as iron, cobalt, and nickel, or Alloys of these metals with metals such as aluminum, cobalt, copper, lead, magnesium, tin, zinc, antimony, beryllium, bismuth, cadmium, calcium, manganese, selenium, titanium, tungsten, vanadium, (3) and these A mixture of

Specific examples of the magnetic material include triiron tetroxide (Fe ₃ O ₄ ), γ-iron trioxide (γ-Fe ₂ O ₃ ), ZnFe ₂ O ₄ , Y ₃ Fe ₅ O ₁₂ , and CdFe ₂ O _4. , Gd ₃ Fe ₅ O ₁₂ , CuFe ₂ O ₄ , PbFe ₁₂ O, NiFe ₂ O ₄ , NdFe ₂ O, BaFe ₁₂ O ₁₉ , MgFe ₂ O ₄ , MnFe ₂ O ₄ , LaFeO ₃ , iron powder, cobalt powder, And nickel powder. These may be used individually by 1 type and may be used in combination of 2 or more type. Among these, fine powders of triiron tetroxide and γ-iron trioxide are particularly preferable.

  Further, magnetic iron oxides such as magnetite, maghemite, and ferrite containing different elements, or a mixture thereof can be used. Examples of different elements include, for example, lithium, beryllium, boron, magnesium, aluminum, silicon, phosphorus, germanium, zirconium, tin, sulfur, calcium, scandium, titanium, vanadium, chromium, manganese, cobalt, nickel, copper, zinc, And gallium. Preferred heterogeneous elements are selected from magnesium, aluminum, silicon, phosphorus, or zirconium. The foreign element may be incorporated into the iron oxide crystal lattice, may be incorporated into the iron oxide as an oxide, or may be present on the surface as an oxide or hydroxide. Is preferably contained as an oxide.

  The different elements can be incorporated into the particles by mixing the salts of the different elements at the time of producing the magnetic substance and adjusting the pH. Moreover, it can precipitate on the particle | grain surface by adjusting pH after magnetic body particle | grains production | generation, or adding salt of each element and adjusting pH.

  As the usage-amount of the said magnetic body, 10-200 weight part of magnetic bodies are preferable with respect to 100 weight part of binder resin, and 20-150 weight part is more preferable. The number average particle diameter of these magnetic materials is preferably 0.1 to 2 μm, and more preferably 0.1 to 0.5 μm. The number average diameter can be obtained by measuring a photograph taken with a transmission electron microscope with a digitizer or the like.

  Further, as the magnetic properties of the magnetic material, those having a coercive force of 20 to 150 oersted, a saturation magnetization of 50 to 200 emu / g, and a residual magnetization of 2 to 20 emu / g are preferable, respectively.

  The magnetic material can also be used as a colorant.

  The second toner production method of the present invention will be described below.

(Toner and toner production method)
The method for producing a toner of the present invention includes a step of granulating a toner by polymerizing at least a polymerizable monomer in at least one of a supercritical fluid and a subcritical fluid, and, if necessary, other steps. Comprising.

  The supercritical fluid or subcritical fluid contains a fluorosurfactant, and the polymerized polymerizable monomer is insoluble in the supercritical fluid or subcritical fluid.

  Here, the polymer of the polymerizable monomer is insoluble in at least one of the supercritical fluid and the subcritical fluid. A polymer as a test material in a high-pressure vessel (50 ml) with an observation window. 1 g is added, and at least one of supercritical fluid and subcritical fluid is mixed, and when the inside of the high-pressure vessel is visually observed after completion of the reaction, it means that the polymer is observed in the same form as in the charged state.

  The polymerizable monomer can be appropriately selected according to the purpose as long as the polymer component obtained in the polymerization step can form an image as a binder resin for toner. Monomer, radical polymerizable monomer having an unsaturated double bond represented by styrene, methyl acrylate, divinylbenzene, n-butyl acrylate, n-butyl methacrylate, 2-ethylhexyl methacrylate and the like are used. It is preferable. A wide variety of polymerizable monomers are commercially available.

  As a monomer used by this invention, although illustrated below about a styrene-type monomer, an acryl-type monomer, and a methacryl-type monomer, it is not limited to these.

  Styrene monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-phenylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, pn-amylstyrene, p-tert-butylstyrene, pn-hexylstyrene, pn-octylstyrene, pn-nonylstyrene, pn-decylstyrene, pn-dodecylstyrene, p-methoxystyrene, p- Examples thereof include styrene such as chlorostyrene, 3,4-dichlorostyrene, m-nitrostyrene, o-nitrostyrene, and p-nitrostyrene, or derivatives thereof.

  As acrylic acid and acrylic acid ester monomers, acrylic acid or methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, n-dodecyl acrylate And acrylic acid such as 2-ethylhexyl acrylate, stearyl acrylate, 2-chloroethyl acrylate, and phenyl acrylate, or esters thereof.

  Methacrylic acid and methacrylic acid ester monomers include methacrylic acid, methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, and n-dodecyl methacrylate. Methacrylic acid or esters thereof such as 2-ethylhexyl methacrylate, stearyl methacrylate, phenyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, and the like.

  Examples of other monomers include the following (1) to (18). (1) Monoolefins such as ethylene, propylene, butylene and isobutylene; (2) Polyenes such as butadiene and isoprene; (3) Vinyl halides such as vinyl chloride, vinylidene chloride, vinyl bromide and vinyl fluoride; (4) Vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate; (5) Vinyl ethers such as vinyl methyl ether, vinyl ethyl ether and vinyl isobutyl ether; (6) Vinyl methyl ketone, vinyl hexyl ketone and methyl. Vinyl ketones such as isopropenyl ketone; (7) N-vinyl compounds such as N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, N-vinyl pyrrolidone; (8), vinyl naphthalenes; (9) acrylonitrile, Such as methacrylonitrile, acrylamide, etc. (10) unsaturated dibasic acids such as maleic acid, citraconic acid, itaconic acid, alkenyl succinic acid, fumaric acid, mesaconic acid; (11) maleic anhydride, citraconic anhydride, Unsaturated dibasic acid anhydrides such as itaconic anhydride and alkenyl succinic anhydride; (12) maleic acid monomethyl ester, maleic acid monoethyl ester, maleic acid monobutyl ester, citraconic acid monomethyl ester, citraconic acid monoethyl ester Monoesters of unsaturated dibasic acids such as citraconic acid monobutyl ester, itaconic acid monomethyl ester, alkenyl succinic acid monomethyl ester, fumaric acid monomethyl ester, mesaconic acid monomethyl ester; (13) dimethylmaleic acid, dimethylfumaric acid, etc. (14) α, β-unsaturated acids such as crotonic acid and cinnamic acid; (15) α, β-unsaturated acid anhydrides such as crotonic acid anhydride and cinnamic anhydride; 16) Monomers having a carboxyl group such as anhydrides of the α, β-unsaturated acids and lower fatty acids, alkenylmalonic acid, alkenylglutaric acid, alkenyladipic acid, acid anhydrides and monoesters thereof; (17) Acrylic acid or methacrylic acid hydroxyalkyl esters such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate; (18) 4- (1-hydroxy-1-methylbutyl) styrene, 4- Examples thereof include a monomer having a hydroxy group such as (1-hydroxy-1-methylhexyl) styrene.

  In the toner of the present invention, the vinyl polymer or copolymer of the binder resin may have a crosslinked structure crosslinked with a crosslinking agent having two or more vinyl groups. Examples of the aromatic monomer include divinylbenzene and divinylnaphthalene as aromatic divinyl compounds. Examples of diacrylate compounds linked by an alkyl chain include ethylene glycol diacrylate, 1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 Examples include hexanediol diacrylate, neopentyl glycol diacrylate, or those obtained by replacing the acrylate of the above compound with methacrylate.

  Examples of diacrylate compounds linked by an alkyl chain containing an ether bond include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, Examples include propylene glycol diacrylate or those obtained by replacing acrylate of the above compound with methacrylate.

  In addition, a diacrylate compound or a dimethacrylate compound linked by a chain containing an aromatic group and an ether bond is also included. Examples of polyester diacrylates include trade name MANDA (Nippon Kayaku Co., Ltd.).

  Examples of the polyfunctional crosslinking agent include pentaerythritol triacrylate, trimethylol ethane triacrylate, trimethylol propane triacrylate, tetramethylol methane tetraacrylate, oligoester acrylate, and acrylates of the above compounds in place of methacrylate, triallyl cyanide. Examples include nurate and triallyl trimellitate.

  These crosslinking agents can be used in an amount of preferably 0.01 to 10 parts by weight, particularly preferably 0.03 to 5 parts by weight, with respect to 100 parts by weight of other monomer components. Among these crosslinkable monomers, those which are preferably used in toner resin from the viewpoint of fixing property and offset resistance include an aromatic divinyl compound (particularly divinylbenzene), an aromatic group and one ether bond. Examples thereof include diacrylate compounds linked by a bonding chain.

  The supercritical fluid exists as a non-condensable high-density fluid in a temperature / pressure region that exceeds the limit (critical point) where gas and liquid can coexist, does not cause condensation even when compressed, and exceeds the critical temperature. As long as the fluid is in a state of a critical pressure or higher, there is no particular limitation, and the material can be appropriately selected according to the purpose.

  The subcritical fluid can be appropriately selected according to the purpose as long as it exists as a high-pressure liquid in the temperature / pressure region near the critical point.

  In the present invention, carbon dioxide is used as the supercritical fluid or subcritical fluid. Since carbon dioxide has a critical pressure of 7.3 MPa and a critical temperature of 31 ° C., it can easily create a supercritical state and is nonflammable, so it is easy to handle. Further, since carbon dioxide is non-aqueous, the toner characteristics are good.

In the present invention, other fluids can be used in combination with supercritical carbon dioxide or subcritical carbon dioxide. The other fluid is preferably easy to control the solubility of the material constituting the toner, and specific examples include N ₂ O, ethane, propane, and ethylene.

  Moreover, an organic solvent can also be used together as an entrainer with supercritical carbon dioxide or subcritical carbon dioxide. This makes it easier to control the solubility of the material constituting the toner. There is no restriction | limiting in particular in the said entrainer, According to the objective, it can select suitably, For example, methanol, ethanol, propanol, ammonia, melamine, urea, thioethylene glycol etc. are mentioned.

  In the dispersion polymerization method, a polymer dispersant that is dissolved in a solvent is added to the solvent, and the polymer is dissolved in the solvent, but the resulting polymer is swollen or hardly dissolved in the organic solvent. Particles are formed by adding more than one kind of vinyl monomer. A reaction of growing in the above-described system using a polymer having a particle size distribution narrower than the target particle size in advance is also included. The monomer used for the growth reaction may be the same monomer as that used to produce the seed particles, or may be another monomer, but the polymer should not be dissolved in the solvent.

  The present invention uses a fluorosurfactant as a polymer dispersant that dissolves in a solvent. The fluorosurfactant is obtained by polymerizing a fluorovinyl monomer or a fluorovinyl monomer. The polymer (homopolymer or copolymer) etc. which can be used can be used. The fluorine-based vinyl monomer can be appropriately selected depending on the purpose, and examples thereof include acrylic acid derivatives having a perfluoroalkyl group (acrylate monomers) and methacrylic acid derivatives (methacrylate monomers). . Since many of these raw materials are commercially available, they can be used appropriately according to the purpose.

  The polymer obtained by polymerizing the fluorinated vinyl monomer is preferably a compound having a structural unit represented by the following general formula (1).

In the general formula (1), R ₁ is a hydrogen atom or a methyl group, R ₂ is a C1-C2 alkylene group, and Rf is a C4-C20 perfluoroalkyl group.

  At this time, the composition ratio of the structural unit represented by the general formula (1) in the polymer is preferably 1 to 100 mol%, more preferably 10 to 100 mol%, and even more preferably 50 to 100 mol%. preferable. When the composition ratio is less than 1 mol%, the surface activity for carbon dioxide may be insufficient.

  Moreover, it is preferable that the said fluorine-type vinyl monomer is a compound which has a structural unit represented by following General formula (3).

In the general formula (3), R ₁ is a hydrogen atom or a methyl group, R ₂ is a C1-C2 alkylene group, and Rf is a C4-C20 perfluoroalkyl group.

In the general formulas (1) and (3), R ₁ is a hydrogen atom or a methyl group, R ₂ is a C1-C2 alkylene group, and R _f is a perfluoro having 4 to 20 carbon atoms. It is an alkyl group. Examples of the C1-C2 alkylene group for R ₂ include a methylene group and an ethylene group.

  The polymer obtained by polymerizing the fluorinated vinyl monomer is preferably a compound obtained by reacting the compound represented by the general formula (3). As a general method for producing a fluorosurfactant, Fluorinert FC-40, FC-43, FC-70, FC-72, FC-75, FC-77 (manufactured by Sumitomo 3M), Asahi Clin AE-3000 , AK-225 (manufactured by Asahi Glass Co., Ltd.), Vertrel XF (Mitsui DuPont Fluorochemical), etc. are synthesized by polymerizing fluorinated vinyl monomers in a fluorinated solvent. It is desirable to use one synthesized using critical carbon dioxide as a reaction solvent because it can reduce environmental burden.

The polymerization reaction is preferably either bulk polymerization or living radical polymerization.
-Bulk polymerization-
The bulk polymerization is a thermal radical generated by heating a monomer composition comprising a polymerizable monomer in a reaction vessel in an inert gas atmosphere such as nitrogen under reduced pressure or normal pressure or increased pressure, and / or Alternatively, a known radical polymerization initiator such as 2,2′-azobisisobutyronitrile (hereinafter abbreviated as AIBN), benzoyl peroxide, or the like is added to the monomer composition, and the polymerization initiator is used. Initiated by the generated radical.

  Examples of the radical polymerization initiator include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, p-chlorobenzoyl peroxide, o-methylbenzoyl peroxide, bis-3,5,5-trimethylcyclohexanol peroxide. Diacyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, t-butylcumyl peroxide, di-t-butyl peroxide, 1,3 A dialkyl peroxide such as bis- (t-butylperoxyisopropyl) benzene; a peroxyketal such as 1,1-di- (t-butylperoxy) cyclohexane; an alkyl perester such as t-butyl peroxybenzoate; Diisopropyl peroxydica Organic peroxides such as carbonates such as bonates; 2,2′-azobis-isobutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobiscyclohexylnitrile, 1 , 1′-azobis (cyclohexane-1-carbonitrile), 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like. These may be used alone or in combination of two or more.

  If the amount of the radical polymerization initiator is decreased, the polymerization is hardly used in the initial stage of polymerization, and the polymerization is difficult to complete.If the amount is increased, the amount of radical generation is increased, and it is difficult to obtain a polymer having a sufficient molecular weight. Preferably it is 0.01-2 weight part with respect to 100 weight part of monomers, More preferably, it is 0.01-1.5 weight part. Moreover, 50-220 degreeC is preferable normally at this time, and 80-150 degreeC is more preferable.

  Furthermore, in the above bulk polymerization, the molecular weight of the resulting polymer can be adjusted by adding a chain transfer agent. Any chain transfer agent may be used as long as it is usually used for polymerization or copolymerization of radical polymerizable monomers. For example, mercaptans such as methyl mercaptan, t-butyl mercaptan, decyl mercaptan, benzyl mercaptan, lauryl mercaptan, stearyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, mercaptoacetic acid, mercaptopropionic acid; methanol, propanol, butanol, iso Examples include alcohols such as butanol, t-butanol, hexanol, benzyl alcohol, and allyl alcohol; halogenated hydrocarbons such as chloroethane, fluoroethane, trichloroethylene, and carbon tetrachloride. Among them, mercaptans are preferable, and n-dodecyl mercaptan (hereinafter abbreviated as n-DM) is more preferable. This chain transfer agent may be charged all at once into the reaction vessel before polymerization, or may be added continuously or sequentially during the polymerization.

  The addition amount of the chain transfer agent is usually preferably 0.01 to 1 part by weight and more preferably 0.05 to 0.5 part by weight with respect to 100 parts by weight of the polymerizable monomer. If the addition amount is less than 0.01 parts by weight, the viscosity of the polymerization system becomes high, which may make it difficult to produce. If it exceeds 1 part by weight, the molecular weight of the resulting polymer may be reduced. .

  As a method for stopping the polymerization, any known method may be used as long as the chain transfer of the growing radical stops and disappears. For this purpose, 50 to 5,000 ppm of a polymerization terminator is added to the polymerization solution, oxygen or air is blown into the polymerization solution, the polymerization solution is cooled to 40 ° C. or less, and these may be used alone or in combination. They can be combined.

  The polymerization terminator is a chemical that reacts quickly with a radical generated from a polymerizable monomer and / or polymerization initiator and converts it into a stable radical or neutral substance that does not subsequently cause polymerization. is there. Specific examples thereof include quinones such as p-benzoquinone, naphthoquinone, phenanthraquinone, and 2,5-diphenyl-p-benzoquinone; hydroquinone, pt-butylcatechol, and 2,5-di-t-butylhydroquinone. Hydroquinones such as mono-t-butylhydroquinone and 2,5-di-t-butylhydroquinone; phenols such as di-t-butyl paracresol hydroquinone monomethyl ether and α-naphthol; organics such as copper naphthenate Inorganic copper salts; amidines such as acetamidine acetate and acetamidine sulfate; hydrazine salts such as phenylhydrazine hydrochloride and hydrazine hydrochloride; trimethylbenzylammonium chloride, laurylpyridinium chloride, cetyltrimethylammonium chloride, phenyltrimethylammonium Quaternary ammonium salts such as Umukurorido; pyrogallol, tannic acid, polyhydric phenols resorcinol and the like; nitro compounds, such as oximes and the like.

-Living radical polymerization-
As the living radical polymerization method, it is preferable to use two living radical polymerization methods such as a TEMPO (2,2,6,6-tetramethylperidinyl-1-oxy) method and an iodine transfer polymerization method. For the TEMPO method, see M.M. K. Reference may be made to the report by Trends Polymer Science, Vol. 2, page 66 (1994) by Georges et al. For the iodine transfer polymerization method, see M.M. Reference can be made to the report of Tatemoto's collection of polymer papers, vol. 49, page 765 (1992).

  In the TEMPO method, a stable nitroxy free radical (= N—O.) Is generally used as a radical capping agent. Such compounds are not particularly limited, but 2,2,6,6-substituted-1-piperidinyloxy radical and 2,2,5,5-substituted-1-pyrrolidinyloxy radical Nitroxy free radicals from cyclic hydroxyamines are preferred. As the substituent, an alkyl group having 4 or less carbon atoms such as a methyl group or an ethyl group is suitable.

  Specific examples of the nitroxy free radical compound include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3 -Tetramethyl-2-isoindolinyloxy radical, N, N-di-t-butylamineoxy radical and the like. Moreover, stable free radicals, such as a galvinoxyl free radical, can also be used instead of a nitroxy free radical.

  These radical capping agents are used in combination with a thermal radical generator. It is considered that the reaction product of the radical capping agent and the thermal radical generator serves as a polymerization initiator to proceed the polymerization of the addition polymerizable monomer, and the combination ratio of both is not particularly limited, but radical capping A suitable amount of the thermal radical generator is 0.1 to 10 moles per mole of the agent.

  There is no restriction | limiting in particular as said thermal radical generator, Although a various compound can be used, The peroxide and azo compound which can generate | occur | produce a radical on superposition | polymerization temperature conditions are preferable. The peroxide is not particularly limited. For example, diacyl peroxides such as benzoyl peroxide and lauroyl peroxide; dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; diisopropyl peroxydicarbonate And peroxycarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate; alkyl peresters such as t-butylperoxyoctoate and t-butylperoxybenzoate. Benzoyl peroxide is particularly preferable. As the azo compound, 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4- And dimethyl valeronitrile) and dimethyl azobisisobutyrate. Among these, dimethyl azobisisobutyrate is particularly preferable.

  Examples of the solvent used in the living radical polymerization include cycloalkanes such as cyclohexane and cycloheptane; saturated carboxylic acids such as ethyl acetate, n-butyl acetate, i-butyl acetate, methyl propionate, and propylene glycol monomethyl ether acetate. Esters; alkyl lactones such as γ-butyrolactone; airs such as tetrahydrofuran, dimethoxyethanes and diethoxyethanes; alkyl ketones such as 2-butanone, 2-heptanone and methyl isobutyl ketone; cycloalkyl ketones such as cyclohexanone Alcohols such as 2-propanol and propylene glycol monomethyl ether; aromatics such as toluene, xylene and chlorobenzene; dimethylformamide, dimethyl sulfoxide, dimethylacetamide , It may be mentioned aprotic polar solvents, or non-solvents such as N- methyl-2-pyrrolidone. These can be used individually by 1 type or in mixture of 2 or more types.

  Moreover, 40-150 degreeC is preferable normally and the reaction temperature in the said polymerization has more preferable 50-130 degreeC. The reaction time is usually preferably 1 to 96 hours, more preferably 1 to 72 hours.

  Fluorosurfactants as polymer compound dispersants have high affinity and adsorbability to the surface of polymer particles, especially in the sense of preventing steric coalescence of polymer particles, and affinity for solvents. In order to enhance the repulsion between particles sterically, the molecular chain has a certain length (with a molecular weight of 5,000 or more), preferably with a molecular weight of 10,000 or more. Further, 50,000 or more is preferable. However, if the molecular weight is too high, the solubility in supercritical fluids and subcritical fluids deteriorates and does not contribute to particle formation. Therefore, the molecular weight is preferably 500,000 or less.

  Here, the weight average molecular weight of the fluorosurfactant was prepared and measured by GPC under the following conditions.

-Sample preparation method-
An HFIP (hexafluoropropanol) solution adjusted so that CF ₃ COONa is 5 mM is used, and the measurement sample is dissolved to a concentration of 0.15 wt%.

-Measurement conditions-
・ Device: HLC-8220-GPC (manufactured by Tosoh Corporation)
Column: TSK-gel GMH HR-M (manufactured by Tosoh Corporation)
・ Temperature: 40 ℃
・ Solvent: HFIP (hexafluoropropanol)
・ Flow rate: 0.2 ml / min ・ Sample: 10 μl of 0.15 wt% sample was injected

  The weight average molecular weight of the fluorosurfactant can be calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample from the molecular weight distribution of the fluorosurfactant measured under the above conditions.

  The smaller the amount of the fluorosurfactant added in the polymerization step, the lower the production cost, which is preferable. However, the amount is preferably 0.01 to 50% by weight, preferably 0.01 to 30% with respect to the polymerizable monomer. % By weight is more preferred, and 0.1-20% by weight is even more preferred. When the addition amount of the fluorosurfactant is less than 0.01% by weight with respect to the polymerizable monomer, toner particles may not be obtained. It becomes expensive and impractical.

  In general, the amount of polymer powder used in the production of seed particles varies depending on the type of polymerizable monomer for forming the target polymer particles, but is 0.1 to 10% by weight based on the supercritical fluid and subcritical fluid. More preferably, it is 1 to 5% by weight. When the concentration of the polymer dispersion stabilizer is low, the produced polymer particles have a relatively large diameter, and when the concentration is high, small particles are obtained. Little effect on diameter reduction.

  The pressure condition in the polymerization step is preferably 8 to 100 MPa, and more preferably 10 to 50 MPa. If the pressurization condition is less than 8 MPa, the amount of surfactant dissolved decreases and the surface activity ability tends to be insufficient, so that toner particles cannot be stably obtained, and the polymerization property in the reaction system is reduced. The monomer concentration cannot be increased, resulting in inefficient production conditions. When the pressure exceeds 100 MPa, the apparatus cost for the pressure resistant equipment may increase, and the toner particles may easily swell or dissolve.

  Moreover, 10-180 degreeC is preferable, as for the heating conditions in a superposition | polymerization process, 30-150 degreeC is more preferable, and 35-130 degreeC is still more preferable. When the heating condition is less than 10 ° C., the reaction time tends to be long or the polymerization conversion rate tends to be low, and when it exceeds 180 ° C., toner particles cannot be obtained stably. Manufacturing energy and manufacturing cost may be high.

  In the polymerization step, it is preferable to further dissolve the release agent in supercritical carbon dioxide or subcritical carbon dioxide to polymerize the polymerizable monomer. Thereby, a toner having good dispersibility of the release agent can be obtained.

  In the present invention, a polymerization initiator can be used when polymerizing the polymerizable monomer. As the polymerization initiator, a normal radical initiator soluble in a supercritical fluid and a subcritical fluid is used, and can be arbitrarily selected in view of a reaction temperature and a 10-hour half-life. For example, azo polymerization initiators such as 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), lauryl peroxide, benzoyl peroxide, tert-butyl peroct And peroxide based initiators such as potassium persulfate. The polymerization initiator may be used in combination with sodium thiosulfate, amine or the like.

  The polymerization initiator is preferably added in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the polymerizable monomer.

  In the polymerization, after completely dissolving the polymer dispersant in the supercritical fluid or subcritical fluid, one or more vinyl monomers, a polymerization initiator, etc. are added, and the flow in the reaction vessel becomes uniform. While stirring at such a speed, heating is performed to a temperature corresponding to the dispersion rate of the initiator used. In addition, since the temperature at the initial stage of polymerization has a great influence on the particle size to be generated, it is desirable to increase the temperature to the polymerization temperature after adding the monomer and to dissolve the initiator in a small amount of solvent.

  In order to polymerize the polymerizable monomer at a high polymerization rate, the polymerization is preferably performed for 5 to 40 hours. However, in order to obtain a toner having a desired particle size and particle size distribution, the polymerization is stopped halfway. Alternatively, the polymerization rate can be increased by sequentially adding a polymerization initiator or by performing a reaction under high pressure.

  In order to adjust the molecular weight, polymerization may be performed by adding a compound having a large chain transfer constant. Examples of such a compound include a low molecular compound having a mercapto group, carbon tetrachloride, carbon tetrabromide and the like.

Here, a method for forming a polymer of a polymerizable monomer using the polymerization granulator will be described. In the polymerization granulator shown in FIG. 6, a reactor vessel 606 having a volume of 1,000 cm ³ was used. In FIG. 6, 601 is a carbon dioxide cylinder, 602 is a pressure pump, 603 is a valve, 604 is a back pressure valve, 605 is a thermostatic bath, 607 is a stirrer, and 608 is a stirrer.

  Carbon dioxide was used as the supercritical fluid gas. A composition containing at least a radical polymerizable monomer was charged into the reaction vessel 606.

  Next, carbon dioxide gas was supplied from a carbon dioxide cylinder 601, pressurized by a pressure pump 602, and introduced into the reaction vessel 606 through a valve 603. Here, by introducing high-pressure carbon dioxide while being pressurized by the pressure pump 602, the pressure in the reaction vessel 606 increases. In addition, the temperature in the reaction vessel 606 was adjusted to 320K in the constant temperature bath 605.

  When the pressure in the reaction vessel 606 is 7.3 MPa or more, the reaction vessel 606 is in a supercritical state. Further, the pressure in the reaction vessel 606 was set to 15 MPa by the back pressure valve 604, and the reaction vessel 606 was in a state in which a composition containing at least a radical polymerizable monomer and a fluorosurfactant was dissolved. In this state, while the stirrer 608 was rotated by the stirrer 607, the temperature in the reaction vessel 606 was raised to 335K and this state was maintained for 12 hours. Thereafter, the back pressure valve 604 is opened, the pressure in the reaction vessel 606 is returned to normal pressure, and the carbon dioxide fluid is vaporized, whereby a polymer can be obtained.

  In the present invention, the weight average molecular weight of the toner binder resin, which is a polymer obtained by polymerizing a polymerizable monomer, can be appropriately selected according to the purpose, but it should be 1,000 or more. Preferably, 2,000 to 10,000,000 is more preferable, and 3,000 to 1,000,000 is particularly preferable. When the weight average molecular weight is less than 1,000, the hot offset resistance may be lowered.

  Further, the weight average molecular weight of the toner binder resin is preferably 3,000 or more, and more preferably 4,000 to 10,000. When the weight average molecular weight is less than 3,000, filming may occur in members in the machine.

  The number average molecular weight and weight average molecular weight of the binder resin were measured by GPC under the following conditions.

・ Apparatus: GPC-150C (manufactured by Waters)
Column: KF801-807 (manufactured by Shodex)
・ Temperature: 40 ℃
・ Solvent: THF (tetrahydrofuran)
・ Flow rate: 1.0 ml / min ・ Sample: 0.1 ml of 0.05-0.6% concentration sample was injected

  From the molecular weight distribution of the binder resin measured under the above conditions, the number average molecular weight and the weight average molecular weight of the binder resin were calculated using a molecular weight calibration curve prepared with a monodisperse polystyrene standard sample.

  The glass transition temperature (Tg) of the toner binder resin can be appropriately selected according to the purpose, but is preferably 30 to 120 ° C, and more preferably 40 to 70 ° C. When the glass transition temperature (Tg) is less than 30 ° C., the storage stability of the toner may be lowered, and when it exceeds 120 ° C., the low-temperature fixability may be insufficient.

  Here, the glass transition temperature (Tg) is specifically determined by the following procedure. Using a Shimadzu TA-60WS and DSC-60 as measurement devices, measurement can be performed under the following measurement conditions.

〔Measurement condition〕
・ Sample container: Aluminum sample pan (with lid)
-Sample amount: 5mg
Reference: Aluminum sample pan (alumina 10 mg)
・ Atmosphere: Nitrogen (flow rate 50ml / min)
・ Temperature condition Start temperature: 20 ℃
Temperature increase rate: 10 ° C / min
End temperature: 150 ° C
Holding time: None Temperature drop: 10 ° C / min
End temperature: 20 ° C
Holding time: None Temperature increase rate: 10 ° C / min
End temperature: 150 ° C

  The measurement results were analyzed using the data analysis software (TA-60, version 1.52) manufactured by Shimadzu Corporation. In the analysis method, the glass transition temperature is obtained from the DrDSC curve which is the DSC differential curve of the second temperature rise using the glass transition point analysis function in the same apparatus. In the present invention, as the glass transition temperature, the temperature of the first shoulder portion where the glass transition starts is defined as the glass transition temperature.

  The internal additive that can be contained in the toner of the present invention can be appropriately selected according to the purpose, and examples thereof include a colorant, a release agent, a charge control agent, inorganic fine particles, and a magnetic substance.

  The colorant is not particularly limited and may be appropriately selected from known dyes and pigments according to the purpose. For example, carbon black, nigrosine dye, iron black, naphthol yellow S, Hansa yellow (10G, 5G, G), Cadmium yellow, Yellow iron oxide, Ocher, Yellow lead, Titanium yellow, Polyazo yellow, Oil yellow, Hansa yellow (GR, A, RN, R), Pigment yellow L, Benzidine yellow (G, GR) , Permanent Yellow (NCG), Vulcan Fast Yellow (5G, R), Tartrazine Lake, Quinoline Yellow Lake, Anthrazan Yellow BGL, Isoindolinone Yellow, Bengala, Pang Dan, Lead Zhu, Cadmium Red, Cadmium Mercury Red , Antimon Zhu, Permanent Red 4R, Parare , Faise red, parachlor ortho nitroaniline red, Resol Fast Scarlet G, Brilliant Fast Scarlet, Brilliant Carmine BS, Permanent Red (F2R, F4R, FRL, FRLL, F4RH), Fast Scarlet VD, Belkan Fast Rubin B, Brilliant Scarlet G, Risor Rubin GX, Permanent Red F5R, Brilliant Carmine 6B, Pigment Scarlet 3B, Bordeaux 5B, Toluidine Maroon, Permanent Bordeaux F2K, Helio Bordeaux BL, Bordeaux 10B, Bon Maroon Light, Bon Maroon Medium, Eosin Lake, Rhodamine Lake B, rhodamine lake Y, alizarin lake, thioindigo red B, thioindigo maroon, oil le Quinacridone red, pyrazolone red, polyazo red, chrome vermilion, benzidine orange, perinone orange, oil orange, cobalt blue, cerulean blue, alkaline blue rake, peacock blue rake, Victoria blue rake, metal-free phthalocyanine blue, phthalocyanine blue, Fast Sky Blue, Indanthrene Blue (RS, BC), Indigo, Ultramarine Blue, Bitumen, Anthraquinone Blue, Fast Violet B, Methyl Violet Lake, Cobalt Purple, Manganese Purple, Dioxane Violet, Anthraquinone Violet, Chrome Green, Zinc Green, Oxidation Chrome, Pyridian, Emerald Green, Pigment Green B, Naphthol Green B, Green Gold, Acid Guri And enamel lake, malachite green lake, phthalocyanine green, anthraquinone green, titanium oxide, zinc white, litbon and the like. These may be used alone or in combination of two or more.

  The content of the colorant in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 to 15% by weight, and more preferably 3 to 10% by weight. When the content of the colorant is less than 1% by weight, the coloring power of the toner may be reduced. When the content exceeds 15% by weight, poor dispersion of the pigment in the toner occurs, and the coloring power and the electrical characteristics of the toner are deteriorated. May decrease.

  The colorant may be used as a master batch combined with a resin. The resin is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, styrene or a substituted polymer thereof, a styrene copolymer, polymethyl methacrylate (polymethyl methacrylate) Methyl methacrylate), polybutyl methacrylate (polybutyl methacrylate), polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, polyester resin, epoxy resin, epoxy polyol resin, polyurethane resin, polyamide resin, polyvinyl butyral resin, polyacrylic acid resin Rosin, modified rosin, terpene resin, aliphatic hydrocarbon resin, alicyclic hydrocarbon resin, aromatic petroleum resin, chlorinated paraffin, paraffin wax and the like. These may be used alone or in combination of two or more.

  Examples of the styrene or substituted polymer thereof include polyester resin, polystyrene, poly (p-chlorostyrene), polyvinyltoluene and the like. As the styrene copolymer, styrene-p-chlorostyrene copolymer, styrene-propylene copolymer, styrene-vinyltoluene copolymer, styrene-vinylnaphthalene copolymer, styrene-methyl acrylate copolymer, Styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-butyl methacrylate Copolymer, styrene-α-chloromethyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ketone copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-acrylonitrile- Indene copolymer, styrene-mer Ynoic acid copolymer, styrene - maleic acid ester copolymers and the like.

  The masterbatch can be produced by mixing or kneading the masterbatch resin and the colorant with a high shear force. At this time, it is preferable to add an organic solvent in order to improve the interaction between the colorant and the resin. Further, when a masterbatch is produced by the flushing method, a wet cake of a colorant can be used directly, it is not necessary to dry the pigment, and it is preferable because a pigment aggregate is not formed at that time. The flushing method is a method of mixing or kneading an aqueous paste containing water of a colorant together with a resin and an organic solvent, and transferring the colorant to the resin to remove moisture and the organic solvent. For mixing or kneading, it is preferable to use a high shear dispersion device such as a three-roll mill.

  As a method of incorporating these colorants into the toner particles, a method of dispersing the colorant in a supercritical fluid before polymerization and incorporating it into the colorant particles simultaneously with polymerization, and using an organic solvent as an entrainer after polymerization. There is a method in which the toner particles are swollen into the supercritical fluid by heating and / or pressurizing in the supercritical fluid, and the colorant particles are pressed into the toner particles.

  In addition, the toner particles can be colored with a dye after polymerization. In the present invention, the binder resin obtained in the polymerization step can be dyed using an entrainer, but in a supercritical fluid. The entrainer used for dyeing the toner resin particles obtained by polymerization is preferably an organic solvent in which the binder resin does not dissolve or a slightly swelled organic solvent. Specifically, the difference between the solubility parameter (hereinafter referred to as SP value) between the entrainer and the binder resin is preferably 1.0 or more, and more preferably 2.0 or more. For example, for styrene-acrylic resins (particles), alcohols such as methanol, ethanol and n-propanol having a high SP value, or n-hexane and n-heptane having a low SP value can be used. . At this time, if the difference in SP value exceeds 5, the wetting of the entrainer with respect to the binder resin (particles) becomes worse, and the dispersibility of the binder resin (particles) decreases, which is not preferable. Therefore, the optimum SP value difference is 2-5.

  The dye used for dyeing has a ratio (D1 / D2) of the solubility D1 with respect to the organic solvent which is the entrainer used and the solubility D2 with respect to the organic solvent capable of dissolving the binder resin is 0.5 or less. Any dye may be used, but in order to increase the powder resistance of the toner after dyeing, it is preferable to use disperse dyes, oil-soluble dyes, vat dyes, etc. Is particularly preferred. Also, several kinds of dyes can be used depending on the coloring. Note that when the powder resistance is lowered, the transfer rate may be lowered.

  As a dyeing method, a binder resin (resin fine particles), a dye and an entrainer are placed in a pressure vessel, and a treatment is performed in a supercritical fluid, or a solution in which the dye is dissolved or dispersed in the entrainer is placed in a pressure vessel. And a method of performing the treatment in a supercritical fluid.

  The weight ratio (weight ratio) of the dye to the binder resin (resin fine particles) can be appropriately selected according to the degree of coloring, but is usually 1 to 20% with respect to 100 parts by weight of the resin fine particles.

  Specific examples of the dye include C.I. I. SOLVENT YELLOW (6, 9, 17, 31, 35, 100, 102, 103, 105), C.I. I. SOLVORANCE ORANGE (2, 7, 13, 14, 66), C.I. I. SOLVEN RED (5,16,17,18,19,22,23,143,145,146,149,150,151,157,158), C.I. I. SOLVENT VIOLET (31, 32, 33, 37), C.I. I. SOLVEN BLUE (22, 63, 78, 83-86, 191, 194, 195, 104), C.I. I. SOLVEN GREEN (24, 25), C.I. I. SOLVENT BROWN (3, 9) and the like.

  Examples of commercially available dyes include Aizen SOT dyes Yellow-1,3,4, Orange-1,2,3, Scarlet-1, Red-1,2,3, Brown-2, Blue-1,2, Violet-1. , Green-1,2,3, Black-1,4,6,8 (above, manufactured by Hodogaya Chemical Co., Ltd.), Sudan dye Yellow-146,150, Orange-220, Red-290,380,460, Blue-670 (Above, manufactured by BASF), Dialresin Yellow-3G, F, H2G, HG, HC, HL, Orange-HS, G, Red-GG, S, HS, A, K, H5B, Violet-D, Blue-J , G, N, K, P, H3G, 4G, Green-C, Brown-A (manufactured by Mitsubishi Kasei), oil color YElow-3 , GG-S, # 105, Orange-PS, PR, # 201, Scarlet- # 308, Red-5B, Brown-GR, # 416, Green-BG, # 502, Blue-BOS, IIN, Black-HBB, # 803, EB, EX (above, manufactured by Orient Chemical Co., Ltd.), Sumiplast Blue GP, OR, Red FB, 3B, Yellow FL7G, GC (above, manufactured by Sumitomo Chemical Co., Ltd.), Kayalon Polyester Black EX-SF300, Kayaset Red-B, Blue A-2R (Nippon Kayaku Co., Ltd.) and the like. Of course, the dye is appropriately selected depending on the combination of the resin fine particles and the organic solvent used at the time of dyeing, and is not limited to the above example.

  There is no restriction | limiting in particular in the said mold release agent, According to the objective, it can select suitably from well-known mold release agents, Waxes etc. can be used. Examples of the waxes include low molecular weight polyolefin waxes, synthetic hydrocarbon waxes, natural waxes, petroleum waxes, higher fatty acids and metal salts thereof, higher fatty acid amides, and various modified waxes thereof. These may be used alone or in combination of two or more.

  Examples of the low molecular weight polyolefin wax include low molecular weight polyethylene wax and low molecular weight polypropylene wax. Examples of the synthetic hydrocarbon wax include Fischer-Tropsch wax. Examples of natural waxes include beeswax, carnauba wax, candelilla wax, rice wax, and montan wax. Examples of petroleum waxes include paraffin wax and microcrystalline wax. Examples of higher fatty acids include stearic acid, palmitic acid, myristic acid and the like.

  The melting point of the release agent is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 40 to 160 ° C, more preferably 50 to 120 ° C, and particularly preferably 60 to 90 ° C. . If the melting point is less than 40 ° C., the wax may adversely affect the heat-resistant storage stability. If it exceeds 160 ° C., it tends to cause a cold offset when fixing at a low temperature, and paper wraps around the fixing machine. Sometimes.

  The content of the release agent in the toner is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0 to 40% by weight, and more preferably 3 to 30% by weight. When the content of the release agent exceeds 40% by weight, the low-temperature fixability may be deteriorated or the image quality may be deteriorated due to excessive glossiness.

  These release agents are easily taken into the toner particles because the release agent is easily dissolved in the supercritical fluid by heating and pressurizing in the supercritical fluid after polymerization.

  The charge control agent is not particularly limited and can be appropriately selected from known charge control agents according to the purpose. However, when a colored material is used, the color tone may change. Close materials are preferable, and examples thereof include metal complex dyes, fluorine-modified quaternary ammonium salts, metal salts of salicylic acid, and metal salts of salicylic acid derivatives. In addition, although a metal can be suitably selected according to the objective, aluminum, zinc, titanium, strontium, boron, silicon, nickel, iron, chromium, zirconium etc. are mentioned.

  Commercially available charge control agents include oxynaphthoic acid metal complex E-82, salicylic acid metal complex E-84, phenol condensate E-89 (above, manufactured by Orient Chemical Industries), LRA-901, Examples thereof include LR-147 (manufactured by Nippon Carlit Co., Ltd.), a quinacridone, an azo pigment, a polymer compound having a sulfonic acid, a carboxylic acid, a quaternary ammonium salt, and the like, which are boron complexes.

  The content of the charge control agent in the toner can be appropriately selected depending on the type of binder resin, the type of additive, the dispersion method, and the like, but it is 0 to 10% by weight with respect to the binder resin. Preferably, 1 to 5% by weight is more preferable. If it exceeds 10% by weight, the chargeability of the toner becomes too large, the effect of the main charge control agent is reduced, the electrostatic attraction with the developing roller is increased, and the flowability of the developer is reduced, The image density may decrease.

  External toners such as a fluidity improver and a cleaning property improver may be added to the toner produced by either production method 1 or production method 2. The fluidity improver improves the fluidity of the toner (becomes easy to flow) when added to the toner surface.

  Examples of the fluidity improver include, for example, carbon black, vinylidene fluoride fine powder, fluorine-based resin powder such as polytetrafluoroethylene fine powder, wet process silica, fine powder silica such as dry process silica, fine powder unoxidized titanium, Examples include finely powdered non-alumina, treated silica obtained by subjecting them to a surface treatment with a silane coupling agent, a titanium coupling agent, or silicone oil, treated titanium oxide, and treated alumina. Among these, fine powder silica, fine powder unoxidized titanium, and fine powder unalumina are preferable, and treated silica obtained by surface-treating these with a silane coupling agent or silicone oil is more preferable.

  The particle size of the fluidity improver is preferably 5 nm to 500 nm and more preferably 7 nm to 120 nm as an average primary particle size.

  The fine powder silica is a fine powder produced by vapor phase oxidation of a silicon halide inclusion, and is called so-called dry silica or fumed silica.

  Examples of commercially available silica fine powders produced by vapor phase oxidation of silicon halogen compounds include AEROSIL (trade name of Nippon Aerosil Co., Ltd., hereinafter the same) -130, -300, -380, -TT600, -MOX170, -MOX80, -COK84: Ca-O-SiL (trade name of CABOT) -M-5, -MS-7, -MS-75, -HS-5, -EH-5: Wacker HDK (trade name of Wacker to Me) N20, V15, -N20E, -T30, -T40: D-CFine Silica (a trade name of Dow Corning): Fransol (a trade name of Flanged).

  Furthermore, a treated silica fine powder obtained by hydrophobizing a silica fine powder produced by vapor phase oxidation of a silicon halogen compound is more preferable. In the treated silica fine powder, it is particularly preferred to treat the silica fine powder so that the degree of hydrophobicity measured by a methanol titration test is preferably 30 to 80%. Hydrophobization is imparted by chemical or physical treatment with an organosilicon compound that reacts or physically adsorbs with silica fine powder. As a preferred method, a method of treating silica fine powder produced by vapor phase oxidation of a silicon halogen compound with an organosilicon compound is preferable.

  Examples of organosilicon compounds include hydroxypropyltrimethoxysilane, phenyltrimethoxysilane, n-hexadecyltrimethoxysilane, n-octadecyltrimethoxysilane, vinylmethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, dimethylvinylchlorosilane, Divinylchlorosilane, γ-methacryloxypropyltrimethoxysilane, hexamethyldisilane, trimethylsilane, trimethylchlorosilane, dimethyldichlorosilane, methyltrichlorosilane, allyldimethylchlorosilane, allylphenyldichlorosilane, benzyldimethylchlorosilane, bromomethyldimethylchlorosilane, α -Chloroethyltrichlorosilane, β-chloroethyltrichlorosilane, chloromethyldimethylchlorosilane , Triorganosilyl mercaptan, trimethylsilyl mercaptan, triorganosilyl acrylate, vinyldimethylacetoxysilane, dimethylethoxysilane, trimethylethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, isobutyltrimethoxysilane, dimethyldimethoxysilane, diphenyldiethoxysilane , Hexamethyldisiloxane, 1,3-divinyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, and 2 to 12 siloxane units per molecule, Examples include dimethylpolysiloxane containing 0 to 1 hydroxyl group bonded to Si. Furthermore, silicone oils such as dimethyl silicone oil can be mentioned. These may be used individually by 1 type, and 2 or more types may be mixed and used for them.

  The number average particle diameter of the fluidity improver is preferably 5 to 100 nm, more preferably 5 to 50 nm.

  The specific surface area by nitrogen adsorption measured by the BET method is preferably 30 m2 / g or more, and more preferably 60 to 400 m2 / g. The surface-treated fine powder is preferably 20 m 2 / g or more, more preferably 40 to 300 m 2 / g. The application amount of these fine powders is preferably 0.03 to 8 parts by weight with respect to 100 parts by weight of the toner particles.

  Examples of the cleaning property improver for removing the developer after transfer remaining on the electrostatic latent image carrier or the primary transfer medium include fatty acid metal salts such as zinc stearate, calcium stearate, stearic acid, and polymethyl methacrylate. Examples thereof include polymer fine particles produced by soap-free emulsion polymerization such as fine particles and polystyrene fine particles, and polymer particles such as silicone, benzoguanamine, and nylon. The polymer fine particles preferably have a relatively narrow particle size distribution and a volume average particle size of 0.01 to 1 μm.

  In the toner of the present invention, as other external additives, for the purpose of protecting the electrostatic latent image carrier / carrier, adjusting thermal characteristics / electrical characteristics / physical characteristics, adjusting the resistance, adjusting the softening point, improving the fixing rate, etc. , Various metal soaps, fluorosurfactants, dioctyl phthalate, tin oxide, zinc oxide, carbon black, antimony oxide, etc. as conductive agents and inorganic fine powders such as titanium oxide, aluminum oxide, alumina, etc. It can be added depending on. These inorganic fine powders may be hydrophobized as necessary. Also, lubricants such as polytetrafluoroethylene, zinc stearate, polyvinylidene fluoride, abrasives such as cesium oxide, silicon carbide, strontium titanate, anti-caking agent, and white and black fine particles having opposite polarity to the toner particles It can also be used as a developability improver.

  These additives include silicone varnishes, various modified silicone varnishes, silicone oils, various modified silicone oils, silane coupling agents, silane coupling agents having functional groups, and other organosilicon compounds for the purpose of charge control and the like. It is also preferable to treat with a treating agent or various treating agents.

  The shape, size, etc. of the toner of the present invention are not particularly limited and can be appropriately selected according to the purpose. The average circularity, weight average particle diameter, weight average particle diameter as follows: And the ratio of the number average particle diameter (weight average particle diameter / number average particle diameter).

  The average circularity is a value obtained by dividing the perimeter of an equivalent circle having the same projected shape as the toner shape by the perimeter of the actual particles, and is preferably 0.900 to 0.980, for example, 0.950 to 0 .975 is more preferred. Note that particles having an average circularity of less than 0.94 are preferably 15% or less.

  If the average circularity is less than 0.900, satisfactory transferability and a high-quality image free from dust may not be obtained. If the average circularity exceeds 0.980, image formation employing blade cleaning or the like is employed. In the system, defective cleaning occurs on the photoconductor and the transfer belt, and in the case of image formation with a high image area ratio such as a photographic image, an untransferred image is formed due to defective paper feeding, etc. The accumulated toner may become a transfer residual toner on the photoconductor, resulting in background smearing of the image, or it may contaminate the charging roller for charging the photoconductor in contact with the original charging ability. It may become impossible to demonstrate.

  Here, the average circularity can be measured by using a flow particle image analyzer (Flow Particle Image Analyzer). For example, it can be measured using a flow type particle image analyzer FPIA-2000 manufactured by Toa Medical Electronics Co., Ltd.

In the measurement, fine dust is removed through a filter, and as a result, in 10 ml of water having 10 or less particles in a measurement range (for example, an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm) in 10 ⁻³ cm ³ of water. Add a few drops of nonionic surfactant (preferably Contaminone N manufactured by Wako Pure Chemical Industries, Ltd.), add 5 mg of the sample to be measured, and 20 kHz, 50 W / 10 cm with an ultrasonic dispersing device (UH-50, manufactured by SMT). ^3. Dispersion treatment for 1 minute under the conditions of ³ and further dispersion treatment for a total of 5 minutes, the particle concentration of the measurement sample is 4,000 to 8,000 particles / 10 ⁻³ cm ³ The particle size distribution of particles having an equivalent circle diameter of 0.60 μm or more and less than 159.21 μm is measured using the sample dispersion liquid (as a target).

  The sample dispersion liquid is passed through a flow path (expanded along the flow direction) of a flat and flat transparent flow cell (thickness: about 200 μm). In order to form an optical path that passes across the thickness of the flow cell, the strobe and the CCD camera are mounted on the flow cell so as to be opposite to each other. While the sample dispersion is flowing, strobe light is irradiated at 1/30 second intervals to obtain an image of the particles flowing through the flow cell, so that each particle has a certain range parallel to the flow cell 2. Taken as a dimensional image. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the equivalent circle diameter.

  In about 1 minute, the equivalent circle diameter of 1,200 or more particles can be measured, and the number based on the equivalent circle diameter distribution and the ratio (number%) of particles having a prescribed equivalent circle diameter can be measured. The results (frequency% and cumulative%) can be obtained by dividing the range of 0.06 to 400 μm into 226 channels (divided into 30 channels per octave). In actual measurement, particles are measured in the range where the equivalent circle diameter is 0.60 μm or more and less than 159.21 μm.

  The weight average particle size and particle size distribution can be measured by using a Coulter counter TA-II or Coulter Multisizer II (both manufactured by Coulter Co.).

  First, 0.1 to 5 ml of a surfactant (alkyl benzene sulfonate) is added as a dispersant to 100 to 150 ml of an electrolytic aqueous solution. Here, the electrolytic solution is prepared by preparing a 1% by weight NaCl aqueous solution using first grade sodium chloride, and for example, ISOTON-II (manufactured by Coulter) can be used. Here, 2 to 20 mg of a measurement sample was further added. The electrolyte in which the sample is suspended is subjected to a dispersion treatment for 1 to 3 minutes with an ultrasonic disperser, and the weight and number of toners are measured with the measuring device using a 100 μm aperture as an aperture, The number distribution was calculated. From the obtained distribution, the weight average particle diameter (D4) and the number average particle diameter (Dn) of the toner can be obtained.

  As channels, 2.00 to less than 2.52 μm; 2.52 to less than 3.17 μm; 3.17 to less than 4.00 μm; 4.00 to less than 5.04 μm; 5.04 to less than 6.35 μm; 6 Less than 35 to 8.00 μm; less than 8.00 to less than 10.08 μm; less than 10.08 to less than 12.70 μm; less than 12.70 to less than 16.00 μm; less than 16.00 to less than 20.20 μm; Uses 13 channels of less than 40 μm; 25.40 to less than 32.00 μm; 32.00 to less than 40.30 μm, and targets particles having a particle size of 2.00 μm to less than 40.30 μm.

  There is no restriction | limiting in particular as a weight average particle diameter of the said toner, Although it can select suitably according to the objective, For example, 1-10 micrometers is preferable and 3-8 micrometers is more preferable.

  When the weight average particle size is less than 1 μm, in a two-component developer, the toner may be fused to the surface of the carrier during a long period of stirring in the developing device, and the charging ability of the carrier may be reduced. In the developer, toner filming on the developing roller and toner fusion to the member such as a blade are likely to occur because the toner layer is thinned. It becomes difficult to obtain an image of an image quality, and when the balance of the toner in the developer is performed, the variation in the particle diameter of the toner may increase.

  The ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) in the toner is preferably 1.00 to 1.15, and more preferably 1.00 to 1.05.

  When the ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) exceeds 1.15, the two-component developer causes the surface of the carrier to remain on the surface of the carrier during long-term agitation in the developing device. The toner may be fused to reduce the charging ability of the carrier. In the case of a one-component developer, the toner filming on the developing roller or the toner is thinned so that the toner is fused to a member such as a blade. May occur easily, and it becomes difficult to obtain a high-resolution and high-quality image, and when the balance of the toner in the developer is performed, the fluctuation of the toner particle size may increase. is there.

  The weight average particle diameter and the ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) are, for example, a particle size measuring device “Coulter Counter TAII” manufactured by Coulter Electronics. Can be measured.

(Developer)
The developer of the present invention contains at least the toner of the present invention and other components appropriately selected such as a carrier. The developer may be a one-component developer or a two-component developer. However, when it is used for a high-speed printer or the like corresponding to the recent improvement in information processing speed, the life is improved. In view of the above, the two-component developer is preferable.

  In the case of the one-component developer using the toner of the present invention, even if the balance of the toner is performed, there is little fluctuation in the particle diameter of the toner, and the filming of the toner on the developing roller or the toner is made thin. Therefore, the toner is not fused to a member such as a blade, and good and stable developability and image can be obtained even when the developing device is used (stirred) for a long time. In addition, in the case of the two-component developer using the toner of the present invention, even if the toner balance for a long time is performed, the fluctuation of the toner diameter in the developer is small, and it is good even for long-term stirring in the developing device. And stable developability can be obtained.

  When the toner of the present invention is used as a two-component developer by mixing with a carrier, the carrier may be a normal carrier such as ferrite or magnetite or a resin-coated carrier.

  The resin-coated carrier comprises a carrier core particle and a coating material that is a resin that coats (coats) the surface of the carrier core particle.

  The material of the carrier core particles is not particularly limited and may be appropriately selected from known materials. For example, 50 to 90 emu / g manganese-strontium (Mn—Sr) -based material, manganese-magnesium (Mn -Mg) -based materials and the like are preferable, and high magnetization materials such as iron powder (100 emu / g or more) and magnetite (75 to 120 emu / g) are preferable in terms of securing image density. Further, a weakly magnetized material such as a copper-zinc (Cu—Zn) -based (30 to 80 emu / g) is advantageous in that it can weaken the contact with the photoconductor in which the toner is in a spiked state and is advantageous in improving the image quality. Is preferred. These may be used alone or in combination of two or more.

  The carrier core particles have a volume average particle size of preferably 10 to 150 μm, more preferably 40 to 100 μm.

  When the volume average particle size is less than 10 μm, there are many fine powder systems in the distribution of carrier particles, the magnetization per particle may be lowered and carrier scattering may occur, and when it exceeds 150 μm, the specific surface area is increased. In some cases, the toner image may be scattered and the toner may be scattered. In the case of a full color having a large solid portion, the reproduction of the solid portion may be deteriorated.

  The material of the resin layer is not particularly limited and can be appropriately selected from known resins according to the purpose. For example, amino resins, polyvinyl resins, polystyrene resins, halogenated olefin resins, Polyester resin, polycarbonate resin, polyethylene resin, polyvinyl fluoride resin, polyvinylidene fluoride resin, polytrifluoroethylene resin, polyhexafluoropropylene resin, copolymer of vinylidene fluoride and acrylic monomer, vinylidene fluoride And a copolymer of vinyl fluoride, a fluoroterpolymer such as a terpolymer of tetrafluoroethylene, vinylidene fluoride, and a non-fluorinated monomer, and a silicone resin. These may be used individually by 1 type and may use 2 or more types together.

  Examples of the amino resins include urea-formaldehyde resins, melamine resins, benzoguanamine resins, urea resins, polyamide resins, and epoxy resins. Examples of the polyvinyl resins include acrylic resins, polymethyl methacrylate resins, and polyacrylonitrile resins. , Polyvinyl acetate resin, polyvinyl alcohol resin, polyvinyl butyral resin and the like. Examples of the polystyrene resin include polystyrene resin and styrene acrylic copolymer resin. Examples of the halogenated olefin resin include polyvinyl chloride. Examples of the polyester resin include polyethylene terephthalate resin and polybutylene terephthalate resin.

  The resin layer may contain conductive powder or the like as necessary. Examples of the conductive powder include metal powder, carbon black, titanium oxide, tin oxide, and zinc oxide. The average particle diameter of these conductive powders is preferably 1 μm or less. When the average particle diameter exceeds 1 μm, it may be difficult to control electric resistance.

  For example, the resin layer is prepared by dissolving the silicone resin or the like in a solvent to prepare a coating solution, and then uniformly coating the coating solution on the surface of the core material by a known coating method, drying, and baking. It can be formed by doing. Examples of the coating method include an immersion method and a spray method.

  There is no restriction | limiting in particular as said solvent, Although it can select suitably according to the objective, For example, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cellosolve, butyl acetate, etc. are mentioned.

  The baking is not particularly limited, and may be an external heating method or an internal heating method. For example, a stationary electric furnace, a fluid electric furnace, a rotary electric furnace, a burner furnace, etc. The method of using, the method of using a microwave, etc. are mentioned.

  The amount of the resin layer in the carrier is preferably 0.01 to 5.0% by weight. When the amount is less than 0.01% by weight, it may not be possible to form a uniform resin layer on the surface of the core. When the amount exceeds 5.0% by weight, the resin layer becomes too thick. As a result, granulation of carriers occurs, and uniform carrier particles may not be obtained.

  When the developer is the two-component developer, the content of the carrier in the two-component developer is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 90 to 98% by weight Is preferable, and 93 to 97 weight% is more preferable.

  Since the developer contains the toner of the present invention, it is possible to stably form a high-quality image with excellent charging performance during image formation.

(Toner container)
The toner-containing container of the present invention comprises the toner or the developer of the present invention contained in a container.

  There is no restriction | limiting in particular as said container, It can select suitably from well-known things, For example, what has a container main body and a cap containing a toner etc. are mentioned suitably.

  The size, shape, structure, material and the like of the container body containing toner are not particularly limited and can be appropriately selected according to the purpose. For example, the shape is preferably cylindrical. A spiral irregularity is formed on the peripheral surface, and the toner as the contents can be transferred to the discharge port side by rotating, and part or all of the spiral part has a bellows function, etc. Is particularly preferred.

  The material of the toner-containing container body is not particularly limited, and those having good dimensional accuracy are preferable. For example, a resin is preferably used. Among them, for example, polyester resin, polyethylene resin, polypropylene resin, polystyrene resin, Preferable examples include vinyl chloride resin, polyacrylic acid, polycarbonate resin, ABS resin, polyacetal resin, and the like.

  The container containing toner is easy to store and transport, has excellent handling properties, and can be attached to a process cartridge, an image forming apparatus, etc., which will be described later, detachably and can be suitably used for replenishing toner.

(Process cartridge)
The process cartridge of the present invention develops an electrostatic latent image carrier carrying an electrostatic latent image and the electrostatic latent image carried on the electrostatic latent image carrier using a developer to form a visible image. And at least developing means for forming the film, and other means appropriately selected as necessary.

  The developing means includes a developer container that contains the toner or developer of the present invention, and a developer carrier that carries and transports the toner or developer contained in the developer container. And a layer thickness regulating member for regulating the thickness of the toner layer to be carried.

  Here, for example, as shown in FIG. 7, the process cartridge includes an electrostatic latent image carrier 701, and includes a charging unit 702, a developing unit 704, a transfer unit 708, and a cleaning unit 707, and further if necessary. And other means. In FIG. 7, reference numeral 703 denotes exposure by exposure means, and 705 denotes a recording medium.

  Next, an image forming process using the process cartridge shown in FIG. 7 will be described. The electrostatic latent image carrier 701 is rotated in the direction of the arrow while being charged by the charging unit 702 and exposed by the exposure unit (not shown). An electrostatic latent image corresponding to the exposure image is formed on the surface. The electrostatic latent image is developed by the developing unit 704, and the obtained visible image is transferred to the recording medium 705 by the transfer unit 708 and printed out. Next, the surface of the latent electrostatic image bearing member after the image transfer is cleaned by the cleaning unit 707, and is further neutralized by the neutralizing unit (not shown), and the above operation is repeated again.

(Image forming method and image forming apparatus)
The image forming apparatus of the present invention includes at least an electrostatic latent image carrier, an electrostatic latent image forming unit, a developing unit, a transfer unit, and a fixing unit, and further appropriately selected as necessary. It has other means, for example, static elimination means, cleaning means, recycling means, control means and the like.

The electrostatic latent image forming step is a step of forming an electrostatic latent image on the electrostatic latent image carrier.
There are no particular restrictions on the material, shape, structure, size, etc. of the electrostatic latent image carrier (sometimes referred to as “photoconductive insulator” or “photoconductor”), and among the known ones The shape is preferably a drum shape, and the material is an organic photoconductor, an inorganic photoconductor such as amorphous silicon or selenium, or the like.

  The formation of the electrostatic latent image can be performed, for example, by uniformly charging the surface of the electrostatic latent image carrier and then performing imagewise exposure, and is performed by the electrostatic latent image forming unit. be able to. The electrostatic latent image forming means includes, for example, at least a charger that uniformly charges the surface of the electrostatic latent image carrier and an exposure device that exposes the surface of the electrostatic latent image carrier imagewise. Prepare.

  The charging can be performed, for example, by applying a voltage to the surface of the electrostatic latent image carrier using the charger.

  The charger is not particularly limited and may be appropriately selected depending on the purpose. For example, a known contact charging device including a conductive or semiconductive roll, brush, film, rubber blade, etc. And non-contact chargers using corona discharge such as corotrons and corotrons.

  The exposure can be performed, for example, by exposing the surface of the latent electrostatic image bearing member imagewise using the exposure device.

  The exposure device is not particularly limited as long as it can expose the surface of the electrostatic latent image carrier charged by the charger so as to form an image to be formed, and is appropriately selected according to the purpose. For example, various exposure devices such as a copying optical system, a rod lens array system, a laser optical system, and a liquid crystal shutter optical system can be used.

  In the present invention, a back light system in which imagewise exposure is performed from the back side of the electrostatic latent image carrier may be employed.

-Development process and development means-
The developing step is a step of developing the electrostatic latent image using the toner or the developer of the present invention to form a visible image.

  The visible image can be formed, for example, by developing the electrostatic latent image using the toner or the developer of the present invention, and can be performed by the developing unit.

  The developing unit is not particularly limited as long as it can be developed using, for example, the toner or the developer of the present invention, and can be appropriately selected from known ones. For example, the toner of the present invention Preferably, a developer containing at least a developer and having at least a developer capable of bringing the toner or the developer into contact or non-contact with the electrostatic latent image is provided. Etc. are more preferable.

  The developing device may be a single color developing device or a multi-color developing device. For example, a stirrer for charging the toner or the developer by frictional stirring, and a rotatable magnet. The thing which has a roller etc. are mentioned suitably.

  In the developing device, for example, the toner and the carrier are mixed and agitated, and the toner is charged by friction at that time, and held on the surface of the rotating magnet roller in a raised state to form a magnetic brush. . Since the magnet roller is disposed in the vicinity of the electrostatic latent image carrier (photoconductor), a part of the toner constituting the magnetic brush formed on the surface of the magnet roller is electrically attracted. It moves to the surface of the electrostatic latent image carrier (photoconductor) by force. As a result, the electrostatic latent image is developed with the toner, and a visible image is formed with the toner on the surface of the electrostatic latent image carrier (photoconductor).

  The developer accommodated in the developing device is a developer containing the toner of the present invention, but the developer may be a one-component developer or a two-component developer. The toner contained in the developer is the toner of the present invention.

-Transfer process and transfer means-
The transfer step is a step of transferring the visible image onto a recording medium. After the primary transfer of the visible image onto the intermediate transfer member using an intermediate transfer member, the visible image is transferred onto the recording medium. A primary transfer step of forming a composite transfer image by transferring a visible image onto an intermediate transfer body using two or more colors, preferably full color toner as the toner, and a composite transfer image; A mode including a secondary transfer step of transferring the transfer image onto the recording medium is more preferable.

  The transfer can be performed, for example, by charging the visible image with the intermediate transfer member or the recording medium using a transfer charger, and can be performed by the transfer unit. The transfer means includes a primary transfer means for transferring a visible image onto an intermediate transfer member to form a composite transfer image, and a secondary transfer means for transferring the composite transfer image onto a recording medium. Embodiments are preferred.

  The intermediate transfer member is not particularly limited and may be appropriately selected from known transfer members according to the purpose. For example, a transfer belt and the like are preferable.

  The transfer means (the primary transfer means and the secondary transfer means) is a transfer for peeling and charging the visible image formed on the electrostatic latent image carrier (photoconductor) to the recording medium side. It is preferable to have at least a vessel. There may be one transfer means or two or more transfer means.

  Examples of the transfer device include a corona transfer device using corona discharge, a transfer belt, a transfer roller, a pressure transfer roller, and an adhesive transfer device.

  The recording medium is not particularly limited and can be appropriately selected from known recording media (recording paper).

  The fixing step is a step of fixing the visible image transferred to the recording medium using a fixing device, and may be performed each time the toner of each color is transferred to the recording medium, or for the toner of each color. You may perform this simultaneously in the state which laminated | stacked this.

  There is no restriction | limiting in particular as said fixing device, Although it can select suitably according to the objective, A well-known heating-pressing means is suitable. Examples of the heating and pressing means include a combination of a heating roller and a pressure roller, a combination of a heating roller, a pressure roller, and an endless belt.

  The heating in the heating and pressing means is usually preferably 120 to 200 ° C.

  In the present invention, for example, a known optical fixing device may be used together with or in place of the fixing step and the fixing unit depending on the purpose.

  The neutralization step is a step of performing neutralization by applying a neutralization bias to the electrostatic latent image carrier, and can be suitably performed by a neutralization unit.

  The neutralization means is not particularly limited, and may be appropriately selected from known neutralizers as long as it can apply a neutralization bias to the electrostatic latent image carrier. Preferably mentioned.

  The cleaning step is a step of removing the toner remaining on the electrostatic latent image carrier and can be suitably performed by a cleaning unit.

  The cleaning means is not particularly limited as long as it can remove the electrophotographic toner remaining on the electrostatic latent image carrier, and can be appropriately selected from known cleaners. Suitable examples include brush cleaners, electrostatic brush cleaners, magnetic roller cleaners, blade cleaners, brush cleaners, web cleaners, and the like.

  The recycling step is a step of recycling the toner removed by the cleaning step to the developing unit, and can be suitably performed by the recycling unit.

  There is no restriction | limiting in particular as said recycling means, A well-known conveyance means etc. are mentioned.

  One mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. An image forming apparatus 800 shown in FIG. 8 includes a photosensitive drum 810 (hereinafter referred to as “photosensitive member 810”) as the electrostatic latent image carrier, a charging roller 820 as the charging unit, and an exposure as the exposure unit. The apparatus 830 includes a developing device 840 as the developing means, an intermediate transfer member 850, a cleaning device 860 as the cleaning means having a cleaning blade, and a static elimination lamp 870 as the static elimination means.

  The intermediate transfer member 850 is an endless belt, and is designed to be movable in the direction of an arrow in the figure by three rollers 851 that are arranged on the inner side and stretch the belt. Part of the three rollers 851 also functions as a transfer bias roller that can apply a predetermined transfer bias (primary transfer bias) to the intermediate transfer member 850. An intermediate transfer body cleaning blade 890 is disposed in the vicinity of the intermediate transfer body 850, and a transfer bias for transferring (secondary transfer) a visible image (toner image) to the recording medium 895 is applied. Possible transfer rollers 880 as the transfer means are arranged to face each other. Around the intermediate transfer member 850, a corona charger 858 for applying a charge to the visible image on the intermediate transfer member 850 is arranged with the electrostatic latent image carrier 810 in the rotation direction of the intermediate transfer member 850. It is disposed between a contact portion with the intermediate transfer member 850 and a contact portion between the intermediate transfer member 850 and the recording medium 895.

  The developing device 840 includes a developing belt 841 as a developer carrier and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and a cyan developing unit 845C provided around the developing belt 841. Yes. The black developing unit 845K includes a developer containing portion 842K, a developer supply roller 843K, and a developing roller 844K. The yellow developing unit 845Y includes a developer accommodating portion 842Y, a developer supply roller 843Y, and a developing roller 844Y. The magenta developing unit 845M includes a developer accommodating portion 842M, a developer supply roller 843M, and a developing roller 844M. The cyan developing unit 845C includes a developer accommodating portion 842C, a developer supply roller 843C, and a developing roller 844C. Further, the developing belt 841 is an endless belt, is rotatably stretched by a plurality of belt rollers, and a part thereof is in contact with the electrostatic latent image carrier 810.

  In the image forming apparatus 800 shown in FIG. 8, for example, a charging roller 820 uniformly charges the photosensitive drum 810. The exposure device 830 performs imagewise exposure on the photosensitive drum 810 to form an electrostatic latent image. The electrostatic latent image formed on the photosensitive drum 810 is supplied with toner from the developing device 840 and developed to form a visible image (toner image). The visible image (toner image) is transferred (primary transfer) onto the intermediate transfer body 850 by the voltage applied from the roller 851, and further transferred onto the transfer paper 895 (secondary transfer). As a result, a transfer image is formed on the transfer paper 895. The residual toner on the photoconductor 810 is removed by the cleaning device 860, and the charge on the photoconductor 810 is temporarily removed by the charge eliminating lamp 870.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The image forming apparatus 900 shown in FIG. 9 does not include the developing belt 841 in the image forming apparatus 800 shown in FIG. 8, and a black developing unit 845K, a yellow developing unit 845Y, a magenta developing unit 845M, and the like around the photosensitive member 810. Except for the fact that the cyan developing unit 845C is directly opposed, it has the same configuration as the image forming apparatus 800 shown in FIG. In FIG. 9, the same components as those in FIG. 8 are denoted by the same reference numerals.

  Another mode for carrying out the image forming method of the present invention by the image forming apparatus will be described with reference to FIG. The tandem image forming apparatus shown in FIG. 10 is a tandem type color image forming apparatus. The tandem image forming apparatus includes a copying apparatus main body 150, a paper feed table 200, a scanner 300, and an automatic document feeder (ADF) 400.

  The copying machine main body 150 is provided with an endless belt-shaped intermediate transfer member 1050 at the center. The intermediate transfer member 1050 is stretched around support rollers 1014, 1015, and 1016, and can rotate clockwise in FIG. An intermediate transfer body cleaning device 1017 for removing residual toner on the intermediate transfer body 1050 is disposed in the vicinity of the support roller 1015. The intermediate transfer member 1050 stretched by the support roller 1014 and the support roller 1015 has a tandem type in which four image forming units 1018 of yellow, cyan, magenta, and black face each other along the conveyance direction. A developing device 120 is disposed. An exposure device 1021 is disposed in the vicinity of the tandem developing device 120. A secondary transfer device 1022 is disposed on the side of the intermediate transfer body 1050 opposite to the side on which the tandem developing device 120 is disposed. In the secondary transfer device 1022, a secondary transfer belt 1024, which is an endless belt, is stretched around a pair of rollers 1023, and the transfer sheet conveyed on the secondary transfer belt 1024 and the intermediate transfer body 1050 are in contact with each other. Is possible. A fixing device 1025 is disposed in the vicinity of the secondary transfer device 1022. The fixing device 1025 includes a fixing belt 1026 that is an endless belt, and a pressure roller 1027 that is pressed against the fixing belt 1026.

  In the tandem image forming apparatus, a sheet reversing device 1028 for reversing the transfer paper for image formation on both sides of the transfer paper is disposed in the vicinity of the secondary transfer device 1022 and the fixing device 1025. .

  Next, formation of a full-color image (color copy) using the tandem developing device 120 will be described. That is, first, a document is set on the document table 130 of the automatic document feeder (ADF) 400, or the automatic document feeder 400 is opened and a document is set on the contact glass 1032 of the scanner 300. 400 is closed.

  When a start switch (not shown) is pressed, when a document is set on the automatic document feeder 400, the document is transported and moved onto the contact glass 1032 and then the document is set on the contact glass 1032. Immediately after that, the scanner 300 is driven, and the first traveling body 1033 and the second traveling body 1034 travel. At this time, the light from the light source is emitted from the first traveling body 1033 and the reflected light from the document surface is reflected by the mirror in the second traveling body 1034 and is received by the reading sensor 1036 through the imaging lens 1035 to be color. A document (color image) is read and used as black, yellow, magenta, and cyan image information.

  Each image information of black, yellow, magenta, and cyan is stored in each image forming unit 1018 (black image forming unit, yellow image forming unit, magenta image forming unit, cyan image) in the tandem developing unit 120. Each of the image forming units forms black, yellow, magenta, and cyan toner images. That is, each image forming means 1018 (black image forming means, yellow image forming means, magenta image forming means, and cyan image forming means) in the tandem developing means 120 is a static image as shown in FIG. An electrostatic latent image carrier 1110 (an electrostatic latent image carrier for black 1010K, an electrostatic latent image carrier for yellow 1010Y, an electrostatic latent image carrier for magenta 1010M, and an electrostatic latent image carrier for cyan 1010C); The electrostatic latent image carrier 1110 is uniformly charged, and the electrostatic latent image carrier is exposed for each color image corresponding image based on each color image information (L in FIG. 11). An exposure device for forming an electrostatic latent image corresponding to each color image on the electrostatic latent image carrier, and the electrostatic latent image for each color toner (black toner, yellow toner, magenta toner). And a cyan toner) to form a toner image with each color toner, a transfer charger 1062 for transferring the toner image onto the intermediate transfer body 1050, a cleaning device 63, And a single-color image (a black image, a yellow image, a magenta image, and a cyan image) based on the image information of each color. The black image, the yellow image, the magenta image, and the cyan image formed in this way are respectively transferred to an electrostatic latent image carrier 1010K for black on an intermediate transfer member 1050 that is rotated by support rollers 1014, 1015, and 1016. The black image formed above, the yellow image formed on the yellow electrostatic latent image carrier 1010Y, the magenta image formed on the magenta electrostatic latent image carrier 1010M, and the electrostatic latent image carrier for cyan The cyan image formed on 1010C is sequentially transferred (primary transfer). Then, the black image, the yellow image, the magenta image, and the cyan image are superimposed on the intermediate transfer member 1050 to form a composite color image (color transfer image).

  On the other hand, in the paper feed table 200, one of the paper feed rollers 142 is selectively rotated to feed out a sheet (recording paper) from one of the paper feed cassettes 144 provided in multiple stages in the paper bank 143. The sheets are separated one by one and sent to the sheet feeding path 146, conveyed by the conveying roller 147, guided to the sheet feeding path 148 in the copying machine main body 150, and abutted against the registration roller 1049 to stop. Alternatively, the sheet feeding roller 142 is rotated to feed out the sheets (recording paper) on the manual feed tray 1054, separated one by one by the separation roller 1058, put into the manual feed path 1053, and abutted against the registration roller 1049 and stopped. . The registration roller 1049 is generally used while being grounded, but may be used in a state where a bias is applied to remove paper dust from the sheet. Then, the registration roller 1049 is rotated in synchronization with the synthesized color image (color transfer image) synthesized on the intermediate transfer member 1050, and a sheet (recording paper) is interposed between the intermediate transfer member 1050 and the secondary transfer device 1022. And transferring the composite color image (color transfer image) onto the sheet (recording paper) by the secondary transfer device 1022, thereby transferring the color image onto the sheet (recording paper). Is formed. The residual toner on the intermediate transfer member 1050 after the image transfer is cleaned by the intermediate transfer member cleaning device 1017.

  The sheet (recording paper) on which the color image has been transferred is conveyed by the secondary transfer device 1022 and sent to the fixing device 1025, where the combined color image (color) is generated by heat and pressure. (Transfer image) is fixed on the sheet (recording paper). Thereafter, the sheet (recording paper) is switched by the switching claw 1055 and discharged by the discharge roller 1056 and stacked on the paper discharge tray 1057 or switched by the switching claw 1055 and reversed by the sheet reversing device 1028 and transferred again. After being guided to the position and recording an image on the back side, it is discharged by the discharge roller 1056 and stacked on the discharge tray 1057.

  In the image forming method and the image forming apparatus of the present invention, the toner of the present invention having a sharp particle size distribution and good toner characteristics such as chargeability, environmental properties, and stability over time is used. A quality image can be formed.

  Examples of the present invention will be described below, but the present invention is not limited to these examples.

(Synthesis Example 1)
-Synthesis of fluorosurfactant 1-
A pressure-resistant reaction cell comprising 500 parts by weight of 1,1-dihydroperfluorooctyl acrylate and 2 parts by weight of V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2,4-dimethylvaleronitrile)) In this case, carbon dioxide was selected as a supercritical fluid, carbon dioxide was supplied into the treatment cell by a supply cylinder, and the pressure was adjusted to 20 MPa and 80 ° C. with a pressure pump and a temperature controller, and the reaction was performed for 24 hours. Next, the temperature was lowered to 0 ° C., and the pressure was lowered to normal pressure using a back pressure valve, to obtain fluorinated surfactant 1. The weight molecular weight (Mw) by GPC measurement was 150,000.

(Synthesis Example 2)
-Synthesis of fluorinated surfactant 2-
500 parts by weight of N-propyl-N- (β-acryloxyethyl) perfluorooctanesulfonamide and V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2,4-dimethylvaleronitrile)) 2 Part by weight is put into a pressure-resistant reaction cell, carbon dioxide is selected as a supercritical fluid, carbon dioxide is supplied into the processing cell by a supply cylinder, and adjusted to 20 MPa and 80 ° C. with a pressure pump and a temperature controller, The reaction was performed for 24 hours. Next, the temperature was lowered to 0 ° C., and the pressure was lowered to normal pressure using a back pressure valve, to obtain fluorinated surfactant 2. The weight molecular weight (Mw) by GPC measurement was 130,000.

(Synthesis Example 3)
-Synthesis of fluorinated surfactant 3-
500 parts by weight of 1,1-dihydroperfluorooctyl acrylate monomer and 25 parts by weight of V-65 (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobis (2,4-dimethylvaleronitrile)) 1,000 ml was put into the connected pressure-resistant reaction cell, carbon dioxide was selected as a supercritical fluid, the carbon dioxide was supplied into the processing cell by a supply cylinder, and 20 MPa, 65 ° C. was supplied by a pressure pump and a temperature controller. The reaction was carried out for 24 hours with stirring.
Subsequently, after completion of the reaction, the temperature was lowered to 0 ° C., and the pressure was lowered to normal pressure and atmospheric pressure using a back pressure valve, to obtain fluorinated surfactant 3 (Compound Example 1). The weight average molecular weight by GPC measurement of the obtained fluorosurfactant was 15,000.

(Synthesis Example 4)
-Synthesis of fluorosurfactant 4-
250 parts by weight of 1,1-dihydroperfluorooctyl acrylate monomer, 250 parts by weight of styrene monomer, 2 parts by weight of AIBN (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobisisobutyronitrile) were added to a stirrer. 1,000 ml was put in the pressure-resistant reaction cell, carbon dioxide was selected as a supercritical fluid, the carbon dioxide was supplied into the processing cell by a supply cylinder, and the pressure was increased to 30 MPa and 85 ° C. with a pressure pump and a temperature controller. The reaction was carried out for 24 hours. Subsequently, after completion of the reaction, the temperature was lowered to 0 ° C., and the pressure was lowered to normal pressure and atmospheric pressure using a back pressure valve, to obtain fluorinated surfactant 4 (Compound Example 2). The weight average molecular weight by GPC measurement of the obtained fluorosurfactant was 140,000.

(Synthesis Examples 5 to 15)
-Synthesis of fluorosurfactants 5 to 15-
Fluorinated surfactants 5 to 15 were synthesized in the same manner as in Synthesis Example 4 except that the fluorinated monomers and copolymerizable monomers were changed to those shown in Table 2.

(Synthesis Example 16)
-Synthesis of fluorosurfactant 16 by bulk polymerization-
A freezing ampoule (glass) containing 100 parts by weight of 2- (perfluorooctyl) ethyl acrylate and 0.2 parts by weight of AIBN (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azobisisobutyronitrile) (1) Freezing in a dewar bottle containing liquid nitrogen and (2) returning to room temperature and thawing while deaeration inside the ampoule with a vacuum pump. The operations from (1) to (2) were repeated about 20 times to deaerate the frozen ampoule, and then the ampoule upper part was heated and melted with a burner and sealed. This was placed in an oil bath at 120 ° C. and reacted for 72 hours while stirring in the ampoule. After completion of the reaction, the reaction mixture was cooled to room temperature, the ampoule upper part was cut, 500 parts by weight of hexafluorobenzene was added, the reaction product was dissolved, and this was dropped into 10,000 parts by weight of methanol for reprecipitation purification. Subsequently, this purification operation was performed three times to obtain a white fluorosurfactant 16 (yield 98%). The weight average molecular weight (Mw) by GPC of the obtained fluorosurfactant 16 was 1,200,000.

(Synthesis Example 17)
-Synthesis of fluorosurfactant 17 by living radical polymerization-
300 parts by weight of 2- (perfluorooctyl) ethyl acrylate, 18 parts by weight of 4-methoxy-2,2,6,6-tetramethylpiperidine 1-oxyl, AIBN (manufactured by Wako Pure Chemical Industries, Ltd., 2,2′-azo) 10 parts by weight of bisisobutyronitrile) is placed in a freezing ampoule (made of glass) containing a stir bar, and (1) after freezing in a dewar bottle containing liquid nitrogen while degassing the inside of the ampoule with a vacuum pump (2) Returned to room temperature and thawed. The operations from (1) to (2) were repeated about 20 times to deaerate the frozen ampoule, and then the ampoule upper part was heated and melted with a burner and sealed. After putting this in a 90 ° C. oil bath, the bath temperature was raised to 155 ° C. over 30 minutes, and the reaction was carried out for 96 hours while stirring the inside of the ampoule. After completion of the reaction, the reaction mixture was cooled to room temperature, the ampoule upper part was cut, 500 parts by weight of hexafluorobenzene was added, the reaction product was dissolved, and this was dropped into 10,000 parts by weight of methanol for reprecipitation purification. Further, this purification operation was performed three times to obtain a white fluorosurfactant 17 (yield 97%). The weight average molecular weight (Mw) by GPC of the obtained fluorosurfactant 15 was 95,000.

(Synthesis Example 18)
-Synthesis of polyester resin 1 as binder resin-
In a reaction vessel equipped with a thermometer, a stirrer, a cooler, and a nitrogen introduction tube, 64 parts of PO adduct (hydroxyl value 320) of bisphenol A, 544 parts of EO adduct (hydroxyl value 343) of bisphenol A, 123 parts of terephthalic acid And 4 parts of dibutyltin oxide, reacted at 230 ° C. for 3 hours at normal pressure, cooled to 180 ° C., 296 parts of dodecenyl succinic anhydride, and further reduced the acid value to 2 mgKOH / g or less at a reduced pressure of 10 to 15 mmHg. It reacted until. Thereafter, 20 parts of trimellitic anhydride was added and reacted at 180 ° C. for 2 hours at normal pressure. The polyester resin 1 was obtained from the reaction vessel. Polyester resin 1 had a Tg of 48 ° C., a number average molecular weight of 9000, a weight average molecular weight of 22,000, an acid value of 10 mgKOH / g, and a hydroxyl value of 17 mgKOH / g.

(Synthesis Example 19)
-Synthesis of polyester resin 2 as binder resin-
636 parts of PO adduct of bisphenol A (hydroxyl value 320), 191 parts of terephthalic acid and 4 parts of dibutyltin oxide were put in the same reactor as in Synthesis Example 17, reacted at 230 ° C. at normal pressure for 3 hours, and then up to 180 ° C. After cooling, 205 parts of dodecenyl succinic anhydride was added, and the reaction was continued under reduced pressure of 10 to 15 mmHg until the acid value became 2 mgKOH / g or less. Thereafter, 20 parts of trimellitic anhydride was added and reacted at 180 ° C. for 2 hours under normal pressure. The polyester resin 2 was obtained from the reaction vessel. Polyester resin 2 had a Tg of 55 ° C., a number average molecular weight of 5000, a weight average molecular weight of 10,000, an acid value of 11 mgKOH / g, and a hydroxyl value of 16 mgKOH / g.

Example 1
-Preparation of polymerizable monomer composition-
10 parts by weight of polystyrene resin (Picolastic A-75 (Mn = 731, softening point = 75 ° C.) manufactured by Rika Hercules Co., Ltd.), 10 parts by weight of styrene, and 5 parts by weight of carbon black (MA-made by Mitsubishi Chemical Corporation) 8) and 0.3 parts by weight of benzyl peroxide are charged into 100 parts by weight of toluene and mixed at a high shearing force with a homomixer (Special Machine Chemical Co., TK type) at 11,000 rpm. The number of rotations was stirred. To this solution, 40 parts by weight of styrene, 20 parts by weight of butyl acrylate, 1 part by weight of fluorosurfactant 1 and 4 parts by weight of ethylene glycol diacrylate are added and mixed to obtain a uniform dispersion. Then, a polymerizable monomer composition 1 was prepared.

<Supercritical polymerization process>
200 parts by weight of the polymerizable monomer composition 1 is filled in a pressure-resistant treatment cell, carbon dioxide is selected as a supercritical fluid, carbon dioxide is supplied into the treatment cell by a supply cylinder, The temperature was adjusted to 30 MPa and 85 ° C. with a temperature controller. To this, 0.5 part by weight of AIBN (azobisisobutyronitrile) as a polymerization initiator was added and reacted for 24 hours.

  After completion of the reaction, using a back pressure valve, supercritical carbon dioxide was flowed at a flow rate of 5.0 L / min for 6 hours to remove residual monomers and solvent, and then paraffin wax HNP-9 (Nippon Seiki Co., Ltd.). Manufactured, melting point: 79 ° C., penetration: 7) 5 parts by weight were added, press-fitted for 1 hour, and then gradually returned to normal temperature and normal pressure to obtain toner 1. When the particle cross section of toner 1 is divided by 20 nm square, the average value of the ratio of fluorine atom to carbon atom (F / C) in the section including the surface and the section adjacent to the section including the surface is 0.90. The average value of the ratio of fluorine atoms to carbon atoms (F / C) in the sections other than the two sections, the section including the surface of toner 1 and the section adjacent to the section including the surface, was 0.0046.

(Example 2)
A toner 2 was prepared by changing the fluorine-based surfactant 1 from the example 1 to the fluorine-based surfactant 2.

(Examples 3 and 4)
Toners 3 and 4 were prepared by changing the amount of the fluorosurfactant 1 from Example 1 to 3 parts by weight and 4 parts by weight.

(Comparative Examples 1 and 2)
Toners 5 and 6 were prepared by changing the amount of the fluorosurfactant 1 from Example 1 to 0.5 parts by weight and 20 parts by weight.

(Example 5)
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.

  Carbon black (Regal 400; manufactured by Cabot) 15 parts by weight and a pigment dispersant 3 parts by weight were primarily dispersed in 82 parts by weight of ethyl acetate using a mixer having stirring blades. Here, Ajisper PB821 (Ajinomoto Fine Techno Co., Ltd.) was used as the pigment dispersant.

  The resulting primary dispersion is filled with 1 mmφ zirconia beads and finely dispersed by a strong shearing force using a horizontal wet disperser (Dynomill, manufactured by Shinmaru Enterprise Co., Ltd.) to completely remove aggregates. Was prepared. Further, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid in which a resin as a binder resin and a wax were added was prepared. 100 parts by weight of polyester resin 1 as a binder resin, 30 parts by weight of carbon black dispersion, 5 parts by weight of carnauba wax, 1 part by weight of fluorine-containing block copolymer Modiper F600 (manufactured by NOF Corporation) As in the preparation of the colorant dispersion, 000 parts by weight was dispersed by stirring for 10 minutes using a mixer having stirring blades. The dispersion liquid at this stage was filtered with a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion liquid, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.4 × 10 ⁻⁷ S / m.

  The obtained dispersion was further diluted with ethyl acetate so that the solid content was 6.0%, and the liquid was supplied to the slurry dispersion storage container 35 of the toner production apparatus shown in FIG. As for the plate having the discharge holes used, ten discharge holes having a perfect circular exit diameter of 8.0 μm were formed on a nickel plate having a thickness of 20 μm on a concentric circle by removal processing by a mask reduction projection method using a femtosecond laser. The portion where the discharge holes exist was a square area with a side of 0.5 mm.

  After preparing the dispersion, after forming droplets under the following toner preparation conditions, the droplets were dried and solidified, and collected with a cyclone to obtain toner 7.

[Toner preparation conditions]
Dispersion solid content: 6.0%
Liquid flow rate: 40 ml / hr
Dry air flow rate: Sheath 2.0 L / min, In-apparatus air 3.0 L / min In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Common reservoir vibration frequency: 601.0 kHz

(Example 6)
Toner 8 was prepared by replacing Example 5 with Fluorine-containing surfactant Footgent F100 (manufactured by Neos) instead of Modiper F600.

(Example 7)
Toner 9 was prepared by changing from Example 5 to Fluorosurfactant 2 instead of Modiper F600.

(Example 8)
-Preparation of colorant dispersion-
First, a carbon black dispersion as a colorant was prepared.
Carbon black (Regal 400; manufactured by Cabot) 15 parts by weight and a pigment dispersant 3 parts by weight were primarily dispersed in 82 parts by weight of ethyl acetate using a mixer having stirring blades. As the pigment dispersant, Ajisper PB821 (manufactured by Ajinomoto Fine Techno Co., Ltd.) was used. The obtained primary dispersion was finely dispersed by a strong shearing force using a dyno mill to prepare a dispersion from which aggregates were completely removed. Further, a liquid having a pore size of 0.45 μm (manufactured by PTFE) and passing through a submicron region was prepared.

-Preparation of dispersion with added resin and wax-
Next, a dispersion liquid in which a resin as a binder resin and a wax were added was prepared. 100 parts by weight of polyester resin 2 as a binder resin, 30 parts by weight of carbon black dispersion, 5 parts by weight of carnauba wax, 1 part by weight of fluorine-containing block copolymer Modiper F600 (manufactured by NOF Corporation) As in the preparation of the colorant dispersion, 000 parts by weight was dispersed by stirring for 10 minutes using a mixer having stirring blades. The dispersion liquid at this stage was filtered with a 0.45 μm filter (made by PTFE) in the same manner as in the preparation of the colorant dispersion liquid, but it was confirmed that no clogging occurred and all passed. The electrolytic conductivity of this dispersion was 3.4 × 10 ⁻⁷ S / m.

-Toner creation-
The obtained dispersion was further diluted with ethyl acetate so that the solid content was 6.0%, and the liquid was supplied to the slurry dispersion storage container 35 of the toner production apparatus shown in FIG. As for the plate having the discharge holes used, ten discharge holes having a perfect circular exit diameter of 8.0 μm were formed on a nickel plate having a thickness of 20 μm on a concentric circle by removal processing by a mask reduction projection method using a femtosecond laser. The portion where the discharge holes exist was a square area with a side of 0.5 mm.

  After the dispersion was prepared, droplets were formed under the following toner preparation conditions, and then the droplets were dried and solidified and collected with a cyclone to obtain toner 10.

[Toner preparation conditions]
Dispersion solid content: 6.0%
Liquid flow rate: 40 ml / hr
Dry air flow rate: Sheath 2.0 L / min, In-apparatus air 3.0 L / min In-apparatus temperature: 27-28 ° C
Dew point temperature: -20 ° C
Vibration frequency: 601.0 kHz

Example 9
Except that 1 part by weight of the fluorine-containing block copolymer Modiper F600 (manufactured by Nippon Oil & Fats Co., Ltd.) in Example 8 was changed to 2 parts by weight, toner was obtained under the same conditions.

(Example 10)
A toner 12 was obtained in the same manner as in Example 8 except that 1 part by weight of the fluorine-containing block copolymer Modiper F600 (manufactured by NOF Corporation) was changed to 0.5 part by weight.

(Example 11)
Toner 13 was prepared in the same manner as in Example 8 except that Modifier F600 was replaced with a trade name: Fluorent F100 (manufactured by Neos), which is a fluorine-containing compound.

(Example 12)
Toner 14 was obtained in the same manner as in Example 8 except that 1 part by weight of Modiper F600 (manufactured by NOF Corporation) was changed to 5 parts by weight of fluorosurfactant 25.

(Example 13)
Toner 15 was obtained in the same manner as in Example 8 except that 1 part by weight of Modiper F600 (manufactured by NOF Corporation) was changed to 10 parts by weight of fluorosurfactant 2.

(Comparative Example 3)
All conditions were the same except that instead of 1 part by weight of the fluorine-containing block copolymer Modiper F600 (manufactured by NOF Corporation) of Example 8, it was changed to 3 parts by weight of a chromium-containing azo dye (Bontron S-34, manufactured by Orient Chemical Co., Ltd.). And toner 16 was obtained. However, Bontron E-84 is finely dispersed in ethyl acetate using a dyno mill, and further a dispersion from which aggregates have been completely removed is prepared and passed through a filter (made of PTFE) having 0.45 μm pores. A dispersion was used.

(Comparative Example 4)
A toner 17 was obtained in the same manner except that 3 parts by weight of the chromium-containing azo dye of Comparative Example 3 was changed to 1 part by weight.

(Example 14)
75 parts by weight of styrene, 25 parts by weight of methyl acrylate, 3 parts by weight of fluorosurfactant 3, 0.3 part by weight of divinylbenzene, 10 parts by weight of pentaerythritol tetrastearate (as a release agent, a melting point of 92 Of natural gas Fischer-Tropsch wax FT-100 (manufactured by D Shell MS Co., Ltd.) at a temperature of 1 ° C. with a TK homomixer (manufactured by Koki Co., Ltd.) capable of mixing with high shearing force. The resulting mixture was uniformly dispersed to prepare a monomer mixture 1.

  Next, 100 parts by weight of the monomer mixture 1 is filled in the pressure-resistant treatment cell, carbon dioxide is selected as a supercritical fluid, carbon dioxide is supplied into the pressure-resistant treatment cell by a supply cylinder, The temperature was adjusted to 30 MPa and 85 ° C. with a temperature controller. Further, 0.5 part by weight of AIBN was added and the reaction was performed for 24 hours.

  Next, after completion of the reaction, supercritical carbon dioxide was flowed at 5.0 L / min for 6 hours using a back pressure valve to remove residual monomers, and then oil black HBB (manufactured by Orient Chemical Co., Ltd.) 0.5 part by weight and 0.02 part by weight of Oil Orange 201 (manufactured by Orient Chemical Co., Ltd.) were added, dyeing was performed for 1 hour, and then gradually returned to normal temperature and normal pressure to obtain toner 18.

(Example 15)
80 parts by weight of styrene, 20 parts by weight of n-butyl acrylate, 10 parts by weight of fluorosurfactant 4, 0.5 part by weight of divinylbenzene, carnauba wax CWT01 (manufactured by Toyo Petrolite Co., Ltd.) 5 parts by weight, and C.I. I. Stir and mix at 11,000 rpm with a TK homomixer (manufactured by Tokki Kako Co., Ltd.) capable of mixing 7 parts of Pigment Blue (15: 3) with high shearing force to perform uniform dispersion. 2 was prepared.

  Next, 100 parts by weight of the monomer mixture 2 and 1 part of silica fine particles having an average particle diameter of 20 nm are filled into a pressure-resistant treatment cell equipped with a homomixer, and carbon dioxide is selected as a supercritical fluid. , Carbon dioxide was supplied into the pressure-resistant treatment cell by a supply cylinder, adjusted to 10 MPa and 65 ° C. with a pressure pump and a temperature controller, and stirred at 10,000 rpm. 5 parts) were added and reacted for 24 hours.

  After completion of the reaction, using a back pressure valve, supercritical carbon dioxide was flowed at 5.0 L / min for 6 hours to remove residual monomer, and then gradually returned to room temperature and normal pressure. Obtained.

(Example 16)
70 parts by weight of styrene, 20 parts by weight of n-butyl methacrylate, 10 parts by weight of 2-ethylhexyl methacrylate, 1 part by weight of fluorosurfactant 5 and 0.3 parts by weight of divinylbenzene can be mixed with high shearing force. A monomer mixture 3 was prepared by stirring at 11,000 rpm with a TK homomixer (manufactured by Special Machine Chemical Co., Ltd.) and mixing uniformly.

  Next, 5 parts by weight of synthetic ester wax WEP05 (manufactured by NOF Corporation), and C.I. I. 7 parts by weight of Pigment Blue (15: 3) is filled in a pressure-resistant cell equipped with a homomixer, carbon dioxide is selected as a supercritical fluid, carbon dioxide is supplied into the pressure-resistant cell by a supply cylinder, and pressurized. The pressure was adjusted to 25 MPa and 80 ° C. using a pump and a temperature controller, and the mixture was sufficiently stirred at 10,000 rpm. This was adjusted to 25 MPa and 50 ° C. to prepare dispersion 1.

  Next, 100 parts by weight of the monomer mixture 3 is filled in a pressure-resistant cell equipped with a stirrer, carbon dioxide is selected as a supercritical fluid, and carbon dioxide is supplied into the pressure-resistant cell by a supply cylinder. The pressure was adjusted to 25 MPa and 80 ° C. with a pressure pump and a temperature controller, and 2 parts by weight of AIBN was added while stirring to react for 24 hours.

  After completion of the reaction, using a back pressure valve, supercritical carbon dioxide was flowed at 5.0 L / min for 6 hours to remove residual monomer, and then dispersion 1 was added at 25 MPa and 50 ° C. to agglomerate. And the toner 20 was obtained.

(Examples 17-22, Comparative Examples 5-7)
In Example 14, toners 21 to 29 were prepared in the same manner as in Example 14 except that fluorinated surfactants 6 to 14 were used instead of the fluorinated surfactant 3.

(Comparative Example 8)
In Example 14, instead of using 25 parts by weight of methyl acrylate and 3 parts by weight of fluorosurfactant 3, 25 parts by weight of perfluorooctyl acrylate and 0.5 parts by weight of fluorosurfactant 3 were used. A toner 30 was prepared in the same manner as in Example 14 except for the above.

(Example 23)
In Example 14, a toner 31 was prepared in the same manner as in Example 14 except that the fluorinated surfactant 15 was used instead of the fluorinated surfactant 3.

(Example 24)
In Example 14, a toner 32 was prepared in the same manner as in Example 14 except that the fluorinated surfactant 16 was used instead of the fluorinated surfactant 3.

(Example 25)
In Example 14, a toner 33 was prepared in the same manner as in Example 14 except that the fluorosurfactant 17 was used instead of the fluorosurfactant 3.

<Distribution of fluorine atoms in the toner>
A toner sample was embedded in an epoxy resin, and a measurement sample was prepared by microtoming MT6000-XL (Keiwa Shoji Co., Ltd.), and the toner was made into an ultrathin section at about 100 nm, and then an electron energy loss spectrometer (Electron Energy Loss Spectroscopy, Gatan). The carbon element map image and the fluorine element map image of the toner are obtained with a transmission electron microscope JEM-2100F (manufactured by JEOL Ltd.) attached with the product, and corrected using the ionization cross section, and fluorine for each 20 nm square. The ratio of atoms to carbon atoms (F / C) was calculated.

  Here, five toner cross-sectional images having a minor axis of 80% or more than the weight average particle size obtained by Coulter Multisizer were selected as the toners to be observed.

  The abundance ratio of fluorine atoms in the toner outermost layer is the ratio of fluorine atoms to carbon atoms in a section including the surface of the toner and a section adjacent to the section including the surface (F / C).

  Further, the thickness of the fluorine-containing layer is mapped by mapping a region showing 0.8 times or more of the average value of the fluorine atom to carbon atom ratio (F / C) on the outermost layer of the toner, and the area is calculated to calculate the toner circumference. Obtained by dividing. Further, the fluorine abundance ratio inside the toner is calculated by calculating the average value of the ratio of fluorine atoms to carbon atoms (F / C) for 10 × 10 segments of 20 nm square at an arbitrary location 500 nm or more away from the surface. did.

  The average value of the ratio of fluorine atoms to carbon atoms (F / C) in the section including the surface of the toner of each example and comparative example and the section adjacent to the section including the surface, the section including the surface, and the surface The thickness of the layer showing the ratio of fluorine atoms to carbon atoms (F / C) that is 0.8 times or more the average value of the ratio of fluorine atoms to carbon atoms (F / C) in the section adjacent to the section including Table 3 shows the average value of the ratio of fluorine atoms to carbon atoms (F / C) in an arbitrary 20 nm square section separated by 500 nm or more from the surface.

Here, since Comparative Example 3 (Toner 16) and Comparative Example 4 (Toner 17) do not contain fluorine, the thickness of the fluorine-containing layer is not measured. In Comparative Example 8 (Toner 30), the fluorine element extends to the toner. Therefore, the thickness of the fluorine-containing layer was not clearly determined.

<Measurement of weight average particle size and particle size distribution>
About each obtained toner, the weight average particle diameter and particle size distribution by Coulter counter method were measured using Coulter counter TA-II. From the obtained distribution, the weight average particle diameter (D4) and number average particle diameter (Dn) of the toner were determined.

Further, the ratio (D4 / Dn) was obtained from the results of the weight average particle diameter (D4) and the number average particle diameter (Dn) of the obtained toner, and the particle size distribution was evaluated according to the following criteria. The results are shown in Table 3.
[Evaluation of particle size distribution (D4 / Dn)]
○: D4 / Dn is less than 1.05 Δ: D4 / Dn is 1.05 or more and less than 1.15 Δ: D4 / Dn is 1.15 or more

-Preparation of developer-
Silicone resin (SR2411: manufactured by Toray Dow Corning Silicone) was diluted to obtain a silicone resin solution having a solid content of 5%. 3% by weight of aminosilane coupling agent H ₂ N (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ is added to the solid content, and the copper-zinc ferrite particles (F -300, manufactured by Powdertech Co., Ltd.), the above silicone resin solution was applied at a rate of about 40 g / min in an atmosphere of 100 ° C., and further heated at 240 ° C. for 2 hours to obtain a silicone resin film. A carrier having a thickness of 0.38 μm was obtained.
On the other hand, 0.2 parts by weight of hydrophobic silica (Aerosil R-972, manufactured by Nippon Aerosil Co., Ltd.) was added to 100 parts by weight of the toner obtained in each Example, and the mixture was mixed with a Henschel mixer. Next, a developer comprising 5 parts by weight of the toner subjected to the external additive treatment and 95 parts by weight of the above-mentioned silicone-coated copper-zinc ferrite carrier was prepared.

  Next, the fixability, image density, image quality, fusion to the photoreceptor, and charge amount were measured for the obtained developer as follows.

<Image density, image quality, fixing quality>
About each obtained developer, the adhesion amount of each developer is 1.00 ± 0.05 mg on copy paper (TYPE6000, manufactured by Ricoh Co., Ltd.) using a tandem color printer (Ipsio CX9000, manufactured by Ricoh Co., Ltd.). An image having a chart area of 5% / cm ² was formed. The image formation was repeated on 10,000 sheets of the copy paper in an environment of 20 ° C. and 60% RH, and then the image density was measured and the image quality was evaluated. Then, after image formation was continuously repeated for 5,000 sheets in the same procedure under the environment of 10 ° C. and 30% RH and 30 ° C. and 90% RH, the image density was measured and the image quality was evaluated.

Here, the image density was measured using a Spectrodensitometer X-Rite 938 (manufactured by X-Rite) _under the conditions of a D65 light source, a viewing angle of 2 °, and a status T, and evaluated based on the following criteria.
〔Evaluation criteria〕
○: 1.4 or more △: 1.2 or more and less than 1.4 ×: less than 1.2

In addition, image evaluation was performed by visually observing and evaluating background stains, image blurring, blurring, and blurring.
〔Evaluation criteria〕
○: No soiling, blurring of image, blur, or blur is observed.
Δ: Any of background stains, image blurring, blurring and blurring is observed, but it is very slight.
X: Any one of background stain, image blur, blur, and blur is observed.
In the case where scumming, image blurring, blurring and blurring were observed, ×, in case of very slight occurrence, Δ in case of no occurrence.

The fixing quality was 10 continuously on each copy of paper (TYPE6000, manufactured by Ricoh Co., Ltd.) by taking a solid image of 50 mm × 30 mm with an adhesion amount of each developer of 1.00 ± 0.05 mg / cm ^2. Sheets were printed, and the 9th and 10th printed images were damaged with a drawing needle, and whether or not the toner was peeled off and the paper texture was visually observed was evaluated.
〔Evaluation criteria〕
○: No peeling is observed at all.
Δ: Partial toner peeling is observed, but not until the paper background is visible.
X: Toner is peeled off and the paper background is observed.

  After durability of 10,000 sheets in the initial stage and 20 ° C and 60% RH environment, after durability of 5,000 sheets in 10 ° C and 30% RH environment (after cumulative durability of 15,000 sheets), 5 in 30 ° C and 90% RH environment Tables 4 and 5 show the evaluation results of the image density, image quality, and fixability after 2,000-sheet durability (after 20,000-sheet durability).

<Charge amount>
After the above-mentioned 10,000 copies of the copy paper were repeatedly formed in an environment of 20 ° C. and 60% RH, continuous image formation of 5,000 sheets was repeated in a 30 ° C. and 90% RH environment at 10 ° C. and 30% RH. After performing the above, each developer was sampled at the time of image evaluation, 0.5 g developer was put into a Faraday gauge, and the toner was blown to obtain the charge amount. The measurement results are shown in Tables 4 and 5.

<Fusion to photoconductor>
After the formation of all the above images (after a total of 20,000 sheets), the fusion of the toner to the organic photoreceptor (OPC) was visually observed and fused to the photoreceptor. evaluated.
〔Evaluation criteria〕
○: No fusion of toner to the photoreceptor was observed.
Δ: Some fusion of toner to the photoreceptor was observed.
X: Fusion of toner to photoreceptor was observed.
Table 5 shows the measurement results.

  From the results of Tables 4 and 5, the developers obtained using the toners of Examples 1 to 25 are superior in charging performance as compared to the developers obtained using the toners of Comparative Examples 1, 5, 6, and 7. It was confirmed that a high image density was obtained. Further, it was found that the toners of Comparative Examples 2 and 8 have inferior fixing characteristics. Here, the image abnormality in the comparative example 1 is caused by the image fading due to the defective toner replenishment, and the abnormal images in the comparative examples 4, 5, and 7 are due to the image thickening and the solid portion transfer failure.

  The toner production method and toner production apparatus of the present invention can produce toner efficiently, and can produce particles having a monodispersibility with an unprecedented particle size. Furthermore, the toner containing the fluorine atom-containing compound produced by the toner production and having the charge control effect suitable for the production method satisfies both excellent charging characteristics and fixability. It is preferably used as a developer for developing an electrostatic image in electrostatic printing or the like.

  The toner manufactured by the toner manufacturing method of the present invention has a sharp particle size distribution, good toner characteristics such as charging property, environmental property, stability over time, low cost, and no waste liquid. No drying process is required, no residual monomer is contained, and the environmental load is small. For example, a laser printer, a direct digital plate making machine, a full-color copying machine using a direct or indirect electrophotographic multicolor image developing system It can be used widely for full-color laser printers and full-color plain paper fax machines.

FIG. 1 is an explanatory diagram of an example of a toner particle manufacturing apparatus. FIG. 2 is an explanatory diagram of an example of a storage unit. FIG. 3 is a schematic view of an apparatus (toner manufacturing apparatus) including a large number of nozzle plates. FIG. 4 is an enlarged schematic view of the droplet forming unit of the toner manufacturing apparatus. FIG. 5 is a scanning electron micrograph of the toner base prepared in Example 8. FIG. 6 is a schematic view showing an example of a polymerization granulator used in the polymerization granulation step of the present invention. FIG. 7 is a schematic explanatory view showing an example of the process cartridge of the present invention. FIG. 8 is a schematic explanatory view showing an example of an image forming apparatus used in the image forming method of the present invention. FIG. 9 is a schematic explanatory view showing another example of an image forming apparatus used in the image forming method of the present invention. FIG. 10 is a schematic explanatory view showing an example of an image forming apparatus (tandem color image forming apparatus) used in the image forming method of the present invention. FIG. 11 is a partially enlarged schematic explanatory view of the image forming apparatus shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Storage part 2 Vibration means 3 Support means 4 Ejection hole 5 Liquid supply means 6 Solvent removal equipment 7 Toner collection part 8 Liquid supply pipe 9 Housing 10 Waveform generator 11 Conductive wire 12 Drain 13 Droplet 14 Drying gas 15 Toner particle 21 Nozzle plate 22 Electrode 23 Solvent removal equipment 24 Static eliminator 25 Toner collection part 26 Toner particle 27 Vortex 28 Electric field curtain 29 Liquid supply pipe 30 Drying container 31 Droplet 32 Toner storage container 33 Drying gas supply pipe 34 Metering pump 35 Slurry dispersion liquid Storage container 37 Liquid supply flow path 39 O-ring 41 Housing 601 Carbon dioxide cylinder 602 Pressure pump 603 Valve 604 Back pressure valve 605 Constant temperature bath 606 Pressure-resistant reaction cell (reaction container)
607 Stirrer 608 Stirrer 810 Photoconductor (Photoconductor drum)
1010K electrostatic latent image carrier for black 1010Y electrostatic latent image carrier for yellow 1010M electrostatic latent image carrier for magenta 1010C electrostatic latent image carrier for cyan 1014 support roller 1015 support roller 1016 support roller 1017 intermediate transfer cleaning device 1018 Image forming means 820 Charging roller 1021 Exposure device 1022 Secondary transfer device 1023 Roller 1024 Secondary transfer belt 1025 Fixing device 1026 Fixing belt 1027 Pressure roller 1028 Sheet reversing device 830 Exposure device 1032 Contact glass 1033 First traveling body 1034 Second Traveling body 1035 Imaging lens 1036 Reading sensor 840 Developing device 841 Developing belt 842K Developer container 842Y Developer container 842M Developer container 842C Developer container 8 3K developer supply roller 843Y developer supply roller 843M developer supply roller 843C developer supply roller 844K development roller 844Y development roller 844M development roller 844C development roller 845K black development unit 845Y yellow development unit 845M magenta development unit 845C cyan Development unit 1049 Registration roller 850 Intermediate transfer member 851 Roller 1052 Separation roller 1053 Manual feed path 1054 Manual feed tray 1055 Switching claw 1056 Ejection roller 1057 Ejection tray 1058 Corona charger 860 Cleaning device 61 Development device 1062 Transfer charger 63 Cleaning device 64 Removal Electric device 870 Static elimination lamp 880 Transfer roller 890 Cleaning blade 895 Transfer paper 800 Image Generating device 701 Electrostatic latent image carrier 702 Charging means 703 Exposure 704 Developing means 705 Recording medium 707 Cleaning means 708 Transfer means 120 Tandem developer 130 Document table 142 Paper feed roller 143 Paper bank 144 Paper feed cassette 145 Separating roller 146 Feeding Paper path 147 Conveying roller 148 Paper feeding path 150 Copier main body 160 Charging device 200 Paper feeding table 300 Scanner 400 Automatic document feeder (ADF)

Claims (62)

  In an electrostatic charge image developing toner containing at least a binder resin and a colorant, when the toner particle cross section is divided by 20 nm square, fluorine atoms and carbon in a section including the surface and a section adjacent to the section including the surface The average value of the ratio to atoms (F / C) is 0.8 or more and less than 1.2, and the ratio of fluorine atoms to carbon atoms (F / C) in an arbitrary 20 nm square section separated by 500 nm or more from the surface ) An average value of 0.02 or less.   The ratio of fluorine atoms to carbon atoms (F / C) that is 0.8 times or more the average value of the ratio of fluorine atoms to carbon atoms (F / C) in the section including the surface and the section adjacent to the section including the surface The toner for developing an electrostatic charge image according to claim 1, wherein the layer representing C) has a thickness of 20 nm or more and less than 400 nm.   3. The toner composition liquid according to claim 1, which is obtained by discharging a toner composition liquid containing a surfactant having fluorine atoms from a discharge hole, forming the toner composition liquid into droplets, and turning the droplets into solid particles in the granulation space. The toner for developing an electrostatic charge image according to 1. The electrostatic image developing toner according to claim 3, wherein the surfactant having a fluorine atom contains a structure represented by the following general formula (1).
(In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.)   The electrostatic image developing toner according to claim 3, wherein the surfactant having a fluorine atom is a block copolymer containing a structure represented by the general formula (1). The electrostatic image developing toner according to claim 3, wherein the surfactant having a fluorine atom has a structure represented by the following general formula (2).
(Chemical formula 2)
Rf-X General formula (2)
Wherein X represents —COOM, SO ₃ M, —O—C ₆ H ₄ —SO ₃ M, —N (R ₁ ) ₃ , or —SO ₂ —N—Y ₂ , wherein R ₁ is Represents a hydrogen atom or a methyl group, M represents an alkali metal such as Na, K, or Li and an ammonium salt such as NH ₄ ; Y represents a hydrogen atom or a terminal hydroxyl group, a carboxy group or a salt thereof, amino An alkyl group which may have a group or a salt thereof, and Rf represents a C5-C8 perfluoroalkyl group, wherein R ₁ and Y may be the same group or different groups.   The electrostatic image developing toner according to claim 3, wherein the content of the surfactant having a fluorine atom is 0.03 to 3 parts by weight with respect to 100 parts by weight of the toner composition.   The electrostatic image developing toner according to claim 1, which is obtained by polymerizing and granulating at least a polymerizable monomer in a supercritical fluid or a subcritical fluid.   At least one of the supercritical fluid and the subcritical fluid contains a surfactant having a fluorine atom, and the polymer of the polymerizable monomer is insoluble in at least one of the supercritical fluid and the subcritical fluid. The toner for developing an electrostatic image according to claim 8.   The electrostatic image developing toner according to claim 9, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide. The electrostatic image developing toner according to claim 9, wherein the surfactant having a fluorine atom is a compound having a structural unit represented by the following general formula (1).
In the formula, R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.   The toner for developing an electrostatic charge image according to claim 11, wherein the composition ratio of the structural unit represented by the general formula (1) in the surfactant having a fluorine atom is 50 to 100 mol%. 11. The electrostatic image developing toner according to claim 9, wherein the surfactant having a fluorine atom is a compound obtained by reacting a compound represented by the following general formula (3).
In the general formula (3), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a C1-C2 alkylene group, and Rf represents a C4-C20 perfluoroalkyl group.   The electrostatic image developing toner according to claim 13, wherein the reaction is performed in supercritical carbon dioxide.   The electrostatic image developing toner according to claim 13, wherein the reaction is one of bulk polymerization and living radical polymerization.   The toner for developing an electrostatic image according to claim 9, wherein the surfactant having a fluorine atom has a weight average molecular weight of 5,000 to 500,000.   The toner for developing an electrostatic charge image according to any one of claims 9 to 16, wherein the content of the surfactant having a fluorine atom is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer.   The toner for developing an electrostatic charge image according to claim 9, wherein the polymerizable monomer is polymerized under a pressure of 8 to 100 MPa.   The toner for developing an electrostatic charge image according to claim 9, wherein the polymerizable monomer is polymerized under heating at 30 to 150 ° C.   The electrostatic charge image developing toner according to claim 9, wherein a release agent is contained in at least one of the supercritical fluid and the subcritical fluid.   21. The weight average particle diameter is 1 to 10 μm, and the ratio of the weight average particle diameter to the number average particle diameter (weight average particle diameter / number average particle diameter) is 1.00 to 1.15. The toner for developing an electrostatic image according to any one of the above.   9. A production method for producing a toner for developing an electrostatic image according to claim 1, comprising at least a binder resin and a colorant, wherein a fluorine-containing layer is formed on the toner particle surface. A discharge step of discharging a toner composition liquid containing a surfactant having fluorine atoms from a discharge hole of the nozzle, a droplet forming step of forming the toner composition liquid into droplets, and converting the droplets into solid particles in the granulation space. And a method for producing a toner for developing an electrostatic charge image.   In the discharging step, by applying pressure to the toner composition liquid in which the toner composition containing at least a binder resin and a colorant is liquefied, the toner composition liquid is continuously discharged from the discharge holes of the nozzles to form a columnar state. 23. The method for producing a toner for developing an electrostatic charge image according to claim 22, wherein the toner composition liquid is formed into droplets by applying vibration to the toner composition liquid in the droplet forming step.   The electrostatic charge image developing toner according to any one of claims 22 to 23, wherein the nozzle plate is formed of a metal plate having a thickness of 5 to 50 µm, and the opening diameter of the discharge hole on the nozzle plate is 3 to 35 µm. Manufacturing method.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 22 to 24, wherein a plurality of ejection holes are present on the nozzle plate.   26. The electrostatic charge image developing according to claim 22, wherein the toner composition liquid contains an organic solvent, and the solidification of the liquid toner composition liquid is performed by removing the organic solvent. Toner manufacturing method.   By causing a dry gas to flow in the same direction as the droplet discharge direction, an air flow is generated, and the air flow causes the droplets to be transported in the solvent removal equipment, and the solvent in the droplets is removed during the transport. 27. The method for producing a toner for developing an electrostatic charge image according to claim 26, wherein the toner particles are formed.   28. The method for producing a toner for developing an electrostatic charge image according to claim 27, wherein the dry gas is one of air and nitrogen gas.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 27 to 28, wherein the temperature of the dry gas is 40 to 200 ° C.   30. The solvent removal equipment has a transport path whose periphery is covered with an electrostatic curtain charged to a polarity opposite to the charge of the droplet, and allows the droplet to pass through the transport path. A method for producing a toner for developing an electrostatic image according to any one of the above.   31. The method for producing a toner for developing an electrostatic charge image according to claim 22, wherein the volume average particle size / number average particle size (Dv / Dn) of the toner particles is in the range of 1.00 to 1.15. .   32. The method for producing a toner for developing an electrostatic charge image according to claim 22, wherein the volume average particle diameter is 1 to 10 [mu] m.   22. A production method for producing an electrostatic charge image developing toner according to claim 1, comprising at least a binder resin and a colorant, and a fluorine-containing layer on the surface of the toner particles. Is a method for producing a toner for developing an electrostatic image, wherein at least a polymerizable monomer is polymerized and granulated in a supercritical fluid or a subcritical fluid. A method for producing a developing toner.   At least one of the supercritical fluid and the subcritical fluid contains a surfactant having a fluorine atom, and the polymer of the polymerizable monomer is insoluble in at least one of the supercritical fluid and the subcritical fluid. 34. A method for producing a toner for developing an electrostatic charge image according to claim 33.   35. The method for producing a toner for developing an electrostatic charge image according to claim 34, wherein at least one of the supercritical fluid and the subcritical fluid contains at least carbon dioxide.   36. The method for producing a toner for developing an electrostatic charge image according to any one of claims 34 to 35, wherein the surfactant having a fluorine atom has a weight average molecular weight of 5,000 to 500,000.   The production of the toner for developing an electrostatic charge image according to any one of claims 34 to 36, wherein the content of the surfactant having a fluorine atom is 0.1 to 20 parts by weight with respect to 100 parts by weight of the polymerizable monomer. Method.   38. The method for producing a toner for developing an electrostatic charge image according to claim 34, wherein the polymerizable monomer is polymerized under a pressure of 8 to 100 MPa.   The method for producing a toner for developing an electrostatic charge image according to any one of claims 34 to 38, wherein the polymerizable monomer is polymerized under heating at 30 to 150 ° C.   40. The method for producing a toner for developing an electrostatic charge image according to claim 34, wherein a release agent is contained in at least one of the supercritical fluid and the subcritical fluid.   8. A production apparatus for producing an electrostatic image developing toner according to claim 1, wherein a toner composition liquid in which a toner composition containing at least a binder resin and a colorant is liquefied is fixed. A droplet forming means for forming a droplet by discharging it from a nozzle plate oscillated at a frequency of, and a toner for forming toner particles by drying the droplet by removing the solvent contained in the droplet And a toner forming apparatus for developing an electrostatic charge image.   42. The apparatus for producing toner for developing an electrostatic charge image according to claim 41, wherein the droplet forming means has a vibrating means for directly vibrating the nozzle plate.   43. The apparatus for producing a toner for developing an electrostatic charge image according to claim 42, wherein the vibrating means vibrates the nozzle plate simultaneously with the passage of the toner composition liquid in which the toner composition is liquid.   44. The electrostatic charge according to claim 41, further comprising a storage unit that stores a toner composition liquid in which the toner composition is liquefied and supplies the liquid toner composition liquid to the droplet forming unit. An image developing toner manufacturing apparatus.   45. The nozzle plate is vibrated at a constant frequency by expansion and contraction of the piezoelectric body, and the number of ejection holes of the nozzle plate vibrated by one piezoelectric body is 1 to 5,000. Apparatus for developing electrostatic image developing toner.   46. The apparatus for producing an electrostatic charge image developing toner according to claim 41, wherein the constant frequency is 50 kHz to 50 MHz.   47. The apparatus for producing a toner for developing an electrostatic charge image according to claim 41, wherein the constant frequency is 100 kHz to 10 MHz.   8. A production apparatus for producing an electrostatic image developing toner according to claim 1, wherein a toner composition liquid in which a toner composition containing at least a binder resin and a colorant is liquid is stored. The toner composition liquid supplied from the storage means and the storage means oscillated at a constant frequency is discharged from the discharge holes to form droplets, and the solvent contained in the droplets is removed. And a toner particle forming means for drying the droplets to form toner particles. An apparatus for producing an electrostatic charge image developing toner, comprising:   49. The apparatus for producing an electrostatic charge image developing toner according to claim 48, wherein the droplet forming means has a vibrating means for directly vibrating the storage means.   50. The apparatus for producing an electrostatic charge image developing toner according to claim 41, comprising a plurality of nozzle plates and drying droplets discharged from each nozzle plate with a single solvent removal facility.   51. The toner particles formed by passing the droplets into the conveyance path are neutralized temporarily by a static eliminator, and then the toner particles are accommodated in the toner collecting portion. An apparatus for producing a toner for developing electrostatic images according to any one of the above.   52. The apparatus for producing a toner for developing an electrostatic charge image according to claim 51, wherein the static elimination by the static eliminator is performed by soft X-ray irradiation.   52. The apparatus for producing a toner for developing an electrostatic charge image according to claim 51, wherein the charge removal by the charge eliminator is performed by plasma irradiation.   The toner collecting portion for collecting the toner particles has a tapered surface whose opening diameter is gradually reduced. From the outlet portion where the opening diameter is reduced from the inlet portion, the toner particles are dried using the dry gas. 54. The apparatus for producing a toner for developing an electrostatic charge image according to claim 41, wherein a gas flow is formed, and toner particles are transferred to the toner storage container by the dry gas flow.   55. The apparatus for producing an electrostatic charge image developing toner according to claim 54, wherein the flow of the dry gas is a vortex.   56. The apparatus for producing an electrostatic charge image developing toner according to claim 41, wherein the toner collecting portion and the toner storage container are formed of a conductive material and are grounded.   57. The apparatus for producing a toner for developing an electrostatic charge image according to any one of claims 41 to 56, which has an exposure prevention specification.   A developer comprising the electrostatic image developing toner according to any one of claims 1 to 21.   A toner-containing container, wherein the electrostatic image developing toner according to claim 1 is contained in the container.   An electrostatic latent image carrier and development for forming a visible image on the electrostatic latent image carrier by developing the electrostatic latent image with the electrostatic image developing toner according to claim 1. A process cartridge having at least means and detachable from a main body of the image forming apparatus.   An electrostatic latent image forming step of forming an electrostatic latent image on the electrostatic latent image carrier, and developing the electrostatic latent image using the electrostatic image developing toner according to any one of claims 1 to 21. A developing process for forming a visible image, a transferring process for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium is heated and pressed using a roller-shaped or belt-shaped fixing member. And an image forming method comprising at least a fixing step of fixing. An electrostatic latent image carrier, an electrostatic latent image forming unit that forms an electrostatic latent image on the electrostatic latent image carrier, and the electrostatic latent image according to any one of claims 1 to 21. Developing means for developing a visible image by developing with toner for developing a charge image, transfer means for transferring the visible image to a recording medium, and a transfer image transferred to the recording medium in a roller shape or a belt shape An image forming apparatus comprising at least fixing means for fixing by heating and pressurizing using the fixing member.